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Materials Today: Proceedings 5 (2018) 18221–18229 www.materialstoday.com/proceedings

ICMPC_2018

Optimisation For Photocatalytic Degradation Of Malathion By

Box–Behnken Design
P.Neelima Reddia,Bejawada Surendrab,Punugoti Thanushac and Meena Vangalapatid*
a
Mtech student,Department of Chemical Engineering, Andhra University, Visakhapatnam, AP, India.
b
Research ScholarDepartment of Chemical Engineering, Andhra University, Visakhapatnam, AP, India
c
B.tech Student, Department of Mechanical Engineering, Andhra University, Visakhapatnam,AP, India
d*
Professor, Department of Chemical Engineering, Andhra University, Visakhapatnam, AP, India.

Abstract

Malathion is a pesticide that is generally utilized as a part of agriculture, private finishing, open amusement regions, and in
general wellbeing nuisance control projects, for example, mosquito annihilation. In the US, it is the most ordinarily utilized
organophosphate insecticide. Malathion is normally used to control mosquitoes and an assortment of creepy crawlies that assault
organic products, vegetables, finishing plants and bushes. It can likewise be found in other pesticide items utilized inside and on
pets to control ticks and creepy crawlies, for example, insects and ants. It is additionally used to control human head and body
lice. It is the last organophosphate pesticide to experience these procedures, and its reasonable all because of the natural
concerns. As there are a few effects the substance can have on various conditions and living beings. In the present investigation,
Optimization of Malathion by photo catalytic reactant process utilizing titanium dioxide as catalyst is performed with different
parameters and observed to be Time(60min),Temperature(30Ԩ), pH(5), Mixing speed(900rpm), and Catalyst concentration(3g/l).
From these conditions the highest rate of degradation of Malathion obtained was 95%.

© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Materials Processing and characterization.

Keywords: Malathion, Chemical properties, First aid measures, photo catalytic process, Titanium dioxide, and risks.

1. Introduction
Agriculture production is mainly depends on water, land, seeds, fertilizers and also pesticides. In present situation
approximately 35-40% production of crop is loosed because of weeds, insects and several diseases. Rest 35% loss of
crops is occurring during the storage of crop production. On observing the report about pesticides utilization in

* Corresponding author. Tel.: +91 9490187300

E-mail address:meena_sekhar09@yahoo.co.in

2214-7853© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Materials Processing and characterization.
18222 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229

India, the local interest for organophosphate is expanding step by step at the rate of 8-9% and furthermore comes
about more fare request at 15-16%. In the USA alone toward the finish of a century ago 27,000 tons were utilized as
a part of agriculture and around 7650 tons were utilized as a part of mono farming applications. Organophosphates
are favored in agriculture because of their low constancy in the earth, yet its segregate utilize influences much
harmful to creatures and people. Organophosphorous mixes, for example, Malathion, Chloropyrifos, parathion and
so on are regularly utilized bug sprays for more than 50 years. Malathion may be an expansive range insecticide
generally utilized worldwide because from claiming its effectiveness for controlling insects and pests. Malathion is a
exceedingly harmful intensify and recorded by the united states ecological security organization (USEPA)
Concerning illustration poisonous quality population (Group 2A). It may be ordered Concerning illustration
successful with people Furthermore animals. Malathion responds with various chemicals within the sight of daylight
in the air to create 40 times more harmful compound malaoxon however separates quickly as shown in below Fig 1.

Figure 1: Structure of Malathion

2. Materials and Methods

2.1. Preparation of synthetic sample of Malathion:10ml of Malathion is dissolved in 1lit of distilled water.

2.2. Procedure:

A Spectrophotometer with filter No. 42 (absorption peak 420 nm) and matched cylindrical test-tube cells 1.2 cm. in
diameter was used by the authors for most of the experimental work. Magnetic stirrer Dissolve approximately 0.25
gram of pure Malathion in ethyl alcohol and dilute volumetrically to 250 ml. with ethyl alcohol. Mix well. Then
transfer a 25-ml. aliquot to a 250-ml. volumetric flask, and dilute to volume rich ethyl alcohol (1 ml. 0.1 mg. of
Malathion). Utilizing this standard arrangement, transfer the samples of 0, 2.5, 5, 10, 15, 20 and 25 ml standard by
the accompanying the system. Transfer the aliquot to a 250-ml. Separatory funnel containing 100 ml. of dis- tilled
carbon tetrachloride, and add ethyl alcohol until the total volume of ethyl alcohol present is 25 ml, then mix well by
swirling. Add 1 ml. of 6N sodium hydroxide and shake vigorously for exactly 1 minute. The procedure from this
point on should be carried out without interruption. Aqueous alkaline and acid solutions of dimethyl
dithiophosphoric acid are stable for short periods only (probably not more than 1 hour). Conditions required to
produce maximum decomposition of the insecticide by alkali to dimethyl dithiophosphoric acid are critical. The
Reaction periods of more than 2 minutes and less than 30 seconds produce low results.

