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Intl' Conf.

on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

Simultaneous Photocatalytic Reduction of


Cr(VI) and Oxidation of Citric Acid in
Aqueous Solutions
Jeffrey. Baloyi, Tumelo. Seadira, Mpfunzeni Raphulu, and Aoyi Ochieng

insufficient treatment facility has become a serious health


hazard in the world [1, 2]. Thus has led to the transport and
introduction of various contaminants into aquatic
environment. Fresh water bodies are contaminated with
different types of pollutants both organic and inorganic. One
of the leading organic pollutants in water bodies are the
aliphatic organic compounds and untreated metals, like
Hg(II), Pd(II), Cd(II), Ag(I), Ni(II), Cu(II) and Cr(VI) were
another source of prolific water pollution. Thus toxic heavy
metals enter aquatic environment through the discharge of
treated or untreated industrial wastewater and municipal
sewage, storm water runoff, acid mine discharge (AMD), and
other diffuse sources [3].
The industrial wastewater such as acid mine discharge
(AMD) contains heavy metals ions that are generated by
acidity of the water from the rocks with which it interacts.
Thus toxic heavy metals are generally non-degradable and
have infinite lifetimes, and build up their concentrations in
food chains to toxic levels [4].
Heavy metals, such as Cr(VI) pollution is of great concern
because their toxicity threatens the human life and the
environment. Chromium is a multivalent ion, among which
Chromium (III) and Chromium (VI) states form stable
compounds. Chromium (VI) compounds (as in chromates,
CrO4- , and dichromates, Cr 2O7-2) [5] are mostly water soluble
and are extremely toxic to human with toxicity one hundred
times higher than that of Chromium (III), while Chromium
(III) lesser toxicity to human and assisted different enzymatic
reaction in human body such as regulate functioning glucose,
lipid, and protein metabolism, but long term exposure to a
high concentration of Cr(III) may cause poisoning symptoms
such as allergic skin reactions [6]. Furthermore Cr(III)
becomes problem in manganese (III/IV)-rich environments
because it can be oxidized to Cr(VI) [7]. Due to its high
toxicity level, efforts for removal of Cr(VI) ions from the
waste water have attracted much attention.
Several methods that have been actively investigated to
remove Cr(VI) ions are chemical precipitation, ion exchange,
adsorption, membrane filtration, electrochemical treatment
technologies, liquid extraction and biological treatment [8, 9].
These methods are non-economical and often ineffective at
low concentrations. Thus, it is clear that the prospect of
developing more efficient and durable systems become
necessary [10]. As a friendly environmental treatment

AbstractSemiconductor heterogeneous photocatalysis is a


relatively new technique for the removal of dissolved Cr(VI) in
wastewater and simultaneously oxidation of citric acid. The
feasibility of heterogeneous photocatalysis for the reduction of
Cr(VI) and oxidation of citric acid in aqueous solution using
titanium dioxide nanoparticles immobilized on ca-alginate beads
were investigated in the present study.
The simultaneous photocatalytic reduction of Cr(VI) and
oxidation of citric acid in aqueous solutions under ultraviolet (UV)
illumination has been studied by determining the amount of Cr(VI)
removed at different irradiation times, the amount of photocatalyst,
the Cr(VI) and citric acid initial concentration, the pH and the
Cr(VI)/citric acid ratio.
Experimental results showed that the photoreductionl rate of
Cr(VI) increased with decreasing the pH values and with increasing
initial citric acid concentration, catalyst dosage. In contrary the
photoreduction rate of Cr(VI) decreased with increasing initial
Cr(VI) concentration. Addition of ferric ion to Cr(VI)-citric acid
complex increased the reduction of Cr(VI). The relationship of the
chemical reaction rate of Cr(VI), Fe(III), citric acid, TiO 2 dosage,
initial pH and changes of initial Cr(VI) concentration was expressed
by the pseudo-first-order kinetic equation. The optimal conditions
were found as: pH 2, 2 g L1 of the photocatalyst and 20 mg/L of
initial Cr(VI) concentration.
These results support the fact that the UV/TiO 2 photocatalytic
reaction, with illuminated TiO2 immobilized on ca-alginate beads,
could be applied to effectively treat wastewater containing both
Cr(VI) and Cit than that containing a single species only.

