CH4030: Process Control Lab, July-Nov 2025

Department of Chemical Engineering, Indian Institute of Technology, Madras

Photocatalytic Degradation of Methyl Orange Dye

Experiment done on: 24/09/2025

Report submitted on: 1/10/2025

BATCH: Wednesday
GROUP: RCL 1

NAME ROLL NUMBER

Bikash Kumar Nath CH22B058

Nanditha CH22B016

Adithyan D S CH22B049

Jadhav saichaitanya CH22B041

Sakshi Talapade Ch22b118

1. Aim

●​ To study the photocatalytic degradation of methylene blue dye using TiO₂ under UV
irradiation.
●​ To evaluate the kinetics of the degradation process by determining the rate constant and
reaction order.
●​ To apply both differential and integral methods for kinetic analysis and compare the results.

2. Abstract
Photocatalysis is an advanced oxidation technique that employs light energy—most often
ultraviolet (UV) or visible radiation—along with a semiconductor catalyst to enhance chemical
transformations. Among the available metal oxides, titanium dioxide (TiO₂) has emerged as the
most common photocatalyst due to its chemical stability, non-toxic nature, and strong oxidative
capability.

When TiO₂ particles are exposed to UV light with energy equal to or greater than their band gap
(~3.2 eV), electron–hole pairs are generated. These charge carriers migrate to the catalyst surface,
where they interact with adsorbed water molecules and dissolved oxygen, giving rise to highly
reactive species such as hydroxyl radicals (·OH) and superoxide anions (O₂·⁻). These reactive
intermediates possess strong oxidizing power and can degrade complex dye molecules stepwise
into smaller fragments, ultimately mineralizing them into harmless products like CO₂, H₂O, and
other stable compounds.

3. Theory
The degradation process typically follows pseudo-first-order kinetics, where the rate of
reaction is expressed in terms of the dye concentration over time with respect to the apparent rate
constant (k). Parameters such as the initial dye concentration (C₀) and the concentration at a given
time (C) are used to model the kinetics.

Because of its efficiency in breaking down persistent organic contaminants, photocatalysis

is regarded as a promising approach for wastewater treatment, particularly for the elimination of
synthetic dyes and other pollutants that are not easily removed by conventional methods. In this
experiment, methyl orange is selected as the model pollutant, and TiO₂ is used as the photocatalyst
under UV irradiation. The reaction kinetics are studied by monitoring the concentration decay with
time, and the order of reaction as well as the rate constants are determined through kinetic analysis.

The photocatalytic degradation of dyes typically follows pseudo-first-order kinetics, expressed as:

ln(C₀ / C) = k × t
where:

●​ C₀ = initial dye concentration​

●​ C = dye concentration at time t​

●​ k = apparent first-order rate constant​

●​ t = irradiation time​

Alternatively, the concentration–time relationship can also be expressed as:

C = C₀ × e−kt

Because of its efficiency in breaking down persistent organic pollutants, photocatalysis is

recognized as a promising method for wastewater treatment, particularly for the removal of
synthetic dyes and other contaminants that resist conventional treatment processes.

Figure 1: Setup of UV lamp and enclosure

4. Apparatus and methods

Apparatus used:
●​ UV Lamp (suitable for photocatalysis)
●​ Black Container with a door (to prevent light leakage)
●​ Spectrophotometer / UV-Vis Spectrophotometer
●​ Centrifuge
●​ Cuvette
●​ Beakers and Measuring Cylinders
 ●​ Measuring Flask
●​ Test Tubes
●​ Test Tube Holder
●​ Magnetic stirrer
●​ Pipette
●​ Timer / Stopwatch
●​ Dropper
●​ Protective Gear (Safety Goggles, Gloves)

Chemicals Required:
●​ Methylene Blue Dye
●​ Titanium Dioxide Catalyst (TiO2)
●​ Distilled Water

Figure 2: Methyl orange dye and set-up to perform photocatalytic degradation of dye

Procedure:

●​ Prepare a 100 ppm stock solution of methylene blue by dissolving the required amount of
dye in distilled water.​

