INTERNATIONAL BACCALAUREATE CHEMISTRY EXTENDED ESSAY Title: Spectrophotometric Investigation of the Photocatalytic Degradation of Tartrazine dye Research Question: How does a change in the pH, from 4.0 to 11.0, affect the absorbance, and hence rate of photocatalytic degradation, of 0.005 mol.dm-3 Tartrazine dye, when exposed to UV light for 60 minutes in the presence of zinc oxide as a catalyst, when measured using a spectrophotometer? Word count: 3859 Session: May 2021 i Table of Contents 1-Introduction ............................................................................................................................................. 1 1.1-Significance........................................................................................................................................ 1 1.2-Scope of research .............................................................................................................................. 2 2-Background Information ........................................................................................................................ 4 2.1-Properties of Tartrazine ................................................................................................................... 4 2.2-Photocatalytic Degradation and its relation to dyes ...................................................................... 5 2.3-Effect of pH on photocatalytic degradation of tartrazine ............................................................. 7 2.4-Spectrophotometry ........................................................................................................................... 8 3-Hypothesis .............................................................................................................................................. 10 4-Methodology ........................................................................................................................................... 10 4.1-Variables .......................................................................................................................................... 10 4.2-Safety and ethical concerns ............................................................................................................ 12 4.3-Experimental Procedure ................................................................................................................ 13 5-Data Collection and Processing ............................................................................................................ 14 5.1-Raw Data ......................................................................................................................................... 14 Qualitative data:................................................................................................................................ 14 Quantitative data .............................................................................................................................. 15 5.2-Calculations and Data processing ............................................................................................. 17 5.3-Data Analysis................................................................................................................................... 19 6-Discussion of results............................................................................................................................... 23 7-Conclusion ............................................................................................................................................ 255 8-Evaluation and extension .................................................................................................................... 255 10-Bibliography: ..................................................................................................................................... 288 10.1-Websites ....................................................................................................................................... 288 10.2-Online Journals ............................................................................................................................. 30 10.3-Books .............................................................................................................................................. 34 11-Appendix................................................................................................................................................ iii 11.1-Materials ......................................................................................................................................... iii 11.2-Preparing the stock solution ......................................................................................................... iv 11.3-Calibration Curve absorbance readings ...................................................................................... iv ii List of Figures Figure 1: Structure of tartrazine .................................................................................................................... 4 Figure 2: Conceptual schematic of photocatalytic oxidation of Tartrazine .................................................. 7 Figure 3: A single beam scanning spectrophotometer .................................................................................. 9 List of Tables Table 1: Controlled Variables ..................................................................................................................... 10 Table 2: Concentration and absorbance ...................................................................................................... 15 Table 3: Raw Data Table: At varying pH ................................................................................................... 17 Table 4: Processed Data Table .................................................................................................................... 