KeywordsCr(VI);
citric
acid;
immobilized
photocatalytic reduction; photocatalytic oxidation.

TiO2;

I. INTRODUCTION

NVIRONMENTAL pollution due to the increase in the


level of global industrialization, urbanization and
inadequate effluents treatment due to lack of awareness and
Jeffrey. Baloyi is with the Center for Renewable Energy and Water, Vaal
University of Technology and Advance Material Division, Mintek, RSA (phone:
+2711 709 4182/ 076 512 4686; fax: +2711 793 2413; e-mail:
jeffreyb@mintek.co.za).
Tumelo. Seadira is with the Center for Renewable Energy and Water, Vaal
University of Technology and Advance Material Division, Mintek, RSA (email: tumelose@mintek.co.za).
Mpfunzeni. Raphulu is with Advanced Material Division, Mintek, RSA, (email: mpfunzenir@mintek.co.za).
Ochieng. Aoyi is with the Center for Renewable Energy and Water, Vaal
University of Technology, RSA, (e-mail: ochienga@vut.ac.za).

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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

process, photocatalysis has proved to be quite promising in


the elimination of Cr(VI) ions, which can comply with the
World Health Organization (WHO) guidelines: to decrease
the maximum concentration at less than 0.05 mg/L [11].
Photocatalytic reduction is a method coupling low-energy
ultraviolet (UV) light with semiconductor particle acting as
catalyst and based on the reduction by the photo-generated
electrons [1]. When semiconductor such as TiO2 is
illuminated by UV light with energy equal or greater than the
band gap of the photocatalyst, electron/hole pairs are
generated within the catalyst particles. The electrons will
initiate photoreduction of some reducible metal ions, while
the hole acts as a strong oxidizing agent. The aim of the
present investigation is to study the factors which affect the
photocatalytic reduction of Cr(VI) solutions using using TiO2
immobilized on calcium alginate.

mercury UV-C lamp (HPR 125 W) of predominant


wavelength 300-400 nm developed by Philips Lighting. The
lamp was placed inside a reactor box about 4 cm above the
cylindrical glass batch reactors containing 250 mL of
K2Cr2O7 (shown in Fig.1). The TiO2 nanoparticles
immobilized in calcium alginate which was in the form of
spherical beads were used as the photocatalyst. The lamp and
reactor were placed inside a dark box, which was covered
with aluminium foil so that no stray light could enter the
reactor.

II. EXPERIMENTAL
A. Materials and photocatalysts
Most chemicals, i.e. Potassium dichromate (K2Cr2O7),
sodium carbonate (Na2CO3), nitric acid (HNO3), Sodium
hydroxide
(NaOH),
mercury-chloride
(HgCl2),
Iron(III)Chloride Hexahydrate (FeCl3.6H2O), Degussa P-25
TiO2 powder and citric acid (cit), were purchased from Merck
Chemicals (Pty) Ltd., R.S.A. While sodium alginate and
calcium chloride (CaCl2), were purchased from Sigma
Aldrich. All of the chemicals were analytical grade and
employed as received. High purity water purified by a Milli-Q
water system (Millipore) was used throughout. Synthesized
pure rutile dandelion TiO2 sample, (surface area of 81 m2.g-1,
according to BET analysis), was employed as photocatalyst in
immobilized forms. Details on the procedures used for
preparation and characterization of the pure rutile dandelion
TiO2 sample can be found on the previous work [12].

Fig. 1 Experimental set-up for photocatalytic oxidation-reduction of


citric acid and toxic heavy metals.

