, Volume 26, Issue 4, pp 2743–2757 | Cite as

Mechanism of H2O2/bleach activators and related factors

  • Kai Liu
  • Kelu YanEmail author
  • Gang SunEmail author
Original Research


A mechanism of H2O2/bleach activator bleaching systems was proposed by using H2O2/tetraacetylethylenediamine (TAED) system as a model. HO· concentrations of the system under different pH conditions was measured by using benzenepentacarboxylic acid as a fluorescent probe. Computational analysis of bond enthalpies of H2O2 and peracids revealed that HO· should be the most effective agent in bleaching process, and peracids formed in H2O2/bleach activator bleaching systems could more easily produce HO·. The formation of peracids in H2O2/TAED system depends on the pH values of bleaching solutions and a nucleophilic substitution of the acid derivative by peroxide anion (HOO). Charge density on carbonyl carbons of bleach activators affects the formation of peracids as well, which was proven from these compounds of TAED, tetraacetylhydrazine, N-[4-(triethylammoniomethyl)-benzoyl]-caprolactam chloride, phthalimide, N-acetylphthalimide and nonanoyloxybenzene sulphonate. It is likely that the charge densities on carbonyl carbon of amide bleach activators should be larger than 0.185. For ester bleach activators, the results were also investigated by activation energy, Gibbs free energy and Hansen solubility parameters. In addition, the ecotoxicity of bleach activators has been evaluated by ECOSAR program. Potential bleach activators can be designed and explored according to these results instead of large amounts of experimental data.

Graphical abstract


Bleach activators Cotton Hydrogen peroxide Charge density Bleaching species 



This work was supported by the Fundamental Research Funds for the Central Universities of Donghua University (Grant No. CUSF-DH-D-2017052). The authors gratefully acknowledge Dr. Xuan Zhang for the experimental equipment and statistical analyses. The first author thanks the scholarship support from China Scholarship Council (CSC).

Supplementary material

10570_2019_2244_MOESM1_ESM.docx (64 kb)
Supplementary material 1 (DOCX 64 kb)


