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@ARTICLE{Bohn:22983,
      author       = {Bohn, B. and Zetzsch, C.},
      title        = {{K}inetics and mechanism of the reaction of {OH} with the
                      trimethlbenzenes - experimental evidence for the formation
                      of adduct isomers},
      journal      = {Physical Chemistry Chemical Physics},
      volume       = {14},
      issn         = {1463-9076},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {PreJuSER-22983},
      pages        = {13933 - 13948},
      year         = {2012},
      note         = {This work was supported within the joint French-German
                      research project ATMOCHEM funded by the Deutsche
                      Forschungsgemeinschaft under grant BO-1580/3-1 and ZE
                      792/6-1. We thank R. Koch for detecting the triexponential
                      feature of the decays of OH in the presence of
                      1,3,5-trimethylbenzene, M. Elend for the GC-analysis of the
                      liquid reactants, and R. Koch and M. Siese for their efforts
                      to improve the instrument.},
      abstract     = {The reversible gas-phase addition of OH radicals to the
                      trimethylbenzenes was investigated in pulsed experiments
                      utilizing VUV flash-photolysis resonance-fluorescence of
                      H(2)O in the temperature range of 275-340 K. Triexponential
                      OH decays were observed in the presence of the
                      trimethylbenzenes, indicating the participation of more than
                      one adduct species. Analytical solutions for the system of
                      differential equations with two adduct isomers were derived,
                      and the OH decay curves were evaluated based on this
                      reaction model. This led to significant improvements of fit
                      qualities and notable changes in OH rate constants compared
                      to a previous model with a single adduct species. The
                      detailed analysis was confined to 1,3,5-trimethylbenzene
                      where reversible formation of two OH-aromatic ortho- and
                      ipso-adduct isomers is feasible in accordance with the
                      extended reaction model. Only after inclusion of additional
                      isomerization reactions, consistent thermochemical data were
                      obtained from the fitted rate constants. Reaction enthalpies
                      of -83 ± 7 kJ mol(-1) and -35 ± 22 kJ mol(-1) were derived
                      for the formation of one adduct isomer and the isomerization
                      into the other, respectively. Based on literature data, the
                      more and less stable adducts were assigned to ipso- and
                      ortho-adduct isomers, respectively. The potential
                      isomerization precluded the determination of primary yields
                      of adduct isomers but formation of the ipso-adduct in any
                      case is a minor process. For the rate constants of the OH +
                      1,3,5-trimethylbenzene reaction an Arrhenius expression
                      k(OH) = 1.32 × 10(-11) cm(3) s(-1) exp(450 ± 50 K/T) was
                      obtained. Based on the same approach, the rate constants of
                      the OH reactions with 1,2,3-trimethylbenzene and
                      1,2,4-trimethylbenzene were derived as k(OH) = 3.61 ×
                      10(-12) cm(3) s(-1) exp(620 ± 80 K/T) and k(OH) = 2.73 ×
                      10(-12) cm(3) s(-1) exp(730 ± 70 K/T), respectively.},
      keywords     = {J (WoSType)},
      cin          = {IEK-8},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {Atmosphäre und Klima},
      pid          = {G:(DE-Juel1)FUEK491},
      shelfmark    = {Chemistry, Physical / Physics, Atomic, Molecular $\&$
                      Chemical},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:22968679},
      UT           = {WOS:000309140400027},
      doi          = {10.1039/c2cp42434g},
      url          = {https://juser.fz-juelich.de/record/22983},
}