Abstract
A distinct understanding for the degradation mechanism of phenol induced by ozone is very essential because the ozonation process, one of the advanced oxidation processes (AOPs), is attractive and popular in wastewater treatment. In the present work, the detailed reactions of ozone and phenol are investigated employing the density functional theory B3LYP method with the 6-311++G (d, p) basis set. The profiles of the potential energy surface are constructed and the possible reaction pathways are indicated. These detailed calculation results suggest two degradation reaction mechanisms. One is phenolic H atom abstraction mechanism, and the other is cyclo-addition and ring-opening mechanism. Considering the effect of solvent water, the calculated energy barriers and reaction enthalpies for the reaction of O3 and phenol in water phase are both lower than those in gas phase, though the degradation mechanisms are not changed. This reveals that these degradation reactions are more favorable in the water solvent. The main reaction products are C6H5OO· radical, a crucial precursor for forming PCDD/Fs and one ring-opening product, which are in good agreement with the experimental observations.
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References
Uberoi V, Bhattacharya S (1997) Toxicity and degradability of nitrophenols in anaerobic systems. Water Environ Res 69:146–156
Veeresh G, Kumar P, Mehrotra I (2005) Treatment of phenol and cresols in upflow anaerobic sludge blanket (UASB) processa review. Water Res 39:154–170
Kulkarni U, Dixit S (1991) Destruction of phenol from wastewater by oxidation with sulfite-oxygen. Ind Eng Chem Res 30:1916–1920
Kujawski W, Warszawski A, Ratajczak W, Porebski T, Capaa W, Ostrowska I (2004) Removal of phenol from wastewater by different separation techniques. Desalination 163:287–296
Seredynska-Sobecka B, Tomaszewska M, Morawski A (2005) Removal of micropollutants from water by ozonation/biofiltration process. Desalination 182:151–157
Huang C, Shu H (1995) The reaction kinetics, decomposition pathways and intermediate formations of phenol in ozonation, UV/O3 and UV/H2O2 processes. J Hazard Mater 41:47–64
Charinpanitkul T, Limsuwan P, Chalotorn C et al (2010) Synergetic removal of aqueous phenol by ozone and activated carbon within three-phase fluidized-bed reactor. J Ind Eng Chem 16:91–95
Santos A, Yustos P, Rodriguez S, Garcia-Ochoa F (2006) Wet oxidation of phenol, cresols and nitrophenols catalyzed by activated carbon in acid and basic media. Appl Catal, B 65:269–281
Liu H, Liang M, Liu C, Gao Y, Zhou J (2009) Catalytic degradation of phenol in sonolysis by coal ash and H2O2/O3. Chem Eng J 153:131–137
Dabrowski A, Podkoscielny P, Hubicki Z, Barczak M (2005) Adsorption of phenolic compounds by activated carbon–a critical review. Chemosphere 58:1049–1070
Caizares P, Lobato J, Paz R, Rodrigo M, Saez C (2005) Electrochemical oxidation of phenolic wastes with boron-doped diamond anodes. Water Res 39:2687–2703
Turhan K, Uzman S (2008) Removal of phenol from water using ozone. Desalination 229:257–263
Lesko T, Colussi A, Hoffmann M (2006) Sonochemical decomposition of phenolevidence for a synergistic effect of ozone and ultrasound for the elimination of total organic carbon from water. Environ Sci Technol 40:6818–6823
Gurol M, Vatistas R (1987) Oxidation of phenolic compounds by ozone and ozone + UV radiationa comparative study. Water Res 21:895–900
Esplugas S, Giménez J, Contreras S, Pascual E, Rodríguez M (2002) Comparison of different advanced oxidation processes for phenol degradation. Water Res 36:1034–1042
Rosenfeldt E, Linden K, Canonica S, Von Gunten U (2006) Comparison of the efficiency of OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2. Water Res 40:3695–3704