18 Table 5: pH and the corresponding change in absorbance, concentration and the linear rate of photocatalytic degradation .......................................................................................................................... 20 Table 6: Calibration Curve absorbance readings ......................................................................................... iv List of graphs Graph 1: Calibration curve of tartrazine ..................................................................................................... 15 Graph 2: Linear regression for dye concentration against time with varying pH ....................................... 19 Graph 3: Rate of dye photocatalytic degradation with varying pH ............................................................ 21 Graph 4: Rate of photocatalytic degradation with varying pH with revised trendline................................ 22 Graph 5: Rate of photocatalytic degradation with varying pH, for last three data points ........................... 23 1 1-Introduction 1.1-Significance Colours and dyes fascinate everyone. I have early memories of making ink solutions from pens to colour chalks blue and purple. Likewise, most people prefer products- food, clothes or books- which are colourful and vibrant. Hence, synthetic dyes, due to their vivid, photo-resistant colour, have increased dramatically in production rates since their discovery in 1856. But few people understand the consequences of prioritizing beauty and profitability over our own health. This fact struck me while looking at the ingredients on a packet of fresh red cherries and seeing “FD&C Red 40 present in product, possible hyperactivity and hypersensitivity reactions1”. Further research revealed that the annual synthetic dye production was almost 1 million tonnes in 20072. Unfortunately, almost 20% of these dyes are released as effluents into water bodies3, changing their COD, BOD, and pH thereby harming aquatic life. Some synthetic dyes, or their metabolites, are carcinogenic, damaging not only aquatic ecosystems but also humans drinking 1 Kobylewski S, Jacobson MF. Toxicology of food dyes. Int J Occup Environ Health. 2012;18(3):220-246. doi:10.1179/1077352512Z.00000000034 (www.Peirsoncenter.com Toxicology article). Accessed July 20 2020 2 Pandey, Anjali, Poonam Singh, and Leela Iyengar. 2007. Bacterial decolorization and degradation of azo dyes. International biodeterioration & biodegradation 59, no. 2 (2007): 73-84. Accessed June 10 2020 3 Farah Maria Drumond Chequer, Gisele Augusto Rodrigues de Oliveira, Elisa Raquel AnastaΜcio Ferraz, JulianoCarvalho Cardoso, Maria Valnice Boldrin Zanoni and Danielle Palma de Oliveira. 2012. Textile Dyes: Dyeing Process and Environmental Impact. March 20. Accessed July 26, 2020. https://www.intechopen.com/books/eco-friendly-textile-dyeing-and-finishing/textile-dyes-dyeingprocess-and-environmental-impact. 2 that water.4 This inspired me to focus this essay on the degradation of synthetic dyes in aqueous solutions, to reduce its adverse effects during disposal and sustain a greener future for aquatic life. 1.2-Scope of research I decided to focus on Tartrazine (trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4- sulfonatophenyl)diazenyl]-4H-pyrazole-3-carboxylate)5, an extremely common dye in the food and cosmetics industry, which also causes hyperactivity and is a potential cytotoxin6. While looking for the right method for degrading tartrazine and its intermediates, I initially thought of using chlorine bleaches, which eliminate conjugated pi-bond systems in dyes to decolourise them7. However, further research revealed that bleach is dangerous and causes skin and lungs irritation8. So, I discarded this idea to look for a safer solution. While studying Bonding, I learned that Ultraviolet light breaks the bonds of ozone and oxygen. I was then introduced to photocatalytic degradation: a promising way to break down complex dyes and their metabolites. UV radiation leads to electron-hole pairs being produced from semiconducting metal oxides (the photocatalyst). In aqueous dye solutions, these pairs react with 4 Sarkar, S., Banerjee, A., Halder, U. et al. 2017. Degradation of Synthetic Azo Dyes of Textile Industry: a Sustainable Approach Using Microbial Enzymes.Water Conserv Sci Eng 2, 121–131 (2017). Accessed May 29 2020 5 "Tartrazine." National Center for Biotechnology Information. PubChem Compound Database. 2021. https://pubchem.ncbi.nlm.nih.gov/compound/Tartrazine#section=Names-and-Identifiers.Accessed February 08, 2021 6 Kobylewski S, Jacobson MF. Toxicology of food dyes. Int J Occup Environ Health. 2012;18(3):220-246. doi:10.1179/1077352512Z.00000000034 (www.Peirsoncenter.com Toxicology article). Accessed July 20 2020 7 Marianna A. Busch, Kenneth W. Busch,. 2019. "Bleaches and Sterilants." Edited by Colin Poole, Alan Townshend, Manuel Miró, Paul Worsfold. Encyclopedia of Analytical Science (Third Edition) (Academic Press) 300-315. https://doi.org/10.1016/B978-0-12-409547-2.14033-8. Accessed December 1 2020. 8 Benzoni T, Hatcher JD. Bleach Toxicity. [Updated 2020 Jun 29]. In: StatPearls [Internet]. Treasure Island (FL): StatPearls Publishing; 2020 Jan-. Available from: https://www.ncbi.nlm.nih.gov/books/NBK441921/ Accessed July 27 2020. 3 various species to produce unstable radicals like hydroxyl radicals, which completely degrade dyes9. For developing the methodology, I researched the necessity of the catalyst in this reaction, and learned that a photocatalyst and a UV source were required for photocatalytic degradation to occur10. For this, I initially chose titanium (IV) oxide due to its high electron-hole pair maintenance efficiency11. However, zinc oxide was used instead since it has a greater band gap energy(3.37eV) than does titanium (IV) oxide (3.2eV), enabling it to absorb more UV radiation12. There are multiple factors, including temperature, dye concentration, and UV-ray intensity which influence the rate of dye photocatalytic degradation. However, the effect of pH is highly complex and variable depending on dye structure, with lower pH increasing H+ concentration, catalyst charge positivity and hence adsorption of anionic dyes (such as tartrazine) on the catalyst surface13, but higher pH indicating higher OH- concentration and higher concentration of hydroxyl radicals. 