DFT calculation on 204 polychlorinated biphenyls: their thermodynamic function and implication of Cl substitute position

Zhai, Zhicai; Wang, Zunyao; Xue-heng, Chen; Wang, Liansheng

doi:10.1016/j.theochem.2004.08.060

Cited by 20 publications

(17 citation statements)

References 14 publications

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“…And in our past research, we also found that most thermodynamic parameters of POPs achieved from ab initio were very well correlated with chlorine number and positions [9,10]. Therefore, in the present work such relationship was further explored.…”

Section: Model 3 Based On the Number And Relative Position Of CL Subsmentioning

confidence: 58%

Quantitative Structure‐retention Relationship for Gas Chromatography of Polychlorinated Naphthalenes by Ab initio Quantummechanical Calculations and a Cl Substitution Position Method

2006

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Three quantitative structure-retention relationship (QSRR) models have been developed for gas chromatographic relative retention indices (RIs) of polychlorinated naphthalene (PCN) congeners. With computation at HF/6-31G* and B3LYP/6-31G* levels in Gaussian98 program, the structural parameters of PCNs were obtained and used as chemical descriptors to correlate with their gas chromatographic RIs by multiple linear regression analysis, resulting in model 1 and model 2. The squared correlation coefficients (r 2 ) of the first two models are 0.9814 and 0.9957, and the crossvalidation correlation coefficients (q 2 ) are 0.9771 and 0.9948, respectively. On the other hand, the third model, model 3, was developed using the relative position of chlorine substitution as molecular descriptor, and its multiple squared correlation coefficient is r 2 ¼ 0.9967 and q 2 ¼ 0.9959, suggesting model 3 is practical and especially has a optimum predictive power.

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Section: Model 3 Based On the Number And Relative Position Of CL Subsmentioning

confidence: 58%

Quantitative Structure‐retention Relationship for Gas Chromatography of Polychlorinated Naphthalenes by Ab initio Quantummechanical Calculations and a Cl Substitution Position Method

2006

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“…Steric effects at the ortho-positions might make it difficult for halogen atoms at the ortho-positions to be removed during the formation of nona-halogenated compounds from deca-halogenated compounds. The enthalpy (ΔH f 0 ) and Gibbs free energy (ΔG f 0 ) are lower for CB-207 than for the other nonachlorobiphenyls (Zhai et al 2005), suggesting that these thermodynamic parameters also contribute to the preferential formation of CB-207. However, higher ΔH f 0 and ΔG f 0 values have been reported by Grabda et al (2007) for BDE-207 than f o r B D E s -2 0 8 a n d -2 0 6 .…”

Section: Proposed Degradation Mechanismmentioning

confidence: 98%

Thermal degradation of polybrominated diphenyl ethers over as-prepared Fe3O4 micro/nano-material and hypothesized mechanism

Yang

et al. 2015

Environ Sci Pollut Res

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The thermal degradation of decabromodiphenyl ether (BDE-209) featuring fully substituted bromines was investigated over an as-prepared Fe 3 O 4 micro/nano-material at 300°C. Degradation followed pseudo-first-order kinetics with k obs =0.15 min −1 higher than that for decachlorobiphenyl (CB-209). Twenty-six newly produced polybrominated diphenyl ether (PBDE) congeners were identified using the available PBDE standards, while four PBDE congener products were predicted using third-order polynomial regression equation. Analysis of the products indicated that BDE-209 underwent stepwise hydrodebromination over as-prepared Fe 3 O 4 . S i m i l a r t o t h e c a s e f o r C B -2 0 9 , t w o i n i t i a l hydrodebromination steps are favored at the BDE-209 metapositions, giving the major products BDE-207 and BDE-197. However, the variance about the preferred products began to emerge from the start of heptabromodiphenyl ethers (heptaBDEs). The majorly produced hepta-BDE isomer with BDE-183 is unbrominated at one ortho-position. However, this is different from the reported degradation of CB-209, which always produced the products chlorinated at all four ortho-positions until the ortho-position had to be removed for the formation of trichlorobiphenyls and dichlorobiphenyl still majorly chlorinated at three or two ortho-positions. The early BDE-209 hydrodebromination steps appear to be strongly influe nced by ster ic effe cts, wher eas su bsequ ent hydrodebromination steps, as more bromine atoms are removed, will be gradually governed more by thermodynamics.

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“…As already noted, in the recent years the enthalpies of formation of different polychlorinated aromatic compounds were predicted from B3LYP calculations using isodesmic reactions [8][9][10][11][12][13][14][15]. To estimate the f H • 298 values of PCDDs, the following reactions may be considered as the most appropriate:…”

Section: Polychlorinated Aromatic Compoundsmentioning

confidence: 99%

“…The thermodynamic properties of chlorinated aromatic species are important in the kinetic modeling their formation during the processes of pyrolysis and oxidation. A large number of studies on the estimation of thermochemical properties of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans, naphthalenes, and biphenyls has been published last years (see [8][9][10][11][12][13][14][15], and references cited therein). In these works, the enthalpies of formation were calculated using the B3LYP total energies and isodesmic reactions.…”

Section: Introductionmentioning

confidence: 99%

Assessment of Gaussian-3X theory for chlorinated organic molecules. Enthalpies of formation of chlorobenzenes and predictions for polychlorinated aromatic compounds

2006

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The enthalpies of formation of chlorinated methanes, ethanes, ethylenes, phenols, and benzenes have been calculated at the G3X level of theory using the atomization energy procedure and the method of isodesmic reactions. By comparing the most reliable experimental data on chlorinated hydrocarbons recommended by Manion [Manion JA (2002) J Phys Chem Ref Data 31:123] with the G3X results, the accuracy of theoretical enthalpies of formation is estimated as ranging from ± 4 to ± 10 kJ/mol. Only for hexachloroethane, the difference between the experimental value and G3X result was outside this range and the experimental enthalpy of formation of hexachloroethane was called into question by theory. The G3X enthalpies of formation of all chlorobenzenes agree well with experimental data which were partly reanalyzed using recent experimental data on enthalpies of sublimation. Based on the G3X results, a set of self-consistent experimental data for chlorobenzenes is recommended. The enthalpies of formation of some polychlorinated dibenzo-p-dioxins were estimated using improved enthalpies of formation for chlorobenzenes. The possible inaccuracy of previously estimated values for polychlorinated aromatic compounds is discussed.

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DFT calculation on 204 polychlorinated biphenyls: their thermodynamic function and implication of Cl substitute position

Cited by 20 publications

References 14 publications

Quantitative Structure‐retention Relationship for Gas Chromatography of Polychlorinated Naphthalenes by Ab initio Quantummechanical Calculations and a Cl Substitution Position Method

Quantitative Structure‐retention Relationship for Gas Chromatography of Polychlorinated Naphthalenes by Ab initio Quantummechanical Calculations and a Cl Substitution Position Method

Thermal degradation of polybrominated diphenyl ethers over as-prepared Fe3O4 micro/nano-material and hypothesized mechanism

Assessment of Gaussian-3X theory for chlorinated organic molecules. Enthalpies of formation of chlorobenzenes and predictions for polychlorinated aromatic compounds

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