Journal of Molecular Modeling

, Volume 17, Issue 9, pp 2285–2296 | Cite as

Theoretical evaluation of isotopic fractionation factors in oxidation reactions of benzene, phenol and chlorophenols

Original Paper

Abstract

We have studied theoretically the rate determining steps of reactions of benzene with permanganate, perchlorate, ozone and dioxygen in the gas phase and aqueous solution as well as phenol and dichlorophenol in protonated and unprotonated forms in aqueous solution. Kinetic isotope effects were then calculated for all carbon atoms and based on their values isotopic fractionation factors corresponding to compound specific isotopic analysis have been evaluated. The influence of the oxidant, substituents, environment and protonation on the isotopic fractionation factors has been analyzed.

Keywords

Aromatic pollutants CSIA DFT Isotopic fractionation Permanganate 

References

  1. 1.
    WHO(IARC), International Agency for Research on Cancer (IARC) (1987) IARC Monographs on the Evaluation of Carcinogenic Risk to Humans. IARC, Lyon, Suppl. 7Google Scholar
  2. 2.
    U.S. EPA. (1998) Carcinogenic Effects of Benzene: An Update, EPA/600/P-97/001-F, U.S. Environmental Protection Agency, Washington, DCGoogle Scholar
  3. 3.
    Budavari S (1996) The Merck Index: An Encyclopedia of Chemical, Drugs, and Biologicals. Merck, Whitehouse Station, NJ Google Scholar
  4. 4.
    Warner MA, Harper JV (1985) Cardiac dysrhythmias associated with chemical peeling with phenol. Anesthesiology 62:366–367CrossRefGoogle Scholar
  5. 5.
    ATSDR (Agency for Toxic Substances and Disease Registry) (2007) CERCLA Priority List of Hazardous Substances, U.S. Department of Health and Human Services, Agency for Toxic Substances and Disease Registry, Division of Toxicology and Environmental Medicine, Atlanta, GA, in cooperation with U.S. Environmental Protection Agency, http://www.atsdr.cdc.gov/cercla/07list.html (accessed 09.09.2010)
  6. 6.
    ATSDR (Agency for Toxic Substances and Disease Registry) (2005) Toxicological Profile for Benzene. Agency for Toxic Substances and Disease Registry, US Public Health ServiceGoogle Scholar
  7. 7.
    Gad SN, Saad SA (2008) Effect of environmental pollution by phenol on some physiological parameters of Oreochromis niloticus. Global Vet 2:312–319Google Scholar
  8. 8.
    Fleeger JW, Carman KR, Nisbet RM (2003) Indirect effect of contaminants in aquatic ecosystem. Sci Total Environ 3170:207–233Google Scholar
  9. 9.
    Mukherjee D, Bhttacharya S, Kumar V, Moitra J (1990) Biological significance of. Phenol accumulation in different organs of a murrel, Chamnna punctatus and the common carp Cyprinus carpio. Biomed Environ Sci 3:337–342Google Scholar
  10. 10.
    ATSDR (Agency for Toxic Substances and Disease Registry) (1989) Toxicological Profile for Phenol. Agency for Toxic Substances and Disease Registry, US Public Health ServiceGoogle Scholar
  11. 11.
    Pera-Titus M, Garcia-Molina V, Banos MA, Gimenez J, Esplugas S (2004) Degradation of chlorophenols by means of advanced oxidation processes: a general review. Appl Catal B 47:219–256CrossRefGoogle Scholar
  12. 12.
    Laoufti NA, Tassalit D, Bentahar F (2008) The degradation of phenol in water solution by TiO2 photocatalisys in helical reactor. Global NEST J 10:404–418Google Scholar
  13. 13.
    Huang K, Zhao Z, Hoag G, Dahmani A, Block P (2005) Degradation of volatile organic compounds with thermally activated persulfate oxidation. Chemosphere 61:551–560CrossRefGoogle Scholar
  14. 14.
