Int. j. eng. sci., Vol(3), No (3), March, 2014. pp.

19-24

TI Journals

ISSN:

International Journal of Engineering Sciences

2306-6474

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Elimination of Hardly Oxidized Organic Pollutants Using

Sunlight/TiO2/H2O2 System
Samia M. Mokhtar
Prof. of chemistry/ Ain shams Uni./Cairo Egypt.

Khaled M. Elsousys *
Assoc. professor of chemistry/ Alaqsa Uni./Gaza Strip.

Monther F. Salem
PhD stusent/ Ain shams Uni./Cairo Egypt.
*Corresponding author: khasousi@yahoo.com

Keywords

Abstract

Sun-light
Organic-pollutants
Hydrogen peroxide
Titanium dioxide
Oxidation
Kinetics

Elimination of five organic dyes having various oxidation potentials was tested. (Sunlight/TiO2/H2 O2)
system was used under the same experimental conditions, where a controllable laboratory simulation system
was built. The tested dyes were: Picric acid, remazol blue B, methyl blue, methyl violet and malachite green.
More detailed kinetic study was conducting concerning the most persisting one which appeared to be picric
acid according to primary test. The influence of the process related parameters such as: Light intensity, pH,
temperature, catalyst dose and the initial pollutant was studied. It follows from the results that the
elimination process is efficient. The rate of elimination was directly proportional to each of: Sunlight
intensity, pollutant and H2 O2 initial concentration and TiO2 dosage. The process was found to be Arhenius
type, exothermal reaction. Electron spin resonance tests confirmed the free radical mechanism through the
oxidation process.

1.

Introduction

The use of photo-catalyst in the presence of oxygen source to destroy organic pollutants in contaminated air or water has been extensively
studied for the last 30 years. [1] The involvement of sun light in this process is well documented.[2] Advanced oxidation processes (AOPs) has
become an important group of techniques to the treatment of organic water contaminants.[3] All AOPs are based on the generation of the
powerful oxidant hydroxyl free radical. AOPs are classified in different ways according to the reaction phase wither homogeneous,
heterogeneous, otherwise to the OH radical generation method (catalytic, electro-chemical, photo-chemical, radio-chemical or photo-catalytic).
Photo-catalytic oxidation process (PCOPs) has a main advantage over other AOPs which is incorporating solar energy in the form of solar
photons to have an additional environmental value. [4]
The powerful OH free radical oxidizer is characterized by low selectivity of attack which is a useful attribute for an oxidant used in waste water
treatment. The OH free radical has the highest oxidation potential among the other clean oxidants such as O, O 3, H 2O2 and O2 .[5,6,7] Advanced
oxidation process can be divided into three main types (1) heterogeneous photo-catalyst, (2) homogeneous photo-catalysts and (3) fentonphoto-process. [8,9] When titanium dioxide TiO2 nano particles adsorbs light or UV radiation, the heterogeneous catalyst surface generates holes
and electrons which produces (OH free radicals or O 2- ions) by the reaction with water, H2O2 or O2 on the catalyst surface.[10,11]
Alkanes, alkenes, alcohols, carboxylic acids, alkynes, dyes phenols, aromatic hydrocarbons, halogenated alkanes and surfactants were reported
to go photo catalytic oxidation in water. Titanium dioxide photo catalyst has beside its heterogeneity; a high chemical stability, energy saving,
cheapness and safety. [8] Many applications, such as air purification, water purification, discoloration and antibacterial coating were reported.
[12, 13]
To date there is evidence supporting the idea that OH free radical is the main oxidizer species responsible for photo oxidation of the majority of
the studied organic compounds. Kinetics (rates) of oxidation under these conditions is thought to be affected by some other parameters like:
Pollutant resistively which is related to the oxidation potential of the organic pollutants and derivatives, processing temperature and acidity of
the aqueous media.
In this study a simulation system was built for a systematic study of the influence of different factors besides the sunlight influencing the process
efficiency, capacity and velocity.

2.

Experimental

2.1 Materials
Nono-powder TiO2 was purchased from Shanghai acid (2, 4 trinitrophenol) was locally prepared by the nitration of phenol [14], Remazole blue
B was purchased from (Briliant Blue Dystar LP, India). Methyl blue, methyl violet and malachite green, sodium hydroxide and hydrogen
peroxide solution 35% were purchased from (Akross/ Begium). Phosphoric acid 85% was analytical grade of (Merck/Germany). Nanling
Chemical products Co. ltd.

Samia M. Mokhtar, Khaled M. Elsousys *, Monther F. Salem

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International Journal of Engineering Sciences Vol(3), No (3), March, 2014.

