skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.

Abstract

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 of 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 ratemore » 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

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
961321
Report Number(s):
ANL/CHM/JA-46606
Journal ID: ISSN 1089-5639; JPCAFH; TRN: US201011%%594
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Phys. Chem. A; Journal Volume: 107; Journal Issue: 49 ; Dec. 11, 2003
Country of Publication:
United States
Language:
ENGLISH
Subject:
08 HYDROGEN; ACETYLENE; ATOMS; DETECTION; HYDROGEN; POTENTIAL ENERGY; PRESSURE RANGE; PRESSURE RANGE MEGA PA 10-100; PYROLYSIS; RADICALS; RESONANCE ABSORPTION; SHOCK TUBES; SPECTROSCOPY; STABILIZATION; TEMPERATURE RANGE 0400-1000 K; TEMPERATURE RANGE 1000-4000 K; VINYL RADICALS

Citation Formats

Michael, J. V., Su, M.-C., Sutherland, J. W., Harding, L. B., Wagner, A. F., Chemistry, Butler Univ., and BNL. Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.. United States: N. p., 2003. Web. doi:10.1021/jp035170n.
Michael, J. V., Su, M.-C., Sutherland, J. W., Harding, L. B., Wagner, A. F., Chemistry, Butler Univ., & BNL. Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.. United States. doi:10.1021/jp035170n.
Michael, J. V., Su, M.-C., Sutherland, J. W., Harding, L. B., Wagner, A. F., Chemistry, Butler Univ., and BNL. Thu . "Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.". United States. doi:10.1021/jp035170n.
@article{osti_961321,
title = {Rate constants for D + C{sub 2}H{sub 2}{r_arrow}C{sub 2}HD + H at high temperature: implications to the high pressure rate constant for H + C{sub 2}H{sub 2}{r_arrow}C{sub 2}H{sub 3}.},
author = {Michael, J. V. and Su, M.-C. and Sutherland, J. W. and Harding, L. B. and Wagner, A. F. and Chemistry and Butler Univ. and BNL},
abstractNote = {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 of 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.},
doi = {10.1021/jp035170n},
journal = {J. Phys. Chem. A},
number = 49 ; Dec. 11, 2003,
volume = 107,
place = {United States},
year = {Thu Dec 11 00:00:00 EST 2003},
month = {Thu Dec 11 00:00:00 EST 2003}
}