Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner
"> Figure 1
<p>The electron densities of <span class="html-italic">syn</span> and <span class="html-italic">anti</span> 2-CP. (<b>A</b>) <span class="html-italic">syn</span> 2-CP; (<b>B</b>) <span class="html-italic">anti</span> 2-CP. 2-CP: 2-chlorophenol.</p> "> Figure 2
<p>Chlorinated dihydrofulvalene formation routes embedded with the potential barriers Δ<span class="html-italic">E</span> (in kcal/mol) and reaction heats Δ<span class="html-italic">H</span> (in kcal/mol) from the 2-CP as forerunner at the MPWB1K/aug-cc-pVTZ//MPWB1K/6-31+G(d,p) level. Δ<span class="html-italic">H</span> is calculated at 0 K. IM: intermediate; TS: transition state.</p> "> Figure 3
<p>PCN formation routes embedded with the potential barriers Δ<span class="html-italic">E</span> (in kcal/mol) and reaction heats Δ<span class="html-italic">H</span> (in kcal/mol) from IM5 at the MPWB1K/aug-cc-pVTZ//MPWB1K/6-31+G(d,p) level. Δ<span class="html-italic">H</span> is calculated at 0 K. PCN: Polychlorinated naphthalene; MCN: monochlorinated naphthalene; DCN: dichlorinated naphthalene.</p> "> Figure 4
<p>PCN formation routes from IM5 proposed by Kim [<a href="#B21-ijms-16-25641" class="html-bibr">21</a>,<a href="#B22-ijms-16-25641" class="html-bibr">22</a>], starting with <span class="html-italic">H</span>-shift step. These routes are embedded with the potential barriers Δ<span class="html-italic">E</span> (in kcal/mol) and reaction heats Δ<span class="html-italic">H</span> (in kcal/mol) at the MPWB1K/aug-cc-pVTZ//MPWB1K/6-31+G(d,p) level. Δ<span class="html-italic">H</span> is calculated at 0 K.</p> "> Figure 5
<p>PCN formation routes embedded with the potential barriers Δ<span class="html-italic">E</span> (in kcal/mol) and reaction heats Δ<span class="html-italic">H</span> (in kcal/mol) from IM10 at the MPWB1K/aug-cc-pVTZ//MPWB1K/6-31+G(d,p) level. Δ<span class="html-italic">H</span> is calculated at 0 K.</p> "> Figure 6
<p>Arrhenius plot of the CVT/SCT rate constants in the temperature range of 600–1200 K for reaction of (<b>A</b>) IM24/IM25 → IM32 via TS34 and (<b>B</b>) IM5 + H → IM19 + H<sub>2</sub> via TS17. CVT: canonical variational transition-state theory; SCT: small curvature tunneling contribution.</p> ">
Abstract
:1. Introduction
2. Results and Discussion
2.1. 2-Chlorophenoxy Radical Formation from 2-Chlorophenols
2.2. Chloro-Dihydrofulvalene Production from Dimerization of 2-Chlorophenoxy Radicals
2.3. PCN Formation from the Following Reactions of IM5
2.4. PCN Formation from the Following Reactions of IM10
2.5. Formation Comparison PCNs and PCDFs from 2-Chlorophenol
2.6. Rate Constant Calculations
Reactions | Arrhenius Formulas |
---|---|
IM1 → IM2 via TS1 | k (T) = (3.12 × 1012) exp (−21,500.36/T) |
IM2 → IM3 + CO via TS2 | k (T) = (2.32 × 1011) exp (−21,473.60/T) |
IM3 → IM4 via TS3 | k (T) = (1.21 × 1013) exp (−21,309.58/T) |
IM4 → IM5 + CO via TS4 | k (T) = (1.17 × 1011) exp (−21,746.24/T) |
IM6 → IM7 via TS5 | k (T) = (1.94 × 1013) exp (−20,475.72/T) |
IM7 → IM8 + CO TS6 | k (T) = (2.41 × 1011) exp (−24,764.15/T) |
IM8 → IM9 via TS7 | k (T) = (5.43 × 1013) exp (−20,072.04/T) |
IM9 → IM10 + CO via TS8 | k (T) = (3.33 × 1011) exp (−21,413.18/T) |