2.2 Instruments
Spectrophotometer (CECEIL instrument/ England) has been used for spectro-photometric measurements, A Hanna pH-meter was used to adjust
the pH of different solutions.

Figure 1: Kinetic experimental installation

Thermo stated water bath connected to thermo jacket was used to maintain process temperature. Locally built working system [a Pyrex beaker in
a thermo stated jacket, with magnetic stirrer, a light source 300 watt- (APOFHS lamp)] all installed like in figure 1. ESR measurements were
conducted by means of (Brruker E 500-Elexsys with CW-X-1 GH).
2.3 Methodology
Photo catalytic oxidation study was conducted for samples identically; working temperature, total volume, stirring power, TiO2 dosage,H2O2
initial concentration and the same light source otherwise mentioned. Substrates concentration was followed spectro-photometrically each at its
proper wave length (max), after getting the maximum absorption frequency and having a calibration curve. Centrifugation was used to separate
TiO2 nono-particles at 4500RPM.
Kinetic investigation was performed such that; In each experimental run one parameter only was changeable while keeping the other parameters
identical. Pseudo first order method was used. Detection error was 2 % maximum for spectral readings at wave lengths: 355 nm for picric acid,
570 nm for Remazole Blue B, 665 nm for methyl blue, 690 nm methyl violet and 625 for malachite green. Reaction parameters such as TiO2
dosage, light dosage per solution volume per unit time J l-1 s-1, process temperature and pH were studied. The resultant rate constants were
plotted clarified the relations graphically.
Sunlight was used one time for three identical runs aiming the comparison with another three identical runs using the artificial light source in our
system. The average readings were taken in consideration, for the same interval (11.00 AM to 1.00 PM, noon, July, 22, Gaza city). The other
controlled experimental runs were out using the artificial simulation system shown in figure 1. Light dosage was controlled depending on the
inverse square law (light intensity is inversely proportional to distance2, where the light source was placed at deferent distances of the reaction
vesicle, getting a precise calculated relative intensity. The reaction pH was adjusted by H3PO4 - NaOH control.
A 1.0 ml volume of reaction mixture including picric acid and H2O2 was taken (at zero time) for electron spin resonance reading. The under peak
area was compared with that for rule spin trap alone 1: (picric alone) and 2: (picric + tempo).

3.

Results and discussion

3.1 Sunlight compared to artificial light source

The sunlight of intensity (110 10 watts Cm-2) was compared experimentally with the approved lamp light under the same conditions (500 mg
TiO2 , 500 ml reaction volume, 25 0.1 0C). It follows from the obtained results that the observed rate constant (k obs) in the case of sunlight was
11.3x10-3 s-1, while it was in the case of artificial lamp 3.1x10-3 , which means relative efficiencies of (3.64 to 1.00). The last ratio means that the
efficient bands of (wave lengths) in the two cases are present at this ratio under the present experimental conditions.

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Elimination of Hardly Oxidized Organic Pollutants Using Sunlight/TiO2/H2O2 System

International Journal of Engineering Sciences Vol(3), No (3), March, 2014.

Figure 2: Comparison between sunlight and artificial lamp light, 25oC, 0.5 g TiO 2,
900 mg/l H2O2, pH 7, 500 ml solution volume, light source distance 8.0 cm.

3.2 Comparison among different organic pollutants

Degradative oxidation rates of; Remazole blue B, methyl violet, methyl blue, malachite green and picric acid where compared. It can be
observed from kobs values that the rates were in the order of (malachite green > Remazole blue B > methyl violet > methyl blue> picric acid) as
shown in fig 3. Picric acid was selected for more detailed study since it was found the most persisting pollutant among the five dyes.

Figure 3: Comparison of Organic pollutant concentrations Vs oxidation time, 25oC, 0.5 g TiO 2,
900 mg/l H2O2, pH 7, 500 ml solution volume, light source distance 8.0 cm.

3.3 Effect of the initial concentration of hydrogen peroxide

The influence of [H2O 2]o was studied under the same operation conditions. In the studied range of H 2O2 concentration; the reaction initial rate
was increasing directly with respect to [H2O2] o at law concentrations as shown in fig 4, which means that the reaction is first order in H2 O2. A
straight line relation was obtained graphically up to (900 mg/l), the next part gave a fractional order period which means non efficiency of
increasing hydrogen peroxide concentration.

Figure 4: Effect of the initial concentration of H2O 2 on the oxidation rate, 25oC, pH 7, 0.5 g TiO 2,
900 mg/l H2O2, 500 ml solution volume, light source distance 8.0 cm.

Samia M. Mokhtar, Khaled M. Elsousys *, Monther F. Salem

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International Journal of Engineering Sciences Vol(3), No (3), March, 2014.

