Elementary reaction path on polychlorinated biphenyls formation from polychlorinated benzenes in heterogeneous phase using ab initio molecular orbital calculation

Mitsuhito Hirota, Hiromitsu Takashita, Junichi Kato, Akio Fuwa

    Research output: Contribution to journalArticle

    4 Citations (Scopus)

    Abstract

    We have investigated the elementary reaction path on the 3,3′,4,4′,5,5′-hexachlorinated biphenyl (HxCB) formation from two 1,2,3,5-tetrachlorobenzenes (TCBz) and the catalytic role of copper on this formation using ab initio molecular orbital calculation. The elementary reaction path on the 3,3′,4,4′,5,5′-HxCB formation from two 1,2,3,5-TCBzs has been shown to occur as follows: Step 1 - the dissociation of Cl atom substituted at 5-position in 1,2,3,5-TCBz, Step 2 - the association between Cl atom substituted at 5-position in another 1,2,3,5-TCBz and the Cl radical formed in Step 1, Step 3 - the elimination of Cl2 molecule from the intermediate species formed in Step 2, and Step 4 - the 3,3′,4,4′,5,5′-HxCB formation from the direct condensation of two 1,2,3-trichlorophenyl radicals formed in Step 1 and Step 3. The geometric factor, which decides the reactivity of this formation, is the C-Cl bond strength of 1,2,3,5-TCBz. The catalytic roles of copper are to stabilize the total energy in the adsorption of 1,2,3,5-TCBz onto the copper surface and to weaken the C-Cl bond strength due to the charge transfer from the 1,2,3,5-TCBz to the copper surface. Moreover, we have achieved the prediction of the minimum energy path on the formation of non- and mono-ortho polychlorinated biphenyls congeners for which TEFs have been determined.

    Original languageEnglish
    Pages (from-to)457-467
    Number of pages11
    JournalChemosphere
    Volume50
    Issue number4
    DOIs
    Publication statusPublished - 2003 Jan

    Fingerprint

    Orbital calculations
    Polychlorinated Biphenyls
    Molecular orbitals
    Benzene
    Polychlorinated biphenyls
    benzene
    PCB
    copper
    Copper
    Atoms
    energy
    Charge transfer
    condensation
    Condensation
    Association reactions
    adsorption
    Adsorption
    Molecules
    1,2,3,5-tetrachlorobenzene
    calculation

    Keywords

    • Ab initio molecular orbital calculation
    • Copper
    • Heterogeneous reaction
    • Polychlorinated biphenyls

    ASJC Scopus subject areas

    • Environmental Chemistry
    • Environmental Science(all)

    Cite this

    Elementary reaction path on polychlorinated biphenyls formation from polychlorinated benzenes in heterogeneous phase using ab initio molecular orbital calculation. / Hirota, Mitsuhito; Takashita, Hiromitsu; Kato, Junichi; Fuwa, Akio.

    In: Chemosphere, Vol. 50, No. 4, 01.2003, p. 457-467.

    Research output: Contribution to journalArticle

    Hirota, Mitsuhito ; Takashita, Hiromitsu ; Kato, Junichi ; Fuwa, Akio. / Elementary reaction path on polychlorinated biphenyls formation from polychlorinated benzenes in heterogeneous phase using ab initio molecular orbital calculation. In: Chemosphere. 2003 ; Vol. 50, No. 4. pp. 457-467.
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    abstract = "We have investigated the elementary reaction path on the 3,3′,4,4′,5,5′-hexachlorinated biphenyl (HxCB) formation from two 1,2,3,5-tetrachlorobenzenes (TCBz) and the catalytic role of copper on this formation using ab initio molecular orbital calculation. The elementary reaction path on the 3,3′,4,4′,5,5′-HxCB formation from two 1,2,3,5-TCBzs has been shown to occur as follows: Step 1 - the dissociation of Cl atom substituted at 5-position in 1,2,3,5-TCBz, Step 2 - the association between Cl atom substituted at 5-position in another 1,2,3,5-TCBz and the Cl radical formed in Step 1, Step 3 - the elimination of Cl2 molecule from the intermediate species formed in Step 2, and Step 4 - the 3,3′,4,4′,5,5′-HxCB formation from the direct condensation of two 1,2,3-trichlorophenyl radicals formed in Step 1 and Step 3. The geometric factor, which decides the reactivity of this formation, is the C-Cl bond strength of 1,2,3,5-TCBz. The catalytic roles of copper are to stabilize the total energy in the adsorption of 1,2,3,5-TCBz onto the copper surface and to weaken the C-Cl bond strength due to the charge transfer from the 1,2,3,5-TCBz to the copper surface. Moreover, we have achieved the prediction of the minimum energy path on the formation of non- and mono-ortho polychlorinated biphenyls congeners for which TEFs have been determined.",
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    AU - Hirota, Mitsuhito

