Dynamics of Excited Hydroxyl Radicals in Hydrogen Based Mixtures Behind Reflected Shock Waves. Supplemental material
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1 Dynamics of Excited Hydroxyl Radicals in Hydrogen Based Mixtures Behind Reflected Shock Waves Proceedings of the Combustion Institute 34, 22 Supplemental material R. MÉVEL, S. PICHON, L. CATOIRE, N. CHAUMEIX, C.-E. PAILLARD and J.E. SHEPHERD The present section provides some complementary results which were not included in the manuscript because of size restriction. Results and discussion Hydrogen peroxide-water vapour mixtures Comparison of experimental and calculated profiles. Rate of production of OH and OH* radicals..8 H2O2+M=OH+OH+M HO2+OH=H2O+O2 H2O2+OH=H2O+HO Normalized ROP H+O+M=OH*+M OH*+Ar=OH+Ar Normalized profiles Excited OH* Fundamental OH Time (µs) Figure S: Rates of production, ROP, for OH* and OH (top) and experimental emission and calculated OH* and OH profiles (bottom) for a H 2 -H 2 O 2 -H 2 O-Ar mixture. Conditions: X H2 =. ; X H2O2 =.5527 ; X H2O =.4473 ; X Ar =.98 ; T 5 =45 K; P 5 =3 kpa.
2 Temperature and temperature gradient profiles. Energy release rate per reaction analysis. Temperature (K) Temperature gradient Temperature Normalized dt/dt Normalized energy profile H2O2+M=OH+OH+M HO2+OH=H2O+O2 H2O2+OH=H2O+HO Time (µs) Figure S2: Calculated temperature and temperature gradient profile (top) and normalized energy release rates per reaction (bottom) for a H 2 -H 2 O 2 -H 2 O-Ar mixture. Conditions: X H2 =. ; X H2O2 =.5527 ; X H2O =.4473 ; X Ar =.98 ; T 5 =45 K; P 5 =3 kpa. Hydrogen-nitrous oxide(-oxygen) mixtures Comparison of experimental and calculated profiles. Rate of production of OH and OH* radicals. Normalized ROP OH+H2=H2O+H O+H2=H+OH H+O2=O+OH N2O+H=N2+OH H+O+M=OH*+M OH*+H2O=OH+H2O Normalized profiles P5= 298 kpa T5= 58 K Mixture 9 Experimental Excited OH* Fundamental OH Time (µs) Figure S3: Rates of production, ROP, for OH* and OH (top) and experimental emission and calculated OH* and OH profiles (bottom) for a H 2 -O 2 -N 2 O-Ar mixture.
3 Temperature and temperature gradient profiles. Energy release rate per reaction analysis. Temperature (K) P5= 298 kpa T5= 58 K Mixture 9 Temperature gradient Temperature Normalized dt/dt Normalized energy profile.8.4 H+O2=O+OH N2O+H=N2+OH OH+H2=H2O+H Time (µs) Figure S4: Calculated temperature and temperature gradient profile (top) and normalized energy release rates per reaction (bottom) for a H 2 -O 2 -N 2 O-Ar mixture.
4 Comparison between [OH*] Full_Model and [OH*] Steady_State Hydrogen-oxygen mixtures x OH* full model OH* steady state OH* concentration [mole/cm 3 ] Time [µs] Figure S5: Comparison between the OH* concentrations obtained with the detailed reaction model and with the QSSA for a H 2 -O 2 -Ar mixture. Conditions: X H2 =.2 ; X O2 =. ; X Ar =.97 ; T=45 K; P=33 kpa. Hydrogen peroxide-water vapour mixtures.9 x -7 OH* full model OH* steady state.8 OH* concentration [mole/cm 3 ] Time [µs] Figure S6: Comparison between the OH* concentrations obtained with the detailed reaction model and with the QSSA for a H 2 O 2 -H 2 O-Ar mixture. Conditions: X H2O2 =.55 ; X H2O =.45 ; X Ar =.99 ; T=2 K; P=33 kpa.
5 Hydrogen-nitrous oxide mixtures x -6 OH* full model OH* steady state OH* concentration [mole/cm 3 ] Time [µs] Figure S7: Comparison between the OH* concentrations obtained with the detailed reaction model and with the QSSA for a H 2 -N 2 O-Ar mixture. Conditions: X H2 =.; X N2O =.; X Ar =.98; T=65 K; P=33 kpa. Hydrogen-nitrous oxide-oxygen mixtures 6 x -5 5 OH* full model OH* steady state OH* concentration [mole/cm 3 ] Time [µs] Figure S8: Comparison between the OH* concentrations obtained with the detailed reaction model and with the QSSA for a H 2 -N 2 O-O 2 -Ar mixture.. Conditions: X H2 =.; X O2 =.5; X N2O =.5; X Ar =.98; T=8 K; P=33 kpa.