9 Andrew W. Skinner, Anthony M. DiBernardo, Arvid M. Masud, Nirupam Aich, Alexandre H. Pinto,. 2020. "Factorial design of experiments for optimization of photocatalytic degradation of tartrazine by zinc oxide (ZnO) nanorods with different aspect ratios." Journal of Environmental Chemical Engineering, 8 (5).. https://doi.org/10.1016/j.jece.2020.104235. Accessed November 2020 10 Benzoni T, Hatcher JD. Bleach Toxicity. [Updated 2020 Jun 29]. In: StatPearls [Internet]. Treasure Island (FL): StatPearls Publishing; 2020 Jan-. Available from: https://www.ncbi.nlm.nih.gov/books/NBK441921/ Accessed July 27 2020. 11 Rauf, Muhammad & Ashraf, Syed. 2009. "Fundamental principles and application of heterogeneous photocatalytic degradation of dyes in solution. " Chemical Engineering Journal. 151. 10-18. 10.1016/j.cej.2009.02.026. 10-18 Accessed July 1 2020 12 M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, Journal of Hazardous Materials, Volume 133, Issues 1–3, 2006, Pages 226-232,ISSN 0304-3894, https://doi.org/10.1016/j.jhazmat.2005.10.022. Accessed August 1 2020 13 M.A. Rauf, M.A. Meetani, S. Hisaindee,. 2011. "An overview on the photocatalytic degradation of azo dyes in the presence of TiO2 doped with selective transition metals." Desalination,Volume 276, Issues 1–3,2011,Pages 1327,ISSN 0011-9164,https://doi.org/10.1016/j.desal.2011.03.071. 13-27. Accessed July 16 2020 4 Hence, this investigation aimed to determine the optimum pH for the rate of photocatalytic degradation of tartrazine in the presence of UV rays. Tartrazine-zinc oxide solutions with varying pH values were irradiated for 60 minutes, with the absorbance of aliquots measured in a calibrated spectrophotometer every 10 minutes. Thus, the research question of this essay is: How does a change in the pH, from 4.0 to 11.0, affect the absorbance, and hence rate of photocatalytic degradation, of 0.005 mol.dm-3 Tartrazine dye, when exposed to UV light for 60 minutes in the presence of zinc oxide as a catalyst, when measured using a spectrophotometer? 2-Background Information 2.1-Properties of Tartrazine According to their functional groups, many classes of synthetic dyes, such as triphenylmethane or anthraquinone, exist. Of these, azo dyes are the most common14, constituting about 50-90% of total synthetic dye production15. Figure 1: Structure of tartrazine16 14 Lade H, Kadam A, Paul D, Govindwar S. 2015. Biodegradation and detoxification of textile azo dyes by bacterial consortium under sequential microaerophilic/aerobic processes. . doi:10.17179/excli2014-642. EXCLI J. 2015;14:158-174. Accessed 1 June 2020 15 Chavan, R.B. 2011. Environmentally friendly dyes,Editor(s): M. Clark,In Woodhead Publishing Series in Textiles, Handbook of Textile and Industrial Dyeing. Woodhead Publishing, Volume 1, 2011, Pages 515-561, ISBN 9781845696955. Accessed 12 July Simmons, M. 2017. Tartrazine — toxicity, side effects, diseases and environmental impacts. December 21.. https://www.naturalpedia.com/tartrazine-toxicity-side-effects-diseases-and-environmental-impacts.html. Accessed January 22, 2021 16 5 Tartrazine is an anionic azo dye. All dyes comprise chromophores, conjugated systems of multiple pi-bonds, that absorb light wavelengths. The azo double-bond (N=N), aromatic rings and carboxylate group in form the chromophore in tartrazine, which consequently appears yellow. During photocatalytic degradation, this azo bond is destroyed, splitting the pi-bond system and rendering the dye unable to absorb visible light. This decolourisation will be used to measure tartrazine degradation. 2.2-Photocatalytic Degradation and its relation to dyes Photocatalytic degradation is an Advanced Oxidation Process (AOP): a process involving the formation of reactive hydroxyl (OHβ) radicals, which oxidise and dissociate organic compounds into simpler molecules like carbon dioxide and water.17 In photocatalytic degradation, when the catalyst (here, zinc oxide) in the aqueous solution is bombarded with UV photons with energies greater than its band gap energy (3.37eV)18, electrons are excited from the valence to the conduction band, creating an electron-hole (electron vacancy) pair. ZnO + βπ£(UV) → ZnO(π − πΆπ΅ + β+ ππ΅ ) (eq-1)19 17 Deng, Yang, and Renzun Zhao. "Advanced Oxidation Processes (AOPs) in Wastewater Treatment." Current Pollution Reports 1, no. 3 (September 18, 2015): 167-76. Accessed January 01, 2021. doi:10.1007/s40726-0150015-z. 18 Gupta, Vinod K, Rajiv Jain, Arunima Nayak, Shilpi Agarwal, and Meenakshi Shrivastava. 2011. "Removal of the hazardous dye—Tartrazine by photodegradation on titanium dioxide surface." Materials Science and Engineering: C, 31 (5): 1062-1067. doi:10.1016/j.msec.2011.03.006. Accessed July 18 2020 19 Ioannis K Konstantinou, Triantafyllos A Albanis,. 2003. "TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations: A review,." Applied Catalysis B: Environmental,Volume 49, Issue 1,2004,Pages 1-14,ISSN 0926-3373,https://doi.org/10.1016/j.apcatb.2003.11.010. 1-14. Accessed July 19 2020 6 where βπ£(UV) is a UV photon, h+VB the hole in the valence band and e-CB the excited electron in the conduction band. The excited electrons either reduce the dye molecule (adsorbed on the catalyst’s surface) itself(eq2), or react with aqueous oxygen to form superoxide(O2β-) ions(eq-3), thereby producing hydrogen peroxide (eq 6) and, indirectly, hydroxyl radicals(eq 8), which further degrade dye molecules(eq11). Simultaneously, the holes in the valence band either oxidize the adsorbed dye (eq-10) or the Zinc oxide-bound water or hydroxyl particles to produce hydroxyl radicals (eq-4 and 5).20 e-CB + dye →dye-reduction products (eq-2) e-CB +O2 → O2β- (eq-3) h+VB +H2O→ H+ + OHβ (eq-4) h+VB +OH-→ OHβ (eq-5) O2β−+ H+ → HO2β (eq-6) HO2β + H+→H2O2 (eq-7) H2O2→ 2OHβ (eq-8) h+VB + dye→ dye-oxidation products (eq-10) OHβ + dye→ dye-degradation products (eq-11) Below lies a schematic of species involved in the photocatalytic degradation of tartrazine. 