    AU - Takashita, Hiromitsu

    AU - Kato, Junichi

    AU - Fuwa, Akio

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    N2 - We have investigated the elementary reaction path on the 3,3′,4,4′,5,5′-hexachlorinated biphenyl (HxCB) formation from two 1,2,3,5-tetrachlorobenzenes (TCBz) and the catalytic role of copper on this formation using ab initio molecular orbital calculation. The elementary reaction path on the 3,3′,4,4′,5,5′-HxCB formation from two 1,2,3,5-TCBzs has been shown to occur as follows: Step 1 - the dissociation of Cl atom substituted at 5-position in 1,2,3,5-TCBz, Step 2 - the association between Cl atom substituted at 5-position in another 1,2,3,5-TCBz and the Cl radical formed in Step 1, Step 3 - the elimination of Cl2 molecule from the intermediate species formed in Step 2, and Step 4 - the 3,3′,4,4′,5,5′-HxCB formation from the direct condensation of two 1,2,3-trichlorophenyl radicals formed in Step 1 and Step 3. The geometric factor, which decides the reactivity of this formation, is the C-Cl bond strength of 1,2,3,5-TCBz. The catalytic roles of copper are to stabilize the total energy in the adsorption of 1,2,3,5-TCBz onto the copper surface and to weaken the C-Cl bond strength due to the charge transfer from the 1,2,3,5-TCBz to the copper surface. Moreover, we have achieved the prediction of the minimum energy path on the formation of non- and mono-ortho polychlorinated biphenyls congeners for which TEFs have been determined.

    AB - We have investigated the elementary reaction path on the 3,3′,4,4′,5,5′-hexachlorinated biphenyl (HxCB) formation from two 1,2,3,5-tetrachlorobenzenes (TCBz) and the catalytic role of copper on this formation using ab initio molecular orbital calculation. The elementary reaction path on the 3,3′,4,4′,5,5′-HxCB formation from two 1,2,3,5-TCBzs has been shown to occur as follows: Step 1 - the dissociation of Cl atom substituted at 5-position in 1,2,3,5-TCBz, Step 2 - the association between Cl atom substituted at 5-position in another 1,2,3,5-TCBz and the Cl radical formed in Step 1, Step 3 - the elimination of Cl2 molecule from the intermediate species formed in Step 2, and Step 4 - the 3,3′,4,4′,5,5′-HxCB formation from the direct condensation of two 1,2,3-trichlorophenyl radicals formed in Step 1 and Step 3. The geometric factor, which decides the reactivity of this formation, is the C-Cl bond strength of 1,2,3,5-TCBz. The catalytic roles of copper are to stabilize the total energy in the adsorption of 1,2,3,5-TCBz onto the copper surface and to weaken the C-Cl bond strength due to the charge transfer from the 1,2,3,5-TCBz to the copper surface. Moreover, we have achieved the prediction of the minimum energy path on the formation of non- and mono-ortho polychlorinated biphenyls congeners for which TEFs have been determined.

    KW - Ab initio molecular orbital calculation

    KW - Copper

    KW - Heterogeneous reaction

    KW - Polychlorinated biphenyls

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