●​ From the stock, dilute 100 ml with 400 ml of distilled water in a 500 ml measuring beaker
to obtain a 20 ppm working solution. Withdraw 10 ml of this solution into a test tube for
later use.​
 ●​ Accurately weigh 3.5 g of TiO₂ catalyst and add it to 100 ml of the 20 ppm methylene blue
solution in a beaker.​

●​ Place the suspension inside a closed black-box container and keep it in the dark for 20
minutes to allow adsorption equilibrium. Afterward, switch on the UV lamp and close the
container to initiate photocatalytic degradation.​

●​ In parallel, prepare calibration standards of 5 ppm, 10 ppm, 15 ppm, 20 ppm (set aside
earlier in step 2), and 30 ppm methylene blue solutions in test tubes.​

●​ Using distilled water as the reference, measure the absorbance of the prepared standards
with a cuvette to construct a calibration curve.​

●​ During photocatalysis, withdraw 5 ml samples from the reaction beaker every 10 minutes
(from t = 0 up to t = 60 minutes, or until the solution becomes nearly colorless). Handle
samples using protective gear.​

●​ Centrifuge each withdrawn sample to remove TiO₂ particles. Carefully collect the clear
supernatant with a dropper and transfer it to a cuvette.​

●​ Record the absorbance of each sample using a UV–Vis spectrophotometer at the two main
absorption peaks of methylene blue (≈615 nm and ≈663 nm).​

●​ Convert the absorbance values into concentration data using the calibration curve equation.​

●​ Tabulate time, absorbance, concentration, and percentage degradation (conversion). Plot

graphs to study the degradation profile and kinetics.​

●​ Analyze the experimental data to determine the reaction order and rate constant using both
the differential and integral methods.

5. Results & Calculations

First, we prepared a 100 ppm stock solution of methyl orange dye and water solution.
For 1 L solution, mass of dye = 100 g
Using the stock solution, we prepare a 20 ppm solution
Volume of stock solution taken = 140 mL
Volume of water = 560 mL
Concentration of solution =(100*140)/700 = 20 ppm
Mass of catalyst taken = 3.5 g
The calibration of concentration vs absorbance was taken using different ppm concentration and
calculating their absorbance using UV-Vis spectrophotometer.

Table1: Readings for calibration Curve

Concentration (in ppm) Absorbance Wavelength (in nm)

5 0.188189 464

10 0.818323 464

15 1.19587 464

20 1.64715 463

25 1.85931 462

Figure 3: concentration vs absorbance calibration plot

Fit Equation: Concentration = 11.6697 * Absorbance + 1.6759

 Table 2: Observations during the reaction and calculations
Time( in Absorbance Wavelength(in Calculated Conversion
minutes) nm) conc. Of dye (in
ppm)

0 1.9589 461 24.54 —--

10 1.71123 457 21.65 0.12

20 1.48737 460 19.03 0.22

30 1.19239 444 15.59 0.36

40 1.07563 406 14.23 0.42

50 0.818646 460 11.23 0.54

60 0.481601 460 7.30 0.70

70 0.31012 460 5.29 0.78

80 0.236212 460 4.43 0.82

90 0.164056 461 3.59 0.85

Sample calculation:
At t = 30min
Concentration of Dye(C)=15.59 ppm
Initial concentration of Dye(C0)=24.54 ppm

𝐶0−𝐶
X=conversion= 𝐶0
= 0. 36

Using differential analysis to find the rate constant and order of reaction we use the following

Equation,
(𝑑𝐶/𝑑𝑡)= 𝑘[𝐶]𝑛
⇒ 𝑙𝑛(−𝑑𝐶/𝑑𝑡 ) = 𝑛*𝑙𝑛[𝐶] + 𝑙𝑛(𝑘)

Hence, from a differential plot, the slope of ln[C] vs ln(-dC/dt) will give us order of reaction and
intercept will give us rate constant.

