scholarly journals Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

2018 ◽  
Vol 612 ◽  
pp. A83 ◽  
Author(s):  
D. Qasim ◽  
K.-J. Chuang ◽  
G. Fedoseev ◽  
S. Ioppolo ◽  
A. C. A. Boogert ◽  
...  
Keyword(s):  
Surface Reaction ◽  
Oh Radicals ◽  
Quadrupole Mass ◽  
Hydrogen Atoms ◽  
Experimental Conditions ◽  
Interstellar Ice ◽  
Reflection Absorption Infrared Spectroscopy ◽  
Temperature Programmed ◽  
Reaction Chain ◽  
Freeze Out

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods. CH4, O2, and hydrogen atoms are co–deposited in an ultrahigh vacuum chamber at 10–20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption – quadrupole mass spectrometry (TPD–QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results. CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10–20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

scholarly journals Formation of interstellar propanal and 1-propanol ice: a pathway involving solid-state CO hydrogenation

2019 ◽  
Vol 627 ◽  
pp. A1 ◽  
Author(s):  
D. Qasim ◽  
G. Fedoseev ◽  
K.-J. Chuang ◽  
V. Taquet ◽  
T. Lamberts ◽  
...  
Keyword(s):  
Solid State ◽  
Co Hydrogenation ◽  
Theoretical Calculations ◽  
Interstellar Space ◽  
Activation Barriers ◽  
Reflection Absorption Infrared Spectroscopy ◽  
Core Phase ◽  
Temperature Programmed ◽  
Freeze Out

Context. 1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of the primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. Aims. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Methods. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) was used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) was used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Results. Here it is shown that recombination of HCO radicals formed upon CO hydrogenation with radicals formed via C2H2 processing – H2CCH and H3CCH2 – offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain to the formation of larger complex organic molecules. The results are compared with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of <0.35−0.55, which is complemented by computationally derived activation barriers in addition to the experimental results.

The application of resonance enhanced multiphoton ionization to the detection of hydrogen atoms during the oscillatory combustion of hydrogen

1991 ◽  
Vol 434 (1891) ◽  
pp. 399-412 ◽  
Keyword(s):  
Numerical Analysis ◽  
Flow Reactor ◽  
Multiphoton Ionization ◽  
Laser Wavelength ◽  
Time Profile ◽  
Experimental Result ◽  
Oh Radicals ◽  
Hydrogen Atoms ◽  
Experimental Conditions ◽  
Concentration Time

The relative concentrations of hydrogen atoms were measured during the oscillatory ignition of hydrogen in a well stirred flow reactor. Comparisons were made with the experimental concentration—time profiles of the hydroxyl radical obtained previously under similar experimental conditions. The predicted concentration profiles obtained from numerical analysis of a thermokinetic model were also compared with the experimental results. Experiments were performed in a 600 cm 3 Pyrex glass, jet-stirred reactor with the reactants, 2H 2 + O 2 , at a total pressure of 16 Torr ( ca . 2132.8 Pa) and at a vessel temperature of 753 K. The mean residence time was 1.2 s. Oscillatory ignition was established at a period of 3 s in which high radical concentrations were attained and in which the temperature rise was almost adiabatic. The concentration-time profile of hydrogen atoms was obtained by a resonance enhanced multiphoton ionization (rempi) which was induced by a laser pulse at energies in the vicinity of 364 nm, with ion collection at a stainless steel probe inserted into the reactor. Supplementary studies were made to characterize the signals and to identify effects of the probe within the reaction volume. A measurement of the relative concentrations of hydrogen atoms was obtained from an integration of the area of the rempi spectrum determined over the laser wavelength range 363.8-364.6 nm. The spectrum was measured at successive times in the oscillatory cycle by imposing a variable delay on the laser firing signal. The results show that, during oscillatory ignition, the maximum concentration of hydrogen atoms was reached and a sharp decay was already well advanced before that of the hydroxyl radicals was attained. The numerical analysis was in very good quantitative accord with this experimental result. The phase difference of the cyclic variation in the H atoms relative to that of OH radicals is a key feature of the kinetic mechanisms which control the oscillatory oxidation of hydrogen.

scholarly journals Extension of the HCOOH and CO2 solid-state reaction network during the CO freeze-out stage: inclusion of H2CO

2019 ◽  
Vol 626 ◽  
pp. A118 ◽  
Author(s):  
D. Qasim ◽  
T. Lamberts ◽  
J. He ◽  
K.-J. Chuang ◽  
G. Fedoseev ◽  
...  
Keyword(s):  
Solid State ◽  
Solid State Reaction ◽  
Reaction Pathway ◽  
Branching Ratio ◽  
Oh Radicals ◽  
Reaction Products ◽  
Experimental Conditions ◽  
Prestellar Cores ◽  
Molecular Abundances ◽  
Freeze Out