Lin S, Wang C (2003) Ozonation of phenolic wastewater in a gas-induced reactor with a fixed granular activated carbon bed. Ind Eng Chem Res 42:1648–1653
Li L, Zhu W, Zhang P, Lu P, Zhang Q, Zhang Z (2007) UV/O3-BAC process for removing organic pollutants in secondary effluents. Desalination 207:114–124
Faria PCC, Órfão JJM, Pereira MFR (2006) Ozone decomposition in water catalyzed by activated carboninfluence of chemical and textural properties. Ind Eng Chem Res 45:2715–2721
Gurol M, Singer P (1982) Kinetics of ozone decompositiona dynamic approach. Environ Sci Technol 16:377–383
Bremner D, Burgess A, Houllemare D, Namkung K (2006) Phenol degradation using hydroxyl radicals generated from zero-valent iron and hydrogen peroxide. Appl Catal, B 63:15–19
Ning B, Graham NJD, Zhang Y (2007) Degradation of octylphenol and nonylphenol by ozone - Part IDirect reaction. Chemosphere 68:1163–1172
Morales-Roque J, Carrillo-Cárdenas M, Jayanthi N, Cruz J, Pandiyan T (2009) Theoretical and experimental interpretations of phenol oxidation by the hydroxyl radical. J Mol Struct (THEOCHEM) 910:74–79
Lundqvist M, Eriksson L (2000) Hydroxyl radical reactions with phenol as a model for generation of biologically reactive tyrosyl radicals. J Phys Chem B 104:848–855
Namkung K, Burgess A, Bremner D, Staines H (2008) Advanced Fenton processing of aqueous phenol solutionsa continuous system study including sonication effects. Ultrason Sonochem 15:171–176
Eisenhauer H (1964) Oxidation of phenolic wastes. J Water Pollut Control Fed 36:1116–1128
Plesničar B, Tuttle T, Cerkovnik J, Koller J, Cremer D (2003) Mechanism of formation of hydrogen trioxide (HOOOH) in the ozonation of 1, 2-diphenylhydrazine and 1, 2-dimethylhydrazineAn experimental and theoretical investigation. J Am Chem Soc 125:11553–11564
Manojlovic D, Ostojic DR, Obradovic BM, Kuraica MM, Krsmanovic VD, Puric J (2007) Removal of phenol and chlorophenols from water by new ozone generator. Desalination 213:116–122
Eisenhauer H (1968) The ozonization of phenolic wastes. J Water Pollut Control Fed 40:1887–1899
Shen Y, Lei L, Zhang X, Zhou M, Zhang Y (2008) Effect of various gases and chemical catalysts on phenol degradation pathways by pulsed electrical discharges. J Hazard Mater 150:713–722
Hoeben W, Veldhuizen E (2000) The degradation of aqueous phenol solutions by pulsed positive corona discharges. Plasma Sources Sci Technol 9:361–365
Zhang Q, Qu X, Wang W (2007) Mechanism of OH-initiated atmospheric photooxidation of dichlorvos:a quantum mechanical study. Environ Sci Technol 41:6109–6116
Frisch MJ, Trucks GW, Schlegel HB et al (2004) Gaussian 2003. Revision D.01. Gaussian Inc, Wallingford, CT
Zhao Y, Truhlar DG (2008) How well can new-generation density functionals describe the energetics of bond-dissociation reactions producing radicals? J Phys Chem A 112:1095–1099
Lozynski M, Rusinska-Roszak D, Mack HG (1998) Hydrogen bonding and density functional calculationsthe B3LYP approach as the shortest way to MP2 results. J Phys Chem A 102:2899–2903
Lee C, Yang W, Parr R (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789
Becke AD (1993) Density-functional thermochemistry III The role of exact exchange. J Chem Phys 98:5648–5652
Fukui K (1981) The path of chemical reactions-the IRC approach. Acc Chem Res 14:363–368
Gonzalez C, Schlegel H (1990) Reaction path following in mass-weighted internal coordinates. J Phys Chem 94:5523–5527
Pauling L (1960) The nature of the chemical bond. in. Cornell University Press, Ithaca, NY
Pakiari AH, Nazari F, Weinhold F (2003) The study of relationship between chemical geometry and electronic configuration of non-Walsh systems. J Mol Struct (THEOCHEM) 629:77–81
