The gas-phase oxidation of n-butane has been studied in an atmospheric jet-stirred reactor (JSR) at temperatures up to 950 K. For the first time, continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared has been used, together with gas chromatography (GC), to analyze the products formed during its oxidation. In addition to the quantification of formaldehyde and water, which is always difficult by GC, cw-CRDS allowed as well the quantification of hydrogen peroxide (H2O2). A comparison of the obtained mole fraction temperature profiles with simulations using a detailed gas-phase mechanism shows a good agreement at temperatures below 750 K, but an overestimation of the overall reactivity above this temperature. Also, a strong overestimation was found for the H2O2 mole fraction at higher temperatures. In order to improve the agreement between model and experimental results, two modifications have been implemented to the model: (a) the rate constant for the decomposition of H2O2 (+M) ↔ 2OH (+M) has been updated to the value recently proposed by Troe (Combust. Flame, 2011, 158, 594-601) and (b) a temperature dependent heterogeneous destruction of H2O2 on the hot reactor walls with assumed rate parameters has been added. The improvement (a) slows down the overall reactivity at higher temperatures, but has a negligible impact on the maximal H2O2 mole fraction. Improvement (b) has also a small impact on the overall reactivity at higher temperatures, but a large effect on the maximal H2O2 mole fraction. Both modifications lead to an improved agreement between model and experiment for the oxidation of n-butane in a JSR at temperatures above 750 K.

Context. Most exoplanets detected so far have atmospheric temperatures significantly higher than 300 K. Often close to their star, they receive an intense UV photons flux that triggers important photodissociation processes. The temperature dependency of vacuum ultraviolet (VUV) absorption cross sections are poorly known, leading to an undefined uncertainty in atmospheric models. Similarly, data measured at low temperatures similar to those of the high atmosphere of Mars, Venus, and Titan are often lacking. Aims. Our aim is to quantify the temperature dependency of the VUV absorption cross sections of important molecules in planetary atmospheres. We want to provide high-resolution data at temperatures prevailing in these media, and a simple parameterisation of the absorption in order to simplify its use in photochemical models. This study focuses on carbon dioxide (CO 2 ). Methods. We performed experimental measurements of CO 2 absorption cross sections with synchrotron radiation for the wavelength range (115-200 nm). For longer wavelengths (195-230 nm), we used a deuterium lamp and a 1.5 m Jobin-Yvon spectrometer. We used these data in our one-dimensional (1D) thermo-photochemical model in order to study their impact on the predicted atmospheric compositions. Results. The VUV absorption cross section of CO 2 increases with the temperature. The absorption we measured at 150 K seems to be close to the absorption of CO 2 in the fundamental ground state. The absorption cross section can be separated into two parts: a continuum and a fine structure superimposed on the continuum. The variation in the continuum of absorption can be represented by the sum of three Gaussian functions. Using data at high temperature in thermo-photochemical models significantly modifies the abundance and the photodissociation rates of many species in addition to CO 2 , such as methane and ammonia. These deviations have an impact on synthetic transmission spectra, leading to variations of up to 5 ppm. Conclusions. We present a full set of high-resolution (∆λ = 0.03 nm) absorption cross sections of CO 2 from 115 to 230 nm for temperatures ranging from 150 to 800 K. A parameterisation allows us to calculate the continuum of absorption in this wavelength range. Extrapolation at higher temperature has not been validated experimentally and therefore should be used with caution. Similar studies on other major species are necessary to improve our understanding of planetary atmospheres.