Immediately add 75 ml. of the sodium chloride solution (cooled to about 150 C.) and shake vigorously for 1 minute.
Allow the phases to separate, then draw off the carbon tetrachloride layer and dis- card it. Add 25 ml. of carbon
tetrachloride to the separator Funnel, shake vigorously for 30 seconds, allow phases to separate, and discard the
carbon tetrachloride layer. Add 7.N hydrochloric acid to the separator funnel, shake vigorously for 30 seconds, al-
low phases to separate. Draw off the carbon tetrachloride layer as totally as could be expected under the
circumstances, and dispose of it and include 2. Ml. of the copper sulfate reagent. Shake vivaciously for 1 minute,
and enable stages to isolated. (A littler measure of carbon tetrachloride might be utilized to extricate the yellow
 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229 18223

shading for estimation if a more delicate method is wanted, yet the exactness will be diminished.) Immediately
measure the absorbance of the )- yellow shading in the carbon tetra-chloride layer at around 418 nm, utilizing a 1-to
1.5-cm. cell and dis-worked carbon tetrachloride as the reference arrangement. (The yellow color of the copper
dimethyl dithiophosphate complex in carbon tetrachloride is not stable for more than 5 minutes.) Prepare the
standard curve by plotting the absorbance of each of the aliquots against the milligrams of Malathion present. 10 to
20% as shown in below Fig 2.

2.3. Optimization for photo-catalytic degradation of Malathion:

The catalytic degradation of Malathion in aqueous phase was finished after the method stock arrangement of
Malathion (4 ppm) was readied and 200 ml of it was taken in the conical flask. To this, the required measure of
catalyst (TiO2) was included. For a base time of 60 minutes, the arrangement was kept up oblivious to guarantee
finish adsorption harmony. The arrangement was then illuminated under light with constant mixing utilizing an
attractive stirrer in Photocatalytic reactor for the required period. The sample was then sifted to evacuate the catalyst
and examined by spectrophotometer. Tests were led to contemplate the variety in the degree of degradation with
changes in parameters, for example, catalyst fixation, pH, contact Time, Temperature, and mixing speed.

Fig2: Photocatalytic reactor

2.4. Response Surface Methodology

Reaction Surface Methodology (RSM) is a gathering of measurable and scientific strategies helpful for creating,
enhancing and advancing procedures.
The most broad uses of RSM are in the specific circumstances where a few information factors conceivably impact
some execution measure or quality normal for the procedure. In this way execution measure or quality trademark is
known as the reaction. The information factors are at times called free factors, and they are liable to the control of
the researcher or designer. The field of reaction surface procedure comprises of the trial methodology for
investigating the space of the procedure or autonomous factors, exact factual demonstrating to build up a proper
approximating connection between the yield and the procedure factors, and enhancement strategies for finding the
estimations of the procedure factors that deliver attractive Values of the reaction. In this report we will focus on the
second system:
2.5.Choice of the experimental design
The rudimentary model which can be utilized as a part of RSM depends on a straight capacity. For its application,
itis fundamental that the reactions acquired are all around fitted to the accompanying condition:

y   0 i 1  i xi  
k

(1)
where k is the number of variables, β0 is the constant term, βi represents the coefficients of the linear parameters, xi
represents the variables, and ε is the residual associated to the experiments.
18224 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229

In this way, the reactions ought not present any arch. To assess arch, a moment arrange show must be utilized. Two-
level factorial outlines are utilized as a part of the estimation of first-arrange impacts, yet they fall flat when extra
impacts, for example, second-arrange impacts, are noteworthy. Thus, an essential issue in two-level factorial
outlines can be utilized for assessing shape. The following level of the polynomial model ought to contain extra
terms, which portray the cooperation between the distinctive exploratory factors. Along these lines, a model for a
moment arrange connection displays the accompanying terms:

 
k k
y  0  i 1
 i xi  1 i  j
 ij x i x j 
(1.1)
where  ij represents the coefficients of the interaction parameters.
So as to decide a basic point (most extreme, least, or seat), it is important for the polynomial capacity to
contain quadratic terms as per the condition exhibited beneath:
  
k k k
y  0  i 1
 i xi  i 1
 ii x i2  1 i  j
 ij x i x j  (1.2)
where  ii represents the coefficients of the quadratic parameter.

