Skip to main content
SpringerLink
Log in

Theoretical study of the degradation mechanism on the reactions 2,3,7,8-tetrachlorinated dibenzo-p-dioxins with hydrogen and chlorine atoms

  • Article
  • Published:
Science China Technological Sciences Aims and scope Submit manuscript

Abstract

The mechanism of the multiple-pathway and multiple-step degradation reactions of 2,3,7,8-tetrachlorinated dibenzo-p-dioxins with H and Cl atoms is investigated using the density functional theory. The electronic structures and the minimum energy path (MEP) are calculated at the B3LYP/6-311+G(d,p) level, and energetic information (single-point) is further refined at the B3LYP/6-311++G(3df,2p) level. The main possible ring opening reaction pathways of the C-O bond breakdown include indirect cleavage ring opening reaction, hydrogen addition reaction, hydrogen addition elimination reaction, and chlorine addition elimination reaction. Ten reaction steps of the six reaction pathways are considered. Our calculations indicate that hydrogen addition reaction step TS1c is of the smallest barrier height, and indirect cleavage ring opening reaction channel has the largest barrier height and is the most endothermic.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Duan H B, Li J H, Liu Y C, et al. Characterization and inventory of pcdd/fs and pbdd/fs emissions from the incineration of waste printed circuit board. Environ Sci Technol, 2011, 45: 6322–6328

    Article  Google Scholar 

  2. Tang Z W, Huang Q F, Yang Y F. PCDD/Fs in fly ash from waste incineration in china: a need for effective risk management. Environ Sci Technol, 2013, 47: 5520–5521

    Article  Google Scholar 

  3. Vejerano E P, Holder A L, Marr L C. Emissions of polycyclic aromatic hydrocarbons, polychlorinated dibenzo-p-dioxins, and dibenzofurans from incineration of nano-materials. Environ Sci Technol, 2013, 47: 4866–4874

    Article  Google Scholar 

  4. Lin C J, Hsu J F, Liao P C. Co-exposure of dioxin-like polychlorin ated biphenyls and polychlorinated dibenzo-p-dioxins and dibenzofurans in free-range hens and implications derived from congener profile analysis. J Agr Food Chem, 2012, 60: 1963–1972

    Article  Google Scholar 

  5. Hites R A. Dioxins: An overview and history. Environ Sci Technol, 2011, 45: 16–20

    Article  Google Scholar 

  6. Burke K. Perspective on density functional theory. J Chem Phys, 2012, 36: 150901

    Article  Google Scholar 

  7. Shi J C, Zuo R, Meng S C. DFT study on adduct reaction paths of GaN MOCVD growth. Sci China Tech Sci, 2013, 56: 1644–1650

    Article  Google Scholar 

  8. Xia X Q, Zhang H, Zhang G L. Theoretical studies of structures and spectroscopic properties of [(tpy)(bpy)RuC ≡ CC6H4R]+(tpy=2,2′:6′, 2″-terpyridine, bpy=2,2′-bipyridine; R=F, Cl, H, Me and OMe). Sci Sci China Tech Sci, 2014, 57: 725–733

    Article  MathSciNet  Google Scholar 

  9. Chrétien S, Metiu H. DFT study of the electronic properties of laocl surfaces. J Phys Chem C, 2012, 116: 681–691

    Article  Google Scholar 

  10. Long H, Pivovar B. Hydroxide degradation pathways for imidazolium cations: a dft study. J Phys Chem C, 2014, 118: 9880–9888

    Article  Google Scholar 

  11. Yu W N, Hu J T, Xu F, et al. Mechanism and direct kinetics study on the homogeneous gas-phase formation of PBDD/Fs from 2-BP, 2,4-DBP, and 2,4,6-TBP as Precursors. Environ Sci Technol, 2011, 45: 1917–1925

    Article  Google Scholar 

  12. Liu G S, Yu J G. Theoretical study on the structure, vibrational frequency and thermodynamic properties of 2,3,7,8-tetrachlorinated dibenzo-p-dioxin. J Mol Struct, 2005, 717: 15–19

    Article  Google Scholar 

  13. Xu F, Wang H, Zhang Q Z, et al. Kinetic properties for the complete series reactions of chlorophenols with oh radicals-relevance for dioxin formation. Environ Sci Technol, 2010, 44: 1399–1404

    Article  Google Scholar 

  14. Zhang Q Z, Yu W N, Zhang R X, et al. Quantum chemical and kinetic study on dioxin formation from the 2,4,6-tcp and 2,4-dcp precursors. Environ Sci Technol, 2010, 44: 3395–3403

    Article  Google Scholar 

  15. Yu W N, Hu J T, Xu F, et al. Mechanism and direct kinetics study on the homogeneous gas-phase formation of pbdd/fs from 2-bp, 2,4-dbp, and 2,4,6-tbp as precursors. Environ Sci Technol, 2011, 45: 1917–1925

    Article  Google Scholar 

  16. Xu F, Yu W N, Zhou Q, et al. Mechanism and direct kinetic study of the polychlorinated dibenzo-p-dioxin and dibenzofuran formations from the radical/radical cross-condensation of 2,4-dichlorophenoxy with 2-chlorophenoxy and 2,4,6-trichlorophenoxy. Environ Sci Technol, 2011, 45: 643–650