20 M.A. Rauf, M.A. Meetani, S. Hisaindee,. 2011. "An overview on the photocatalytic degradation of azo dyes in the presence of TiO2 doped with selective transition metals." Desalination,Volume 276, Issues 1–3,2011,Pages 1327,ISSN 0011-9164,https://doi.org/10.1016/j.desal.2011.03.071. 13-27. Accessed July 16 2020 7 Figure 2: Conceptual schematic of photocatalytic oxidation of Tartrazine21 2.3-Effect of pH on photocatalytic degradation of tartrazine The effect of pH on the rate of photocatalytic degradation of this dye is complex, with both H+ as well as OH- concentrations positively affecting the rate. The surface charge of the photocatalyst is affected by pH. Zinc oxide in solution exists as particles bonded to hydrogen ions (ZnO-H+), which critically influence its charge22: At low pH, ππππ» + π» + → ππππ»2 + At high pH, ππππ» + ππ» − → πππ− + π»2 π 21 22 El-Deen, Tarek S. Jamil & S. E. A. Sharaf. 2016. "Removal of persistent tartrazine dye by photodegradation on TiO2 nanoparticles enhanced by immobilized calcinated sewage sludge under visible light." Separation Science and Technology, 51:10, 1744-1756, DOI:. doi:10.1080/01496395.2016.1170036. Accessed October 18 2020 Mashkour, M. & Alkaim, Ayad & Ahmed, Luma & Hussein, Falah. (2011). "Zinc Oxide assisted Photocatalytic decolorization of reactive red 2 dye." International Journal of Chemical Science (9): 969-979. Accessed January 1, 2021. https://www.tsijournals.com/abstract/zinc-oxide-assisted-photocatalytic-decolorization-of-reactive-red-2-dye10649.html. 8 Tartrazine, an anionic dye (with sulfonate (SO3-) and ethanoate functional groups), adsorbs more frequently on the positively charged ZnOH2+ compared to the negatively charged ZnO-, leading to greater catalyst-dye interaction and hence greater rate of degradation, at low pH. However, as OH- concentration increases, so does rate of OHβ formation. As seen in figure 2, OHβ radicals significantly control dye degradation, and hence, higher pH also influences the rate of dye degradation positively. Therefore, one would infer that an optimum pH would exist for degrading this dye, close to a neutral pH: near 7, and not an extreme value, as while one effect is enhanced, the other will be diminished. Considering that OHβ radicals can diffuse throughout the solution and react with dye molecules unadsorbed on the catalyst surface, OH- ion concentration would affect degradation rate more be more impactful than greater adsorption rate. 2.4-Spectrophotometry Measuring absorbance, using spectrophotometers or colorimeters, is one way to measure the concentration of a dissolved substance. The Beer-Lambert Law states that the absorbance, the amount of light absorbed at a wavelength23, of a dissolved substance is directly proportional24 to its concentration in a solution25. Quantitatively, π΄ = πππ 23 Brown, Catrin, and Mike Ford. 2014. "Analysis of the Protein concentration of a sample." Chap. 14 in Pearson Baccalaureate Higher Level Chemistry, by Catrin Brown and Mike Ford, edited by Tim Jackson, 706-707. Accessed June 1, 2020. 24 Rafferty, J.P. 2019. Beer's Law. November 20. https://www.britannica.com/science/Beers-law. Accessed August 3, 2020 25 Clark, J, and G Gunawardena. 2020. The Beer-Lambert Law. August 16. https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Mod ules_(Physical_and_Theoretical_Chemistry)/Spectroscopy/Electronic_Spectroscopy/Electronic_Spectroscopy_Basic s/The_Beer-Lambert_Law. Accessed 1 1, 2021 9 Where A is the absorbance of the substance, c the concentration, ε the absorptivity and b the optical path-length. A spectrophotometer is a device that electronically measures the transmittance of different wavelengths of light through a coloured sample. It consists of a visible light source, comprising all wavelengths, which are diffracted, dispersed and separately transmitted through the sample, using a diffraction grating and a movable slit, respectively. Figure 3: A single beam scanning spectrophotometer26 A detector27 at the end of the path of the transmitted light, measures the absorbance of the sample, with reference to a previously measured colourless solution (usually distilled water) that does not absorb any light. 26 Vista, Shree. (2015). Use of Humic acid in agriculture, Accessed January 1 2021 Instruments, Shimadzu Scientific. “Uv-Vis Frequently Asked Questions - Instrument Design,” September 25, 2019. Accessed January 30 2021. https://www.ssi.shimadzu.com/products/uv-vis-spectrophotometers/faqs/instrument-design.html. 27 10 3-Hypothesis Predictions can be made on the effect of the independent variable on the dependent variable: The rate of photocatalytic tartrazine degradation will increase up till it reaches pH 8, as the concentration of hydroxyl radicals will increase; after 8, the rate will decrease, as the adsorption of dye on the catalyst surface will decrease due to repulsion between the anionic dye and the negatively charged zinc oxide surface. 4-Methodology 4.1-Variables Independent variable: The pH was varied from 4.0 to 6.0, 8.0, 10.0 and 11.0 by using buffer solutions to dilute the dye-zinc oxide solutions of concentration 0.005 mol.dm-3, using a droppipette. This will be measured using a pH sensor. Dependent variable: The absorbance of the dye solution was recorded every 10 minutes for 60 minutes using a spectrophotometer. From the absorbance, the rate of photocatalytic degradation will be calculated. Table 1: Controlled Variables Variable Reason for controlling variable Controlled Method for controlling variable Exposure to Any external light would affect the rate of The experiments were external degradation of the dye (as an extraneous conducted in a dark room radiation variable) and cause random errors by shutting the curtains. The apparatus was placed in a wooden box. 11 External Changes in temperature in the surroundings Experiments were change in could change the equilibrium point and rates conducted at the same Temperature of electron-hole recombination, reduction time every day, and oxidation, creating random errors. maintaining temperature at 27°C using air-condition set up. Beyond that, however, fluctuations in room temperature could affect the results. pH sensor Changing this could cause systematic errors. The same sensor was used for all experiments. Distilled Changes in impurities could affect the Distilled water from the water activity and concentration of reactants and same source was used for products and create random and systematic all solutions. errors. Mass of the Different photocatalyst concentrations would 250 mg of ZnO was added photo-catalyst cause changes in catalyst activity and rate of to all the solutions. used. degradation. Initial dye Varying initial dye concentration would The irradiated solutions in concentration make the values of absorbance and, hence, the pH-rate experiment all rate of degradation, inconsistent and possessed a concentration unreliable. of 5 × 10−5 moldm-3. 