6 Comparison between several reaction models List of reaction model tested In each model, a sub-model for OH* chemistry was added for direct comparison with ignition delay time derived from emission at 36 nm. Stanford: Hong Z., Davidson D.F. and Hanson R.K., An improved H 2 /O 2 mechanism based on recent shock tube/laser absorption measurements, Combustion and Flame 58 (2) USC: Wang H., Xiaoqing Y., Ameya V.J., Davis G.D., Laskin A., Egolfopoulos F. and Law C.K., USC Mech Version II. High-temperature combustion reaction model of H 2 /CO/C -C 4 compounds. Available at: GRI: Smith G., Golden D., Frenklach M., Moriarty N., Eiteneer B., Goldenberg M., Bowman C., Hanson R., Song S., Gardiner W., Lissianski V., and Qin Z., GRI-mech release 3. Dagaut: Le Cong T., Etude expérimentale et modélisation de la cinétique de combustion de combustibles gazeux : Méthane, gaz naturel et mélanges contenant de l'hydrogène, du monoxyde de carbone, du dioxyde de carbone et de l'eau, Université d'orléans, 27, 257 p. Konnov: Konnov A., Detailed reaction mechanism for small hydrocarbons combustion. Release.5., 2. Present study: Mével R., Javoy S., Lafosse F., Chaumeix N., Dupré G., and Paillard C.-E., Hydrogen-nitrous oxide delay time: shock tube experimental study and kinetic modeling, Proceedings of The Combustion Institute, 29, 32, Mével R., Javoy S., and Dupré G., A chemical kinetic study of the oxidation of silane by nitrous oxide, nitric oxide and oxygen, Proceedings of The Combustion Institute, 2, 33, Pichon S., Etude cinétique de systèmes hypergoliques et propergoliques à base d'éthanol et de peroxide d'hydrogène, Université d'orléans, 25, 25 p.
7 Hydrogen peroxide-water vapor mixtures Mixtures: - N 6: X H2O2 =.5527; X H2O =.4473; X Ar = N 7: X H2O2 =.27635; X H2O =.22365; X Ar =.995. Delay-time definitions: The delay-times are defined as the times to 5% and % of emission maximum. Stanford model: Mean error =59 % Figure S9: Experimental and calculated (Stanford) 5% and % for H 2 O 2 -H 2 O-Ar mixtures. USC model: Mean error =3 % Figure S: Experimental and calculated (USC) 5% and % for H 2 O 2 -H 2 O-Ar mixtures.
8 GRI model: Mean error =87 % Figure S: Experimental and calculated (GRI) 5% and % for H 2 O 2 -H 2 O-Ar mixtures. Dagaut model: Mean error =85 % Figure S2: Experimental and calculated (Dagaut) 5% and % for H 2 O 2 -H 2 O-Ar mixtures.
9 Konnov model: Mean error =86 % Figure S3: Experimental and calculated (Konnov) 5% and % for H 2 O 2 -H 2 O-Ar mixtures. Present model: Mean error =38 % Figure S4: Experimental and calculated (Mevel) 5% and % for H 2 O 2 -H 2 O-Ar mixtures.
10 Hydrogen-oxygen mixtures Mixtures: - N : X H2 =.69; X O2 =.8; X Ar = N 2: X H2 =.2; X O2 =.5; X Ar =.975. Delay-time definition: The delay-time is defined as time to emission onset. Stanford model: Mean error =55 % Figure S5: Experimental and calculated (Stanford) onset for H 2 -O 2 -Ar mixtures. USC model: Mean error =42 % Figure S6: Experimental and calculated (USC) onset for H 2 -O 2 -Ar mixtures.
11 GRI model: Mean error =6 % Figure S7: Experimental and calculated (GRI) onset for H 2 -O 2 -Ar mixtures. Dagaut model: Mean error =28 % Figure S8: Experimental and calculated (Dagaut) onset for H 2 -O 2 -Ar mixtures.
12 Konnov model: Mean error =3 % Figure S9: Experimental and calculated (Konnov) onset for H 2 -O 2 -Ar mixtures. Present model: Mean error =3 % Figure S2: Experimental and calculated (Mevel) onset for H 2 -O 2 -Ar mixtures.
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