Parametric and

Kinetic Studies on the

Decolorization of
Aqueous Methyl Red
Solution using
Electrolyzed Water
Significance of the
Study
 Improvement in wastewater treatment
technology
 Reduction of environmental hazards
 For further optimization and scale-up
studies
Objectives of the
Study
The general objective of this study is to conduct parametric and
kinetic studies on the decolorization of aqueous methyl red dye
solution using electrolyzed water. Specifically, this study aims:

1. to characterize the electrolyzed water based on its pH and free

chlorine concentration of electrolyzed water;

2. to evaluate the effects of concentration of aqueous methyl red

dye solution, ratio of electrolyzed water to synthetic wastewater,
reaction time and temperature on the decolorization of dye solution
via split plot two-level factorial experiment using Design Expert ®
Software v. 10;
 3. to assess the combination of parameters that will have
the highest color removal of aqueous methyl red dye
solution per amount of free chlorine used using
electrolyzed water; and

4. to determine the kinetic parameters: kinetic constant, k

and order of reaction, n, of the decolorization process at
the best parametric conditions using integral
method.
› RE VIE W OF
LITE RATURE
Textile Wastewater
Characteristic Components
s:
 Acids and bases
 High suspended  Leveling agent
solid  Recalcitrant
 High chemical organics
oxygen demand  Softener
(COD)  Dye Residues
 Colored
Electrolyzed water
generator
 Cawolo CA-5 as one of the electrolyzed water
generator
 Types of EW
1. Acidic electrolyzed water
2. Basic electrolyzed water
 Presence of free chlorine

Source: Rahman, Khan, &

Oh, 2016
› MATERIALS &
METHODS
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Preparation of
Wastewater
Preparation of
Wastewater
Characterization of
Wastewater

LCD Digital Pen DR-2800 Hach

Shape pH Meter Spectrophotome
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Preparation of Electrolyzed
Water

Cawolo
Disinfectant
Generator CA-5
Preparation of Electrolyzed
Water

Commercial
Grade Salt
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Free Chlorine Content of
the EW

DPD Powder
Pillow
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Parametric Study

Parameter Unit Value

Initial Dye 5 (-)
Ppm
Concentration 20 (+)
Volume Ratio of EW to 0.25:9.75 (-)
mL:mL
MR 1:9 (+)
5 (-)
Reaction Time Mins.
30 (+)
RT (-)
Reaction Temperature Deg. Celsius
50 (+)
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Experimental Design

No. of Factors Design Runs

Spli plot two-level
4 32
factorial
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
General Flowchart of the
Procedure

Preparation
Preparation Preparation
and Determination
and and
Construction of the FCC of
Characterizati Characterizati
of Standard EW
on of WWT on of EW
Curve

Experimental Parametric
Analysis Kinetic Study
Design Study
Data AnalysiS
Thank You!
› RESULTS &
DISCUSSION
Electrolyzed Water
Characterization

PARAMETER VALUES
Free Chlorine 1050
Concentration
(ppm)
pH 8.2

Determination of free chlorine content of

electrolyzed water
Crystal Violet
Crystal Violet Wastewater
Characterization

PARAMETER 200 PPM 300 PPM

Actual 194.78 293.71
Concentration
(ppm)
pH 6.3 6.5

200 and 300 ppm aqueous crystal violet

wastewater.
Parametric Study
Parametric Study
Transform Natural Logarithm
Confidence Level 95%
Model Main Effects
Significant (p-value < 0.0001)
Lack of Fit Insignificant (p-value 0..9754)
Predicted R2 0.9999
Adjusted R2 0.9999
Adequate Precision 726.852 (greater than 4)
Behavior of Residuals Well-behaved
Conclusion Model provides good prediction

Note: Run No. 7 was ignored for the analysis of the study
 Significant
Parameters

PARAMETER F-VALUE P-VALUE SIGNIFICAN

S CE
Initial 1.128 x 105 <0.0001 SIGNIFICANT
Concentratio
n
Volume Ratio 1.128 x 105 <0.0001 SIGNIFICANT