12 4.2-Safety and ethical concerns a) Health hazards ο· As UV rays are harmful to skin and can cause sunburns or skin cancer, as well as inflammation of eyes28, the entire apparatus was placed in a hard, black cardboard box, and safety goggles were used. ο· Nitrile gloves were used while handling the zinc oxide, tartrazine powder and aqueous solutions, as these chemicals are irritants29 if inhaled or in contact with skin. b) Care for apparatus and chemical disposal ο· Do not place the pH sensor in the beaker while pouring hydrochloric acid or sodium hydroxide, to prevent damage to the instrument. Take it out of the solution before turning the UV lamp on. ο· Dilute all solutions before disposal as zinc oxide30 and tartrazine are toxic for aquatic and human life. ο· Dispose the excess acid or alkali after neutralizing and diluting. ο· Dispose of gloves by removing such that it does not come in contact with skin. They must be disposed of in a designated waste bin for used gloves. c) Sustainable solution consumption ο· Dilute the hydrochloric acid and sodium hydroxide solutions to 0.01 moldm-3 or less as they are corrosive. 28 Kuijk, F. J Van. "Effects of Ultraviolet Light on the Eye: Role of Protective Glasses." Environmental Health Perspectives 96 (December 1991): 177-84. Accessed November 2, 2020. doi:10.1289/ehp.9196177. 29 Chemical Info for Zinc Oxide. November 23, 2015. Accessed February 1, 2021. https://chemicalsafety.com/sds1/sdsviewer.php?id=30469074&name=Zinc oxide. 30 Chemical Info for Zinc Oxide. November 23, 2015. https://chemicalsafety.com/sds1/sdsviewer.php?id=30469074&name=Zinc oxide. Accessed November 1, 2020 13 ο· Maintain a maximum mass of 250 mg for zinc oxide (per solution) and maximum concentration of 0.005 moldm-3 for Tartrazine. 4.3-Experimental Procedure Part A: Determining wavelength of maximum absorbance (λmax) of tartrazine (before UV exposure) to obtain calibration curve. 1) Prepare a stock solution of 9.0 cm3 0.005 molβdm-3 tartrazine dye (as given in appendix) 2) Prepare 5.0 cm3 of 1.0 × 10−5 moldm-3 dye solution, by pipetting out 0.01 cm3 stock solution in a volumetric flask. 3) Measure out 250mg of zinc oxide using a weigh balance and transfer to the flask. 4) Dilute it up to the mark with distilled water and place it on a magnetic stirrer for 5 minutes. 5) Calibrate the spectrophotometer by placing a 5 cm3 distilled water solution in the spectrophotometer and set the absorbance to 0.000. 6) Pipette out 5.0cm3 of the 1.0 × 10−5 moldm-3 tartrazine solution in the cuvette to record maximum absorbance set at different wavelengths from 380nm to 700nm. 7) Record the wavelength that produces maximum absorbance. 8) Repeat recording absorbance with 1.0 × 10−5 moldm-3 tartrazine solution setting at the wavelength with maximum absorbance recorded in step 7 ,thrice. 9) Repeat step 8, taking 5.0 × 10−5 , 5.0 × 10−5 , 1.0 × 10−4 , 1.5 × 10−5 , 2.0 × 10−4 moldm-3 dye-catalyst solutions, to obtain a calibration curve. Note: Conduct experiment in a dark area. When not using zinc oxide solutions, place them in dark containers to prevent dye degradation which would create inconsistent results. 14 Part B: Determining the effect of pH on rate of photocatalytic degradation 1) Prepare 30cm3 of a 5.0 × 10−5 molβdm-3 solution, of tartrazine by adding 0.3cm3 5.0 × 10−5 molβdm-3 to a 100 cm3 volumetric flask. 2) Add 250 mg of zinc oxide at the end (to prevent reaction initiation before irradiation), measured using a digital weigh balance and add to the flask. 3) Dilute with pH 4.0 buffer solution up to the mark. 4) Measure initial absorbance: extract 5 cm3 of solution, set the wavelength to the maximum-absorbance wavelength found from the previous experiment and set absorbance of blank solution to 0.000. Then measure the absorbance of the irradiated aliquot at the same wavelength. 5) Place the solution 10 cm away from the UV lamp. 6) Extract 5 cm3 of the solution obtained in step 3 for every 10 minutes to measure absorbance in the spectrophotometer for 60 minutes. 7) Repeat steps 4-6 for two more trials. 8) Repeat steps 1-6, using pH 6.0, 8.0, 10.0 and 11.0 in step 3 each time. 5-Data Collection and Processing 5.1-Raw Data Qualitative data: The tartrazine solution, initially strongly yellow, faded after all irradiation trials. Basic pH solutions faded faster than acidic solutions did. The cuvette was also hotter after irradiation, as some of the light was converted into heat energy. It was also observed that effervescence– due to evolved carbon dioxide– was present at the cuvette rim. 15 Quantitative data There was no change in dye absorbance at varying pH (before irradiation). The wavelength of maximum absorbance was recorded at 428 nm,31 as per procedure in part A. This value was supported by research32. The average absorbance was plotted against concentration for the calibration curve. Table 2: Concentration and absorbance Dye Concentration 10-5 molβdm-3 (±0.01) 1.00 5.00 10.00 15.00 20.00 Average Absorbance (±0.001) 0.351 1.759 3.560 5.350 7.050 Graph 1: Calibration curve of tartrazine 31 M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, Journal of Hazardous Materials, Volume 133, Issues 1–3, 2006, Pages 226-232,ISSN 0304-3894, https://doi.org/10.1016/j.jhazmat.2005.10.022. Accessed August 1 2020 32 Gobara, Mohamed & Baraka, Ahmad. (2014). 