To evaluate these parameters in Eq. (1.2), this specific trial configuration needs to fulfils every single
concentrated variable are done no less than three factorial levels. In this way, two demonstrating, symmetrical
reaction surface outlines are accessible. Among the more known second request symmetrical outlines are the three-
level factorial plan, Box– Behnken outline, focal composite outline, and Doehlert plan. These symmetrical plans
contrast from each other regarding their choice of trial focuses, number of levels for factors, and number of runs and
squares.

2.6.Box–Behnken design
Box and Behnken recommended the three-level factorial game plan, which permits the productive estimation of the
first-and second-arrange coefficients of the numerical model. These outlines are, thusly, more effective and sparing
then their comparing 3k plans, fundamentally for countless.
In Box– Behnken plans, the trial focuses are situated on a hyper circle equidistant from the essential issue, as
exemplified for a three-factor outline. Its central attributes are:
1. It requires a trial number as indicated by N= 2k(k−1) + cp, where k is the quantity of components and (cp)
is the quantity of the main issues;

2. All factor levels must be balanced just at three levels (−1, 0, +1) with similarly separated interims between
these levels.

This trial configuration has been connected for the enhancement of a few synthetic and physical procedures

3. Results and Discussion:

3.1 Effect of various parameters:

There are various parameters which effect the Photo catalytic Degradation of Malathion
1.Effect of Time: The degradation of Malathion is assessed for each 10 min. The degradation of Malathion is
assessed from 10 min to till it comes stable. The rate degradation is expanded and it is steady at 60 min and however
the procedure proceeds encourage there is no adjustment in the Malathion fixation which implies that expansion in
the season of treatment with utilizing catalyst TiO2 does not impact on Malathion. Because of the nearness of UV
light response rate builds with the goal that the rate debasement is more in starting stages. In the underlying phases
of debasement of Malaoxon is more as for time in light of the fact that the accessible pore estimate is huge,
henceforth the rate of response is speedier. The rate of response diminishes in the later stages likely because of the
moderate pore dissemination.
 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229 18225

Effect of Solvent for the extraction of BPA

Conc of BPA (µg/ml)

0.3

0.2

0.1

0
Distilled water Methanol Ethanol Toulene Chloroform
Type of Solvent

Fig3: Effect of solvent on % Degradation of Malathion

2.Effect of Catalyst Concentration: At beginning stages the quantity of photons and tainted atoms adsorbed are
accounted for to increment with an expansion in the quantity of TiO2 particles from the range 0 to 3g/l. So by
expanding the TiO2 focus, the aggregate surface territory accessible for contaminant adsorption increments, and
therefore the degradation effectiveness can be upgraded. %. The productivity diminishes marginally when the
measure of TiO2 is over 3 g/L. The explanation behind this reduction in debasement rate is the conglomeration of
TiO2 particles at high focuses causing an abatement in the quantity of surface dynamic locales. Additionally the
suspended particles of the catalyst will obstruct the UV-light entry and increment the light diffusing as shown in
below Fig 4 and Above Fig 3.

Effect of Time
Conc of BPA(µg/ml)

0.3
0.25
0.2
0.15
0.1
0.05
0
2 4 6 8 10

Soaking Time

Fig4: Effect of Catalyst concentration

3.Effect of Temperature
The effect of temperature in the degradation reaction was studied by keeping pH (5), catalyst concentration
(3g/L), stirrer speed (900) and time (60min) constant, varying the temperature of the stock solution from 200C to
500C.
18226 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229

Effect of Weight dosage

Conc of BPA(µg/ml)
0.25
0.2
0.15
0.1
0.05
0
0.5 1 1.5 2 2.5
Weight dosage(g)

Fig5: Effect of Temperature

4.Effect of pH: It is found that percentage degradation increases when the pH value increases from 2-6 and
decreases thereafter in basic medium. The point of zero charge of TiO2 is 6.3. So the TiO2 surface is
decidedly charged in acidic arrangement and adversely charged in fundamental arrangement. Electrostatic
attraction or repulsion between the catalyst's surface and the natural atom is occurring, contingent upon the
ionic type of the natural compound (anionic or cationic) and accordingly thus improves or represses the
photo degradation effectiveness separately.

Effect of pH
Conc of BPA(µg/ml)

0.3
0.2
0.1
0
3 4 5 6 7 8
pH

Fig 6: Effect of pH
5.Effect of Mixing speed: The initial degradation rates were investigated at different angular velocities
mixing speeds from 200 to 900. The reaction rates were determined after one hour of photocatalytic
reactions.