Reaction 21.10 0.0004 SIGNIFICANT

Time
Note: Run No. 7 was ignored for the analysis of the study
Summary of Results
 Effect of Initial
Concentration
As the initial concentration
of crystal violet increases,
the amount of WW removed
per amount of free chlorine
used also increases
Concentrati Highest amount of
on (ppm) wastewater removed per
amount of free chlorine
used (mg/mg)
200 1.04
Effect of initial concentration of crystal violet 300 1.57
on the amount of wastewater removed per
free chlorine used.
 Effect of Initial
Concentration
Experimental Result: low [CV],
high %decolorization

Klidi et al (2017)
Treatment: Electochemical
oxidation
Unnu et al. (2015)
Treatment: Fenton oxidation

Result: low [CV], high

Effect of initial concentration on the %decolorization
decolorization of crystal violet dye.
(Run 10 (high [CV]) Run 11 (low [CV]))
Effect of Volume
Ratio
As the volume ratio of EW to
crystal violet solution
increases, the amount of
WW removed per amount of
free chlorine used decreases

Volum Highest amount of

e wastewater removed per
Ratio amount of free chlorine
(mL/m used (mg/mg)
L)
1.5:8.5 1.57
Effect of volume ratio on the amount of 2.5: 0.83
wastewater removed per free chlorine used.
Effect of Volume
Ratio
Experimental Result: high volume
ratio, high % decolorization

Cruz (2017)
Treatment: Electrolyzed water
(paint wastewater)

Result: high volume ratio, high %

decolorization
Effect of volume ratio on the
decolorization of crystal violet dye.
(Run 12 (high ratio) Run 14 (low ratio))
Effect of Reaction
Time
As the reaction time is
increased, the amount of
wastewater removed per
free chlorine used also
increases (but only a little)

Reaction Highest amount of

Time (hr) wastewater removed
per amount of free
chlorine used (mg/mg)
0.5 1.55
3 1.57
Effect of reaction time on the amount of
wastewater removed per free chlorine used.
Effect of Reaction
Time
Experimental Result: longer time, higher
% decolorization

Cruz (2017)
Treatment: Electrolyzed water (paint
wastewater)
Palma-Goyes et al. (2010)
Treatment: Electrochemical oxidation
Shabbir et al. (2017)
Treatment: Periphyton bioreactor

Result: longer time, higher %

Effect of reaction time on the decolorization
decolorization of crystal violet dye.
(Run 4 (longer time) Run 11 (shorter time))
 Final Wastewater
Characteristics (pH)
 Highest Dye
Removal
Combination of Factors:
Initial [CV] : 300 ppm
Volume Ratio: 1.5:8.5
Reaction Time: 3 hrs

Amount of WW removed per

amount of free chlorine
used: 1.57 mg/mg
Treated sample with the highest removal.
Kinetics Study
12

Crystal Violet Concentration, ppm

10

Reaction R-squared 8
Order value
6
0 0.9764
1 0.9948 4

2 0.9922
2
3 0.9702
0
0 20 40 60 80 100 120 140 160 180 200
Time, min
Time profile of the concentration of crystal violet solution
upon addition of electrolyzed water.
Integral Method
3

2.5
f(x) = - 0x + 2.4

ln (CV Concentration)
Order of Reaction: 1st
2
R² = 0.99

Linearized equation: ln(C)

= -4.556 x10-3 t + 2.3984 1.5

Kinetic rate constant (k): 1

-4.556 x10-3 min-1

0.5

0
0 20 40 60 80 100 120 140 160 180 200

Time, min

Linearized graph for the 1st order decolorization of

crystal violet using electrolyzed water.
Related Kinetics Study on
Decolorization of CV
Treatment Order of
Method reaction
Sanroman et Electrochemic 1st order
al. (2004) al
Decolorization
Medien & Fenton 1st order
Khalil (2010) reaction
Su & Wang Fenton 1st order
(2010) reaction
 Electrochemical
Decolorization of CV
(Sanroman et al., 2004)

Structurally different dyes exhibit decolorization

pattern depending on its chemical structure and
substituent.