2014. "Tartrazine Solution as Dosimeter for Gamma Radiation Measurement." International Letters of Chemistry, Physics and Astronomy. doi:33. 106-117. 10.18052. Accessed October 1 2020 16 The zero-value y-intercept showed that there was absorbance is directly proportional to concentration. Hence, results were valid. By the Beer-Lambert Law, π¨ = πΊππ = ππ × 10−5 Here, A is the absorbance, ε the molar absorptivity, b the path length (cuvette side-length), m the line slope and x, the dye concentration. ∴ π = π β π β 10−5 ; π π π = 105 β π 0.354 = 105 β = 2.832π₯104 π 1.25 ≈ 2.83π₯104 ππ3 β πππ −1 β ππ−1 Although the result is only valid for 3 significant figures, it matched the literature value33, 28321.61, to 4 significant figures, and was hence used for calculations. The table below gives the absorbance, taken every 10 minutes for 60 minutes, with varying pH of 4.0, 6.0, 8.0, 10.0 and 11.0. The control conditions were an initial concentration of 5.00 × 10−5 moldm-3, temperature of 250C and 250 mg zinc oxide. 33 food and agricultural organization, UN. n.d. TOTAL COLOURING MATTERS CONTENT (VOLUME 4).Database, food and agricultural organization. http://www.fao.org/3/a0691e/Total_colouring_matters_volume%204.pdf. Accessed October 15 2020. 17 Table 3: Raw Data Table: At varying pH Absorbance of solution (± 0.001) Time (minutes) (±0.1) pH 4.0 (± 0.1) pH 6.0 (± 0.1) pH 8.0 (± 0.1) pH 10.0 (± 0.1) pH 11.0 (± 0.1) 0.0 Trial Trial 1 2 3 1 2 3 1 1.770 1.770 1.770 1.770 1.770 1.770 1.770 Trial Trial 2 3 1 2 3 1 1.770 1.770 1.770 1.770 1.770 1.770 Trial 2 3 1.770 1.770 10.0 1.667 1.703 1.738 1.591 1.627 1.662 1.267 1.303 1.338 1.248 1.283 1.319 1.108 1.143 1.179 20.0 1.646 1.682 1.717 1.521 1.556 1.591 1.032 1.067 1.103 0.952 0.988 1.023 0.581 0.616 0.651 30.0 1.634 1.669 1.705 1.499 1.535 1.570 0.752 0.788 0.823 0.701 0.736 0.772 0.384 0.425 0.455 40.0 1.621 1.657 1.692 1.464 1.499 1.535 0.501 0.536 0.572 0.499 0.535 0.570 0.280 0.319 0.350 50.0 1.597 1.632 1.667 1.448 1.483 1.519 0.388 0.423 0.458 0.313 0.349 0.384 0.173 0.212 0.244 60.0 1.595 1.630 1.666 1.432 1.467 1.503 0.142 0.177 0.212 0.145 0.181 0.216 0.099 0.142 0.170 5.2-Calculations and Data processing For the sample calculation, readings at pH 4.0 and 10.0 minutes will be taken. Calculation of average absorbance Average Absorbance = sum of absorbance values for each pH per time interval 3 = 1.667 + 1.703 + 1.738 = 1.703 ± 0.001 3 Calculation of concentration π΄ = πππ, ∴π= π΄ 1.703 = = 4.810 × 10−5 πππ β ππ−3 ππ 28312 x 1.25 18 βπ΄ βπ Percentage uncertainty in concentration = [ π΄ + π ], since absolute uncertainty is the product of the absolute value and the total percentage uncertainty, and as path length cannot be assumed as infinitely precise. For the error bars, absolute uncertainty was used: Δπ βπ΄ βπ π΄ βπ΄ βπ = [ + ] ; ∴ Δπ = × [ + ] π0 π΄ π ππ π΄ π Δπ 0.001 0.005 =[ + ] = 0.459% ≈ ±0.5% π0 1.703 1.25 Δπ = 1.703 0.001 0.005 + [ ] = ±0.221 × 10−6 mol β dm−3 28320 x 1.25 2.804 1.25 Concentration, being extremely small, was plotted in terms of 10-5 molβdm-3. Approximate uncertainties are shown at acidic and basic pH. Table 4: Processed Data Table Concentration x (10-5 molβdm-3) at π₯π ≈ ±0.5% π π₯π ≈ ±1% π Time (minutes) (±0.1) 0.0 pH 4.0 5.000 pH 6.0 5.000 pH 8.0 5.000 pH 10.0 5.000 pH 11.0 5.000 10.0 4.810 4.595 3.680 3.625 3.230 20.0 4.750 4.395 3.015 2.790 1.740 30.0 4.715 4.335 2.225 2.080 1.190 40.0 4.680 4.235 1.515 1.510 0.893 50.0 4.610 4.190 1.195 0.985 0.593 60.0 4.605 4.145 0.500 0.510 0.387 19 5.3-Data Analysis To find the change in rate of photocatalytic degradation, average rate values for every pH were required. Hence, linear trendline graphs of tartrazine concentration against time were obtained, the gradients of which were taken as the rate of change of dye concentration. Like the concentration, the rate values were obtained in terms of 10-5 moldm-3min-1. As the trendline equations were in a π¦ = ππ₯ + π format, their slopes were the average linear rate of change of reactant concentration. Both vertical and horizontal error bars were to too small to be noticed. Graph 2: Linear regression for dye concentration against time with varying pH For pH = 4.0, π¦ = −0.0059π₯ + 4.916 20 ∴ π ππ‘π ππ ππππππππ‘πππ = −(πππ‘π ππ πβππππ ππ πππππ‘πππ‘ πππππππ‘πππ‘πππ) = −(m) = +0.0059 β 10−5 πππ β ππ−3 πππ−1 To calculate rate uncertainties, Δrate Δ(Δπ) Δt = + πππ‘π (Δπ)0 π‘ Where Δc is change of dye concentration. Δπ = πππππ‘πππ − ππππππ = 5.000 ± 0.0228 − 4.605 ± 0.0212 = 0.395 ± 0.0440 ∴ Δ(Δπ) 0.0440 Δ(Δπ) Δt = ≈ ±11.3%; ∴ Δrate = πππ‘π0 × ( + ) (Δπ)0 (Δπ)0 0.395 π‘ = 0.59 × 10−7 × (0.113 + 0.1 ) = ±0.067 × 10−7 πππ ππ−3 β πππ−1 60 Table 5: pH and the corresponding change in absorbance, concentration and the linear rate of photocatalytic degradation pH (±0.1) Change in Absorbance Change in concentration Average linear Rate of photocatalytic (±0.002) (10-5 moldm-3) ±0.044 degradation (10-5 moldm-3min-1) 4.0 0.140 0.395 0.0059 ± 0.0007 6.0 0.303 0.855 0.0126 ± 0.0006 8.0 1.593 4.500 0.0713 ± 0.0006 10.0 1.590 4.490 0.0715 ± 0.0006 11.0 1.633 4.613 0.0713 ± 0.0005 21 A graph was then created, taking average degradation rate on the Y-axis and pH on the X-axis. An estimate of the average rate uncertainty for all rates was added. Plotted error bars were not visible. Graph 3: Rate of dye photocatalytic degradation with varying pH Rate of phtocatalytic degradation (x 10-7 moldm-3 min-1) ± 6 x10-4 0.09 0.08 0.07 0.06 y = 0.0108x - 0.0378 R² = 0.824 0.05 0.04 0.03 0.02 0.01 0 3 4 5 6 7 8 9 10 11 12 pH (±0.1) However, as the last 3 data points were roughly constant a linear trend was considered an unfit match. Hence, a polynomial (degree 2) curve was chosen instead. 