Linnett J (1964) The electronic structure of moleculesa new approach. Methuen London
Pakiari A, Nazari F (2003) New suggestion for electronic structure of the ground state of ozone. J Mol Struct THEOCHEM 640:109–115
Fujimoto H (1997) Frontier orbitals and reaction pathsselected papers of Kenichi Fukui. World Scientific, Singapore Inc
Fleming I (1976) Frontier orbitals and organic chemical reactions. Wiley, New York
Vleeschouwer FD, Speybroeck VV, Waroquier M, Geerlings P, Proft FD (2008) An intrinsic radical stability scale from the perspective of bond dissociation enthalpies:a companion to radical electrophilicities. J Org Chem 73:9109–9120
de Heer MI, Korth H-G, Mulder P (1999) Poly methoxy phenols in solution O − H bond dissociation enthalpies, structures, and hydrogen bonding. J Org Chem 64:6969–6975
Yamada S, Naito Y, Takada M, Nakai S, Hosomi M (2008) Photodegradation of hexachlorobenzene and theoretical prediction of its degradation pathways using quantum chemical calculation. Chemosphere 70:731–736
Ren X, Sun Y, Zhu L, Cui Z (2010) Theoretical studies on the OH-initiated photodegradation mechanism of dicofol. Comput Theor Chem 963:365–370
Suegara J, Lee BD, Espino MP, Nakai S, Hosomi M (2005) Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory. Chemosphere 61:341–346
Lim DH, Lastoskie CM (2009) Density functional theory studies on the relative reactivity of chloroethenes on zerovalent iron. Environ Sci Technol 43:5443–5448
Zhao Y, Zhang R, Wang H, He M, Sun X, Zhang Q, Wang W, Ru M (2010) Mechanism of atmospheric ozonolysis of sabineneA DFT study. J Mol Struct (THEOCHEM) 942:32–37
Denisova T, Denisov E (1998) Reactivity of ozone as a hydrogen-atom acceptor in reactions with antioxidants. Polym Degrad Stab 60:345–350
Janoschek R, Fabian W (2003) Thermodynamic properties of chlorinated phenols, cyclo-C5 compounds, and derived radicals from G3MP2B3 calculations. J Mol Struct 661:635–645
Berho F, Lesclaux R (1997) The phenoxy radicalUV spectrum and kinetics of gas-phase reactions with itself and with oxygen. Chem Phys Lett 279:289–296
Asatryan R, Davtyan A, Khachatryan L, Dellinger B (2005) Molecular modeling studies of the reactions of phenoxy radical dimersPathways to dibenzofurans. J Phys Chem A 109:11198–11205
Altarawneh M, Dlugogorski BZ, Kennedy EM, Mackie JC (2009) Mechanisms for formation, chlorination, dechlorination and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Prog Energy Combust Sci 35:245–274
Asatryan R, Davtyan A, Khachatryan L, Dellinger B (2002) Theoretical study of open-shell IPSO-addition and bis-keto dimer interconversion reactions related to gas-phase formation of PCDD/FS from chlorinated phenols. Organohalogen Compd 56:277–280
Plesničar B, Cerkovnik J, Tekavec T, Koller J (1998) On the mechanism of the ozonation of isopropyl alcohol:an experimental and density functional theoretical investigation 17O NMR Spectra of hydrogen trioxide (HOOOH) and the hydrotrioxide of isopropyl alcohol. J Am Chem Soc 120:8005–8006
Acknowledgments
This work is supported by a project of Shandong Province Science and Technology Department (No. 2010177) and a Project of Shandong Province Higher Educational Science and Technology Program (No. J09LB08). We also thank China Postdoctoral Science Foundation (No.20090461215 and 20100481303).
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Youmin, S., Xiaohua, R., Zhaojie, C. et al. The degradation mechanism of phenol induced by ozone in wastes system. J Mol Model 18, 3821–3830 (2012). https://doi.org/10.1007/s00894-012-1376-5
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DOI: https://doi.org/10.1007/s00894-012-1376-5