Gas Phase Research Articles

The amenability of different solvents to electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry is capable of transferring ions from solution to the gas phase across a broad range of solvents. A systematic investigation of the relative performance of different solvents has not been previously conducted, and we sought to remedy this situation. Fourteen solvents across a wide range of polarities were investigated for their ability to provide strong signals for four permanently charged ions. We found the best solvents to be acetone, acetonitrile, dichloromethane, tetrahydrofuran, and the previously unused (in an ESI-MS context) trifluorotoluene.

Effect of relative humidity on passive spore release from substrate surfaces

Fungal spores are abundant in ambient air and exposure to this type of bioaerosols are found to cause significant health and climatic effects. In this study, we investigated the influence of air relative humidity (RH) on the passive release of spores from solid substrates. Preliminary investigations into the effect of RH on fungal spore release indicated an increase in spore flux with reduced air RH. The change in spore emission flux occurred very quickly in response to a change in ambient RH. To verify the hypothesis of extremely rapid drying under lower RH, experiments were conducted using a quartz crystal microbalance with dissipation (QCM-D) to understand the timescales of spore moisture uptake and drying. The analysis of mass transfer of water to and from the spores indicated that the bulk of the transfer occurred within a minute of exposure to any RH. The effect of the ambient RH was explained using a mathematical model with the spotlight on the parameter, E, that represented the energy required to aerosolise one spore. This study demonstrates the application of QCM-D to study interaction between ambient aerosol particles and various vapor phase and gas phase environments. The study enhances the overall understanding and capability to characterise passive fungal spore release under varying humidity conditions in the natural environment.

An Effective Method for Reproducing the Flow of a Gas-Liquid Mixture Using a Flow Standard

The appearance on the market of measuring equipment of multiphase flowmeters used in the oil and gas industry to measure the amount of extracted hydrocarbons directly at wells without preliminary separation and performing the function of operational accounting raised the question of their metrological support in accordance with the requirements of regulatory documents of the sphere of state regulation in this field of measurements. His decision was to create a reference base, the basis of which was the State primary special standard for units of mass flow of gas-liquid mixtures GET 195-2011 and a verification scheme for measuring multiphase flow rates, regulated by GOST 8.637-2013. When transmitting units of volume and mass flow of a multiphase mixture with the required accuracy, the main problem is the difficulty of reproducing and maintaining stability of several flow parameters at once – mass flow and content of liquid components (water and oil simulator) and volume flow of the gas phase. It should also be borne in mind that test programs for the purpose of approving the type of multiphase flow measuring instruments, as well as verification and calibration methods, provide for changing the modes of reproduction of a gas-liquid mixture, covering the measurement ranges of multiphase flowmeters. Such standards used in practice represent a very complex measuring system consisting of storage tanks for components, supply pumping and compressor units, control equipment, mixers and separators, measuring instruments for the physical parameters of multiphase flow components and an automated control system. Given the high cost of multiphase standards, when creating them, effective methods and methods should be used to reproduce the flow of a multiphase mixture with specified parameters, as well as to make a fairly rapid transition to the next mode provided by the program or methodology, which will reduce the time and production costs for the procedure of transferring units of measurement from the standard to the working measuring instrument. This article describes a method for reproducing the flow rate of a gas-liquid mixture according to the original technological scheme introduced during the development of the 1st category standard. Constructive solutions are presented that increase the efficiency of the liquid component separation apparatus to increase the dosing accuracy, as well as expand the range of reproduction of the flow rate and parameters of the multiphase flow, ensuring the consistency of the composition of the liquid mixture at a given regime. An original rational method of compressing and maintaining the pressure of the gas phase is described, which allows you to quickly switch to the next mode, confirmed by the results of experimental studies of the standard.

Stark seasonal contrast of fine aerosol levels, composition, formation mechanism, and characteristics in a polluted megacity.