IM6 → IM11 via TS9 | k (T) = (2.14 × 1013) exp (−26,398.65/T) |
IM11 → IM12 + CO via TS10 | k (T) = (6.17 × 1011) exp (−21,840.02/T) |
IM12 → IM13 via TS11 | k (T) = (1.37 × 1013) exp (−39,956.40/T) |
IM13 → IM10 + CO via TS12 | k (T) = (3.70 × 1011) exp (−28,457.34/T) |
IM5 + H → IM19 + H2 via TS17 | k (T) = (6.47 × 10−13) exp (−3826.40/T) |
IM19 → IM20 via TS20 (0.93) | k (T) = (5.80 × 1012) exp (−4953.85/T) |
IM19 → IM21 via TS21 (0.04) | k (T) = (2.76 × 1012) exp (−7312.34/T) |
IM19 → IM22 via TS22 (0.02) | k (T) = (3.09 × 1012) exp (−8295.86/T) |
IM19 → IM23 via TS23 (0.01) | k (T) = (4.04 × 1012) exp (−9165.93/T) |
IM22 → IM26 via TS26 | k (T) = (1.70 × 1013) exp (−11,865.38/T) |
IM23 → IM27 via TS27 | k (T) = (1.82 × 1013) exp (−11,673.73/T) |
IM24/IM25 → IM28 via TS28 (0.06) | k (T) = (1.77 × 1012) exp (−7432.09/T) |
IM24/IM25 → IM30 via TS31 (0.50) | k (T) = (2.48 × 1012) exp (−5572.69/T) |
IM24/IM25 → IM32 via TS34 (0.40) | k (T) = (2.24 × 1012) exp (−5708.95/T) |
IM24/IM25 → IM34 via TS37 (0.11) | k (T) = (1.61 × 1012) exp (−7509.02/T) |
IM26/IM27 → IM36 via TS40 (0.11) | k (T) = (1.98 × 1012) exp (−7696.65/T) |
IM26/IM25 → IM37 via TS42 (0.18) | k (T) = (3.29 × 1012) exp (−7701.35/T) |
IM37 → 1-MCN + Cl via TS43 | k (T) = (2.03 × 1013) exp (−6825.08/T) |
IM26/IM27 → IM38 via TS44 (0.69) | k (T) = (2.77 × 1012) exp (−6154.47/T) |
IM26/IM27 → IM40 via TS47 (0.03) | k (T) = (7.40 × 1011) exp (−8061.95/T) |
IM40 → 1-MCN + Cl via TS48 | k (T) = (3.50 × 1013) exp (−5895.30/T) |
IM10 + H → IM42 + HCl via TS68 | k (T) = (1.56 × 10−11) exp (−4151.85/T) |
IM10 + OH → IM42 + H2O via TS69 | k (T) = (6.16 × 10−12) exp (−10,425.51/T) |
IM10 + Cl → IM42 + Cl2 via TS70 | k (T) = (1.04 × 10−10) exp (−5075.97/T) |
IM42 → IM43 via TS53 (0.92) | k (T) = (1.98 × 1012) exp (−7696.65/T) |
IM42 → IM44 via TS54 (0.08) | k (T) = (1.09 × 1012) exp (−6633.06/T) |
IM44 → IM46 via TS56 | k (T) = (2.16 × 1013) exp (−13,348.67/T) |
IM45 → IM47 via TS57 (0.51) | k (T) = (2.90 × 1012) exp (−5798.88/T) |
IM45 → IM49 via TS60 (0.49) | k (T) = (2.75 × 1012) exp (−5797.29/T) |
IM46 → IM51 via TS63 (0.91) | k (T) = (3.40 × 1012) exp (−5853.60/T) |
IM46 → IM53 via TS66 (0.09) | k (T) = (2.94 × 1012) exp (−8057.90/T) |
IM53 → N + Cl via TS67 | k (T) = (1.93 × 1013) exp (−6496.42/T) |
IM10 + H → IM54 + H2 via TS71 | k (T) = (6.32 × 10−11) exp (−3311.61/T) |
IM54 → IM22 via TS74 (0.62) | k (T) = (2.34 × 1012) exp (−5539.60/T) |
IM54 → IM23 via TS75 (0.38) | k (T) = (3.71 × 1012) exp (−6473.85/T) |
3. Experimental Section
3.1. Density Functional Theory
3.2. Kinetic Calculation
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Xu, F.; Zhang, R.; Li, Y.; Zhang, Q.; Wang, W. Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner. Int. J. Mol. Sci. 2015, 16, 25641-25656. https://doi.org/10.3390/ijms161025641
Xu F, Zhang R, Li Y, Zhang Q, Wang W. Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner. International Journal of Molecular Sciences. 2015; 16(10):25641-25656. https://doi.org/10.3390/ijms161025641
Chicago/Turabian StyleXu, Fei, Ruiming Zhang, Yunfeng Li, Qingzhu Zhang, and Wenxing Wang. 2015. "Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner" International Journal of Molecular Sciences 16, no. 10: 25641-25656. https://doi.org/10.3390/ijms161025641