Abstract

Indigo carmine is an anionic synthetic dye widely used in textile, food, and pharmaceutical industries. The discharge of this dye into water bodies poses severe environmental concerns due to its intense color, more stability, and resistance to biodegradation. Consequently, the oxidation and degradation of this dye through electron transfer reactions have been widely investigated. The present review focuses on studies related to oxidation of indigo carmine dye using various oxidizing agents like persulphate, peroxydiphosphate, bromate, iodate and N-Bromo succinimide. The degradation efficiency, reaction kinetics, and possible mechanisms involved in the dye removal process are discussed in detail. The oxidation process leads to the cleavage of the chromophoric structure of the dye, resulting in effective decolorization. Experimental parameters, such as dye concentration, oxidant concentration, pH, and surfactant concentration, significantly influence the rate of oxidation. Spectrophotometric analysis demonstrates progressive decline in absorbance at the characteristic wavelength of the dye, confirming its degradation. The review highlights effectiveness of oxidation processes in the treatment of dye-contaminated water and provides insights into optimizing reaction conditions for improved environmental remediation. The review also examines the kinetics of oxidation of dye in the environment of various oxidants in acidic medium under aqueous and in micellar media. The catalytic effects in micellar and in sub-micellar media were also discussed with their mechanistic pathways involved in the oxidation process. The rate equation for selected oxidants is presented, and both unimolecular and bimolecular catalytic patterns are interpreted using the Berezin kinetic model and the Piszkiewicz model. The reaction order with respect to substrate, oxidant, and medium concertation was determined by isolation method. A comparative analysis of oxidation of indigo carmine is presented by considering various kinetics and mechanistic parameters. Additionally, the binding constants obtained under different conditions are reported and discussed.

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1. Gallego-Ramírez C, Chica E, Rubio-Clemente A. Elimination of indigo carmine in water by Pinus patula biochar: Adsorption process optimization, kinetics and isotherms. J Environ Chem Eng. 2024;12(3):112425. doi: 1016/j.jece.2024.112425.
2. Manjunatha JG. A novel poly (glycine) biosensor towards the detection of indigo carmine: A voltammetric study. J Food Drug Anal. 2018;26(1):292–9. doi: 1016/j.jfda.2017.05.002.
3. Andreotti A, Bonaduce I, Colombini MP, Ribechini E. Characterisation of natural indigo and shellfish purple by mass spectrometric techniques. Rapid Commun Mass Spectrom. 2004;18(11):1213–20.
4. Curr E. Encyclopedia of microscopic stain. London: Leonard Hall (Books) Ltd.; 1960. p. 235.
5. Jalil AA, Triwahyono S, Adam SH, Rahim ND, Aziz MA, Hairom NH, et al. Adsorption of methyl orange from aqueous solution onto calcined Lapindo volcanic mud. J Hazard Mater. 2010;181(1–3):755–62.
6. Scholz F. Electroanalytical methods. 2nd ed. Berlin: Springer; 2010. p. 85.
7. El Hamd MA, Derayea SM, Abdelmageed OH, Askal HF. Spectrophotometric method for determination of five 1,4-dihydropyridine drugs using N-bromosuccinimide and indigo carmine dye. Int J Spectrosc. 2013;2013:243059.
8. Hamad HA, Sadik WA, Abd El-latif MM, Kashyout AB, Feteha MY. Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO₂ nanoparticles. J Environ Sci. 2016;43:26–39.
9. Jalil AA, Triwahyono S, Adam SH, Rahim ND, Aziz MA, Hairom NH, et al. Adsorption of methyl orange from aqueous solution onto calcined Lapindo volcanic mud. J Hazard Mater. 2010;181(1–3):755–62.
10. Guler UA, Ersan M, Tuncel E, Dügenci F. Mono and simultaneous removal of crystal violet and safranin dyes from aqueous solutions by HDTMA-modified Spirulina sp. Process Saf Environ Prot. 2016;99:194–206.
11. Aissa MA, Khairy M, Khalifa ME, Abdelrahman EA, Raza N, Masoud EM, et al. Facile synthesis of TiO₂@ZnO nanoparticles for enhanced removal of methyl orange and indigo carmine dyes: Adsorption and kinetics. Heliyon. 2024;10(10):e31351.
12. Marathe YV, Shrivastava VS. Degradation of indigo carmine dye by sol-gel deposited nanocrystalline cadmium sulphide thin film. Adv Sci Lett. 2012;5(1):173–7. doi: 1166/asl.2012.2140.
