An official website of the United States government
Abstract Here, we used a combination of laser‐induced experiments and density functional theory (DFT) calculations to study the mechanism of growth of carbonaceous species on the Mg surface. Experimental observations revealed that the carbon deposit forms upon laser illumination on the Mg surface, with the deposit being clearer and better structured in the presence of 1,3‐butadiene (C4H6) compared to ethylene (C2H4) gas. DFT thermodynamic and kinetic calculations of C2−C4hydrocarbons interaction on low‐index Mg(0001) were used to explain this experimental observation. Our results on Mg(0001) showed that the cis isomer of C4H6binds more strongly than its trans isomer via a [4+2] cycloaddition mechanism. We also investigated the adsorption of two units of C2H4and C4H6molecules, as well as the subsequent dehydrogenation stages that produce radical species responsible for chain growth mechanisms. The results showed that free energy change of dehydrogenation of two units of cis‐C4H6[i. e. cis‐C8H12] is lower than the dehydrogenation of trans conformer of C4H6and C2H4molecule, indicating that the dehydrogenation of two units of cis‐C4H6facilitates the initiation of growth of carbonaceous species on Mg surfaces. Therefore, the DFT calculations pinpoint the origin of the experimental observation of clearer carbon deposits on the Mg surface.
more »
« less
Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes
Abstract The current work presents new experimental autoignition and speciation data on the twocis‐hexene isomers:cis‐2‐hexene andcis‐3‐hexene. The new data provide insights on the effects of carbon‐carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure‐time histories. Stoichiometric (ϕ = 1.0) mixtures at dilution levels of inert gas to O2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted atT = 900 K for the twocis‐hexene isomers, where fast‐gas sampling and gas chromatography were used to identify and quantify the twocis‐hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon‐carbon double bond and the stereoisomeric structure (cis‐trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2‐hexene showed strong selectivity to propene, acetaldehyde, and 1,3‐butadiene, and 3‐hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. There was generally good agreement for the model predictions of the species data for 2‐hexene; however, the mechanism overpredicted some of the small aldehyde (C2‐C4) species for 3‐hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H‐atom abstraction reactions at the conditions studied (P = 11 atm,T > 900 K), and not by C3‐C4scission as observed in high‐temperature (>1300 K) hexene ignition studies. Improved estimates for 3‐hexene + OH reactions may improve model predictions for the species measured in this work.
more »
« less
- Award ID(s):
- 1701343
- PAR ID:
- 10454750
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- International Journal of Chemical Kinetics
- Volume:
- 53
- Issue:
- 2
- ISSN:
- 0538-8066
- Page Range / eLocation ID:
- p. 287-298
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Poly- and Perfluorinated alkyl substances (PFAS) pose environmental and public health concerns. While incineration remains the most common PFAS remediation method, the complete combustion and pyrolysis mechanism of PFAS is unknown. This study aims to expand our understanding of the kinetics of gas-phase PFAS incineration by measuring the effect of difluoromethane (CHF) on propane ignition delay times (IDTs). The ignition delay times were measured by OH* emission and end-wall pressure time histories behind the reflected shock wave. Different concentrations of CH2F2 were mixed with fuel-lean propane-oxygen mixtures diluted in argon. Experiments were conducted at a nominal reflected shock pressure of P5 = 1 atm and reflected shock temperatures of 1200 < T5 < 1800 K. A new detailed chemical kinetic mechanism is presented. 135 new rate constants were computed using RRKM/ME theory, based upon stationary points computed using ANL0. The new mechanism is in excellent agreement with the measured ignition delay time. A novel sensitivity analysis helps to explain the elementary steps by which CH2F2 increases the ignition delay time.more » « less
-
