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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Ed. by Rademann, Klaus

12 Issues per year

IMPACT FACTOR 2016: 1.012

CiteScore 2016: 0.99

SCImago Journal Rank (SJR) 2016: 0.463
Source Normalized Impact per Paper (SNIP) 2016: 0.470

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Volume 229, Issue 4 (Apr 2015)


Kinetics of the Reactions of Hydroxyl Radicals with Diacetylene and Vinylacetylene

Jörg Sommerer
  • Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany
/ Matthias Olzmann
  • Corresponding author
  • Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany
  • Email:
Published Online: 2014-11-21 | DOI: https://doi.org/10.1515/zpch-2014-0618


Highly unsaturated hydrocarbons like diacetylene (C4H2) or vinylacetylene (C4H4) are important intermediates in combustion that can have impact on soot formation. One of their major loss channels is reaction with hydroxyl radicals (OH). We studied the reactions C4H2 + OH → products (1) and C4H4 + OH → products (2) in a quasi-static reactor with helium as bath gas. The hydroxyl radicals were produced by laser flash-photolysis of nitric acid at a wavelength of 248 nm and detected by laser-induced fluorescence with excitation at 282 nm. The rate coefficients were obtained from the intensity-time profiles under pseudo-first order conditions with respect to OH. We found a virtually temperature-independent rate coefficient for reaction (1): k1 = (1.0 ± 0.3) × 10−11 cm3 s1 (T = 290–670 K, P = 2.7–30.5 bar) and a weakly negative temperature-dependent rate coefficient for reaction (2): k2(T) = (6.4 ± 1.9) × 10−12 exp (486 K/T) cm3 s1 (T = 295–740 K, P = 1.7–19.2 bar). For neither of the two reactions pressure dependence was observed. From comparisons with analogous reaction systems, we conclude that the dominating reaction pathway is OH addition, where in the case of C4H4 the double bond is preferred over the triple bond.

Keywords: Reaction Kinetics; Elementary Chemical Steps; Laser-Induced Fluorescence; Diacetylene; Vinylacetylene; Hydroxyl Radicals

About the article

Accepted: 2014-10-22

Received: 2014-09-18

Published Online: 2014-11-21

Published in Print: 2015-04-28

Citation Information: Zeitschrift für Physikalische Chemie, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2014-0618.

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