    Liang CJ, Bruell CJ, Marley MC, Sperry KL (2004) Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple. Chemosphere 55:1213–1223CrossRefGoogle Scholar
  15. 15.
    Nadim F, Huang K, Dahmani A (2006) Remediation of soil and ground water contaminated with PAH using heat and Fe(II)-EDTA catalyzed persulfate oxidation. Water Air Soil Pollut Focus 6:227–232CrossRefGoogle Scholar
  16. 16.
    Zazo JA, Casas JA, Mohedano AF, Gilarranz MA, Rodriguez JJ (2005) Chemical Pathway and Kinetics of Phenol Oxidation by Fenton’s Reagent. Environ Sci Technol 39:9295–9302CrossRefGoogle Scholar
  17. 17.
    Munter R (2001) Advanced oxidation processes. Current status and prospects. Proc Est Acad Sci Chem 50:59–80Google Scholar
  18. 18.
    Freeman F (1975) Possible criteria for distinguishing between cyclic and acyclic activated complexes and among cyclic activated complexes in addition reactions. Chem Rev 75:439–490CrossRefGoogle Scholar
  19. 19.
    Gardner KA, Mayer JM (1995) Understanding C-H bond oxidations: H* and H- transfer in the oxidation of toluene by permanganate. Science 269:1849–1851CrossRefGoogle Scholar
  20. 20.
    Rudakov ES, Lobachev VL (1994) The kinetics, kinetic isotope effects, and substrate selectivity of alkylbenzene oxidation in aqueous permanganate solutions. II. Reaction with HMnO4. Kinet Catal 35:180–187Google Scholar
  21. 21.
    Rudakov ES, Lobachev VL (2000) The first step of oxidation of alkylbenzenes by permanganates in acidic aqueous solutions. Russ Chem Bull 49:761–777CrossRefGoogle Scholar
  22. 22.
    Mvula E, Naumov S, von Sonntag C (2009) Ozonolysis of Lignin Models in Aqueous Solution: Anisole, 1,2-Dimethoxybenzene, 1,4-Dimethoxybenzene, and 1,3,5-Trimethoxybenzene. Environ Sci Technol 43:6275–6282CrossRefGoogle Scholar
  23. 23.
    Koester CJ, Simonich SL, Esser BK (2003) Environmental Analysis. Anal Chem 75:2813–2829CrossRefGoogle Scholar
  24. 24.
    Elsner M, Zwank L, Hunkeler D, Schwarzenbach RP (2005) A new concept linking observable stable isotope fractionation to transformation pathways of organic pollutants. Environ Sci Technol 39:6896–6916CrossRefGoogle Scholar
  25. 25.
    Dybala-Defratyka A, Szatkowski L, Kaminski R, Wujec M, Siwek A, Paneth P (2008) Kinetic isotope effects on dehalogenations at an aromatic carbon. Environ Sci Technol 42:7744–7750CrossRefGoogle Scholar
  26. 26.
    U.S. EPA (2008) A Guide for assessing biodegradation and source indentification of organic groundwater contaminants usung Compound Specific Isotope Analysis (CSIA). EPA/600/R-08/148, U.S. Environmental Protection Agency, Washington, DCGoogle Scholar
  27. 27.
    Frisch MJ et al. (2004) Gaussian 03, Revision E.01. Gaussian Inc, WallingfordGoogle Scholar
  28. 28.
    Frisch MJ et al. (2009) Gaussian 09, Revision A.02. Gaussian Inc, Wallingford, CTGoogle Scholar
  29. 29.
    Zhao Y, Schultz NE, Truhlar DG (2006) Design of density functionals by combining the method of constraint satisfaction with parametrization for thermochemistry, thermochemical kinetics, and noncovalent interactions. J Chem Theory Comput 2:364–382CrossRefGoogle Scholar
  30. 30.
    Zhao Y, Truhlar DG (2008) Density functionals with broad applicability in chemistry. Acc Chem Res 41:157–167CrossRefGoogle Scholar
  31. 31.
    Hariharan PC, Pople JA (1973) Influence of polarization functions on MO hydrogenation energies. Theor Chim Acta 28:213–222CrossRefGoogle Scholar
  32. 32.
    Ditchfield R, Hehre WJ, Pople JA (1971) Self-consistent molecular-orbital methods. IX. Extended Gaussian-type basis for molecular-orbital studies of organic molecules. J Chem Phys 54:724–728CrossRefGoogle Scholar
