Hydrocarbon Molecules Research Articles

Association and diffusion of cationic and nonionic surfactants with hydrocarbon molecules as a model for enhanced oil recovery

The association mechanisms and diffusion of surfactants with oil in an aqueous medium are studied using mesoscale numerical simulations. The types of surfactants modeled, one cationic and one nonionic, are chosen because they are known to be effective in coreflood experiments, among other applications. A novel molecular oil model is introduced, consisting of five types of light hydrocarbons, ranging from pentane to octane, and three heavy hydrocarbon molecules, namely decane, pentadecane, and icosane. It is found that the association mechanisms of the surfactants with oil differ markedly between the cationic and nonionic cases. While in the former, a single complex agglomerate is formed, trapping all oil components, in the latter, several oil droplets surrounded by the surfactants’ tails are produced. To test the mobility of these aggregates, their diffusion coefficients are predicted as the surfactant concentration increases. The diffusion of the agglomerate composed of oil and cationic surfactants is an order of magnitude greater than that of the oil-nonionic surfactant droplets. It is concluded that the cationic surfactant can encapsulate oil molecules and increase their diffusion more efficiently than the nonionic one, at the same concentration. The implications of our findings are discussed in the context of current research and applications.

Investigation on the Hydrothermal Condition in Synthesis of Active Matrix from Metakaolin: Physicochemical Properties and Intrinsic Cracking Activities

The current trends in research and development of FCC catalyst is focused on the formulation of active matrices that serve as pre-crackers, with the objective of reducing the diffusional resistance of the longer chain hydrocarbon molecule in the feed. In this study, an aluminosilicate active matrix was synthesised from metakaolin using hydrothermal method. The experimental variables that were varied were hydrothermal temperature, in the range of 80 to 110 °C, and hydrothermal time, in the range of 12 to 72 hours, to investigate the best conditions for synthesising the active matrix. Subsequently, the active matrix was subjected to a series of analyses, including X-ray fluorescence, X-ray diffraction, N2 physisorption, NH3-temperature programmed desorption, Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetry, with the objective of determining its composition, crystal characteristics, surface characteristics, acidity, functional groups, material structure, and thermal characteristics. Additionally, the active matrix was tested for its intrinsic cracking activity using the micro activity test (MAT). The results indicate that the best temperature for hydrothermal synthesis of the active matrix is 80 °C. The active matrix synthesised with a heating time of 24 hours demonstrated the highest light cycle oil yield, reaching 38.9 wt%. Meanwhile, the active matrix synthesised at 48 hours exhibited the most favourable characteristics, with a specific surface area of 144.23 m2/g and a pore volume of 0.9933 cm3/g, as well as the highest cracking conversion of 70.0 wt%. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Experimental Investigation and Chemical Kinetics Analysis of Carbon Dioxide Inhibition on Hydrogen-Enriched Liquefied Petroleum Gas (LPG) Explosions

The utilization of hydrogen-enriched liquefied petroleum gas (LPG) is an effective means of reducing carbon emissions, but the special physical and chemical properties of hydrogen have raised concerns among the public. To delve into the intricate chemical kinetic mechanisms governing the inhibitory effect of CO2 on the explosion of hydrogen-enriched LPG, this study systematically investigated the influence of varying CO2 concentrations (3%, 6%, and 9%) on the explosion characteristics of hydrogen-enriched LPG (hydrogen ratio ranging from 0 to 0.5) within a 20 L spherical explosion chamber. Subsequently, a chemical kinetic analysis was conducted, focusing on the explosion reaction dynamics of the H2/LPG/CO2/Air mixture, encompassing temperature sensitivity assessments and the production rates of key free radicals. The findings reveal that although hydrogen incorporation does not significantly alter the maximum explosion pressure of LPG, it markedly accelerates the explosion reaction rate, posing a challenge for CO2 in effectively inhibiting the explosion of hydrogen-enriched LPG. CO2 functions as a stabilizing third body within the reaction system, diminishing the collision frequency among free radicals, hydrogen molecules, hydrocarbon molecules, and oxygen molecules, thereby slowing down the reaction rate. As the proportion of hydrogen increases, the concentration of ·H radicals, known for their high reactivity, escalates, rapidly completing the propagation phase of the chain reaction and intensifying the overall generation rates of critical free radicals, including ·H, ·O, and ·OH. Notably, the key reaction H+O2⇋O+OH, which governs the reaction temperature, undergoes significant enhancement, further accelerating the explosion reaction rate and ultimately diminishing the inhibitory efficacy of CO2 against the hydrogenated LPG explosion. Furthermore, as the amount of hydrogen added increases, hydrogen’s competitiveness for oxygen within the reaction system markedly improves, attenuating the oxidation of hydrocarbons. Concurrently, the alkane recombination reaction, exemplified by C3H6+CH3(+M)⇋sC4H9(+M), is strengthened. These insights provide valuable understanding of the complex interactions and mechanisms during the explosion of hydrogen-enriched LPG in the presence of CO2, with implications for the safe application of hydrogen-enriched LPG.

