MANIPAL UNIVERSITY JAIPUR

Department of chemical Engineering

CHEMICAL REACTION ENGINEERING LAB

VII YEAR, SEMESTER-6

EXPERIMENT#1
PHOTOCATYLITIC REACTOR

INSTRUCTUR
IR.Nandna Chakinala

NAME-Amoluck Bhatia
ID-209101001

DATE OF EXPERIMENT-16/01/2023

EXECUTIVE SUMMARY…………………………………………………………............... (10)

INTRODUCTION/OBJECTIVES/SCOPE/PROCEDURE ……………………….….. (30)
RESULTS & DISCUSSION…………………………………………………………............. (30)
CONCLUSION…………………………………………………………………………………….. (10)

REFERENCES …………………………………………………………………………………….. (5)

APPENDIX Original data, sample calculations, other information………. (5)

GENERAL COMPLETENESS Conciseness and neatness………………………… (10)

TOTAL…………………………………………………………………………………………………. (100)

CONTENT TABLE
EXECUTIVE SUMMARY
1.OBJECTIVE
2.INTRODUCTION
3.EXPERIMENTAL SETUP
4.PROCEDURE
5.RESULTS AND DISCUSSION
6.CONCLUSION AND RECOMMENDATION
7.REFRENCE
8.APPENDEX
Executive summary
The experiment for the Rhodamine-B dye solution is carried out using the
photocatalyst of titanium oxide under isothermal conditions to explore the
kinetics of photocatalytic degradation of dye and identify the order and rate
constant of reaction. Every 10 minutes during the 60-minute experiment, the
concentrations of the samples from the setup were measured. The dye
solution's concentration falls, as it is recorded to go from 12 ppm to 6 ppm.
The data is then fitted in straight line equations for irreversible unimolecular
first and second order reaction equations, with irreversible unimolecular first
order reaction providing the best match for the data. As a result, the rate
constant calculated from the straight-line slope value is 0.0077min-1.
OBJECTIVE
To study the kinetics of photocatalytic degradation of dye and determine
i. Order of reaction
ii. Rate constant

INTRODUCTION
These compounds colour the water and make penetration of sunlight to the
lower layers impossible and, hence affecting aquatic life. Many of these are
toxic, carcinogenic, mutagenic, or even stable to biological degradation.
Coloured compounds comprising pigments and dyes are used widely in textile,
plastic, food, dyeing, paper, printing, pharmaceutical and cosmetic industries.
The conventional wastewater treatment methods are usually ineffective in
removal of these compounds or just transfer the contamination from one
phase to another. Moreover, some biodegradation by-products are more toxic
than the degraded compound. Advanced oxidation processes have gained
importance in the last decade because of their application in the purification of
wastewater containing toxic, recalcitrant, and/or coloured compounds.
Photocatalytic degradation, as an advanced oxidation process, can oxidize a
wide variety of toxic and persistent organic compounds to harmless inorganics
such as mineral acids, carbon dioxide and water. The mechanism of the
degradation consisted of promoting an electron from the valence band to the
conduction band of the semiconducting oxide to give an electron/hole pair.
The valence band potential is positive enough to generate hydroxyl radicals at
the surface and the conduction band is negative enough to reduce molecular
O2. The hydroxyl radical is a powerful oxidizing agent and attacks organic
pollutants present at or near the surface of the TiO 2. TiO2 semiconductor
photocatalysts, is the most used owing to its stable, harmless and inexpensive
properties. It also activated with ultraviolet (UV) light. TiO 2 has been used for
the degradation of different kinds of compounds.
Rhodamine B is one of the most important dyes of the xanthene group, which
is highly water soluble. It is found as a reddish violet powder and comes under
the trade name of D&C Red No. 19. It is harmful if swallowed by human beings
and animals, and causes irritation to the skin, eyes and respiratory tract and is
widely used in many industrial processes, such as paper dyeing and the
production of dye laser.
Figure 1 Rhodamine B dye molecular structure
UV reactor are systems that expose the flowing water to light from UV lamps.
TiO2 catalyst is used because of its stability, optical and electrical properties. As
UV light luminates the TiO2 particles, electrons in the valence band can be
promoted to the conduction band, generating electron-hole pair.