    Article  Google Scholar 

  17. Lee J E, Choi W, Mhin B J, et al. Theoretical study on the reaction of OH radicals with polychlorinated dibenzo-p-dioxin. J Phys Chem A, 2004, 108: 607–614

    Article  Google Scholar 

  18. Zhang C X, Sun T L, Sun, X M. Mechanism for OH-initiated degradation of 2,3,7,8-tetrachlorinated dibenzo-p-dioxins in the presence of O2 and NO/H2O. Environ Sci Technol, 2011, 45: 4756–4762

    Article  Google Scholar 

  19. Sun X M, Zhang C X, Zhao Y Y, et al. Atmospheric chemical reactions of 2,3,7,8-tetrachlorinated dibenzofuran initiated by an OH radical: Mechanism and kinetics. Environ Sci Technol, 2012, 46: 8148–8155

    Article  Google Scholar 

  20. Kruse H, Goerigk L, Grimme S. Why the standard b3lyp/6-31g* model chemistry should not be used in dft calculations of molecular thermochemistry: understanding and correcting the problem. J Org Chem, 2012, 77: 10824–10834

    Article  Google Scholar 

  21. Torres E, DiLabio G A. A (nearly) universally applicable method for modeling noncovalent interactions using b3lyp. J Phys Chem Lett, 2012, 3: 1738–1744

    Article  Google Scholar 

  22. Jimenez-Izal E, Chiatti F, Corno M, et al. Glycine adsorption at nonstoichiometric (010) hydroxyapatite surfaces: a b3lyp study. J Phys Chem C, 2012, 116: 14561–14567

    Article  Google Scholar 

  23. Lu L L, Hu H, Hou H, et al. An improved b3lyp method in the calculation of organic thermochemistry and reactivity. Comput Theor Chem, 2013, 1015: 64–71

    Article  Google Scholar 

  24. Motoyuki S, Hiroshi F. A quantum generalization of intrinsic reaction coordinate using path integral centroid coordinates. J Chem Phys, 2012, 136: 184103

    Article  Google Scholar 

  25. Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian. Revision A.02. Wallingford (CT): Gaussian Inc., 2009

    Google Scholar 

  26. Liu Y Y, Wang W L, Zhang T L, et al. On the kinetic mechanism of the hydrogen and oxygen abstraction reactions of CH3S with HOO: A dual-level direct dynamics study. Comput Theor Chem, 2011, 964: 169–175

    Article  Google Scholar 

  27. Wang L, Wen J M, He H Q, et al. A dual-level direct dynamics study on the hydrogen abstraction reaction of oxygen atom with methyl hydrazine. Int J Quantum Chem, 2013, 113: 2338–2344

    Google Scholar 

  28. Zhang H, Zhang G L, Liu J Y, et al. Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms. Theor Chem Acc, 2010, 125: 75–82

    Article  Google Scholar 

  29. Hu W P, Truhlar D G. Factors affecting competitive ion-molecule reactions: ClO- + C2H5Cl and C2D5Cl via E2 and SN2 channels. J Am Chem Soc, 1996, 118: 860–869

    Article  Google Scholar 

  30. Corchado J C, Chuang Y Y, Fast P L, et al. POLYRATE. version 9.7. Minneapolis (MN): Department of Chemistry and Supercomputer Institute, University of Minnesota. 2007

    Google Scholar 

  31. Truhlar D G, Garrett B C. Variational transition state theory. Accounts Chem Res, 1980, 13: 440–448

    Article  Google Scholar 

  32. Truhlar D G, Isaacson A D, Garrett B C. Generalized Transition State Theory. In: Baer M, eds. The Theory of Chemical Reaction Dynamics. Boca Raton, FL: CRC Press, 1985. 65

    Google Scholar 

  33. Garrett B C, Truhlar D G. Criterion of minimum state density in the transition state theory of bimolecular reactions. J Chem Phys, 1979, 70: 1593–1598

    Article  Google Scholar 

  34. Garrett B C, Truhlar D G. Generalized transition state theory. Bond Energy-Bond Order method for canonical variational calculations with applications to hydrogen atom transfer reactions. J Am Chem Soc, 1979, 101: 4534–4548

    Article  Google Scholar 

  35. Garrett B C, Truhlar D G, Grev R S, et al. Improved treatment of threshold contributions in variational transition state theory. J Phys Chem, 1980, 84: 1730–1748

    Article  Google Scholar 

  36. Lu D H, Truong T N, Melissas V S, et al. POLYRATE 4: A new version of a computer program for the calculation of chemical reaction rates for polyatomics. Comput Phys Commun, 1992, 71: 235–262

    Article  Google Scholar 

  37. Liu Y P, Lynch G C, Truong T N, et al. Molecular modeling of the kinetic isotope effect for the [1,5]-sigma tropic rearrangement of cis-1,3-pentadiene. J Am Chem Soc, 1993, 115: 2408–2415

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin, 150080, China

    Hui Zhang, Kun Zhang & ShengMin Sun

Authors
  1. Hui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kun Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. ShengMin Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hui Zhang.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, H., Zhang, K. & Sun, S. Theoretical study of the degradation mechanism on the reactions 2,3,7,8-tetrachlorinated dibenzo-p-dioxins with hydrogen and chlorine atoms. Sci. China Technol. Sci. 58, 181–188 (2015). https://doi.org/10.1007/s11431-014-5736-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11431-014-5736-5

Keywords

Search

Navigation