Advancing the development of supersonic natural gas liquefaction through understanding heavy hydrocarbon crystallization mechanism

During supersonic natural gas liquefaction, the solidification of heavy hydrocarbon molecules can be used to improve the efficiency of the liquefaction. This study investigates the supersonic crystallization of n-hexane using an experimental system designed by ourself for precise measurement of liquid heavy hydrocarbon vaporization. The results demonstrate that n-hexane gas condenses rapidly 1.5 cm downstream of the nozzle throat, releasing significant latent heat. The subsequent crystallization of these droplets transitions the substance fully from liquid to solid, and the latent heat released during crystallization is much lower than that during condensation. Under different conditions, we found that higher partial pressures intensify n-hexane crystallization, accelerating liquid phase growth despite slower solid phase mass increase. Furthermore, larger nozzle expansion ratios shorten the time and space distribution of the liquid phase mass fraction. Molecular dynamics simulations reveal n-hexane’s melting and surface crystallization temperatures to be approximately 160 ± 1 K and 158 ± 1 K, respectively, with a supercooling degree of 2 K, explaining the observed crystallization behavior in supercooled droplets.

Vuv/vis absorption spectroscopy of different PAHs

AbstractThe present study provides new solid-phase absorption data of different Polycyclic Aromatic Hydrocarbon (PAHs) molecules in the Far Ultraviolet (FUV) and UV/Visible regions. Two features of interstellar extinction curves fall in this region: the FUV rise and the UV bump. Here, thin films of PAHs were prepared by means of the spin coating method onto a transparent substrate, and their solid phase absorption spectra were recorded. Spectra of isolated molecules simulated by Time-Dependent Density Functional Theory (TD-DFT) calculations were also produced for comparison. The results fit quite well with the FUV rise but not with the UV bump. Given the scarcity of FUV experimental absorption data of PAHs in the literature and especially in solid phase, these results are also interesting for reference for other studies ranging from thin films applications to interstellar medium models.

Where Have All the Sulfur Atoms Gone? Polycyclic Aromatic Hydrocarbon as a Possible Sink for the Missing Sulfur in the Interstellar Medium. I. The C–S Band Strengths

Despite its biogenic and astrochemical importance, sulfur (S), the 10th most abundant element in the interstellar medium (ISM) with a total abundance of S/H ≈ 2.2 × 10−5, largely remains undetected in molecular clouds. Even in the diffuse ISM where S was previously often believed to be fully in the gas phase, in recent years, observational evidence has suggested that S may also be appreciably depleted from the gas. What might be the dominant S reservoir in the ISM remains unknown. Solid sulfides like MgS, FeS, and SiS2 are excluded as major S reservoirs due to the nondetection of their expected infrared spectral bands in the ISM. In this work, we explore the potential role of sulfurated polycyclic aromatic hydrocarbon (PAH) molecules—PAHs with sulfur heterocycles (PASHs)—as a sink for the missing S. Utilizing density function theory, we compute the vibrational spectra of 18 representative PASH molecules. It is found that these molecules exhibit a prominent C–S stretching band at ∼10 μm and two relatively weak C–S deformation bands at 15 and 25 μm that are not mixed with the nominal PAH bands at 6.2, 7.7, 8.6, 11.3, and 12.7 μm. If several parts per million of S (relative to H) are locked up in PAHs, the 10 μm C–S band would be detectable by Spitzer and the James Webb Space Telescope (JWST). To quantitatively explore the amount of S/H depleted in PASHs, a detailed comparison of the infrared emission spectra of PASHs with the Spitzer and JWST observations is needed.