22 Graph 4: Rate of photocatalytic degradation with varying pH with revised trendline Rate of phtocatalytic degradation x 10-5 moldm-3 min-1 ± 6 x10-4 0.09 y = -0.0011x2 + 0.0272x - 0.0925 R² = 0.8554 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 3 4 5 6 7 8 9 10 11 12 pH (±0.1) The rate of degradation and pH was best represented with a polynomial equation: π¦ = −0.0011π₯ 2 + 0.0272π₯ − 0.0925 , with y as rate and x as pH. Although the trendline does not depict the exact change of rate with pH, it does represent the trend followed by the variables, of rate increasing with pH 8.0 after which it reaches a constant value. To determine the significance of the difference between rates at pH 8.0, 10.0 and 11.0, the same rate-pH graph, only at these three pH values, was plotted. 23 Graph 5: Rate of photocatalytic degradation with varying pH, for last three data points Rate of photocaalytic degradation (10-5 mol dm-3 min-1 ± 6 x10-4 0.0722 0.072 0.0718 0.0716 0.0714 0.0712 0.071 0.0708 0.0706 7 8 9 10 11 12 pH (± 0.1) Although uncertainties appear large in the second graph, since the uncertainty range of the last three points (approximately (0.02 ± 0.01)× 10−7moldm-3min-1) were minimal compared to the difference between the acidic (pH 4.0 and 6.0) and basic (pH 8.0 to 11.0) solution degradation rates (approximately (6.21 ± 0.04) × 10−7 moldm-3min-1). Hence, the rate was concluded to be roughly constant between pH 8.0 and 11.0. 6-Discussion of results It was found that, as seen in graph 3, the rate of photocatalytic degradation increased with increasing pH, but settling at a maximum at pH 10. The high R2 value, 0.86, indicates a strong relationship between pH and rate34. 34 Agnes Ogee, Mark Ellis, Bruno Scibilia, Cheryl Pammer. 2013. Regression Analysis: How Do I Interpret Rsquared and Assess the Goodness-of-Fit? Edited by Minitab Blog Editor. May 30. Accessed 11 27, 2020. 24 At low pH, H+ concentration is greater, and Hydrogen ions are attracted to the aromatic rings of the dye, reducing the negative electric attraction between the anionic dye and the hydroxyl radicals, hindering the relative reactivity between the species and hence, the rate of photocatalytic degradation. One research study35 also found that zinc oxide converts into Zn2+ ions in acidic pH, significantly reducing catalyst activity. As pH increases, greater concentration of hydroxide(OH-) ions increases the negative charge density, facilitating a greater oxidative effect of OHβ36. In addition, greater OH- concentration will increase the rate of hydroxyl ion (OHβ) formation, and consequently enhance the rate of dye degradation37. One can reason that the positive effect of greater pH on OHβ concentration– and OHβ radical reaction–supersedes the positive effect of H+ ions on rate of photocatalytic degradation. However, it can be seen in Graph 3 that the curve settles at the last 3 rate values (7.13 × 10−7 , 7.13 × 10−7 , 7.13 × 10−7 moldm-3min-1).But this similarity in rates is likely due the positive effect of low pH on the rate of degradation, which counters the positive effect of OH- ions at pH 8.0, 10.0 and 11.0. Although more hydroxyl ions are present at higher pH, they interact less https://blog.minitab.com/blog/adventures-in-statistics-2/regression-analysis-how-do-i-interpret-r-squared-andassess-the-goodness-of-fit. 35 El-Deen, Tarek S. Jamil & S. E. A. Sharaf. 2016. "Removal of persistent tartrazine dye by photodegradation on TiO2 nanoparticles enhanced by immobilized calcinated sewage sludge under visible light." Separation Science and Technology, 51:10, 1744-1756, DOI:. doi:10.1080/01496395.2016.1170036. Accessed October 18 2020 36 Gupta, Vinod K, Rajiv Jain, Arunima Nayak, Shilpi Agarwal, and Meenakshi Shrivastava. 2011. "Removal of the hazardous dye—Tartrazine by photodegradation on titanium dioxide surface." Materials Science and Engineering: C, 31 (5): 1062-1067. doi:10.1016/j.msec.2011.03.006. Accessed July 15 2020 25 frequently with anionic dye molecules which are not easily adsorbed on the negatively charged catalyst-surface, hence leading to negligible increase in rate. Hence the rate of photocatalytic degradation increases up till reaching pH 8.0, after which it remains constant. 7-Conclusion This investigation focused on the determining the effect of pH on the rate of photocatalytic degradation of the dye tartrazine. It was found that the rate of photocatalytic degradation increased with pH, with pH 4.0 displaying the smallest linear rate, 5.91 × 10−8 moldm-3min-1 until reaching a roughly constant value at pH 8.0 till 11.0 of 7.14 × 10−7 moldm-3min-1. Thus, the hypothesis- that rate of tartrazine degradation will increase up till pH 8.0, after which, the rate will decrease, is partially proven. The Research Question- “How does a change in the pH, from 4.0 to 11.0, affect the absorbance, and hence rate of photocatalytic degradation, of 0.005 mol.dm-3 Tartrazine dye, when exposed to UV light for 60 minutes in the presence of zinc oxide as a catalyst, when measured using a spectrophotometer?” has been successfully answered through this investigation. 8-Evaluation and extension To determine the validity of this investigation, results were compared with existing research on the photocatalytic degradation of Tartrazine with a zinc oxide catalyst38.This also showed that rates were much greater at high pH, with a nearly constant average rate between 8.0 and 11.0. This 38 M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, Journal of Hazardous Materials, Volume 133, Issues 1–3, 2006, Pages 226-232,ISSN 0304-3894, https://doi.org/10.1016/j.jhazmat.2005.10.022. Accessed August 1 2020 26 indicates that this experiment possesses high validity. Another study, El-Deen et al39, which investigated the optimum factors for photocatalytic degradation of tartrazine using a titanium (IV) oxide-sludge mixture, under visible light, found that pH 8.0 produced the maximum photocatalytic degradation rate significantly more than that at pH 10.0, indicating that the results obtained in this investigation may not be valid when complex mixtures (like sludge) exist in the tartrazine solution. There were limitations to the results obtained, which could be improved on. ο· The temperature of the dye solution increased during UV ray exposure. This would affect the rate of photocatalytic degradation by increasing the frequency of molecule collisions and rate constant40, and creating inconsistencies in results. This could be reduced by placing the flask in a thermally insulated chamber during irradiation, to maintain constant temperature. ο· The results of this study did not consider extreme pH values beyond the 4.0-11.0, as other factors– such as the dissolution of zinc oxide in concentrated acidic solutions into zinc salts41 and, in highly alkaline solutions, into alkali zincate salts– take place in such conditions. The study could have taken a broader pH range of 2.0 to 13.0 to understand the optimum pH for degradation. 