Kinetic rate constant of CV: 5.96 x 10-4 s-1 (3.576 x 10-2

min-1)
Experimental rate constant: 4. 556 x 10-3 min -1
Methyl
Orange
CharacTerization of MO
wastewater
PARAMETER VALUE
Concentration, 300 150
ppm
pH 6.4 6.1
Color (in terms of 2.840 (10x 1.462 (10x
absorbance unit) dilution) dilution)
›Parametri
c Study
ANOVA TABLE
SUM OF MEAN F P-VALUE
SOURCE DF
SQUARES SQUARE VALUE PROB > F
significa
Model 8.77 3 2.92 67321.07 < 0.0001
nt
A-
Concentratio 1.71 1 1.71 39471.13 < 0.0001
n
B-Volume of
7.06 1 7.06 1.624E+005 < 0.0001
EW
C-Reaction 3.052E-
1 3.052E-003 70.25 < 0.0001
time 003
Curvature 0.000 0
4.335E-
Curvature 1 4.335E-004 9.98 0.0065
004
6.517E-
Residual 15 4.345E-005
004
not
2.086E-
Lack of Fit 4 5.214E-005 1.29 0.3308 significa
004
nt
Effect of initial dye concentration

The amount of
wastewater removed
per amount of free
chlorine used shows a
direct relationship with
the initial concentration
of MO
Effect of volume ratio

Volume
Ratio

mg MO/mg
FC
Effect of reaction time

Reaction mg MO/
Time mg FC
›Kinetic
Study
Kinetic study
60

50

40
Concentration (ppm)

n R2
0 0.7811
30
1 0.8889
20 2 0.9506
3 0.9496
10

0
0 30 60 90 120 150 180 210 240 270 300
Time (min)
Kinetic study
0.14000

0.12000
PARAMET METHYL
ER ORANGE 0.10000

1/Cmo (1/ppm)
Order of 2nd order 0.08000

reaction 0.06000

R-squared 0.9506
0.04000
value
Kinetic rate 2 x 10-4 0.02000

constant min/ppm 0.00000

0 30 60 90 120 150 180 210 240 270 300
Time (minutes)
Congo Red
ANOVA Table
PARAMETE F VALUE P-VALUE SIGNIFICA
RS (PROB>F) NCE

Temperatu 155.28 <0.0001 significant

re (a)
Concentrat 22107.35 <0.0001 significant
ion (B)
Reaction 2.59 0.1190 insignificant
time (C)
Ratio (D) 82476.90 <0.0001 significant
Statistical data
PARAMETER VALUE

Standard Deviation 0.651571

Mean 1.47456

R-squared 1.0

Adjusted R-squared 1.0

Effect of
Temperature
Significant parameter

Temperature

response
Effect of Initial Dye
Concentration
Significant parameter

Concentration

response

*response = mg wastewater
removed/ mg free chlorine
Effect of Reaction
time

Insignificant parameter

* optimum condition
Effect of EW to WW
ratio

Significant parameter

Ratio

response
Kinetic Study on the Decolorization
Of congo red
ASSUMED R2 SLOPE
ORDER
Zero 0.9375 -0.094

First 0.9694 0.0054

Second 0.9889 0.0003

Third 0.9833 0.00003

 Second Order
0.09
0.08
0.07 f(x) = 0x + 0.04
0.06 R² = 0.99
0.05
0.04
0.03
0.02
0.01
0
0 20 40 60 80 100 120 140
Average Linear (Average)
Methyl Red
Characterization of
the Methyl Red
Solution

DENR Standard: pH 6-9.5

Parametric Study on
the Decolorization of
MR
Effect of the Initial Dye
Concentration