Context. Formic acid (HCOOH) and carbon dioxide (CO2) are simple species that have been detected in the interstellar medium. The solid-state formation pathways of these species under experimental conditions relevant to prestellar cores are primarily based off of weak infrared transitions of the HOCO complex and usually pertain to the H2O-rich ice phase, and therefore more experimental data are desired. Aims. Here, we present a new and additional solid-state reaction pathway that can form HCOOH and CO2 ice at 10 K “non-energetically” in the laboratory under conditions related to the “heavy” CO freeze-out stage in dense interstellar clouds, i.e., by the hydrogenation of an H2CO:O2 ice mixture. This pathway is used to piece together the HCOOH and CO2 formation routes when H2CO or CO reacts with H and OH radicals. Methods. Temperature programmed desorption – quadrupole mass spectrometry (TPD-QMS) is used to confirm the formation and pathways of newly synthesized ice species as well as to provide information on relative molecular abundances. Reflection absorption infrared spectroscopy (RAIRS) is additionally employed to characterize reaction products and determine relative molecular abundances. Results. We find that for the conditions investigated in conjunction with theoretical results from the literature, H + HOCO and HCO + OH lead to the formation of HCOOH ice in our experiments. Which reaction is more dominant can be determined if the H + HOCO branching ratio is more constrained by computational simulations, as the HCOOH:CO2 abundance ratio is experimentally measured to be around 1.8:1. H + HOCO is more likely than OH + CO (without HOCO formation) to form CO2. Isotope experiments presented here further validate that H + HOCO is the dominant route for HCOOH ice formation in a CO-rich CO:O2 ice mixture that is hydrogenated. These data will help in the search and positive identification of HCOOH ice in prestellar cores.

scholarly journals Novel Preparation of Cu and Fe Zirconia Supported Catalysts for Selective Catalytic Reduction of NO with NH3

Catalysts ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 55
Author(s):  
Katarzyna Świrk ◽  
Ye Wang ◽  
Changwei Hu ◽  
Li Li ◽  
Patrick Da Costa ◽  
...  
Keyword(s):  
Selective Catalytic Reduction ◽  
Catalytic Reduction ◽  
Supported Catalysts ◽  
Catalytic Performance ◽  
Experimental Conditions ◽  
One Pot ◽  
Nh3 Scr ◽  
Scr Of No ◽  
Temperature Programmed ◽  
Stationary Sources

Copper and iron promoted ZrO2 catalysts were prepared by one-pot synthesis using urea. The studied catalysts were characterized by XRD, N2 physisorption, XPS, temperature-programmed desorption of NH3 (NH3-TPD), and tested by the selective catalytic reduction by ammonia (NH3-SCR) of NO in the absence and presence of water vapor, under the experimental conditions representative of exhaust gases from stationary sources. The influence of SO2 on catalytic performance was also investigated. Among the studied catalysts, the Fe-Zr sample showed the most promising results in NH3-SCR, being active and highly selective to N2. The addition of SO2 markedly improved NO and NH3 conversions during NH3-SCR in the presence of H2O. The improvement in acidic surface properties is believed to be the cause.

scholarly journals The formation of the building blocks of peptides on interstellar dust grains

2019 ◽  
Vol 15 (S350) ◽  
pp. 216-219
Author(s):  
N. F. W. Ligterink ◽  
J. Terwisscha van Scheltinga ◽  
V. Kofman ◽  
V. Taquet ◽  
S. Cazaux ◽  
...  
Keyword(s):  
Interstellar Dust ◽  
Reaction Network ◽  
Building Blocks ◽  
Dust Grains ◽  
Reaction Products ◽  
Experimental Conditions ◽  
Interstellar Dust Grains ◽  
Temperature Programmed ◽  
Life On Earth ◽  
Emergence Of Life

AbstractThe emergence of life on Earth may have its origin in organic molecules formed in the interstellar medium. Molecules with amide and isocyanate groups resemble structures found in peptides and nucleobases and are necessary for their formation. Their formation is expected to take place in the solid state, on icy dust grains, and is studied here by far-UV irradiating a CH4:HNCO mixture at 20 K in the laboratory. Reaction products are detected by means of infrared spectroscopy and temperature programmed desorption - mass spectrometry. Various simple amides and isocyanates are formed, showing the importance of ice chemistry for their interstellar formation. Constrained by experimental conditions, a reaction network is derived, showing possible formation pathways of these species under interstellar conditions.