  1. Bhattacharyya L, Rohrer JS (2012) Appendix 1: dissociation constants (pKa) of organic acids (at 20°C). In: Bhattacharyya L, Rohrer JS (eds) Applications of ion chromatography for pharmaceutical and biological products. Wiley, New York. CrossRefGoogle Scholar
  2. Bianchetti GO, Devlin CL, Seddon KR (2015) Bleaching systems in domestic laundry detergents: a review. RSC Adv 5:65365–65384. CrossRefGoogle Scholar
  3. Cai JY, Evans DJ, Smith SM (2001) Bleaching of natural fibers with TAED and NOBS activated peroxide systems. AATCC Rev 1:31–34Google Scholar
  4. Cao J, Ren Q, Chen F, Lu T (2015) Comparative study on the methods for predicting the reactive site of nucleophilic reaction. Sci China Chem 58:1845–1852. CrossRefGoogle Scholar
  5. Chen W, Wang L, Wang D, Zhang J, Sun C, Xu C (2016) Recognizing a limitation of the TBLC-activated peroxide system on low-temperature cotton bleaching. Carbohydr Polym 140:1–5. CrossRefGoogle Scholar
  6. Chen J, Xu X, Zeng X, Feng M, Qu R, Wang Z, Nesnas N, Sharma VK (2018) Ferrate (VI) oxidation of polychlorinated diphenyl sulfides: kinetics, degradation, and oxidized products. Water Res 143:1–9. CrossRefGoogle Scholar
  7. Dannacher J, Schlenker W (1996) The mechanism of hydrogen peroxide bleaching. Text Chem Colorist 28:24–28Google Scholar
  8. ECOSAR (2017) Ecological Structure Activity Relationships (ECOSAR) Predictive Model. Accessed 17 May 2018
  9. Fei X, Yao J, Du J, Sun C, Xiang Z, Xu C (2015) Analysis of factors affecting the performance of activated peroxide systems on bleaching of cotton fabric. Cellulose 22:1379–1388. CrossRefGoogle Scholar
  10. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC et al (2009) Gaussian 09 Revision A.02. WallingfordGoogle Scholar
  11. Hansen CM (2007) Hansen solubility parameters: a user’s handbook, 2nd edn. CRC Press, Boca RatonCrossRefGoogle Scholar
  12. Haynes WM (2015) CRC handbook of chemistry and physics, 96th edn. CRC Press, Boca RatonGoogle Scholar
  13. Hirshfeld FL (1977) Bonded-atom fragments for describing molecular charge densities. Theor Chim 44:129–138. CrossRefGoogle Scholar
  14. Hofmann J, Just G, Pritzkow W, Schmidt H (1992) Bleaching activators and the mechanism of bleaching activation. J Prakt Chem Chem Ztg 334:293–297. CrossRefGoogle Scholar
  15. Iamazaki E, Orblin E, Fardim P (2013) Topochemical activation of pulp fibres. Cellulose 20:2615–2624. CrossRefGoogle Scholar
  16. Jackson ND (1999) The mechanism of action of peroxygen biocides. Dissertation, University of YorkGoogle Scholar
  17. Ji B, Tang P, Yan K, Sun G (2015) Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification. Carbohydr Polym 132:228–236. CrossRefGoogle Scholar
  18. Lee J, Hinks D, Lim S-H, Hauser P (2010) Hydrolytic stability of a series of lactam-based cationic bleach activators and their impact on cellulose peroxide bleaching. Cellulose 17:671–678. CrossRefGoogle Scholar
  19. Liu Y, Tao J, Sun J, Chen W (2014) Removing polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H2O2/TAED/NaHCO3 system. Carbohydr Polym 112:416–421. CrossRefGoogle Scholar
  20. Liu K, Zhang X, Yan K (2017) Low-temperature bleaching of cotton knitting fabric with H2O2/PAG system. Cellulose 24:1555–1561. CrossRefGoogle Scholar
  21. Liu K, Zhang X, Yan K (2018a) Bleaching of cotton fabric with tetraacetylhydrazine as bleach activator for H2O2. Carbohydr Polym 188:221–227. CrossRefGoogle Scholar
  22. Liu K, Zhang X, Yan K (2018b) Development of o-phthalic anhydride as a low-temperature activator in H2O2 bleaching system for cotton fabric. Cellulose 25:859–867. CrossRefGoogle Scholar
  23. Long X, Xu C, Du J, Fu S (2013) The TAED/H2O2/NaHCO3 system as an approach to low-temperature and near-neutral pH bleaching of cotton. Carbohydr Polym 95:107–113. CrossRefGoogle Scholar
  24. Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33(5):580–592CrossRefGoogle Scholar
  25. Luo X, Sui X, Yao J, Fei X, Du J, Sun C, Xiang Z, Xu C, Wang S (2015) Performance modelling of the TBCC-activated peroxide system for low-temperature bleaching of cotton using response surface methodology. Cellulose 22:3491–3499. CrossRefGoogle Scholar
  26. Milne NJ (1998) Oxygen bleaching systems in domestic laundry. J Surfactants Deterg 1:253–261. CrossRefGoogle Scholar
  27. Ochterski JW (2000) Thermochemistry in Gaussian. Accessed 26 Oct 2017
  28. Peng M, Wu S, Du J, Sun C, Zhou C, Xu C, Hu X (2018) Establishing a rapid pad-steam process for bleaching of cotton fabric with an activated peroxide system. ACS Sustain Chem Eng 6:8599–8603. CrossRefGoogle Scholar
  29. Reinhardt G, Borchers G (2008) Application of bleaching detergent formulations. In: Zoller U (ed) Handbook of detergents, part E: applications. CRC Press, Boca Raton, pp 375–418CrossRefGoogle Scholar
  30. Reuschenbach P, Silvani M, Dammann M, Warnecke D, Knacker T (2008) ECOSAR model performance with a large test set of industrial chemicals. Chemosphere 71:1986–1995. CrossRefGoogle Scholar
  31. Shao J, Huang Y, Wang Z, Liu J (2010) Cold pad–batch bleaching of cotton fabrics with a TAED/H2O2 activating system. Color Technol 126:103–108. CrossRefGoogle Scholar
  32. Si F, Yan K, Zhang X (2014a) Study on H2O2/TAED and H2O2/TBCC bleaching mechanism related to hydroxyl radical with a fluorescent probe. Carbohydr Polym 103:581–586. CrossRefGoogle Scholar
  33. Si F, Zhang X, Yan K (2014b) The quantitative detection of HO˙ generated in a high temperature H2O2 bleaching system with a novel fluorescent probe benzenepentacarboxylic acid. RSC Adv 4(12):5860–5866. CrossRefGoogle Scholar
  34. Špička N, Tavčer PF (2015) Low-temperature bleaching of knit fabric from regenerated bamboo fibers with different peracetic acid bleaching processes. Text Res J 85:1497–1505. CrossRefGoogle Scholar
  35. Tang P, Sun G (2017) Generation of hydroxyl radicals and effective whitening of cotton fabrics by H2O2 under UVB irradiation. Carbohydr Polym 160:153–162. CrossRefGoogle Scholar
  36. UNECE (United Nations Economic Commission for Europe) (2015) Globally harmonized system of classification and labelling of chemicals (GHS), Sixth revised edition. United Nations, Geneva. Accessed 18 May 2018
  37. Wang G, Umbuzeiro GdA, Vendemiatti JA, de Oliveira AC, Vacchi FI, Hussain M, Hauser PJ, Freeman HS, Hinks D (2017) Synthesis, characterization, and toxicological properties of new cationic bleach activators. J Surfactants Deterg 20:277–285. CrossRefGoogle Scholar
  38. Winkler J, Smith ER, Compton RG (1997) A study of the mechanism of bleaching cotton using peracids and hydrogen peroxide as model systems. J Colloid Interface Sci 195:229–240. CrossRefGoogle Scholar
  39. Xu C, Long X, Du J, Fu S (2013) A critical reinvestigation of the TAED-activated peroxide system for low-temperature bleaching of cotton. Carbohydr Polym 92:249–253. CrossRefGoogle Scholar
  40. Xu C, Hinks D, Sun C, Wei Q (2015) Establishment of an activated peroxide system for low-temperature cotton bleaching using N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride. Carbohydr Polym 119:71–77. CrossRefGoogle Scholar
  41. Yang CQ (1993) Effect of pH on nonformaldehyde durable press finishing of cotton fabric: FT-IR spectroscopy study: part I: ester crosslinking. Text Res J 63:420–430. CrossRefGoogle Scholar
  42. Yu J, Shao D, Sun C, Xu C, Hinks D (2017) Pilot-plant investigation on low-temperature bleaching of cotton fabric with TBCC-activated peroxide system. Cellulose 24:2647–2655. CrossRefGoogle Scholar
  43. Zeng H, Tang R-C (2015) Application of a novel bleach activator to low temperature bleaching of raw cotton fabrics. J Text Inst 106:807–813. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.National Engineering Research Center for Dyeing and Finishing of TextilesDonghua UniversityShanghaiPeople’s Republic of China
  2. 2.College of Chemistry, Chemical Engineering and BiotechnologyDonghua UniversityShanghaiPeople’s Republic of China
  3. 3.Division of Textiles and ClothingUniversity of CaliforniaDavisUSA

Personalised recommendations