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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the High-Temperature H2S Decomposition (1994)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 12958-12963 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100100a024
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  • 2
    Electronic Resource
    Electronic Resource
    A shock tube-laser flash photolysis study of the reaction carbonyl sulfide + sulfur .dblharw. carbon monoxide + sulfur dimer (1993)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 9682-9685 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100140a026
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  • 3
    Electronic Resource
    Electronic Resource
    Measurement of O( $^1$ D) formation during thermal decomposition of CO $_2$ behind shock waves (1996)
    Springer
    Shock waves 6 (1996), S. 79-83 
    Details
    ISSN: 1432-2153
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics , Technology
    Notes: Abstract. Atomic Resonance Absorption Spectroscopy (ARAS) was applied to measure the time dependent concentration of electronically excited O( $^1$ D)-atoms during the thermal decomposition of CO $_2$ behind reflected shock waves. The experiments were performed in the temperature range 4102 K $ \le $ T $ \le $ 6375 K at pressures 0.2 to 1.9 bar with initial gas mixtures of 100 to 1000 ppm CO $_2$ diluted in Ar. The measured O( $^1$ D)-formation rate at early reaction times divided by the initial reactant concentrations was found to obey the Arrhenius law: \beo &&\frac{d[{\rm O(^1D)}]/dt}{{\rm [CO_2]_0 \, [Ar]}} \Biggr|_{t \approx 0} \\ &&\quad = 1.23 \times 10^{14} \exp \left( -74810 {\rm K}/T \right){\rm cm^{3} mol^{-1} s^{-1}} \eeo The assumption of a fast thermalisation between the O( $^3$ P) and O( $^1$ D) states is in agreement with previous measurements of the O( $^3$ P) formation during the thermal decomposition of CO $_2$ , see Burmeister and Roth (1990).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001930050023
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  • 4
    Electronic Resource
    Electronic Resource
    A shock tube study on the thermal decomposition of CS2 based on S(3P) and S(1D) concentration measurements (1994)
    Springer
    Shock waves 4 (1994), S. 95-99 
    Details
    ISSN: 1432-2153
    Keywords: ARAS ; Chemical shock tube ; Thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics , Technology
    Notes: Abstract The thermal decomposition of CS2 highly diluted in Ar was studied behind reflected shock waves by monitoring time-dependent absorption profiles of S(3P) and S(1D) using atomic resonance absorption spectroscopy (ARAS). The rate coefficient of the reaction: (R1) $$\begin{gathered} CS_2 + M\mathop \to \limits^{k_1 } CS + S + M, \hfill \\ k_1 = 5.1 \times 10^{14} \exp \left( {\frac{{ - 38150K}}{T}} \right)cm^3 mol^{ - 1} s^{ - 1} \hfill \\ \end{gathered} $$ . was determined in experiments with initial concentrations of CS2 between 5 and 50 ppm at post-shock conditions of 2300 K≤T≤3360 K and total densities between 2.2×1018 cm−3 and 3.9×1018 cm−3. In experiments with higher initial concentrations of 100 ppm CS2 in Ar, the S(3P) concentrations were found to reach quasi-stationary values. From the steady state assumption a value for the rate coefficient of the most probable S consuming reaction: (R2) $$\begin{gathered} CS_2 + S\mathop \rightleftharpoons \limits^{k_2 } CS + S_2 , \hfill \\ k_2 \approx 1.2 \times 10^{13} cm^3 mol^{ - 1} s^{ - 1} \hfill \\ \end{gathered} $$ . was estimated at temperatures between 2100 K and 2340 K.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01418572
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  • 5
    Electronic Resource
    Electronic Resource
    High-temperature kinetics of Si-containing precursors for ceramic processing (1997)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 2670-2678 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental investigations of high-temperature kinetics of Si-precursor molecules relevant to CVD and ceramic processing are described. Reaction systems using SiH4, Si2H6, and SiCl4 highly diluted in argon were studied in a shock tube, a high-temperature wave reactor, by monitoring in situ the concentrations of atomic or radical reactants Si, H, Cl, SiH, and SiH2. Because of the very high dilution, the measured properties are sensitive to a limited number of elementary reactions, allowing a relatively direct determination of the respective rate coefficients. Both thermal pyrolysis and laser flash photolysis methods were used to expand the investigated temperature range. An overview of the bimolecular Si-atom reactions is given.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690431311
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the initiation step of the thermal decomposition of SiCl4 (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 415-420 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiation reaction of the thermal decomposition of silicon tetrachloride \documentclass{article}\pagestyle{empty}\begin{document}$$ SiCl_4\,+\,M\,{\buildrel{k_1}\over{\longrightarrow}} SiCl_3\,+Cl\,+M \eqno(R1) $$\end{document} was studied behind reflected shock waves at temperatures between 1550 K and 2370 K and pressures between 1 and 1.5 bar. Atomic resonance absorption spectrometry (ARAS) was applied for time-resolved measurements of H atoms at the Lα-line in SiCl4/H2/Ar systems. Additional experiments were performed in the SiCl4/Ar system following the absorption of SiCl4 at the Lα-line. Rate coefficients for the reaction (RI) were determined to be: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1=4.8\times 10^{16}\exp(-40954 K/T) cm^3 mol^{-1} s^{-1}. $$\end{document} The choice between two possible alternatives of the first decomposition step, namely elimination of either Cl2 or Cl, has been made in favor of the second reaction on the basis of kinetic and energetic considerations. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 415-420, 1997.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Oxidation of S and SO by O2 in high-temperature pyrolysis and photolysis reaction systems (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 59-71 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of S atoms with O2 was studied behind reflected shock waves applying atomic resonance absorption spectroscopy (ARAS) for concentration measurements of S and O atoms. S atoms were generated either by laser-flash photolysis (LFP) of CS2 or by the high-temperature pyrolysis of COS, respectively. The concentrations of O2 in the mixtures ranged between 50 ppm and 400 ppm, and those of the S precursors, CS2 and COS, between 5 and 25 ppm. The rate coefficient of the reaction was determined from the observed decay of the S absorption signals for temperatures 1220 K ≤ T ≤ 3460 K. The measured O-atom concentration profiles in COS/O2/Ar reaction systems were evaluated, using simplified kinetic mechanism, to verify the given rate coefficient k5. In experiments with the highest value of the [O2]/[COS] ratio the measured O-atom concentrations were found to be sensitive to the reaction: The fitting of the calculated O-atom profiles to the measured ones results in mean value of: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_6 = 8.0 \times 10^{11} \,{\rm cm}^{\rm 3} \,{\rm mol}^{{\rm - 1}} \,{\rm s}^{{\rm - 1}} $$\end{document} which is to be valid for the temperature range 2570 K ≤ T ≤ 2980 K.A first-order analysis of the observed S absorption decay in LFP shock wave experiments on CS2/Ar gas mixtures resulted in a rate coefficient of the background reaction (R4): for temperatures 1260 K ≤ T ≤ 1820 K. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270108
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  • 8
    Electronic Resource
    Electronic Resource
    A shock tube study of the reaction S + H2 ⇌ SH + H in pyrolysis and photolysis systems (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 547-553 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atomic resonance absorption spectroscopy (ARAS) was applied to measure S atoms, behind shock waves in COS/H2 pyrolysis or CS2/H2 photolysis systems. Both the pyrolysis of COS and the photolysis CS2 was used to generate the S atoms, which subsequently reacts with H2 via the reaction: The photolysis experiments were designed to provide clear first-order conditions for reaction (R3); i.e., the H2 concentration exceeds that of S by at least a factor of 100. The S atom profiles obtained during pyrolysis of highly diluted COS/H2/Ar mixtures were analyzed by computer simulations based on a simplified reaction mechanism using the rate coefficient k3 as a fitting parameter. Both groups of experiments covered the temperature range of 1257 K ≤ T ≤ 3137 K and lead to a rate coefficient of: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 \,\, = \,\,6.0 \times 10^{14} \,{\rm exp}\left({ - 12070{{\rm K} \mathord{\left/ {\vphantom {{\rm K} T}} \right. \kern-\nulldelimiterspace} T}} \right){\rm cm}^{\rm 3} \,{\rm mol}^{ - 1} \,{\rm s}^{ - 1} $$\end{document}. © 1995 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270604
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  • 9
    Electronic Resource
    Electronic Resource
    A shock tube study of the reaction of H atoms with SiCl4 (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 469-472 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of H atoms with SiCl4 was studied behind reflected shock waves at temperatures between 1530 K and 1730 K and pressures around 1.5 bar by applying atomic resonance absorption spectroscopy (ARAS) for time resolved measurements of H atoms at the Lα-line. The thermal decomposition of a few ppm ethyl iodide (C2H5l) was used as a H-atom source. In the presence of a high excess of the molecular reactant SiCl4 a slow consumption of H was observed, which follows a pseudo-first-order rate law. Rate coefficient for the consumption of H by the reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ H+SiCl_4\,{\buildrel{k_1}\over{\longrightarrow}} SiCl_3\,+HCl \eqno(R1) $$\end{document} was determined to be: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1=1.4\times 10^{13}\exp(-4800 K/T) cm^3 mol^{-1} s^{-1}. $$\end{document} © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 469-472, 1997.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    N-Atom measurements in high temperature C2N2/NO/Ar reaction systems (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 35-41 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-atom concentration profiles were measured in highly diluted C2N2/NO/Ar reaction systems behind reflected shock waves at temperatures between 3050 K and 4430 K by applying atomic resonance absorption spectroscopy (ARAS). C2N2 served as a thermal source for CN radical which react with both, NO and the subsequently formed N atoms. Computer simulations based on a simplified reaction mechanism revealed strong sensitivity of the measured N atoms to the elementary reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{cl} \rm{CN} + \rm{NO} {\buildrel{\it k}_5\over\rightleftharpoons} \rm{NCO} + \rm{N} & (\rm{R}5)\\ \rm {CN} + \rm{N} {\buildrel{\it k}_9\over\rightleftharpoons} \rm{C} + \rm{N}_2 & (\rm{R}9)\\ \end{array} $$\end{document} A fitting procedure of all experiments allowed determination of individual values of the rate coefficients: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{lr} \rm {\it k}_5\ =\ 9.6\times 10^{13}\ \exp(-21200K/T)\ cm^3\ mol^{-1}\ s^{-1} & (1)\\ \rm {\it k}_9\ =\ 1.9\ .\ .\ .\ 6.0\times 10^{13}\ cm^3\ mol^{-1}\ s^{-1} & (2)\\ \end{array} $$\end{document} The present results enlarge the temperature range of the recommended Arrhenius expression of k5 |1| and confirm recent measurements of the backward reaction of (R-9) |2,3|. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 35-41, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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