In this study, we investigated the temporal variation of organic and inorganic aerosol with its optical properties in Mumbai (India), an urban coastal region. Mean PM2.5concentrations during the sampling period were 175μg/m3 (winter) and 90μg/m3 (summer). During winter, the average concentrations of organic (OC), elemental (EC), and water-soluble organic carbon (WSOC) were three times higher than in summer. Secondary organic carbon (SOC) contribution in OC was higher in summer (78%) than in winter (53%), and strong solar radiation in summer likely caused this outcome. Aerosols were slightly acidic in both seasons, with an average pH of 5.7 (winter) and 6.0 (summer). A correlation was observed between SOC and the acidity of particles in summer (R2 = 0.6), indicating some amount of acid-catalysed SOC formation. In both seasons, the sulphate oxidation ratio (SOR) was higher than the nitrate oxidation ratio (NOR), which may reflect a preference for SO2 oxidation over NO2 or the difference in partitioning ammonium nitrate into ammonium sulphate under high RH. The dominant mechanism of SOC formation (gas vs aqueous phase oxidation) also showed seasonal variation. In winter, a relatively steep reduced major axis (RMA) slope of O3/CO suggests gas phase oxidation was the dominant mechanism of SOC production. Winter has more BrC fraction than summer, indicating higher absorbing aerosols, though the efficiency of absorbing the light was higher in summer. To assess the radiative forcing of PM2.5 on a local scale, an effective carbon ratio (ECR) was computed. The findings pointed to a local radiative heating impact caused by PM2.5. The spectral slope ratio and MAE at 250 to 300nm ratio (E2/E3) revealed a higher abundance of high molecular weight species in WSOC during summer than in winter.

Femtosecond Laser Assisted Chemical Ionization Mass Spectrometry: Toward Sub-ppq Detection Limits for Organic Molecules.

Ultrasensitive analysis of organic molecules is crucial for various fundamental research and applications. State-of-the-art techniques for this purpose can achieve detection limits of several hundred ppq (parts-per-quadrillion), while a higher sensitivity is pursued constantly. To achieve this goal, we develop femtosecond laser assisted chemical ionization for mass spectrometry. This technique combines the advantages of femtosecond laser ionization and chemical ionization, either of which enables subppt (parts-per-trillion) mass spectrometry analysis of organic molecules. The results demonstrate that the developed ionization technique, when employed in mass spectrometry, can surpass femtosecond laser ionization by more than 3 orders of magnitude in sensitivity, while still maintaining good versatility and the ability to work under ambient conditions. This work paves the way for subppq analysis of organic molecules in gas phase and even in ambient environments, which can open up new research fields for trace substance analysis in atmospheric environment, clinical diagnosis, biomedical studies, etc.

Ice origins of OCS and chemistry of CS2-bearing ice mantles

Abstract Understanding the formation of carbonyl sulfide (OCS) in interstellar ices is key to constrain the sulfur chemistry in the interstellar medium (ISM), since it is the only ice S-bearing molecule securely detected thus far. Two general pathways for OCS formation have been proposed: sulfurization of CO (CO+S) and oxidation of CS (CS+O), but their relative contribution in interstellar ices remains unconstrained. We have evaluated the contribution of both pathways to OCS formation upon energetic processing in isotopically-labeled CO2:CS2 and CO:CS2 ice samples at 7−50 K. Our results indicated that formation of OCS through the CS+O pathway was more favorable than through the CO+S pathway, as previously suggested by theoretical calculations. In addition, its relative contribution increased at higher temperatures. Therefore, this pathway could play a role in the ice formation of OCS, especially in warm regions where CO is expected to be preferentially in the gas phase. At the same time, we have explored the chemistry of CS2-bearing, CO2-, CO-, and also H2O-rich ices, that could be relevant to the sulfur interstellar chemistry. We observed formation of a variety of S-bearing products in addition to OCS, including SO2, C3S2, and S2. However, a significant fraction of sulfur was not detected at the end of the experiments, and could be locked in long, undetectable sulfur allotropes, one of the potential carriers of the missing sulfur in the dense ISM.

Characterizing the development of gravity-driven slug flows using high-speed imaging and PIV-PLIF techniques

