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Title: High temperature rate constants for H/D + n -C 4 H 10 and i -C 4 H 10

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Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
Grant/Contract Number:
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Proceedings of the Combustion Institute
Additional Journal Information:
Journal Volume: 35; Journal Issue: 1; Related Information: CHORUS Timestamp: 2017-05-17 09:42:28; Journal ID: ISSN 1540-7489
Country of Publication:
United States

Citation Formats

Peukert, Sebastian L., Sivaramakrishnan, Raghu, and Michael, Joe V. High temperature rate constants for H/D + n -C 4 H 10 and i -C 4 H 10. United States: N. p., 2015. Web. doi:10.1016/j.proci.2014.05.104.
Peukert, Sebastian L., Sivaramakrishnan, Raghu, & Michael, Joe V. High temperature rate constants for H/D + n -C 4 H 10 and i -C 4 H 10. United States. doi:10.1016/j.proci.2014.05.104.
Peukert, Sebastian L., Sivaramakrishnan, Raghu, and Michael, Joe V. 2015. "High temperature rate constants for H/D + n -C 4 H 10 and i -C 4 H 10". United States. doi:10.1016/j.proci.2014.05.104.
title = {High temperature rate constants for H/D + n -C 4 H 10 and i -C 4 H 10},
author = {Peukert, Sebastian L. and Sivaramakrishnan, Raghu and Michael, Joe V.},
abstractNote = {},
doi = {10.1016/j.proci.2014.05.104},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 35,
place = {United States},
year = 2015,
month = 1

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.proci.2014.05.104

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Cited by: 3works
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  • The reflected shock tube technique with D atom atomic resonance absorption spectrometry (ARAS) detection has been used to study the bimolecular reaction, D + C{sub 2}H{sub 2} {yields} C{sub 2}HD + H. D atoms were produced from the thermal decomposition of C{sub 2}D{sub 5}I above {approx}1150 K. The initially formed C{sub 2}D{sub 5} radicals rapidly decompose to give D + C{sub 2}D{sub 4}. Rate constant values were obtained from both reactant and product hydrogen atom measurements, and these were found to be identical within experimental error. The title reaction proceeds through a vibrationally excited vinyl radical, and the equivalence ofmore » results based on reactant and product measurements suggests that radical stabilization is negligible over the temperature and pressure ranges of the experiments. For 1100 {<=} T {<=} 1630 K, the results can be described by the linear-least-squares Arrhenius expression: k = (2.77 {+-} 0.45) x 10{sup -10} exp(-3051 {+-} 210 K/T) in units of cm{sup 3} molecule{sup -1} s{sup -1}, with the one standard deviation of the values from the equation being {+-}10.7%. Application of RRKM theory with negligible stabilization shows that k = k{sub D{infinity}}{l_angle}k{sub f{var_epsilon}}/(k{sub f{var_epsilon}}+ k{sub b{var_epsilon}}){r_angle} where the k{sub i{var_epsilon}}'s refer to RRKM evaluated specific rate constants for forward and backward dissociations, and k{sub D{infinity}} is the high-pressure limiting rate constant for D addition to acetylene. Hence, the present measurements coupled with earlier measurements and modern ab initio potential energy determinations allow for specification of the high-pressure limiting rate constants. The same model can then be used for the protonated reaction, H + C{sub 2}H{sub 2}, where a considerable ambiguity has existed for about 30 years.« less
  • Rate constants for /sup 4/He--H/sub 2/ and /sup 4/He--D/sub 2/ vibrational relaxation are computed using the phase modulated semiclassical sudden approximation and compared with experiments for 100 K
  • The reaction of CH{sub 3} with O{sub 2} has been studied in a reflected shock tube apparatus between 1600 and 2100 K. CH{sub 3} was prepared from the fast thermal decomposition of CH{sub 3}I and O atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t}. [CH{sub 3}I]{sub 0} was sufficiently low so that most secondary reactions were negligible, allowing for unambiguous determination of the rate constant for CH{sub 3} + O{sub 2} {yields} CH{sub 3}O + O. The rate constant expression for this reaction derived to match the experimental data is {kappa} = (3.90 {+-} 0.40)more » {times} 10{sup {minus}11} exp({minus}16858 {+-} 1127 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. To explain O atom concentration buildup at longer times, a fast reaction between H{sub 2}CO and O{sub 2} was postulated. Rate constants for this process were derived by fitting the long-time O atom profiles. Last, the four-center reaction CH{sub 3} + O{sub 2} {yields} CH{sub 2}O + OH was found to be of negligible importance over the temperature range of the study.« less
  • The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm, using either 36 or 60 optical passes corresponding to total path lengths of 3.25 or 5.25 m, respectively, has been used to study the bimolecular reactions, OH + CF3H CF3 + H2O (1) and CF3 + H2O OH + CF3H (-1), between 995 and 1663 K. During the course of the study, estimates of rate constants for CF3 + OH products (2) could also be determined. Experiments on reaction -1 were transformed through equilibrium constants to k1, giving the Arrhenius expression k1 = (9.7more » {+-} 2.1) x 10{sup -12} exp(-4398 {+-} 275K/T) cm3 molecule-1 s-1. Over the temperature range, 1318-1663 K, the results for reaction 2 were constant at k2 = (1.5 {+-} 0.4) x 10{sup -11} cm3 molecule-1 s-1. Reactions 1 and -1 were also studied with variational transition state theory (VTST) employing QCISD(T) properties for the transition state. These a priori VTST predictions were in good agreement with the present experimental results but were too low at the lower temperatures of earlier experiments, suggesting that either the barrier height was overestimated by about 1.3 kcal/mol or that the effect of tunneling was greatly underestimated. The present experimental results have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range of 252-1663 K. The three parameter expression k1 = 2.08 x 10{sup -17} T1.5513 exp(-1848 K/T) cm3 molecule-1 s-1 describes the rate behavior over this temperature range. Alternatively, the expression k1,th = 1.78 x 10{sup -23} T3.406 exp(-837 K/T) cm3 molecule-1 s-1 obtained from empirically adjusted VTST calculations over the 250-2250 K range agrees with the experimental evaluation to within a factor of 1.6. Reaction 2 was also studied with direct CASPT2 variable reaction coordinate transition state theory. The resulting predictions for the capture rate are found to be in good agreement with the mean of the experimental results and can be represented by the expression k2,th = 2.42 x 10{sup -11} T-0.0650 exp(134 K/T) cm3 molecule-1 s-1 over the 200-2500 K temperature range. The products of this reaction are predicted to be CF2O + HF.« less