Initial Dye
mg MR/mg
Concentrati
FC
on
Dye Concentration
mg MR/mg FC
(ppm)
5 0.1
20 0.25
Effect of the Volume
Ratio of EW to MR

Volume mg MR/mg
Ratio FC
Volume Ratio (mL:mL) mg MR/mg FC
0.25:9.75 0.3
1:9 0.1
Effect of Reaction Time

Reaction
mg MR/mg
Time
FC
Reaction Time (mins.) mg MR/mg FC
5 0.15
30 0.18
Effect of Reaction
Temperature

Reaction
mg MR/mg
Temperatur
FC
e
Reaction Temperature
mg MR/mg FC
(deg. C)
RT 0.15
30 0.18
Best Parametric
Combination
Kinetic Study on the
Decolorization of MR
12.00

10.00

8.00
Concentration (ppm)

6.00

4.00

2.00

0.00
0 3 6 9 12 15 18 21 24 27 30 33
Time (minutes)
Kinetic Study on the
Decolorization of MR
Kinetic Study on the
Decolorization of MR
3.00

2.50

2.00 f(x) = - 0.06x + 2.27

R² = 0.98
ln CMR

1.50

1.00

0.50

0.00
0 3 6 9 12 15 18 21 24 27 30 33

Time (minutes)
› SUMMARY &
CONCLUSION
Wastewater Characterization
DYE CONCENTRATIO pH
N
200 6.3
Crystal Violet
300 6.5
150 6.1
Methyl Orange
300 6.4
200 7.7
Congo Red
300 7.7
5 5.5
Methyl Red
20 5.7
 Electrolyzed Water
Characterization

PARAMETER VALUES
Free Chlorine Content
1050
(ppm)
pH 8.2
 Parametric Study
CRYSTA METHYL METHYL RED CONGO
L ORANGE RED
VIOLET
Initial Dye As the initial dye concentration increases, the amount of
Concentratio wastewater removed per amount of free chlorine used
n also increases
Volume Ratio As the volume ratio increases, the amount of wastewater
of EW to Dye removed per amount of free chlorine used also
Solution decreases

Reaction The longer is the reaction time, the higher is the amount
Time of wastewater removed per amount of free chlorine used
Reaction N/A As the temperature insignificant
Temperature increases, the
amount of
wastewater
removed per free
chlorine increases
 Highest Amount of Wastewater
Removed per Amount of Free Chlorine
Used
DYE HIGHEST COMBINATION OF FACTORS
AMOUNT OF Initial Dye Volume Reaction Reaction
WASTEWATER Concentration Ratio Time (hr) Temperature
REMOVED PER (ppm) (mL/mL) (degC)
AMOUNT OF FREE
CHLORINE USED
(MG/MG)

Crystal 1.57 300 (+) 1.5:8.5 (-) 3 (+) N/A

Violet
Methyl 2.41 300 (+) 1:9 (-) 5 (+)
Orange
Congo 2.48 300 (+) 1:9 (-) 2 (-) 50 (+)
Red
Methyl 0.66 20 (+) 0.25:9.75 0.5 (+) 50 (+)
 KineticS Study
PARAMET CRYSTAL METHYL METHYL CONGO
ER VIOLET ORANGE RED RED
Order of 1st order 2nd order 1st order 2nd order
reaction
R-squared 0.9948 0.9506 0.9807 0.9889
value
Kinetic 4.56 x 10-3 2 x 10-4 5.93 x 10-2 3 x 10-4
rate min-1 min/ppm min-1 min/ppm
constant
› RECOMMENDATION
Recommendation
 Actual wastewater
 Temperature range

 TCU determination
 FTIR analysis

 Optimization
 Scale-up
Response Calculation: mg congo red removed per mg free
chlorine
Conditions:
Initial Concentration of congo red: 200 ppm
(1mL electrolyzed H2O: 9 mL Wastewater)
Reaction time: 5 hours
› SAMPLE
CALCULATIONS