Although developing gravity-driven slug flow frequently occurs in oil and gas, and energy systems, its development dynamics remain underexplored; this gap, in turn, has left the underlying relationships between flow evolution and transport phenomena in these applications inadequately characterized as well. The present study experimentally investigates the spatiotemporal-spectral development of gravity-driven air–water and CO2-water slug flows in a vertical 25.4 mm ID pipe. Enhanced flow visualization techniques, utilizing high-speed imaging and particle image velocimetry-planar laser induced fluorescence (PIV-PLIF), were employed to determine the behaviors of gas and liquid phases and interactions at four positions along the pipe axis. A machine vision-based algorithm was employed to extract slug unit cell characteristics and instantaneous void fraction signals, allowing for a comprehensive statistical analysis of gas phase behavior across the flow domain. A novel algorithm was also developed to preprocess raw PIV-PLIF images, facilitating phase discrimination and noise reduction before PIV cross-correlation analyses are conducted. The results showed a logarithmic growth in the lengths of Taylor bubbles, liquid slugs, and slug unit cells along the pipe, with liquid slugs constituting nearly 60 % of slug units downstream. Taylor bubble length distributions correlated well with log-normal fits, while liquid slug and unit cell lengths transitioned from log-normal patterns upstream to near-normal distributions downstream with broader and less peaked shapes. Taylor bubble velocities and appearance frequencies of the flow structures declined exponentially along the pipe, with Taylor bubble velocities showing narrower and more peaked near-normal distributions downstream. Instantaneous void fraction signals exhibited fewer, wider peaks and troughs with reduced small-amplitude oscillations downstream. The analysis of the signals indicated a complete bubbly-to-slug transition at Z/D=30. Gas-liquid phase interactions, classified as almost-zero, weak, and strong, impacted liquid phase velocity profiles and the behavior of Taylor bubbles, with minimum stable liquid slug lengths of 8–9 D and a wake length of 1.8 D observed. Empirical correlations were developed to represent the spatiotemporal-spectral aspects of flow development, with spectral parameters, particularly liquid slug frequency, identified as the most reliable indicators of the fully developed region, predicting entrance lengths of 114.0 D and 113.4 D for air–water and CO2-water, respectively. Gas density was found to strongly influence flow characteristics and transition, accelerating the approach to the fully developed region.

Analytical optical methods for measuring organic peroxides and hydroperoxides: An evaluation

Hydrogen peroxide, organic peroxides and hydroperoxides exhibit high reactivity and play a pivotal role in atmospheric chemistry. These compounds are formed during the oxidation of volatile organic compounds in both gaseous and aqueous phases, particularly under low NOx conditions. Their significant contribution to the mass of secondary organic aerosols (SOA) is well-documented, and they are believed to have significant health implications. Several spectrophotometric methods have been employed to measure SOA-bound peroxides in laboratory samples, but systematic comparisons are lacking. In this study, we have assessed the advantages and limitations of these methods, including the traditional and microwave-assisted iodometric methods, the 4-nitrophenyl boronic acid assay (NPBA), and the Fenton reaction-assisted ferrous-xylenol (FOX2) assay. Besides, a comprehensive evaluation of these methodologies was conducted for the first time across a substantial cohort of commercial peroxides and hydroperoxides, employing diverse solvents (namely, water, 1-propanol, acetonitrile, methanol and chloroform) to provide broader insights compared to previous work. Ultimately, the four methods were applied and compared for peroxide determination in laboratory-generated SOA resulting from gas-phase ozonolysis of α-pinene. This study opens new opportunities for future mechanistic investigation into SOA formation and reactivity.

Comprehensive investigation of flue gas component separation and CO2 sequestration in water-saturated porous media of subsurface formation

Flue gas poses subsurface direct storage inefficiency due to its high non-CO2 content, while surface separation, desulfurization and denitrification processes require additional equipment and financial resources. To address these challenges, flue gas subsurface component separation and CO2 sequestration within aquifer were proposed in this paper. CO2 migrates notably slower than N2, leading to the gathering of N2 at gas flooding front and the occurrence of CO2 hysteresis during flue gas filtration within the aquifer. The phenomenon, characterized by gas composition deviations from the original injection mole fractions of N2 and CO2, is referred to as the flue gas component separation. Numerical simulation results indicate that the solubility difference between N2 and CO2 is the primary force driving the separation of components, and the asynchronous filtration velocities of the gas and aqueous phases further promote the separation. Thus, simultaneous N2 separation and CO2 storage can achieve by the optimized gas-water alternate injection, and the efficiencies of N2 separation and CO2 storage are inversely correlated. Increasing N2 mole fraction within the injected flue gas enhances the efficiency of N2 separation, while having a slight effect on CO2 storage. Water vapor in flue gas condenses and integrates into the liquid phase, while O₂ component is produced slightly later than N₂, leading to a marginal reduction in N₂ separation efficiency. The synergistic influences of aquifer temperature and pressure exhibit bidirectionality, stemming from the shift between the dominant factors between CO2 dissolution and gas sweep efficiency. Conditions of relatively lower aquifer temperatures and moderate pressures, particularly in medium permeability aquifers, are more favorable for enhancing N₂ separation and CO₂ storage. This proposal method holds the potential for efficient subsurface separation of flue gas components and concurrent underground storage of CO2, thereby contributing to the reduction of greenhouse gas emissions and mitigation of climate change.

