Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C₆H₆ = HCl + C₆H₅

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Article on studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C₆H₆ = HCl + C₆H₅.

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7 p.

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Alecu, I. M.; Gao, Yide; Hsieh, P-C; Sand, Jordan P.; Ors, Ahmet; McLeod, A. et al. February 7, 2007.

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Article on studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C₆H₆ = HCl + C₆H₅.

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7 p.

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Abstract: The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 × 10-12 exp(−18.1 kJ mol-1/RT) cm3 molecule-1 s-1 over 578−922 K and k(Cl + C6D6) = 6.2 × 10-12 exp(−22.8 kJ mol-1/RT) cm3 molecule-1 s-1 over 635−922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 × 10-11 exp(−31.6 kJ mol-1/RT) cm3 molecule-1 s-1 for 296−922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 × 10-12 exp(+5.2 kJ mol-1/RT) cm3 molecule-1 s-1 over 294−748 K, k(C6H5 + DCl) = 7.7 × 10-13 exp(+4.9 kJ mol-1/RT) cm3 molecule-1 s-1 over 292−546 K, an approximate k(C6H5 + C6H5I) = 2 × 10-11 cm3 molecule-1 s-1 over 300−750 K, and an upper limit k(Cl + C6H5I) ≤ 5.3 × 10-12 exp(+2.8 kJ mol-1/RT) cm3 molecule-1 s-1 over 300−750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D298(C6H5−H) = 472.1 ± 2.5 kJ mol-1 and thus the enthalpy of formation ΔfH298(C6H5) = 337.0 ± 2.5 kJ mol-1.

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2007 American Chemical Society.

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  • Journal of Physical Chemistry A, 2007, Washington D.C.: American Chemical Society, pp. 3970-3976

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 111
  • Issue: 19
  • Page Start: 3970
  • Page End: 3976
  • Pages: 7
  • Peer Reviewed: Yes

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  • February 7, 2007

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  • March 17, 2015, 10:38 a.m.

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Alecu, I. M.; Gao, Yide; Hsieh, P-C; Sand, Jordan P.; Ors, Ahmet; McLeod, A. et al. Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C₆H₆ = HCl + C₆H₅, article, February 7, 2007; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc501397/: accessed November 22, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.