  33. 33.
    Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, DeFrees DJ, Pople JA (1982) Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements. J Chem Phys 77:3654–3665CrossRefGoogle Scholar
  34. 34.
    Clark T, Chandrasekhar J, Spitznagel GW, Von Ragué SP (1983) Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, lithium to fluorine. J Comput Chem 4:294–301CrossRefGoogle Scholar
  35. 35.
    Frisch MJ, Pople JA, Binkley JS (1984) Self-consistent molecular orbital methods. XXV. Supplementary functions for Gaussian basis sets. J Chem Phys 80:3265–3269CrossRefGoogle Scholar
  36. 36.
    Miertus S, Scrocco E, Tomasi J (1981) Electrostatic interaction of a solute with a continuum. A direct utilization of ab initio molecular potentials for the prevision of solvent effects. Chem Phys 55:117–129CrossRefGoogle Scholar
  37. 37.
    Rappe AK, Casewit CJ, Colwell KS, Goddard WA III, Skiff WM (1992) UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. J Am Chem Soc 114:10024–10035CrossRefGoogle Scholar
  38. 38.
    Dybala-Defratyka A, Adamczyk P, Paneth P (2011) A DFT study of Trichloroethene reaction with permanganate in aqueous solution. Env Sci Technol 45(7):3006–3011CrossRefGoogle Scholar
  39. 39.
    McWeeny R, Dierksen G (1968) Self-consistent perturbation theory. II. Extension to open shells. J Chem Phys 49:4852–4856CrossRefGoogle Scholar
  40. 40.
    Peng C, Ayala PY, Schlegel HB, Frisch MJ (1996) Using redundant internal coordinates to optimize equilibrium geometries and transition states. J Comput Chem 17:49–56CrossRefGoogle Scholar
  41. 41.
    Reed AE, Weinhold F (1983) Natural bond orbital analysis of near-Hartree–Fock water dimer. J Chem Phys 78:4066–4073CrossRefGoogle Scholar
  42. 42.
    Fukui K (1970) Formulation of the reaction coordinate. J Phys Chem 74:4161–4163CrossRefGoogle Scholar
  43. 43.
    Anisimov V, Paneth P (1999) ISOEFF98. A program for studies of isotope effects using Hessian modifications. J Math Chem 26:75–86CrossRefGoogle Scholar
  44. 44.
    Bigeleisen J (1949) The relative reaction velocities of isotopic molecules. J Chem Phys 17:675–678CrossRefGoogle Scholar
  45. 45.
    Hofstetter TB, Schwarzenbach RP, Bernasconi SM (2008) Assessing transformation processes of organic compounds using stable isotope fractionation. Environ Sci Technol 42:7737–7743CrossRefGoogle Scholar
  46. 46.
    Fox AD, Hobson KA, Ekins G, Grantham M, Green AJ (2010) Isotopic forensic analysis does not support vagrancy for a Marbled Duck shot in Essex. Br Birds 103:464–467Google Scholar
  47. 47.
    Mueller R, Lingens F (1986) Microbial degradation of halogenated hydrocarbons: a biological solution to pollution problems. Angew Chem Int Ed Engl 25:779–789CrossRefGoogle Scholar
  48. 48.
    Tratnyek PG, Hoigne J (1994) Kinetics of reactions of chlorine dioxide (OClO) in water. II. Quantitative structure-activity relationships for phenolic compounds. Water Res 28:57–66CrossRefGoogle Scholar
  49. 49.
    Tratnyek PG, Hoigne J (1991) Oxidation of substituted phenols in the environment: a QSAR analysis of rate constants for reaction with singlet oxygen. Environ Sci Technol 25:1596–1604CrossRefGoogle Scholar
  50. 50.
    Tratnyek PG (1998) Correlation analysis of the environmental reactivity of organic substances. In: Macalady DL (ed) Perspectives in Environmental Chemistry. Oxford, New York, pp 167–194Google Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  1. 1.Institute of Applied Radiation Chemistry, Faculty of ChemistryTechnical University of LodzLodzPoland

Personalised recommendations