To calculate the term dC/dt, we use the central difference method,

 Table 3: Calculations for the differential method
Time (in minutes) Concentration (in ln(Concentration) ln(-dc/dt)
ppm)

10 21.65 3.075 -1.2905091

20 19.03 2.946 -1.1948963

30 15.59 2.747 -1.4260997

40 14.23 2.655 -1.5229207

50 11.23 2.419 -1.0595637

60 7.30 1.987 -1.2149755

70 5.29 1.667 -1.9436471

80 4.43 1.489 -2.4624469

Figure 4 : Differential method to find order of reaction and rate constant

From Figure 4, we get slope = 0.57, intercept = -2.87, R2 = 0.5279
Hence, order of reaction = 0.57, rate constant = 0.056.

For doing integral analysis, we plot zero-order and first-order plots and see which one gives us a
better fit. The equations for both are as follows:

Zero-order:​ [𝐶] = [𝐶]0− 𝑘𝑡

First-order: ln[C] = ln[C]0 -kt

Figure 5: Zero-order curve with linear fitting

From Figure 5, we get slope: -0.2458, intercept: 23.749, R2 = 0.98

Hence, order of reaction = 0, rate constant = 0.2458 mol L-1 min-1
 Figure 6: First-order graph with linear fitting

From Figure 6, we get slope: -0.0226, intercept: 3.3638, R2 = 0.97

Hence, order of reaction = 1, rate constant = 0.0226min-1

As we can see, the zero-order model gives a better fit.

Table 4: summary of Results

Method Order of Reaction Rate Constant

Differential Method 0.573 0.056

Integral Method 0 0.2458

7. Discussion
●​ Methyl orange was almost completely degraded by TiO₂ under UV, confirming its strong
photocatalytic activity.
●​ Initial adsorption on TiO₂ before irradiation enhanced dye accessibility for photocatalytic
attack.
●​ Zero-order behavior indicates surface-saturation of catalyst sites; fractional order likely due
to experimental noise.
●​ Minor deviations arise from light intensity variation, TiO2 agglomeration, or scattering
losses.
 ●​ In TiO₂ photocatalysis, degradation kinetics shift between first and zeroth-order depending
on concentration and loaded amount of catalyst.

8. Error Analysis
●​ Mathematical formulae for error analysis based on any data-point
➢​ In this section, the uncertainties are evaluated by taking the natural logarithm of each
formula and differentiating.
(i) Concentration from Calibration

C = (A-b)/m
Taking log on both sides;

ln C = ln(A-b) - ln m
Differentiating:

(ii) Conversion

X = (C0-C)/C0 = 1-(C/C0)
For ratio form:

Hence for X:

​
(iii) Rate ( Differential method)

Log form:

Relative error:
 (iv) First-order rate constant

ln C = ln C0 -kt
k = (1/t)*(ln(C0/C)

Log of k: lnk=ln(C0/C)−lnt

Relative error:

(v) Zero-order rate constant

C = C0 - kt
=> k = (C0-C)/t
Relative error :

●​ Sources of error:
➢​ Spectrophotometer accuracy: includes instrument noise, finger prints on cuvette, impurities
of TiO2 etc.
➢​ Centrifugation: Operating the instrument at lower RPM for lower time periods resulted in
less efficient separation of TiO2 catalyst from the solution, resulting in interference in
readings.

9. Acknowledgements
We would like to express our sincere thanks to Prof. Dr. Abhijit P. Deshpande, Dr. Kallol
Roy, Dr. Rashmi Prava Mohanty, and Dr. R. Vinu for their valuable support, guidance, and
encouragement throughout the course and [Link] also like to thank our teaching assistants
for their patience, clear explanations, and practical advice during the experiments, as well as to the
laboratory staff for their assistance in preparing and maintaining the equipment. Last but not the
least, we also acknowledge the university for providing access to its facilities, resources, and
technical infrastructure, without which this work would not have been possible.
10. Appendix
The data collected during the lab hours is attached here below:

11. References
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[3] Hoffmann MR, Martin ST, Choi W, Bahnemann DW (1995) Environmental applications of
semiconductor photocatalysis. Chem Rev 95:69-96.
[4] Fujishima A, Rao TN, Tryk DA (2000) Titanium dioxide photocatalysis. J Photochem
Photobiol C: Photochem Rev 1:1-21.
[5] Carp O, Huisman CL, Reller A (2004) Photoinduced reactivity of titanium dioxide. Prog
Solid State Chem 32:33-177.