Trimodal Watch-Type Wearable Health Monitoring Device

In the domain of healthcare, wearable health monitoring devices have emerged as essential tools for the advancement of patient health tracking. These devices facilitate the provision of real-time medical data to clinicians, enabling early diagnosis, timely intervention, and enhanced management of individual health. This study introduces an innovative trimodal wearable health monitoring device in the form of a wristwatch. The device integrates a breath analyzer for the assessment of gaseous phase biomarkers, a sweat analyzer for the evaluation of aqueous-phase biomarkers, and an infrared sensor for the measurement of body temperature in the optical phase. Engineered on a compact 3 cm × 3 cm printed circuit board, the device has been optimized for wearability, power efficiency, and seamless integration with both wired and wireless charging and communication systems. Furthermore, custom software applications, designed for both Windows and Android platforms, have been developed to facilitate intuitive data visualization and storage on personal computers and smartphones. Empirical results from real-time chemical testing substantiate the device’s efficacy and potential as an advanced solution for wearable health monitoring.

Numerical Analysis of A Two-Phase Turbine: A Comparative Study Between Barotropic and Mixture Models

Abstract Two-phase turbines offer the potential to significantly enhance the performance of power generation and refrigeration systems. However, their development has been hindered by comparatively lower efficiencies resulting from additional loss mechanisms absent in single-phase turbines. To date, most multiphase CFD studies on turbomachinery have focused on condensation in the final stages of steam turbines, and on cavitation in hydraulic pumps and turbines. These applications, however, are not representative of the conditions in two-phase turbines, where a liquid-dominated mixture undergoes a large expansion ratio, leading to a significant increase in the gas phase volume fraction throughout the entire flow. This paper aims to identify a suitable modeling methodology for two-phase turbines. Our evaluation is centered around two models: the mixture model and the barotropic model. The validity and accuracy of these two modeling approaches is assessed using existing experimental data from a single-stage impulse turbine operating with several mixtures of water and nitrogen as working fluid. The results indicate that both the mixture and barotropic models are consistent and accurately predict the nozzle mass flow rate, yet, both models systematically overpredict the nozzle exit velocity and rotor torque. Adding correction terms for windage and unsteady pumping losses significantly improves the torque predictions, bringing them within the uncertainty range of the experimental data. In addition, refining the models to account for the effect of slip presents a promising avenue to enhance the prediction of nozzle exit velocity and overall performance of two-phase turbines.

XPS and DFT studies of γ-Al2O3 modified by NO

The modification of γ-Al2O3 after NO treatment and during the NO + H2 reaction was studied using X-ray photoelectron spectroscopy (XPS) and density functional theory. The XPS N1s spectra contain features with binding energies BE = 399.0 and 403.0 eV; the first is preserved, and the second disappears when NO is removed from the gas phase. The features were identified from experimental and modeled O-KLL regions of possible modification products − NAln oxynitrides (n = 3; 4) of the γ-Al2O3(110) surface and adsorbed states. Calculations show that NAln adsorbs NO, forming normal states with a distance to the surface d = 1.32–1.70 Å and distant (d-NO) states (d = 1.91–2.06 Å) in which the spin-polarized NO molecule is retained due to magnetic NAln and Coulomb interaction. An increase in the similarity of the O-KLL spectra in the sequence of NO/γ-Al2O3(110), NO/NAln and d-NO/NAln at an adsorption heat of ∼ 0.53, 1.33 and 1.26 eV, respectively, suggests that the modification includes the formation of NO/NAl4 corresponding to BE = 399.0 eV and d-NO/NAl4, which corresponds to BE = 403.0 eV and, being chemically unbound, is able to leave the surface in the absence of NO in the reaction medium.