D. Photocatalytic treatment
Photocatalytic experiments were carried out in a batch type
photoreactor at room temperature (25 2oC). Batch
experiments were carried out to investigate the effects of
initial pH, photo catalyst dosage, initial Cr(VI) concentration,
Fe(III) and citric acid on the reduction of Cr(VI). A desired
amount of photocatalyst was added to a reaction flask
containing 250 mL of an aqueous solution of K2Cr2O7, Fe(III)
and citric acid with defined concentrations (10 to 100 mg/L).
The stock solutions of Cr(VI), citric acid and Fe(III) were
prepared (1000 mg/L) by dissolving K2Cr2O7, citric acid and
FeCl3.6H2O, respectively in 1.0 L of high purity water. The
stock solutions were diluted with high purity water to obtain
the desired concentration range of Cr(VI), citric acid and
Fe(III) solutions. Constant stirring of solution has been
operated continuously by using magnetic stirrer for proper
mixing. The initial pH of solutions was adjusted by HNO3 or
NaOH aqueous solutions. Prior to photocatalytic experiments,
the UV-C lamp was preheated for 30 min to obtain a constant
light intensity. As the reaction progressed, 5 mL samples of
solution were withdrawn from the batch reactors at specific
time intervals for analysis. The absorbance of Cr(VI) was
measured using UV-vis spectrophotometer (HITACHI U2000) at 360 nm wavelength. Performance of the processes
was evaluated by analyzing the responses of Cr(VI).

B. Immobilization of TiO2 on biopolymer- Calcium


Alginate
The immobilizations of both photocatalysts were carried
out according to the procedures described by Harikumar et al.
[13]. One step encapsulation method for immobilization of
nanoparticles in semi permeable alginate beads was used. A
solution containing TiO2 nanoparticles (2.0 wt %) and
sodium alginate (2.0 wt %) was prepared with high purity
water, and stirred for 30 min at 25 2oC. After thoroughly
mixing, the calcium alginate beads were prepared by
dropping the former suspension in an aqueous solution of
CaCl2 (8.0 wt %) with the aid of a peristaltic pump, where
spherical gel beads were formed with a size of 1-2 mm. The
gel beads were retained in the CaCl2 solution for 12 h for
hardening and then washed with high purity water.
C. Experimental setup
The cylindrical glass batch photoreactors were used for
experimental purpose. The ultraviolet light source used was a
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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

alkaline conditions probably occurs via the following


reactions [14, 15]:

1) The effect of initial pH


The effect of initial pH experiments were performed with
250 mL of 20 mg/L initial Cr(VI) concentration. The effect of
initial pH on the photocatalytic removal was investigated in
the pH range 2.0 - 12 at 25 2oC. The initial pH of the
Cr(VI) solution was adjusted to the desired values by adding
few drops of 1.0 M HNO3 or NaOH.

Cr2O72- +14H+ + 6e 2Cr3+ +7H2O

(1)

Cr2O72-+ 14H2O + 3e Cr(OH)3+ 5OH

(2)

The photocatalytic reduction of Cr(VI) to Cr(III) consumes


protons in acidic solution and produces hydroxyls in alkaline
solution [16]. As the pH value increased, the photoreduction
rate of dichromate ions gradually decreased because the
increase of pH value reduced the adsorption of dichromate
ions on the surface of the photocatalyst; also, at alkaline pH
value, Cr(OH)3 covered the surface active position of TiO2 so
that the Cr(III) deposits on TiO2 depressed the photocatalytic
activity. The results are in agreement with the obtained
results in the presence of other studies [16, 17, 18, 19, 20],
who discussed the influence of different pH values of
photocatalyst on the reduction of Cr(VI) by UV/TiO2
photoreduction processes.