13. Lam WH, Tee LH, Ban ZH. A facile and rapid immobilization method of titanium dioxide-alginate composite for the photocatalytic removal of reactive black-5. Bull Chem React Eng Catal. 2024;19(2):230–41.
14. Umoru PE, Nkole IU, Ezeh TT. Degradation of indigo carmine dye with peroxydisulphate ion in aqueous sulphuric acid phase: Kinetic study. Int J Chem Kinet. 2024;56(6):339–46.
15. Mutnuru KC, Krishna KR. Micellar effects of cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) on oxidation of indigo carmine with potassium peroxy diphosphate. Novel Aspects Chem Biochem. 2024;9:9–29.
16. Mutnuru KC, Gummaluri RK, Karipeddi R. Kinetics and mechanism of oxidation of indigo carmine dye with potassium peroxydisulphate in micellar and sub-micellar medium. J Indian Chem Soc. 2025;102(2):101554.
17. Kalyana CM, Ramakrishna K, Subba Rao PV. Kinetics and mechanism of oxidation of indigo carmine with potassium bromate: Effect of CTAB and SDS micelles. Int J Chem Sci. 2017;15(4):220.
18. Mutnuru KC, Krishna KR. Micellar effects of cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) on oxidation of indigo carmine with potassium peroxy diphosphate. Novel Aspects on Chemistry and Biochemistry. 2024;9:9–29.
19. Yagub MT, Sen TK, Afroze S, Ang HM. Dye and its removal from aqueous solution by adsorption: A review. Adv Colloid Interface Sci. 2014;209:172–84.
20. Benaïssa H, Elouchdi MA. Biosorption of copper (II) ions from synthetic aqueous solutions by drying bed activated sludge. J Hazard Mater. 2011;194:69–78.
21. Falodun SO, Idris SO, Ojo EO, Iyun JF. Kinetics and mechanism of the oxidation of indigo carmine by permanganate ion in aqueous acidic medium. Int J Chem Biomol Sci. 2015;1(4):255–9.
22. Tandel AV, Padhiyar NB. Kinetics of oxidation of indigo carmine by vanadium (V) in presence of surfactants. Res J Chem Sci. 2015;5(11):24–30.
23. Setiyanto H, Saraswaty V, Firdausy GL, Setiyorini DA, Zulfikar MA. Enhancing the degradation potential of indigo carmine by a mediated electrochemical oxidation using Ce⁴⁺ mediator and Ag⁺ catalyst ions. Asian J Chem. 2022;15(3):1750–1756.
24. Palma-Goyes RE, Silva-Agredo J, González I, Torres-Palma RA. Comparative degradation of indigo carmine by electrochemical oxidation and advanced oxidation processes. Electrochim Acta. 2014;140:427–33.
25. Edokpayi JN, Iyun JF, Idris SO. A kinetic study of the redox reaction of indigo carmine by nitrite ion in aqueous hydrochloric acid medium. Phys Chem Indian J. 2011;6(1):9–13.
26. Othman I, Mohamed RM, Ibrahem FM. Study of photocatalytic oxidation of indigo carmine dye on Mn-supported TiO₂. J Photochem Photobiol A Chem. 2007;189(1):80–5.
27. Puttaswamy, Mahadevappa DS, Gowda NM. Kinetics and mechanism of oxidation of indigo carmine by hypohalites. Int J Chem Kinet. 1991;23(1):27–35.
28. Subba Rao PV, Venkateswara Rao N. Kinetics of oxidation of indigo carmine by potassium peroxydisulphate. Z Phys Chem (Leipzig). 1972;249(1):321–4.
29. Mutnuru KC, Gummaluri RK, Karipeddi R. Kinetics and mechanism of oxidation of indigo carmine dye with potassium peroxydisulphate in micellar and sub-micellar medium. J Indian Chem Soc. 2025;102(2):101554. doi: 1016/j.jics.2024.101554.
30. Das AK, Mondal SK, Kar D, Das M. Micellar effect on the reaction of picolinic acid catalyzed chromium (VI) oxidation of dimethyl sulfoxide in aqueous acidic media: A kinetic study. Int J Chem Kinet. 2001;33(3):173–81. doi: 1021/ja00447a044.
31. Bunton CA, Wolfe B. Problem of pH in micellar catalyzed reactions. J Am Chem Soc. 1973;95(11):3742–9.
32. Nakagawa T, Shinoda K. Physicochemical studies in aqueous solutions of nonionic surface active agents. In: Shinoda K, Nakagawa T, Tamamushi BI, Isemura T, editors. Colloidal Surfactants: Some Physicochemical Properties. New York: Academic Press; 1963. p. 97–178.