3.4 Effect of dosage of TiO2 photo-catalyst

The reaction rate was increasing directly up to 500 mg of TiO2 per 500 ml of the treated water (reaction volume), this point can be considered
the optimal condition with respect to catalyst dosage. Increasing the dose is not efficient since the reaction rate is decreasing by increasing the
dosage higher than the considered optimum dosage. The relation is plotted in figure 5. It can be thought that increasing the dosage above
500mg/500ml causes higher light scattering which prevents the incident light to penetrate through the reaction solution.

Figure 5: Effect of the photo-catalyst (TiO 2) dosage on the oxidation rate, 25oC, pH 7,
500 ml solution volume, 900 mg/l H2O2light source distance 8.0 cm.
3.5 Effect of processing temperature
The oxidation process was studied in the range of (40 to 60oC), It is clear in fig 6 that there is an inverse relationship between ln kobs and (1/T). A
straight line was obtained which means an Arrhenius type reaction.

Figure 6: Arrhenius plot for photo-catalytic oxidation of picric acid, pH 7,

light source distance 8.0 cm, 0.5 g TiO2, 900 mg/l H2O2, 500 ml solution volume.

3.7 Effect of pH on the process rate

The influence of pH of the reaction aqueous media was examined, choosing three ph values; 5.0, 7.0 and 9.0. Values of the obtained kobs were
respectively 2.3x10-3, 3.0 1x10-3 and 4.0 x10-3s-1 . The last result means that more basic treated water is expected to be treated faster.
3.8 light intensity Effect of on the process rate
Light intensity was changed by changing the distance between the light source and the reaction surface. It was obtained as shown in fig 7 that the
oxidation rate was increasing by decreasing the distance square root (1/r 2) and hence increasing the light intensity. Increasing light intensity is
thought to produce more holes and electrons on the photo catalyst which enhances the formation of hydroxyl free radicals (OH.).

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Elimination of Hardly Oxidized Organic Pollutants Using Sunlight/TiO2/H2O2 System

International Journal of Engineering Sciences Vol(3), No (3), March, 2014.

Figure 7: Effect of light source distance (light intensity) on the oxidation rate, pH 7, 0.5 g TiO2, 900 mg/l H2O 2, 500 ml solution volume.

3.9 Electron spin resonance Measurements ERS

ERS were conducted concerning the presence of free radicals through the reaction processing, the test was positive. The formation of OH free
radicals through the reaction course was confirmed. The decease of the area under peak; classified clearly that the produced hydroxyl free radical
associated with the 4 hydroxy-tempo (spin trap) and led to this decrease.
3.10 Evaluation of the relative coast and efficiency
Comparison of the present method with other similar methods is shown in table 1. [15] It is obvious after calculations based on international
market prices, concerning also the processing rate that this method is the cheapest among the other compared methods but not the fastest.
Relative coast and efficiency of removing picric acid was calculated for (one hr treatment/ one cubic meter of treated water containing 1000 g of
picric acid as an organic pollutant).
Table 1: Advanced oxidation methods, efficiencies and costs.
Method
T1/2, hr.
Coast, $. hr-1.m-3
Relative coast

1
9.36
1.8
16.8

2
7.80
2.2
10.36

3
13.5
1.6
9.1

4
7.05
2.8
13.96

5
8.2
2.0
2.0

6
4.7
1.2
3.76

Methods in comparison: 1- Ozone with ultraviolet 256 nm Ultraviolet radiation (O3/ UV), 2- Ozone with hydrogen peroxide (O3/ H2O2), 3Ultraviolet radiation 256 with hydrogen peroxide (UV/ H 2O2), 4-Qzone with ultraviolet radiation and hydrogen peroxide (O3/ UV/H2O2), 5(TiO 2/ sunlight/ H2O2), 6- Vacuumed ultra violet radiation 172 nm with atmospheric oxygen (VUV/ O2).

4.

Conclusions

The primary goal of this research was too study the photo-catalytic degradative oxidation of persisting industrial organic pollutants using sun
light. With the aid of TiO2 and H2O2 the method was efficient. The present technique can be preferable over other techniques in three ways: 1H2O2 is a clean oxidizer where no harmful side products are included, 2- The ease of separation of TiO2 after the treatment and reusability and 3the energy coast is mostly cheep since the sunlight is free when available. It can be recommended for a realistic industrial water treatment; case
studies should be performed concerning pollutant's persistivity, sun light intensity and the needed capacity of the project.

Acknowledgment
We are grateful to the UNESCO for funding this research, we are also grateful to the Palestinian National Commission for Education, Culture
and Science for well cooperation.

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