2) The effect of photo catalyst dosage


The catalyst dose experiments were also performed with
250 mL of 20 mg/L of Cr(VI) solutions. Varying the TiO2
dosage masses (1 to 2.5 g/L of solution at 25 2oC). The pH
of the solution was adjusted to optimum pH 2. Performance of
the processes was evaluated by analyzing the difference
between unabsorbed and adsorbed Cr(VI) metal ions.
3) The effect of initial Cr(VI) concentration
The effect of initial concentration is one of the important
parameters in photocatalytic process. Photocatalyst of 2 g was
added to 250.0 mL of Cr(VI) solution, varying initial
concentrations (10, 20, 30, 40, 50 mg/L) for Cr(VI) in
different 250.0 mL cylindrical glass batch photoreactors.
4) The effect of ferric ions and citric acid on the
photoreduction of Cr(VI)
To investigate the effect of ferric ions and citric acid on the
photoreduction of Cr(VI), photocatalytic experiments were
conducted in single and binary systems at optimum pH 2,
photocatalyst loading of 2 g/L. The initial concentrations used
were 20 mg/L Cr(VI), 20 mg/L of Fe(III) and 20-100 mg/L
citric acid solutions. Thus was done in order to evaluate the
possible synergistic effect of the simultaneous photooxidationphotoreduction of the Cr(VI) pollutants
III. RESULTS AND DISCUSSION
In order to understand the influence of initial pH,
photocatalyst dosage, initial Cr(VI) concentration, ferric ions
and citric acid on photoreduction of Cr(VI), this research was
carried out in two parts. The first part investigated the effect
of various experimental parameters mentioned above on the
photoreduction of Cr(VI), and the second part evaluated the
kinetic of the Cr(VI) photoreduction. These parameters were
considered one after the other as they influenced the
photoreduction of Cr(VI) in wastewaters. All the
investigations were carried out as batch experiments.

Fig. 2 Effect of initial pH on the reduction of Cr(VI) in solution (20


mg/L, 250 mL) with 2 g/L of TiO2.

B. Effect of photocatalyst dosage


Photoreduction patterns of Cr(VI) at different catalyst
dosage of TiO2 are shown in Figure 3. It was observed that
the photoreduction rate increased when the catalyst dosage
was increased from 1 to 2 g/L. However, further increase in
catalyst dosage to 2.5 g/L decreased the rate of
photoreduction. Decreased photoreduction efficiency at
higher catalyst dosage has been observed in photocatalytic
reactions by [21]. This behavior may be attributed to the
shielding at higher concentrations where the TiO2
photocatalyst reduces the penetration of light to the solution.
Ma et al., [22] and Wang et al., [23] have also observed that
photoreduction of Cr(VI) increased with increasing amount of
photocatalyst reaching highest value at optimum catalyst
loading of 2 g/L and then decreased.

A. Effect of initial pH
The reduction of Cr(VI) at different initial pH over time
under different pH values are shown in Figure. 2. The
variation of pH had an apparent influence on the reduction of
Cr(VI). The Cr(VI) reduction was gradually decline, with
increase of pH values. Higher reduction efficiency was
obtained when experiments were performed in acidic
solutions than that in alkaline solutions. At pH = 2, the
reduction rate was 88.75 %, but, at pH = 12, the reduction
rate was only 8.75 %. The reduction of Cr(VI) in acidic and
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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

D. The influence of citric acid on the photoreduction of


Cr(VI)
The wastewater contaminated by toxic heavy metals often
co exists with organic pollutants in actual wastewater
pollution systems. Theoretically, the photocatalytic reduction
of Cr(VI) on TiO2 should be more efficient in the metalorganic-TiO2 system than in the single system because of the
accelerating effect by the preferential photocatalytic oxidation
of the organics. In such metal-organic-TiO2 system, the
organic compound receives holes from valence band directly
or indirectly, and is oxidized [23]. Thus increasing the
photoreduction efficiency of Cr(VI) by suppressing the
electron-hole recombination. In an attempt to understand how
citric acid influences Cr(VI) reduction under photocatalytic
conditions, Cr(VI) reduction was analyzed on the systems
containing different initial citric acid concentration (20, 40,
60 and 80 mg/L).