HCOOH + H2O2  2H2O2 + CO2

Photocatalyst Characterization:
The structure and morphology of the prepared TiO 2/AC were analysed by a
scanning electron microscope (SEM) equipped with energy dispersive X-ray
spectroscopy (EDX) (Zeiss Supra 35VP). The chemical compositions of the
sonocatalyst were determined using Thermo Scientific, Nicolet iS10 Fourier
Transform Infrared Spectroscopy (FTIR). The sample was tested after the
completion of the blank spectrum scanning. The scanning range was set from
400 to 4000 cm-1.
Analysis of Liquid sample:
After desired reaction time, all samples were filtered, and the filtrates were
sent for the measurement of RB concentration. The final concentration of RB
by using a UV-Vis spectrophotometer (Model: Shimadzu UV-160PC) set at a
wavelength of 554.3 nm. The degradation efficiency of RB dye is defined by:

Where P is the percentage (%) of degradation, C O and Ct are the initial dye
concentration and dye concentration at measurable time t, respectively
(mg/L).
Material Balance:
Where, t= time of reaction in sec
NAO= initial number of moles of reactant
V= volume of the reactor in L
XA= conversion of reactant
-rA= rate of reaction in mol/Lsec

SCOPE:
Wastewater treatment on a commercial scale can be carried out using
photocatalytic reaction with titanium oxide as a photocatalyst for dye
degradation and destroying chemical compounds.

EXPERIMENTAL SETUP
The setup is used to study the photocatalytic reaction using a UV source
provided in the form of an UV tube, this setup can be used to carry out a
parameter study under batch/continuous flow condition. A photo catalyst like
TiO2 can be used. This set-up can also be used to study the mineralization of
liquid effluent industrial streams -rA and for purification of water. The setup
consists if reactor with inside reflecting surface.

Figure 2 Experimental setup for Photocatalytic Reactor

PROCEDURE
Chemicals Required:
1. Rhodamine B dye
2. Titanium oxide (TiO2)
3. RO water
Preparation of dye solution:
1. Take 20 mg of Rhodamine B dye and add it to 1L of water to make 20
ppm dye solution.
2. Make 10 mL of all the even integral concentration from 1-10 ppm from
the 20 ppm solution.
Concentration-Absorbance Curve using UV Spectrophotometer:
1. Solution of different concentration (1-10 ppm) of dye are made.
2. The absorbance of the solutions is measured using UV-spectrometer.
3. Absorbance v/s concentration curve is plotted.
Experimental Procedure:
1. Make 500mL of 20 ppm sample of dye in water and add 1.25g of TiO 2
catalyst to the solution.
2. Fill cold water or ice to the ice bath.
3. Feed the prepared solution to the apparatus and switch on the
apparatus.
4. Take 10mL of sample at every 10 mins till 60 mins.
5. Centrifuge the samples taken and filter them out.
6. Find the absorbance of the filtered samples using UV-
spectrophotometer.
7. After taking all the readings turn off the ice bath, drain all the tanks and
wash the apparatus completely.
8. Turn off the main supply.
Precautions:
1. Always wear lab coat while working in the lab.
2. Make sure that the readings are taken carefully.
3. The apparatus should be switched off while not in use.
Results and discussions
This experiment was carried out in two stages. Firstly, calibration data is taken
by determining absorbance for dye samples at a wavelength of 554 nm for
known concentration of 1 to 10ppm using a UV spectrometer. The calibration
data is shown in APPENDIX Table 1. The same data is then represented in a
graphical way, as shown in Figure 3. This graph represents a straight line which
means the Absorbance increases linearly with increase in concentration.

Calibration data
2.5

2 f(x) = 0.207236363636364 x
R² = 0.999672279496023
1.5
Absorbance

0.5

0
0 2 4 6 8 10 12
Concentration

Figure 3 Calibration curve btw Absorbance and concentration

The second part of the experiment was carried out by adding 1.25 gram to
500mL of 20 ppm solution in the photocatalytic reactor. Ice cubes are added
through another inlet to the setup to carry out the reaction at a lower
temperature. The experiment is conducted in Isothermal conditions but due to
some losses in environment, the reactor temperature fluctuates between 64 to
94°C. The experiment is run for 60 minutes while taking samples every 10
minutes using microfilters to remove TiO2 from the sample solution to alter the
absorbance value. These samples are firstly centrifuged and then filtered and
then immediately analyzed to determine its absorbance. These absorbance
values give concentration of the sample using the calibration curve shown in
figure 3. The concentration values determined for these samples show a clear
decreasing trend which indicates the photocatalytic reaction insures
degradation of Rhodamine-B dye solution. The initial concentration of the
solution is was taken 20 ppm but due to some experimental errors, measured
concentration at time 0 was found to be 12ppm. The experimental data shows
the decrease in concentrations from 12 ppm to 6.4 ppm. We fit the
concentration-time data to determine the rate constant and order of the
reaction involved.

