Hydrogen Peroxide Decomposition Rate: A Shock Tube Study Using Tunable Laser Absorption of H₂O near 2.5 μm

Abstract

The thermal decomposition of hydrogen peroxide was measured behind reflected shock waves in hydrogen peroxide/inert gas mixtures using a sensitive laser diagnostic for water vapor. In these mixtures, the formation rate of water is predominantly controlled by the decomposition rate of hydrogen peroxide. Rate determinations were made over a temperature range of 1000-1200 K and a pressure range of 0.9-3.2 atm for both argon and nitrogen carrier gases. Good detection sensitivity for water was achieved using tunable diode laser absorption of water at 2550.96 nm within its v(3) fundamental band. Hydrogen peroxide decomposition rates were found to be independent of pressure at 0.9 and 1.7 atm and showed only slight influence of pressure at 3.2 atm. The best fit of the current data to the low-pressure-limit rate for H(2)O(2) dissociation in argon bath gas is k(1,0) = 10(15.97+/-0.10) exp(-21 220 +/- 250 K/T) [cm(3) mol(-1) s(-1)] (1000-1200 K). Experiments conducted in a nitrogen bath gas show a relative collision efficiency of argon to nitrogen of 0.67.

Comprehensive H2/O2 kinetic model for high‐pressure combustion

“…Both studies [93,94] fitted E values to match available experimental data. Troe [94] regards that the two theoretical studies [93,94] represent the experimental data within their scatter equally well, though we find that predictions of the present model using k 15 from Troe [94] yield better agreement than that of Sellevåg et al [93] with the experimental data of Hong et al [87,92] at combustion-relevant temperatures. In fact, predictions of the present model that use the k 15 expression from Troe [94] actually represent the experimental data of Hong et al [87,92] better than predictions of the present model that use the k 15 expression that Hong et al derive from their data (see Fig.…”

“…The validation set here includes the full validation set from our previous models [12,47] as well as more recent measurements that have become available since the publication of the model of Li et al [12]; many of these newly available measurements focus on high-pressure, low-temperature conditions. For example, new measurements have become available for speciation during H 2 oxidation [42], H 2 O reaction with O 2 [71], and H 2 O 2 decomposition [87,92]; ignition delay times in shock tubes [10] and rapid compression machines (RCM) [11]; and flame speeds and mass burning rates [5][6][7][8][9].…”

IR laser absorption diagnostic for C2H4 in shock tube kinetics studies

“…Incident shock speeds were extrapolated to the end wall by measuring the incident shock arrival times using five piezoelectric pressure transducers (PCB 134) spread over the last meter of the driven section. Temperatures and pressures behind the reflected shock waves were calculated using standard normal-shock relations and the measured incident shock speed, with an uncertainty of ∼1% over the high-quality test time of 2 ms [13]. The laser diagnostic, along with a Kistler piezoelectric pressure transducer (601B1) for pressure measurements, was located in the test section at 2 cm from the end wall.…”

“…In future work, the H 2 O concentration during hydrocarbon oxidation could be measured directly and accurately using tunable diode laser absorption near 2.5 μm, a method which has been developed and widely applied in shock tube studies of H 2 /O 2 combustion system in our laboratory [13,23,24]. Alternatively, a second CO 2 line (i.e., the P(28) transition at 10.675 μm), which is away from the peak ethylene absorption, could be selected to account for the H 2 O interfering absorbance.…”

Bayesian optimal experimental design for the Shock-tube experiment

“…Given our assumption that the model discrepancy is not time dependent we choose five data points where the level of the error is assumed to be constant. The detailed description of the shock tube experiment is provided in [5].…”