Enhanced DC surface discharge characteristics of epoxy composites treated by dielectric barrier discharge plasma fluorination and its mechanisms

Surface flashover is a destructive high-voltage discharge phenomenon greatly limiting the update of modern power electronic and electrical equipment. Surface plasma treatment is a high-energy, eco-friendly, and convenience method, it changes the surface properties and owns potential to improve flashover voltage. In the present work, plasma fluorination (PF) technique are used to treat EP/Al2O3 composites, surface morphology, element and bonds content, surface trap, conductivity, charging, and DC flashover voltage are tested and simulated, the effects of plasma on surface discharge are explained through the investigation from microscopic molecular reactions to macroscopic flashover characteristics. It indicates the 20 min PF modified sample exhibits the superior DC flashover performance, increasing by 17 % compare to untreated sample. During PF modification, the epoxy chains are degraded and fluorinated, the degradation rather than fluorination of molecular chains introduce large amounts of shallow traps into the composites, accelerating carriers’ migration and improving surface conductivity, causing surface charges to dissipate through surface conductance. Consequently, the surface electric field distortion degree reduces, and the subsequent gas ionization and plasma formation in the gas phase is suppressed, leading to the improvement of DC flashover voltage after PF modifications.

Laser Spectroscopic Characterization of Supersonic Jet-Cooled 2,6-Diazaindole (26DAI).

The article presents a comprehensive laser spectroscopic characterization of a nitrogen-rich indole derivative, namely, 2,6-diazaindole (26DAI), in the gas phase. A supersonic jet-cooled molecular beam of 26DAI was characterized using two-color resonant two-photon ionization (2C-R2PI) and laser-induced fluorescence spectroscopy (LIF) to investigate the electronic excitation. The S1 ← S0 origin transition was obtained at 33915 cm-1, which was red-shifted from that of one (indole) and two (7-azaindole) nitrogen-containing indole derivatives by 1317 and 713 cm-1, respectively. The molecular orbital and energy analysis for the S1 ← S0 transition shows the significant stabilization of LUMO on subsequent N-insertion, resulting in the lowering of the S1 ← S0 (ππ*) transition energy. The single vibronic level fluorescence spectrum from the vibrationless S1 state of the molecule was recorded. The spectrum displayed an extensive Franck-Condon activity until 2500 cm-1 for the vibrational modes of the S0 state of the 26DAI molecule. The experimental ground state vibrational frequencies were compared to the calculated ones obtained at three different levels of theories. More accurate results were found at DFT B3LYP-D4 than those at the wave function-based MP2 and CCSD levels of theories. Further, the N-H stretching frequency of 26DAI in the S0 state was measured at 3524 cm-1 using fluorescence-dip infrared (FDIR) spectroscopy. The stability of 26DAI against ionization radiation was probed by measuring the two-color photoionization energy (IE2P) of 26DAI at 71866 cm-1. The IE2P value is significantly higher than those of N-poor counterparts (indole and 7-azaindole). The NBO charges and spin density (SD) values of the 26DAI molecule have shown that electronegative N(6) makes the cationic ground state less stable due to the position of the positive centers on the N atom. The results provided insights into the stability of N-rich biomolecules against photodamage. The current investigation can shed light on nature's way of stabilizing biomolecules with a possible N-insertion mechanism.

Modification of activated carbon to enhance the absorption of PCDD/F and dl-PCBs emissions in flue gas in South Africa

Activated carbon (AC) adsorption is commonly used for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) removal from flue gas. However, the AC available in the market predominantly possesses a substantial specific surface area and numerous micropores leading to significant variations in their adsorption characteristics. In this study, three types of activated carbon (AC) impregnated with different activating agents, namely K2CO3, KOH, and H3PO4 were evaluated for their effectiveness in removing PCDD/Fs and dl-PCBs compounds. For dl-PCBs, AC impregnated with H3PO4 resulted in a substantial reduction of PCB concentrations with an impressive 98% reduction achieved. Impregnation with KOH proved even more effective attaining a remarkable 99% reduction. In contrast, impregnation with K2CO3 while still effective achieved a slightly lower reduction rate of 95%. For PCDD/F, LACH3PO4 showed selectivity in achieving high reductions across both CDD and CDF congeners however proved effective in reducing the ∑PCCDF from 403.94 ng/Nm3 to 3.463 ng/Nm3 and ∑TEQ from 41.34 ng I-TEQ/Nm3 to 0.35 ng I-TEQ Nm3. LACKOH proved effective in reducing the ∑PCCDF from 540.45 ng/Nm3 to 0.25 ng/Nm3 and ∑TEQ from 57.42 ng I-TEQ/Nm3 to 0.12 ng I-TEQ Nm3 obtaining the overall removal efficiency of 99.5%. While the LACKOH injections were successful in the absorption of PCDD/Fs from the gas phase, it was observed that certain PCDD/F congeners became desorbed and entrapped within the ash necessitating further treatment of the ash residue. The ash underwent a thermal treatment first at 300 °C and 500 °C. The thermal treatment at 500 °C achieved a remarkable degradation of 99.7% removal efficiency rendering the ash and residue safe for disposal in a landfill site.Graphical

Deciphering the Two-Step Hydride Mechanism of Monoamine Oxidase Flavoenzymes.