39 El-Deen, Tarek S. Jamil & S. E. A. Sharaf. 2016. "Removal of persistent tartrazine dye by photodegradation on TiO2 nanoparticles enhanced by immobilized calcinated sewage sludge under visible light." Separation Science and Technology, 51:10, 1744-1756, DOI:. doi:10.1080/01496395.2016.1170036. Accessed October 18 2020 40 M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, Journal of Hazardous Materials, Volume 133, Issues 1–3, 2006, Pages 226-232,ISSN 0304-3894, https://doi.org/10.1016/j.jhazmat.2005.10.022. Accessed August 1 2020 41 M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, Journal of Hazardous Materials, Volume 133, Issues 1–3, 2006, Pages 226-232,ISSN 0304-3894, https://doi.org/10.1016/j.jhazmat.2005.10.022. Accessed August 1 2020 27 ο· Although the rate of tartrazine degradation was measured using absorbance values, no information on its colourless intermediates was obtained. To determine the rate of the dye’s mineralization into carbon dioxide and water, and hence the destruction of harmful products, the rate of change of mass of the solution (which changed with carbon dioxide effervescence) could be measured over time to measure photocatalytic degradation and mineralization. ο· Due to the arrangement of apparatus, UV rays could have been unequally distributed to different sections of the solution and only irradiated the surface, leading to systematic errors in absorbance values, and hence calculated rate of photocatalytic degradation. By placing the dye solution on a magnetic stirrer and simultaneously irradiating it, a more accurate result could be obtained. ο· In this investigation, rate of photocatalytic degradation was assumed constant over the entire reaction duration. However, Table 5 shows that maximum change in concentration was at pH 11.0, while linear rate of degradation was slightly greater at pH 10, indicating that average rate (considering the first and last concentrations) and linear rate (considering all concentration values) are not equal, and that rate changes with time. This indicates that the effect of pH on rate of photocatalytic degradation changes with reaction duration. To counter this systematic error in the results, the effect of pH on rate of photocatalytic degradation, at different times, could be measured to understand how the relationship between rate and pH changes with time. The experiment was successful overall, however¸ due to its strengths: ο· The data involved averages of 3 trials, which would give precise results with diminished random error. 28 ο· The initial concentration of the dye and the concentration of catalyst were standardised, which improved the relation between the independent and dependent variables. ο· The use of sophisticated instruments– a magnetic stirrer, digital pH sensor, spectrophotometer and Logger Pro software lead to more reliable results. ο· The procedure successfully facilitated an exploration of the relationship between pH and rate of photocatalytic degradation, thereby answering the research question of this investigation, by manipulating pH and measuring the change in absorbance. As an extension to this investigation, the effect of initial dye concentration, temperature and catalyst concentration on photocatalytic degradation rate could be investigated, to better understand the rates and kinetics of such reactions, using theoretical models such as the LangmuirHinshelwood Model42. This would help in better understanding optimum conditions to best eliminate toxic dyes from aquatic ecosystems and reducing their adverse effects on our environment. 10-Bibliography: 10.1-Websites 1. Agnes Ogee, Mark Ellis, Bruno Scibilia, Cheryl Pammer. 2013. Regression Analysis: How Do I Interpret R-squared and Assess the Goodness-of-Fit? Edited by Minitab Blog Editor. May 30. Accessed 11 27, 2020. https://blog.minitab.com/blog/adventures-in-statistics2/regression-analysis-how-do-i-interpret-r-squared-and-assess-the-goodness-of-fit. 42 Gupta, Vinod K., Rajeev Jain, Alok Mittal, Tawfik A. Saleh, Arunima Nayak, Shilpi Agarwal, and Shalini Sikarwar. 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Accessed June 1, 2020.11- iii 11-Appendix 11.1-Materials Instruments: 1 6 W UV Lamp An analytical balance (±0.001 g) Logger Pro software Spectrophotometer Vernier spectro-vis (software) for the spectrophotometer 2 Quartz cuvettes (5 cm3) 2 Volumetric flasks (500 cm3) Pipette (10 cm3) Rubber gloves Goggles 6 Test tubes (10cm3) Magnetic stirrer Magnetic Stirring rod Temperature probe (±0.1oC) Black cardboard box (blackened from both sides) 1 digital pH meter (±0.1) Stopwatch (±0.01 s) iv Chemicals Tartrazine 20% zinc oxide 0.01 mol dm-3 Hydrochloric acid 0.01 mol dm-3 Sodium Hydroxide pH 4.0 buffer solution pH 6.0 buffer solution pH 8.0 buffer solution pH 10.0 buffer solution pH 11.0 buffer solution distilled water 11.2-Preparing the stock solution 1. Weigh 6.679 g tartrazine powder using an analytical balance. 2. Transfer through funnel into a volumetric flask. 3. Add distilled water solution up till the 500cm3 mark. 4. Place the solution on a magnetic stirrer for 10 minutes. 11.3-Calibration Curve absorbance readings Table 6: Calibration Curve absorbance readings Dye Concentration (moldm-3) 1.00 5.00 10.00 15.00 20.00 Absorbance (±0.001) Trial 1 0.353 1.769 3.539 5.309 7.079 Trial 2 0.354 1.770 3.540 5.310 7.080 Trial 3 0.355 1.771 3.541 5.311 7.081 Average absorbance(±0.001) 0.354 1.770 3.540 5.310 7.080