The impact of hetero-aromatic rings on optoelectronic and charge transport properties of fused polycyclic compounds

The structural, optoelectronic, and charge-transport properties of linearly fused polycyclic hydrocarbon molecules with heteroatoms (NH, O, S, and Se) in five-membered rings have been investigated using the DFT approach. The hybrid functional B3LYP in combination with the 6–311 + G (d,p) basis set is utilized in the Gaussian 16 W software package for all the calculations. The absorption and emission energies are investigated by using time-dependent density functional theory (TD-DFT) at the same level of theory. To investigate the stability of each molecule concerning its aromaticity, nucleus-independent chemical shift (NICS) values are computed. Electron affinity (EA), hole extraction potential (HEP), ionization potential (IP), and electron extraction potential (EEP) are also reported. The simulated hole (λ h) and electron (λ e) reorganization energies for the majority of the molecules are lower than the characteristics hole and electron-transporting materials. The reported fused polycyclic compounds may have potential applications in optoelectronic devices.

Hydrogen Evolution Reactions of Hydrocarbons and Hydroborons Promoted by Superatomic Nbn- Clusters.

Hydrogen evolution reactions (HER) are crucial for producing renewable and ecological hydrogen energy. Here we report the finding that ethyl acetylene (C2H2), borane (B2H6), and benzene (C6H6) undergo drastic dehydrogenation reactions upon interaction with niobium cluster anions (Nbn-). This finding was enabled by our very sensitive and specialized mass spectrometer, which monitored the cluster ions and the resulting metal carbide and boride products in real time. Through mass spectrometry experiments and density functional theory computations, we delved into the varying reactivities of these common gas molecules with small Nbn- clusters and elucidated the underlying reaction mechanisms. These findings shed light on the HER mechanisms of hydrocarbon and hydroboron molecules on superatomic Nbn- clusters, furnishing valuable insights pertinent to the advancement of hydrogen energy resources.

Photoelectron spectroscopy of deprotonated benzonitrile.

The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]-). The adiabatic detachment energy was determined as 1.70 ± 0.01eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm-1 ring deformation mode. [Bzn-H]- lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]- is unlikely to be stable in many interstellar environments.

Development of GC–MS coupled to GC–FID method for the quantification of cannabis terpenes and terpenoids: Application to the analysis of five commercial varieties of medicinal cannabis

Cannabis terpenes and terpenoids are among the major classes of pharmacologically active secondary metabolites of therapeutic interest. Indeed, these hydrocarbon molecules, responsible for the characteristic aroma of cannabis flowers, are thought to be involved in a synergistic effect known as the “entourage effect”, together with cannabinoids. Numerous analytical studies have been carried out to characterize the terpene and terpenoid contents of some cannabis varieties, but they have not proposed any real quantification or have described a limited number of analytical standards or average response factors, which may have led to over- or underestimation of the real content of the cannabis flowers. Real and reliable quantification is necessary to justify the entourage effect. Here, we report a rigorous and precise GC–FID and GC–MS method for the identification and quantification of cannabis terpenes and terpenoids. This method is distinguished by the use of a high number of analytical standards, the determination of retention indices for all compounds studied, an exhaustive comparison of databases and scientific literature, the use of relevant response factors, and internal calibration for reliable results. It was applied to the study of terpenic compounds in five commercial varieties of medicinal cannabis produced by Bedrocan International: a CBD-rich (Bedrolite®), a THC/CBD balanced (Bediol®), and three THC-dominant (Bedrocan®, Bedica® and Bedrobinol®). Two extraction solvents are described (ethanol and hexane) to compare their selectivity towards target molecules, and to describe as exhaustively as possible the terpenic profile of the five pharmaceutical-grade varieties. Twenty-three standards were used for accurate dosages. This work highlights that the choice of solvent and the analysis method reliability are critical for the study of these terpenic compounds, regarding their contribution to the entourage effect.

Impact of heteroatoms and chemical functionalisation on crystal structure and carrier mobility of organic semiconductors

The substitution of heteroatoms and the functionalisation of molecules are established strategies in chemical synthesis. They target the precise tuning of the electronic properties of hydrocarbon molecules to improve their performance in various applications and increase their versatility. Modifications to the molecular structure often lead to simultaneous changes in the morphology such as different crystal structures. These changes can have a stronger and unpredictable impact on the targeted property. The complex relationships between substitution/functionalization in chemical synthesis and the resulting modifications of properties in thin films or crystals are difficult to predict and remain elusive. Here we address these effects for charge carrier transport in organic crystals by combining simulations of carrier mobilities with crystal structure prediction based on density functional theory and density functional tight binding theory. This enables the prediction of carrier mobilities based solely on the molecular structure and allows for the investigation of chemical modifications prior to synthesis and characterisation. Studying nine specific molecules with tetracene and rubrene as reference compounds along with their combined modifications of the molecular cores and additional functionalisations, we unveil systematic trends for the carrier mobilities of their polymorphs. The positive effect of phenyl groups that is responsible for the marked differences between tetracene and rubrene can be transferred to other small molecules such as NDT and NBT leading to a mobility increase by large factors of about five.