33. Berezin IV, Martinek K, Yatsimirskii AK. Physicochemical foundations of micellar catalysis. Russ Chem Rev. 1973;42(10):787–802.
34. Anderson MO, Edwards JO, Green AA, Wiswell MD. An examination of the rate constant data for glycine, alanine, phenylalanine, serine and threonine reveals that the presence of electron-withdrawing groups. Inorg Chem Acta. 1969;3(4):655.
35. Green AA, Edwards JO, Peter J. The oxidation reactions of peroxydiphosphate: The kinetics and mechanism of the reaction with tris(1,10-phenanthroline)iron(II). Inorg Chem. 1966;5(11):1858–64.
36. Eleanor C, Inge IC, Edwards JO. The reactivity and reaction pathway of Fenton reactions driven by substituted 1,2-dihydroxybenzenes. Inorg Nucl Chem Lett. 1971;7(1):1–6.
37. Lussier RJ, Risen WM, Edwards JO. Acid dissociation constant and decay kinetics of the perhydroxyl radical. J Phys Chem. 1970;74:4039–43.
38. Mandal SK, Das M, Kar D, Das AK. Micellar effect on the reaction of chromium (VI) oxidation of formaldehyde in the presence and absence of picolinic acid in aqueous acid media: A kinetic study. Indian J Chem A. 2001;40A:352–60.
39. Salem JK. Ground water quality. J Al-Azhar Univ Gaza. 2004;7:1–10.
40. Saha A. Effect of sodium dodecyl sulphate on the kinetics of reaction between persulphate and iodide ions. Int J Curr Res Chem Pharm Sci. 2014;1(7):31–5.
41. Salem MA. Ag(I) catalysed persulphate oxidation of phenylazodiphenylamine. Z Phys Chem. 1995;192S:87–99.
42. Jonnalagadda BS, Simoyi RH. A kinetic study of the oxidation of indigo carmine with acidic bromate. J Chem Soc Perkin Trans. 1988;—.
43. Edokpayi JN, Iyun JF, Idris SO. Kinetics and mechanism of the electron transfer reaction between tetraoxoiodate(VII) ion and indigo carmine in aqueous hydrochloric acid medium. Adv Appl Sci Res. 2011;2(3):1.

Abstract

Indigo carmine is an anionic synthetic dye widely used in textile, food, and pharmaceutical industries. The discharge of this dye into water bodies poses severe environmental concerns due to its intense color, more stability, and resistance to biodegradation. Consequently, the oxidation and degradation of this dye through electron transfer reactions have been widely investigated. The present review focuses on studies related to oxidation of indigo carmine dye using various oxidizing agents like persulphate, peroxydiphosphate, bromate, iodate and N-Bromo succinimide. The degradation efficiency, reaction kinetics, and possible mechanisms involved in the dye removal process are discussed in detail. The oxidation process leads to the cleavage of the chromophoric structure of the dye, resulting in effective decolorization. Experimental parameters, such as dye concentration, oxidant concentration, pH, and surfactant concentration, significantly influence the rate of oxidation. Spectrophotometric analysis demonstrates progressive decline in absorbance at the characteristic wavelength of the dye, confirming its degradation. The review highlights effectiveness of oxidation processes in the treatment of dye-contaminated water and provides insights into optimizing reaction conditions for improved environmental remediation. The review also examines the kinetics of oxidation of dye in the environment of various oxidants in acidic medium under aqueous and in micellar media. The catalytic effects in micellar and in sub-micellar media were also discussed with their mechanistic pathways involved in the oxidation process. The rate equation for selected oxidants is presented, and both unimolecular and bimolecular catalytic patterns are interpreted using the Berezin kinetic model and the Piszkiewicz model. The reaction order with respect to substrate, oxidant, and medium concertation was determined by isolation method. A comparative analysis of oxidation of indigo carmine is presented by considering various kinetics and mechanistic parameters. Additionally, the binding constants obtained under different conditions are reported and discussed.

🔒 This is a subscription article

Full text is available to subscribers and institutional members. Please choose an option below to access it.

1. Gallego-Ramírez C, Chica E, Rubio-Clemente A. Elimination of indigo carmine in water by Pinus patula biochar: Adsorption process optimization, kinetics and isotherms. J Environ Chem Eng. 2024;12(3):112425. doi: 1016/j.jece.2024.112425.
2. Manjunatha JG. A novel poly (glycine) biosensor towards the detection of indigo carmine: A voltammetric study. J Food Drug Anal. 2018;26(1):292–9. doi: 1016/j.jfda.2017.05.002.