Fig 7: Effect of mixing speed

 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229 18227

The whole process has been repeated once again by maintaining all the optimized parameters.
At the end of the process the maximum Percentage degradation of Malathion was found to be 94.99% with
3g/l.Titanium dioxide concentration 1 hr time, pH 5 mixing speed 900 RPM and the Temperature 300C optimized
conditions as shown in above Fig 5 and Fig 6 ,Fig 7.

3.2.Response surface methodology-Box- Behnken Design

The relation between the responses (extraction activity) with the factors is represented by the following quadratic
equation:

Degradation of Malathion= 95.12+ 0.76A +1.43B -0.3C +0.61AB +1.06AC+ 0.96BC-6.74A2-1.49B2-1.04 C2

The "Pred R-Squared" of 0.6789 is not as close to the "Adj R-Squared" of 0.9541 as one might normally expect.
This may indicate a large block effect or a possible problem with your model and/or data. Things to consider are
model reduction, response transformation, outliers, etc. "Adeq Precision" measures the signal to noise ratio. A ratio
greater than 4 is desirable. Your ratio of 15.057 indicates an adequate signal. This model can be used to navigate
the design space. The obtained R2 value = 95.12% as shown in below Fig 8 -10

Design-Expert® Software
Factor Coding: Actual
R1
Design points above predicted value
Design points below predicted value
95.12

85
96
X1 = A: catalyst
X2 = B: pH 94

Actual Factor 92
C: Temp = 303.00
90

88
R1

86

84

82

7.00 5.00
6.00 4.00
5.00 3.00
4.00 2.00
B: pH A: catalyst
3.00 1.00

Fig: 8 3D plot between catalyst and pH

Design-Expert® Software
Factor Coding: Actual
R1
Design points above predicted value
Design points below predicted value
95.12

85
96
X1 = A: catalyst
X2 = C: Temp 94

Actual Factor 92
B: pH = 5.00
90

88
R1

86

84

82

323.00 5.00
315.00 4.00
307.00
3.00
299.00
2.00
C: Temp 291.00 A: catalyst
283.00 1.00

Figure 9: 3D plot between temperature and pH

18228 P.Neelima Reddi et al./ Materials Today: Proceedings 5 (2018) 18221–18229

Design-Expert® Software
Factor Coding: Actual
R1
Design points above predicted value
Design points below predicted value
95.12

85
96
X1 = B: pH
X2 = C: Temp 94

Actual Factor 92
A: catalyst = 3.00
90

88

R1
86

84

82

323.00 7.00
315.00 6.00
307.00
5.00
299.00
4.00
C: Temp 291.00 B: pH
283.00 3.00

Figure 10: 3D plot between temperature and pH

4. Conclusion

Experimental results showed that the Degradation of Malathion from wastewater is done by Photocatalytic process
using TiO2 and ZnO2 as a catalyst. In this process absorbance of Malathion was estimated by using UV-Visible
Spectrophotometer at wavelength 420nm. The effects of various parameters like Time, Temperature, pH, Catalyst
concentration, mixing speed, both in the presence of absence of UV light were studied and optimized.
Optimization is done for the parameters catalyst concentration, pH, by using Box Behnken design. From
this maximum degradation obtained is 95.12%

5.Acknowledgements

I wish to acknowledge my heartiest thanks to Dr.Meena Vangalapati, Professor Department of Chemical

Engineering, A.U.College of Engineering (A), Andhra University, for her skilful guidance and encouragement
during research work.

5. References

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Society. 1995. p. 80
3) abcd"NIOSH Pocket Guide to Chemical Hazards #0375". National Institute for Occupational Safety and Health (NIOSH).
4) Abc”Malathion". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
5) Alanwood.net". Retrieved 2007-09-16.
6) Malathion for mosquito control, US EPA
7) Bonner MR, Coble J, Blair A, et al. (2007). "Malathion Exposure and the Incidence of Cancer in the Agricultural Health Study". American
Journal of Epidemiology. 166 (9): 1023–1034. doi:10.1093/aje/kwm182. PMID17720683.
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control of Mediterranean fruit fly in South Australia". Environ. Res. 103 (1): 38–45. doi:10.1016/j.envres.2006.06.001. PMID16914134.
9) Winnipeg.ca-UD: Public Works: Insect Control Branch
10) Malathion Winnipeg ^National Guideline Clearinghouse | Guidelines for the diagnosis and treatment of pediculosiscapitis (head lice) in
children and adults 2008.
11) Malathion in Drinking-water Background document for development of WHO Guidelines for Drinking-water Quality
12) MATERIAL SAFETY DATA SHEET OF MALATHION 57 EC reviewed by environmental regulatory services.
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Singh, B.N Rai.
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Mervat E. Mohamed
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Zhiyong Xiao, Fang Chen, Yiqiangge ,Jihon g Wu , Xiaosong Hu.