scholarly journals Laboratory study on new particle formation from the reaction OH + SO<sub>2</sub>: influence of experimental conditions, H<sub>2</sub>O vapour, NH<sub>3</sub> and the amine tert-butylamine on the overall process

2010 ◽  
Vol 10 (3) ◽  
pp. 6447-6484 ◽  
Author(s):  
T. Berndt ◽  
F. Stratmann ◽  
M. Sipilä ◽  
J. Vanhanen ◽  
T. Petäjä ◽  
...  
Keyword(s):  
Relative Humidity ◽  
High Sensitivity ◽  
Particle Growth ◽  
Counting Efficiency ◽  
Oh Radicals ◽  
Atmospheric Conditions ◽  
Promoting Effect ◽  
Experimental Conditions ◽  
H2so4 Concentration ◽  
Tert Butylamine

Abstract. Nucleation experiments starting from the reaction of OH radicals with SO2 have been performed in the IfT-LFT flow tube under atmospheric conditions at 293±0.5 K for a relative humidity of 13–61%. The presence of different additives (H2, CO, 1,3,5-trimethylbenzene) for adjusting the OH radical concentration and resulting OH levels in the range (4–300)·105 molecule cm−3 did not influence the nucleation process itself. The number of detected particles as well as the threshold H2SO4 concentration needed for nucleation was found to be strongly dependent on the counting efficiency of the used counting devices. High-sensitivity particle counters allowed the measurement of freshly nucleated particles with diameters down to about 1.5 nm. A parameterization of the experimental data was developed using power law equations for H2SO4 and H2O vapour. The exponent for H2SO4 from different measurement series was in the range of 1.7–2.1 being in good agreement with those arising from analysis of nucleation events in the atmosphere. For increasing relative humidity, an increase of the particle number was observed. The exponent for H2O vapour was found to be 3.1 representing a first estimate. Addition of 1.2·1011 molecule cm−3 or 1.2·1012 molecule cm−3 of NH3 (range of atmospheric NH3 peak concentrations) revealed that NH3 has a measureable, promoting effect on the nucleation rate under these conditions. The promoting effect was found to be more pronounced for relatively dry conditions. NH3 showed a contribution to particle growth. Adding the amine tert-butylamine instead of NH3, the enhancing impact for nucleation and particle growth appears to be stronger.

Photon and thermal processing of CH3NH2-bearing ices. Synthesis of prebiotic species at low temperature (such as formamide, ethylamine, and methylcyanide), and N-heterocycles during warm up.

2021 ◽  
Author(s):  
Héctor Carrascosa ◽  
Cristóbal González Díaz ◽  
Guillermo M. Muñoz Caro ◽  
Pedro C. Gómez ◽  
María Luz Sanz
Keyword(s):  
Vacuum Chamber ◽  
Organic Molecules ◽  
Solid Phase ◽  
High Vacuum ◽  
Ultra High Vacuum ◽  
Quadrupole Mass ◽  
Warm Up ◽  
Methyl Cyanide ◽  
Interstellar Ice ◽  
Complex Organic

&lt;p&gt;Hexamethylentetramine has drawn a lot of attention due to its potential to produce prebiotic species. This work aims to gain a better understanding in the chemical processes concerning methylamine under astrophysically relevant conditions. In particular, this work deeps into the formation of N-heterocycles in interstellar ice analogs exposed to UV radiation, which may lead to the formation of prebiotic species.&lt;/p&gt; &lt;p&gt;Experimental simulations of interstellar ice analogs were carried out in ISAC. ISAC is an ultra-high vacuum chamber equipped with a cryostat, where gas and vapour species are frozen forming ice samples. Infrared and ultraviolet spectroscopy were used to monitor the solid phase, and quadrupole mass spectrometry served to measure the composition of the gas phase. The variety of species detected after UV irradiation of ices containing&amp;#160; methylamine revealed the presence of 12 species which have been already detected in the ISM, being 4 of them typically classified as complex organic molecules: formamide (HCONH&lt;sub&gt;2&lt;/sub&gt;), methyl cyanide (CH&lt;sub&gt;3&lt;/sub&gt;CN), CH&lt;sub&gt;3&lt;/sub&gt;NH and CH&lt;sub&gt;3&lt;/sub&gt;CHNH. Warming up of the irradiated CH&lt;sub&gt;3&lt;/sub&gt;NH&lt;sub&gt;2&lt;/sub&gt;-bearing ice samples lead to the formation of trimethylentriamine (TMT), a N-heterocycle precursor of HMT, and the subsequent synthesis of HMT at temperatures above 230 K.&lt;/p&gt;

Sign in / Sign up

Export Citation Format

Share Document