3. Andreotti A, Bonaduce I, Colombini MP, Ribechini E. Characterisation of natural indigo and shellfish purple by mass spectrometric techniques. Rapid Commun Mass Spectrom. 2004;18(11):1213–20.
4. Curr E. Encyclopedia of microscopic stain. London: Leonard Hall (Books) Ltd.; 1960. p. 235.
5. Jalil AA, Triwahyono S, Adam SH, Rahim ND, Aziz MA, Hairom NH, et al. Adsorption of methyl orange from aqueous solution onto calcined Lapindo volcanic mud. J Hazard Mater. 2010;181(1–3):755–62.
6. Scholz F. Electroanalytical methods. 2nd ed. Berlin: Springer; 2010. p. 85.
7. El Hamd MA, Derayea SM, Abdelmageed OH, Askal HF. Spectrophotometric method for determination of five 1,4-dihydropyridine drugs using N-bromosuccinimide and indigo carmine dye. Int J Spectrosc. 2013;2013:243059.
8. Hamad HA, Sadik WA, Abd El-latif MM, Kashyout AB, Feteha MY. Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO₂ nanoparticles. J Environ Sci. 2016;43:26–39.
9. Jalil AA, Triwahyono S, Adam SH, Rahim ND, Aziz MA, Hairom NH, et al. Adsorption of methyl orange from aqueous solution onto calcined Lapindo volcanic mud. J Hazard Mater. 2010;181(1–3):755–62.
10. Guler UA, Ersan M, Tuncel E, Dügenci F. Mono and simultaneous removal of crystal violet and safranin dyes from aqueous solutions by HDTMA-modified Spirulina sp. Process Saf Environ Prot. 2016;99:194–206.
11. Aissa MA, Khairy M, Khalifa ME, Abdelrahman EA, Raza N, Masoud EM, et al. Facile synthesis of TiO₂@ZnO nanoparticles for enhanced removal of methyl orange and indigo carmine dyes: Adsorption and kinetics. Heliyon. 2024;10(10):e31351.
12. Marathe YV, Shrivastava VS. Degradation of indigo carmine dye by sol-gel deposited nanocrystalline cadmium sulphide thin film. Adv Sci Lett. 2012;5(1):173–7. doi: 1166/asl.2012.2140.
13. Lam WH, Tee LH, Ban ZH. A facile and rapid immobilization method of titanium dioxide-alginate composite for the photocatalytic removal of reactive black-5. Bull Chem React Eng Catal. 2024;19(2):230–41.
14. Umoru PE, Nkole IU, Ezeh TT. Degradation of indigo carmine dye with peroxydisulphate ion in aqueous sulphuric acid phase: Kinetic study. Int J Chem Kinet. 2024;56(6):339–46.
15. Mutnuru KC, Krishna KR. Micellar effects of cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) on oxidation of indigo carmine with potassium peroxy diphosphate. Novel Aspects Chem Biochem. 2024;9:9–29.
16. Mutnuru KC, Gummaluri RK, Karipeddi R. Kinetics and mechanism of oxidation of indigo carmine dye with potassium peroxydisulphate in micellar and sub-micellar medium. J Indian Chem Soc. 2025;102(2):101554.
17. Kalyana CM, Ramakrishna K, Subba Rao PV. Kinetics and mechanism of oxidation of indigo carmine with potassium bromate: Effect of CTAB and SDS micelles. Int J Chem Sci. 2017;15(4):220.
18. Mutnuru KC, Krishna KR. Micellar effects of cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) on oxidation of indigo carmine with potassium peroxy diphosphate. Novel Aspects on Chemistry and Biochemistry. 2024;9:9–29.
19. Yagub MT, Sen TK, Afroze S, Ang HM. Dye and its removal from aqueous solution by adsorption: A review. Adv Colloid Interface Sci. 2014;209:172–84.
20. Benaïssa H, Elouchdi MA. Biosorption of copper (II) ions from synthetic aqueous solutions by drying bed activated sludge. J Hazard Mater. 2011;194:69–78.
21. Falodun SO, Idris SO, Ojo EO, Iyun JF. Kinetics and mechanism of the oxidation of indigo carmine by permanganate ion in aqueous acidic medium. Int J Chem Biomol Sci. 2015;1(4):255–9.
22. Tandel AV, Padhiyar NB. Kinetics of oxidation of indigo carmine by vanadium (V) in presence of surfactants. Res J Chem Sci. 2015;5(11):24–30.