Fig 3. Effect of photocatalyst dosage on the reduction of Cr(VI) in


solution (20 mg/L, 250 mL) with pH 2.

C. Effect of initial concentration


The effect of initial Cr(VI) concentration on Cr(VI)
photoreduction rate was investigated over the range of 10 to
50 mg/L. As illustrated in Figure 4, Cr(VI) reduction
efficiency gradually decreases with increasing the initial
concentration of Cr(VI) from 10 to 50 mg/L. After 120 min,
the percentage of Cr(VI) was at 88.7% at concentration of 10
mg/L and 42.5% at concentration of 50 mg/L under the same
operating conditions. As the light intensity, catalyst amount
and irradiation time are constant, with increasing initial
Cr(VI) concentration, there will be fewer active sites on the
catalyst available for photoreduction of Cr(VI) to Cr(III)
[14,15].

Fig. 5 Influence of citric acid concentration on the Cr(VI)


photoreduction in solution ( optimum experimental conditions; pH
2, 20 mg/L initial Cr(VI) concentration and 2 g/L catalyst dosage ).

The influence of citric acid on photoreduction of Cr(VI) are


shown in Figure 5. In the presence of 20 and 40 mg/L citric
acid, 62.5% and 90% was removed after 120 min
illumination, respectively. While, after 60 min illumination,
100% and 97.5% was removed in the presence of 60 and 80
mg/L, respectively. The photoreduction rate increases with
increase of initial citric acid concentration from 20 to 60
mg/L. Further increase in the initial citric acid concentration
to 80 mg/L leads to decrease in the photoreduction rate. The
observed faster complete photoreduction of Cr(VI) in the
initial citric acid concentration of 60 mg/L can be attributed
to the minimum electron-hole recombination due to sufficient
concentration of hole scavenger. At this initial citric acid
concentration the oxidation of citric acid consumes
photogenerated holes rapidly and efficiently from TiO2
particles, which suppress electron-hole recombination and
accelerates photoreduction Cr(VI) on TiO2. Previous studies
reveal that the presence of organic compounds as sacrificial

Fig. 4 Effect of initial Cr(VI) concentration on the reduction of


Cr(VI) in solution (250 mL) with optimum catalyst dosage of 2 g/L
and pH 2.

At higher concentration the path length of photons


entering the solution decreased, and a fewer photons reached
the catalyst surface. Furthermore, an increase in Cr(VI)
concentration can lead to the saturation of the limited number
of accessible active sites on the photocatalyst surface,
resulting in a reduction in the Cr(VI) photoreduction rate.

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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

electron donor can accelerate the photoreduction of Cr(VI)


[24, 4, 25]. At initial citric acid concentration (80 mg/L)
beyond the optimum, the tendency towards saturation of
limited number of accessible active sites on the TiO2
increases, resulting in a decrease in photoreduction rate.
As discussed above, Cr(VI) was reduced through
photocatalytic reduction by the photogenerated electrons from
TiO2 photocatalyst and redox between the excited citric acid.
The over reaction in this photocatalysis is the reduction of
Cr(VI) to Cr(III) and the oxidation of citric acid to CO2
which is generally depicted as follows:

are the two conditions which is good for enhancement of


Cr(VI) photoreduction. Furthermore Fe(III) can be absorbed
by TiO2 and, subsequently, easily photoreduced to Fe(II) by
accepting photo-reduced electrons on the surface of the TiO2
catalyst. In the presence of Fe(III), Cr(VI) is reported by [23]
to be photoreduced by the following redox reactions:

4Cr2O72- + C6H5O73- + 41H+ + 6e23H2O

F. The kinetic model analysis of photoreduction of Cr(VI)


The previous part of this study investigated the effect of
various experimental parameters namely, initial pH, catalyst
dosage and initial concentration on the photocatalytic
reduction-oxidation of Cr(VI), citric acid ferric ions. The
results indicated that all selected experimental parameters
plays an important role on the photocatalytic reduction of
Cr(VI).
This section aims to evaluate its kinetics rates since
understanding kinetics of this process would allow
appropriate design when this technique is applied in watertreatment systems. And further determine a kinetics rate
expression which can be used to model the photocatalytic
reduction of Cr(VI) as function of time. Numerous kinetic
models were tested in the present study. On the basis of
experimental data obtained, the kinetics rate expression of the
reactions was assumed to be the pseudo-first-order with
respect to the initial concentration:

Fe(III) + e-

Fe(II)

3Fe(II) + Cr(VI) 3Fe(III) + Cr(III)

8Cr3+ + 6CO2 +
(3)

E. Effect of Fe(III) on the photocatalytic reduction of


Cr(VI) by citric acid

(4)
(5)

(6)

where r is the rate of reaction, C is the Cr(VI)


concentration at time t, C0 Cr(VI) is the concentration at the
initial time and kapp (min-1) is the apparent Cr(VI) rate
constant. The integration of Eq. (6) with boundary conditions
of C = C0 at t = 0 yields:

Figure 6. Influence of Fe(III) on the Cr(VI) photoreduction in


solution ( optimum experimental conditions; pH 2, 20 mg/L initial
Cr(VI) concentration, 20 mg/L Fe(III) and 2 g/L catalyst dosage ).

Figure 6 shows the Cr(VI)-citric acid complex


photocatalytic reduction-oxidation profiles at pH 2 with 2 g/L
of TiO2 in the absence and in the presence of Fe(III). It can be
seen in Figure 6 that the addition of Fe(III) improves Cr(VI)
photoreduction. This can be attributed to the Fe(III), which
can maintain the acidic pH during the process. The
enhancement of the photoredution of Cr(VI) by the addition
of Fe(III) may be explained as follows. In the acid solution,
Fe(III) should be present as Fe3+ which is easily reduced to
Fe2+ by catching the electrons provided by photocatalyst.
Based on the reduction of Fe3+, there sholud be a competition
between Cr(VI) and Fe3+ in the photoreduction.
Consequently, the photoreduction of Cr(VI) should be lower
than that occuring in the absence of Fe3+. This is in contrast
with the result obtained in this study. The results obtained can
be possible be explained by Fe2+ resulted from the Fe3+
oxidation is oxidized back rapidly by OH radicals present in
the solution with releasing electron which is used for Cr(VI)
reduction. The capturing OH radical and donating electron

(7)

where t is the time of the reaction.

Fig. 7 Relationship of the Cr(VI) rate constant under different pH


values of the solution. (optimum initial concentration of 20 mg/L
and 2 g/L of TiO2 catalyst).
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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg
TABLE II
THE FIRST ORDER KINETIC PARAMETERS OF DIFFERENT TIO2 DOSAGE IN
CR(VI) SOLUTION

The linear trend observed in Figure 7 proves that the


photoreduction of Cr(VI) at the conditions of the reactions
follows a pseudo-first-order kinetics. As pH values increased,
the photoreduction rate of dichromate ions gradually
decreased because the increase of pH value reduced the
adsorption of dichromate ions on the surface of the TiO2. At
high pH value, Cr(OH)3 covered the surface active sites of
TiO2 so that the Cr(III) deposits on TiO2 depressed the
photocatalytic activity [18]. Similar observation was reported
for photoreduction of Cr(VI) by Ma et al [22]. The apparent
Cr(VI) rate constant calculated from the slopes of lines and
their corresponding pH values are shown in Table 1. It is
apparent from the results in Table 1 that the data fits well
with the pseudo-first-order kinetic model equation.
TABLE I
THE FIRST ORDER KINETIC PARAMETERS OF DIFFERENT INITIAL PH OF CR(VI)

Fig 9 Relationship of the Cr(VI) rate constant under different initial


Cr(VI) concentration. (optimum catalyst dosage of 2 g/L, at pH 2 of
the solution was present).