Leveraging normalizing flows for orbital-free density functional theory

Abstract Orbital-free density functional theory (OF-DFT) for real-space systems has historically depended on Lagrange optimization techniques, primarily due to the inability of previously proposed electron density approaches to ensure the normalization constraint. This study illustrates how leveraging contemporary generative models, notably normalizing flows (NFs), can surmount this challenge. We develop a Lagrangian-free optimization framework by employing these machine learning models for the electron density. This diverse approach also integrates cutting-edge variational inference techniques and equivariant deep learning models, offering an innovative reformulation to the OF-DFT problem. We demonstrate the versatility of our framework by simulating a one-dimensional diatomic system, LiH, and comprehensive simulations of hydrogen, lithium hydride, water, and four hydrocarbon molecules. The inherent flexibility of NFs facilitates initialization with promolecular densities, markedly enhancing the efficiency of the optimization process.

Data-driven approaches to study the spectral properties of chemical structures

The molecular energy, which is the sum of all eigenvalues, is crucial in determining the total π-electron energy of conjugated hydrocarbon molecules. We used machine learning techniques to calculate the energy, inertia, nullity, signature, and Estrada index of molecular graphs for bismuth tri-iodide and benzene rings embedded in P-type surfaces within 2D networks. We applied MATLAB to extract the actual eigenvalues from the data and developed general equations for these molecular properties. We then used these equations to estimate the values and compared them to the actual values through graphical analysis. Our results demonstrate the potential of data-driven techniques in predicting molecular properties and enhancing our understanding of spectral theory.

Diffusion behaviors of binary mixtures of alkanes and aromatics through ZSM‐5 zeolite: A kinetic Monte Carlo study

AbstractDiffusion of hydrocarbon species in an MFI‐type zeolite was investigated using a coarse‐grained approach combined with Kinetic Monte Carlo (KMC) simulations. The model was employed to capture and isolate the essential characteristics of hydrocarbon diffusion such as molecular pushing, passing, and blocking. A modified Lennard‐Jones type forcefield was used to approximate interactions between molecules, and molecules with the oxygen in the zeolite lattice. The basis for the rate expressions is configurational diffusion theory, which has been adjusted to account for an accurate representation of the motions of hydrocarbon molecules trapped in the zeolite. Diffusion coefficients were estimated for low and high loading of single hydrocarbons as well as binary mixtures. In all cases studied, reasonable agreement was achieved with reported experimental data and molecular dynamics simulations. The model is conceptualized as an analytical tool that may be used to address key engineering topics such as applications of zeolites as size‐selective barriers.

Study of molecular arrangement and density estimation of soybean oil biodiesel-diesel blends employing molecular dynamic simulation

Blends of diesel–biodiesel are a crucial alternative for petrodiesel substitution. However, biodiesel faces challenges such as high density and kinematic viscosity, which can affect the properties and performance of the blends. Based on this, the investigation of the impact of adding biodiesel into diesel fuel at percentages of 12%, 15%, 18%, and 21% using molecular dynamic simulations is presented. The density of the blends was experimentally measured and calculated with good agreement, which indicates a favorable description of the interactions by the OPLS-AA force field. Obtained results suggest that alkanes and isoalkanes showed higher fluctuations and were most sensitive to the variation of the percentage of biodiesel in diesel. The other classes of molecules did not show significant variations in interactions, suggesting that π-π interactions are unaffected by the biodiesel addition. The spatial distribution functions revealed that diesel molecules are organized homogeneously around methyl oleate and methyl linoleate, whereas aliphatic hydrocarbon and aromatic molecules are in distinct regions. The diffusion coefficients (Di) showed that the diesel molecules possess higher values, and the biodiesel addition increases the Di of the blend due to the methyl esters carbon chains, which present lower diffusion than diesel molecules. Finally, physical parameters and simulations revealed that the biodiesel addition into diesel fuel in the proportion up to 21% did not negatively impact the density and viscosity limits established by standards ASTM, EN, and ANP Resolution.