23. Setiyanto H, Saraswaty V, Firdausy GL, Setiyorini DA, Zulfikar MA. Enhancing the degradation potential of indigo carmine by a mediated electrochemical oxidation using Ce⁴⁺ mediator and Ag⁺ catalyst ions. Asian J Chem. 2022;15(3):1750–1756.
24. Palma-Goyes RE, Silva-Agredo J, González I, Torres-Palma RA. Comparative degradation of indigo carmine by electrochemical oxidation and advanced oxidation processes. Electrochim Acta. 2014;140:427–33.
25. Edokpayi JN, Iyun JF, Idris SO. A kinetic study of the redox reaction of indigo carmine by nitrite ion in aqueous hydrochloric acid medium. Phys Chem Indian J. 2011;6(1):9–13.
26. Othman I, Mohamed RM, Ibrahem FM. Study of photocatalytic oxidation of indigo carmine dye on Mn-supported TiO₂. J Photochem Photobiol A Chem. 2007;189(1):80–5.
27. Puttaswamy, Mahadevappa DS, Gowda NM. Kinetics and mechanism of oxidation of indigo carmine by hypohalites. Int J Chem Kinet. 1991;23(1):27–35.
28. Subba Rao PV, Venkateswara Rao N. Kinetics of oxidation of indigo carmine by potassium peroxydisulphate. Z Phys Chem (Leipzig). 1972;249(1):321–4.
29. Mutnuru KC, Gummaluri RK, Karipeddi R. Kinetics and mechanism of oxidation of indigo carmine dye with potassium peroxydisulphate in micellar and sub-micellar medium. J Indian Chem Soc. 2025;102(2):101554. doi: 1016/j.jics.2024.101554.
30. Das AK, Mondal SK, Kar D, Das M. Micellar effect on the reaction of picolinic acid catalyzed chromium (VI) oxidation of dimethyl sulfoxide in aqueous acidic media: A kinetic study. Int J Chem Kinet. 2001;33(3):173–81. doi: 1021/ja00447a044.
31. Bunton CA, Wolfe B. Problem of pH in micellar catalyzed reactions. J Am Chem Soc. 1973;95(11):3742–9.
32. Nakagawa T, Shinoda K. Physicochemical studies in aqueous solutions of nonionic surface active agents. In: Shinoda K, Nakagawa T, Tamamushi BI, Isemura T, editors. Colloidal Surfactants: Some Physicochemical Properties. New York: Academic Press; 1963. p. 97–178.
33. Berezin IV, Martinek K, Yatsimirskii AK. Physicochemical foundations of micellar catalysis. Russ Chem Rev. 1973;42(10):787–802.
34. Anderson MO, Edwards JO, Green AA, Wiswell MD. An examination of the rate constant data for glycine, alanine, phenylalanine, serine and threonine reveals that the presence of electron-withdrawing groups. Inorg Chem Acta. 1969;3(4):655.
35. Green AA, Edwards JO, Peter J. The oxidation reactions of peroxydiphosphate: The kinetics and mechanism of the reaction with tris(1,10-phenanthroline)iron(II). Inorg Chem. 1966;5(11):1858–64.
36. Eleanor C, Inge IC, Edwards JO. The reactivity and reaction pathway of Fenton reactions driven by substituted 1,2-dihydroxybenzenes. Inorg Nucl Chem Lett. 1971;7(1):1–6.
37. Lussier RJ, Risen WM, Edwards JO. Acid dissociation constant and decay kinetics of the perhydroxyl radical. J Phys Chem. 1970;74:4039–43.
38. Mandal SK, Das M, Kar D, Das AK. Micellar effect on the reaction of chromium (VI) oxidation of formaldehyde in the presence and absence of picolinic acid in aqueous acid media: A kinetic study. Indian J Chem A. 2001;40A:352–60.
39. Salem JK. Ground water quality. J Al-Azhar Univ Gaza. 2004;7:1–10.
40. Saha A. Effect of sodium dodecyl sulphate on the kinetics of reaction between persulphate and iodide ions. Int J Curr Res Chem Pharm Sci. 2014;1(7):31–5.
41. Salem MA. Ag(I) catalysed persulphate oxidation of phenylazodiphenylamine. Z Phys Chem. 1995;192S:87–99.
42. Jonnalagadda BS, Simoyi RH. A kinetic study of the oxidation of indigo carmine with acidic bromate. J Chem Soc Perkin Trans. 1988;—.
43. Edokpayi JN, Iyun JF, Idris SO. Kinetics and mechanism of the electron transfer reaction between tetraoxoiodate(VII) ion and indigo carmine in aqueous hydrochloric acid medium. Adv Appl Sci Res. 2011;2(3):1.