Context. Evidence that the chemical characteristics around low- and high-mass protostars are similar has been found: notably, a variety of carbon-chain species and complex organic molecules (COMs) form around both types. On the other hand, the chemical compositions around intermediate-mass (IM) protostars (2M⊙<m*< 8M⊙) have not been studied with large samples. In particular, it is unclear the extent to which carbon-chain species form around them. Aims. We aim to obtain the chemical compositions of a sample of IM protostars, focusing particularly on carbon-chain species. We also aim to derive the rotational temperatures of HC5N to confirm whether carbon-chain species are formed in the warm gas around these stars. Methods. We conducted Q-band (31.5–50 GHz) line survey observations toward 11 mainly IM protostars with the Yebes 40 m radio telescope. The target protostars were selected from a subsample of the source list of the SOFIA Massive Star Formation project. Assuming local thermodynamic equilibrium, we derived the column densities of the detected molecules and the rotational temperatures of HC5N and CH3OH. Results. Nine carbon-chain species (HC3N, HC5N, C3H, C4Hlinear-H2CCC,cyclic-C3H2, CCS, C3S, and CH3CCH), three COMs (CH3OH, CH3CHO, and CH3CN), H2CCO, HNCO, and four simple sulfur-bearing species (13CS, C34S, HCS+, and H2CS) are detected. The rotational temperatures of HC5N are derived to be ~20–30 K in three IM protostars (Cepheus E, HH288, and IRAS 20293+3952). The rotational temperatures of CH3OH are derived in five IM sources and found to be similar to those of HC5N. Conclusions. The rotational temperatures of HC5N around the three IM protostars are very similar to those around low- and high-mass protostars. These results indicate that carbon-chain molecules are formed in lukewarm gas (~20–30 K) around IM protostars via the warm carbon-chain chemistry process. Thus, carbon-chain formation occurs ubiquitously in the warm gas around protostars across a wide range of stellar masses. Carbon-chain molecules and COMs coexist around most of the target IM protostars, which is similar to the situation for low- and high-mass protostars. In summary, the chemical characteristics around protostars are the same in the low-, intermediate- and high-mass regimes.more » « less
-
The structural diversity of lipids presents significant challenges for accurate identification and characterization, ne-cessitating advanced analytical tools. Among these challenges is the differentiation between cis and trans isomers of lipids, which differ only by the geometry of a carbon-carbon double bond. This study employs ozonolysis kinetics to distinguish these isomers based on the reactivity of their gas phase ions with ozone. To achieve precise differentia-tion, it is essential to use an ion adduct that enhances reactivity, thereby improving the sensitivity of the kinetic assays. We evaluated various ion types, including protonated lipids as well as lipids cationized with lithium, sodium, and potassium, using a modified quadrupole ion trap mass spectrometer. Our results demonstrate that lithium-adducted lipids exhibit the highest reaction efficiency and greatest sensitivity for distinguishing between cis and trans isomers. Subsequent analysis of cis and trans isomer mixtures of PC 18:1/18:1 (Δ9), PC 16:1/16:1 (Δ9), and PC 14:1/14:1 (Δ9) confirmed the method's robustness.more » « less
-
Abstract The catalytic one‐bond isomerization (transposition) of 1‐alkenes is an emerging approach toZ‐2‐alkenes. Design of more selective catalysts would benefit from a mechanistic understanding of factors controllingZselectivity. We propose here a reaction pathway forcis‐Mo(CO)4(PCy3)(piperidine) (3), a precatalyst that shows highZselectivity for transposition of alpha olefins (e. g., 1‐octene to 2‐octene, 18 : 1Z : Eat 74 % conversion). Computational modeling of reaction pathways and isotopic labeling suggests the isomerization takes place via an allyl (1,3‐hydride shift) pathway, where oxidative addition offac‐(CO)3Mo(PCy3)(η2‐alkene) is followed by hydride migration from one position (cisto allyl C3carbon) to another (cisto allyl C1carbon) via hydride/CO exchanges. Calculated barriers for the hydride migration pathway are lower than explored alternative mechanisms (e. g., change of allyl hapticity, allyl rotation). To our knowledge, this is the first study to propose such a hydride migration in alkene isomerization.more » « less