Table 3 shows the fitting results of the kinetic models


basing on the experimental data with different initial
concentrations in figure 9. It can be seen that all the fitting
results show a well linear relationship of apparent rate
constant as function of initial concentration. According to the
results, the reaction rate was decreased with increasing the
initial Cr(VI) concentration. This is attributed to the reduced
number of reached photons at the TiO2 surface.
TABLE III
THE FIRST ORDER KINETIC PARAMETERS OF DIFFERENT INITIAL CR(VI)
CONCENTRATIONS

Fig. 8 Relationship of the Cr(VI) rate constant under different TiO 2


dose. (optimum experimental conditions: initial concentration was
20 mg/L and initial pH 2).

Figure 8 shows the apparent rate constant as a function of


TiO2 dosage using the pseudo-first-order kinetic. As it can be
seen the photoreduction of Cr(VI) was successfully fitted
using pseudo-first-order kinetic, as confirmed by the obtained
straight line. The photoreduction reaction rate increased as
the TiO2 dosage increases, indicating that the increase of
TiO2 dosage aided the photocatalytic reaction. The values
which correspond to different catalyst dosages, along with the
regression coeffients, are listed in Table 2.

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Intl' Conf. on Chemical, Integrated Waste Management & Environmental Engineering (ICCIWEE'2014) April 15-16, 2014 Johannesburg

the apparent rate constant on the initial Cr(VI) concentration,


initial pH and catalyst dosage is expressed by a linear
equation.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]

Fig. 10 Kinetics of photoreduction of Cr(VI) in absence and


presence of citric acid at optimal experimental conditions of pH 2, 2
g/L of TiO2, 20 mg.L-1 initial Cr(VI) concentration and 60 mg.L-1
initial citric acid concentration.

[11]
[12]

Figure 10 shows the kinetic analysis of Cr(VI) reduction in


the absence and presence of citric acid. Plotting Ln (C0/C) as
function of illumination time (t) yields a straight line, thus
confirms that the experimental data obtained can be described
by the pseudo-first-order kinetic. After the addition of citric
acid as hole scavenger, the pseudo-first-order Cr(VI)
photoreduction rate was higher than before the addition. It is
apparent from the results in Table 4 that the experimental
data obtained in the absence and presence of citric acid fits
well with the pseudo-first-order kinetic model equation.

[13]
[14]
[15]
[16]
[17]
[18]
[19]

TABLE IV
THE FIRST ORDER KINETICS OF PHOTOCATALYTIC DEGRADATION OF CR(VI) IN
PRESENCE AND ABSENCE OF CITRIC ACID AT OPTIMAL CONDITIONS OF PH 2, 20
-1
-1
MG.L INITIAL CONCENTRATION AND 2 G.L T IO2

[20]
[21]
[22]
[23]
[24]

IV. CONCLUSION

[25]

The photoreduction of Cr(VI) in aqueous solution was


successfully achieved using pure rutile dandelion-like TiO2
under UV irradiation. The photoreduction reaction rate
decreased with increasing the initial Cr(VI) concentration
and pH values of the solution. On the other hand the
photoreduction reaction rate increases with increasing the
TiO2 dosage. The photoreduction was favourable at optimal
dose of 20 mg/L initial Cr(VI) concentration, 2 g/L catalyst
dose of solution at pH 2. It can be concluded that the presence
of citric acid significantly improves the photoreduction of
Cr(VI) ion into non-toxic Cr (III) ion, as a function of
concentration. Addition of ferric ions to Cr(VI)-citric acid
complex are shown to have a dramatic accelerating influence
on the Cr(VI) reduction, which was accomplished within 30
min of illumination time. The photoreduction of Cr(VI) fits
well with a pseudo-first-order kinetic and the dependence of
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