We perform an integral method of analysis by fitting the data in irreversible

unimolecular first order reaction equation which is shown in equation 1.
Equation 1 Irreversible unimolecular First order reaction integrated rate law
C
−ln =kt
C0

Fitting experimental data in first order reaction

0.7

0.6

0.5
f(x) = 0.00767272256341738 x
0.4
-ln(C/Co)

R² = 0.869761102463675

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70
Time (min)

Figure 4 Fitting experimental data in first order reaction.

The experimental data shows increasing deviation for the first half and then
decreasing deviation in the remaining experiment runtime. The slope for the
fitted trend line in this case gives the rate constant i.e., k1=0.0077 min-1.
Along with fitting the data in first order reaction, the data is also fitted in the
equation for irreversible unimolecular second order reaction shown in
equation 2.
Equation 2 Irreversible unimolecular Second order reaction integrated rate law
1 1
= +kt
C Co

Fitting experimental data in second order reaction

0.18
0.16
0.14
0.12 f(x) = 0.000826949065637138 x + 0.083213
R² = 0.831235895409393
0.1
1/C

0.08
0.06
0.04
0.02
0
0 10 20 30 40 50 60 70
t min

Figure 5 fitting experimental data in second order reaction.

The experimental data shows deviation for the experiment runtime. The R-
square value for the graph is high as compared to the first order reaction
curve. The intercept from the trend line equation is 0.0832 gives the inverse of
the initial concentration and the slope for the fitted trendline in this case gives
the rate constant k2= 0.0008 min-1.
On comparing the results for integral analysis for both first and second order,
it can be clearly determined that data best fit for the reaction occurred in the
system is irreversible unimolecular first order reaction.

CONCLUSION AND RECCOMENDATION

The aim of this experiment to study the kinetics of photocatalytic degradation
of dye was achieved. It is concluded from the reaction that the dye solution
concentration decreases from 12 ppm to 6.4ppm. The concentration-time data
when fitted in irreversible unimolecular first order reaction equation gives the
rate constant value to be 0.0077min-1.
It is recommended that while preparing the dye solution, dye is measured
carefully to prepare the correct concentration dye solution.

REFERENCE
1. Levenspiel, O. Chemical Reaction Engineering, 3rd ed., Wiley India Pt Ltd.,
2010.
2. Wong Y. C. Steto, Y. S. Cheung W. H., and Mckay, G. 2003. Equilibrium
studies for acid dye adsorption onto chitosan. Langmuir, 19: 7888-7894.
3. Ma. Y, and Yao, I.N, 1998. Photodegradation of Rhodamine B catalyzed by
Ti02 thin Ailms Journal of Photochemistry and Photobiology A: Chemistry, 116:
167-170.
4. S. L. N. Zulmajdi, S. N.F. H. Ajak. I.Hobley;, N. Duraman, M. H. Harunsani, H.
M. Yasin, M Nur, and A. Usman, "Kinetics of Photocatalytic Degradation of
Methylene Blue in Aqueous Dispersions of Ti02 Nanoparticles under UV-
LED Irradiation."

APPENDIX
Table 1 Calibration data
Concentration Absorbance
1 0.219
2 0.452
3 0.634
4 0.831
5 1.045
6 1.289
7 1.448
8 1.638
9 1.872
10 2.039
Table 2 Observation and Calculation table
Sample Time Temp 1 Temp 2 Absorbance Concentration 1/C -ln C/Co ln (C) 1/ln(C)
0 0 15 64 2.49 12.01737452 0.083213 0 2.486353479 0.4021954
1 10 17 69 2.46 11.87258687 0.084228 0.012121 2.474232119 0.4041658
2 20 21 75 2.451 11.82915058 0.084537 0.015787 2.470566873 0.4047654
3 30 24 81 2.313 11.16312741 0.089581 0.073737 2.412616152 0.4144878
4 40 27 86 1.96 9.459459459 0.105714 0.239338 2.247015242 0.4450348
5 50 29 90 1.67 8.05984556 0.124072 0.399459 2.086894395 0.4791809
6 60 31 94 1.33 6.418918919 0.155789 0.627104 1.859249711 0.5378514

SAMPLE CALCULATIONS