High-Throughput Computational Screening of Hydrocarbon Molecules for Long-Wavelength Infrared Imaging

High-Throughput Computational Screening of Hydrocarbon Molecules for Long-Wavelength Infrared Imaging

Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface.

Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon-neutral sources. CeO2-δ (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH4, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm-doped ceria thin-film model cell that selectively monitors CH4 direct-electro-oxidation on the ceria surface. Using impedance spectroscopy, operando X-ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H2O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH4 in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high-performance, environmentally sustainable fuel cells.

Cymbopogon citratus Allelochemical Volatiles as Potential Biopesticides against the Pinewood Nematode.

Traditional pesticides are based on toxic compounds that can reduce biodiversity, degrade the environment, and contribute to less healthy living. Plant allelochemicals can provide more environmentally friendly and sustainable alternatives. Essential oils (EOs) are complex mixtures of plant secondary metabolites that show strong biological activities. In the present study, the EOs of Cymbopogon citratus were screened for activity against the pinewood nematode (PWN), the causal agent of pine wilt disease. To understand their nematicidal properties, EOs were fractioned into hydrocarbon molecules and oxygen-containing compounds, and their main compounds were acquired and tested separately against the PWN. The EO oxygen-containing molecules fraction was highly active against the PWN (EC50 = 0.279 µL/mL), with citral and geraniol showing higher activities (EC50 = 0.266 and 0.341 µL/mL, respectively) than emamectin benzoate (EC50 = 0.364 µL/mL), a traditional nematicide used against the PWN. These compounds were additionally reported to be less toxic to non-target organisms (fish, invertebrates, and algae) and safer to human health (with higher reported toxicity thresholds) and predicted to exert fewer environmental impacts than traditional nematicides. Resorting to approved natural compounds can quickly leverage the development of sustainable alternatives to traditional nematicides.

Interference Effects in Micro-Raman Spectroscopy Enable Mapping of Chemical Gradients on an Elastomer Surface.

Chemically modified elastomer surfaces are important to many applications, including microfluidics and soft sensors. Sensitive characterization of the interfacial chemistry of soft materials has been a persistent challenge, given their structural and chemical complexity. This article reports a method to probe local chemical states of elastomer surfaces that leverages the interference effects observed in micro-Raman spectroscopy. Unexpectedly, systematic variations of Raman scattering intensity were observed across a chemical wettability gradient grafted to the surface of a poly(dimethylsiloxane) (PDMS) film. Specifically, hydrophobic surface regions with a high graft density of long-chain hydrocarbon molecules showed suppressed Raman intensity. An optical interference model that accounts for molecular filling and swelling of an interfacial glassy layer during chemical modifications of the PDMS surface quantitatively reproduces experimental observations. This work establishes the spectroscopic signatures of interfacial chemical modifications on elastomer surfaces and enables a noncontact optical probe of local chemical states at the micro- and nanoscale compatible with the complex interfaces of soft materials.

Revisit the PAH and soot formation in high-temperature pyrolysis of methane

As the major component of natural gas, most basic and stable hydrocarbon molecule, methane (CH4) is an important source in industrial processing. The polycyclic aromatic hydrocarbons (PAHs) and the soot produced in the utilization of CH4 also attract particular attention. In this work, CH4 pyrolysis was studied with gas chromatographs (GCs) and a gas chromatography-mass (GC-MS) spectrometry within the temperature range of 1073–1623 K at atmospheric pressure. Mole fraction profiles of 11 species, including CH4, C2H2, C2H4, C2H6, aC3H4, pC3H4, C3H6, C4H6, C6H6, C10H8 (naphthalene) and C12H8 (acenaphthylene) were quantified. C10H8 and C12H8 were detected during the pyrolysis of CH4. A detailed kinetic model involving 300 species and 1840 reactions was proposed with reasonable prediction against the measured data. During pyrolysis, CH4 is mainly consumed by the H-abstraction reactions. 2CH3=C2H5+H and C9H7+C3H3=A2R5+H2 are the two major reactions controlling CH4 consumption according to sensitivity analysis. In addition, the soot generated in the reactor was analyzed by Raman spectroscopy and Scanning Electron Microscope (SEM), showing the morphology and structural characteristics of the soot. The detailed formation and consumption pathways of PAHs such as naphthalene and acenaphthylene were analyzed. This work will enrich the understanding of CH4 pyrolysis and promote experimental and theoretical studies on the formation of PAHs and soot.