The complete two-step hydride transfer mechanism of amine oxidation involved in the metabolism of monoamine neurotransmitters was scrutinized by DFT calculations. In living organisms, this process is catalyzed by monoamine oxidase enzymes. Herein, we focus on some intriguing aspects of the reaction that may have been previously noticed but have not been clarified to date. The first step of the reaction includes the C-H bond cleavage on the methylene group vicinal to the amino group of the monoamine substrate and the subsequent transfer of hydrogen to the N5 atom of the flavin prosthetic group of the enzyme. We confirmed the nature of this step to be hydride transfer by evaluation of the pertinent HOMO-LUMO gap together with analysis of orbital contours alongside the intrinsic reaction coordinate profile. Next, we investigated the rather peculiar intermediate adduct that may form between the amine substrate and the flavin molecule, featuring an unusually long C-N bond of ∼1.62 Å. Although this bond is quite stable in the gas phase, the presence of just a few explicit water molecules facilitates its dissociation almost without energy input so that the amine-flavin intermediate can form an ionic pair instead. We attribute the existence of the unusual C-N bond to a fragile balance between opposing electronic structure effects, as evaluated by the natural bond orbital analysis. In line with this, the intermediate in the solution or in the enzyme active site can exist in two energetically almost equivalent forms, namely, as a covalently bound complex or as an ion pair, as suggested by previous studies. Finally, we characterized the transformation of the intermediate to the fully reduced flavin and imine products via proton transfer from the amino group to the flavin N1 atom, completing the reductive part of the catalytic cycle. Although we found that explicit solvation substantially boosts the kinetics of this step, the corresponding barrier is significantly lower than that in the hydride transfer step, confirming hydrogen abstraction as the rate-limiting step of amine oxidation and validating the two-step hydride transfer mechanism of monoamine oxidases.

Tutorial on Umbrella Sampling Simulation with a Combined QM/MM Potential: The Potential of Mean Force for an SN2 Reaction in Water.

We present a tutorial to carry out umbrella-sampling free-energy simulations with a combined quantum mechanical and molecular mechanical (QM/MM) potential, which may also be used in a computational or biophysical chemistry curriculum for first-year graduate and undergraduate students. In this article, we choose the Type II SN2 Menshutkin reaction between ammonia and chloromethane to construct the potential of mean force (PMF) for the reaction in aqueous solution. In this exercise, we wish to accomplish three tasks: (1) an understanding of the concept of PMF and the umbrella-sampling free-energy simulation method, (2) the use of a combined QM/MM potential in molecular dynamics simulation of chemical reactions, and (3) an understanding of solvent effects and intermolecular interactions on chemical reactions through comparison with gas-phase results. Analysis of the simulation results allows students to appreciate the difference between the transition state along a PMF from statistical simulations versus the optimized saddle point in the gas phase, the shift of transition state with respect to solvation, and the significance of electronic polarization. Through this tutorial, students will gain the necessary skills to carry out free energy simulations of chemical reactions in solution and in enzymes both in a classroom and in the laboratory.

Applied Investigation of Methyl, Ethyl, Propyl, and Butyl Mercaptan as Potential Poisons in the Gas Phase Polymerization Reaction of Propylene.

The polypropylene (PP) synthesis process is crucial in the plastics industry, requiring precise control as it directly impacts the catalytic activity and the final product's performance. This study investigates the effects of trace amounts of four different mercaptans on the polymerization of propylene using a fourth-generation Ziegler-Natta (ZN) catalyst. Various concentrations of these mercaptans were tested, and results showed that their presence significantly reduced the melt flow index (MFI) of the final PP. The most notable MFI decrease occurred at 37.17 ppm of propyl mercaptan and 52.60 ppm of butyl mercaptan. Methyl and ethyl mercaptan also reduced the MFI at lower concentrations, indicating that mercaptans act as inhibitors by slowing down the polymerization process and reducing the fluidity of molten PP. The highest MFI increase was observed at lower concentrations of each mercaptan, suggesting that smaller molecular inhibitors require less concentration. This trend was also seen in the catalyst's productivity, where lower concentrations of methyl mercaptan reduced PP production more effectively than higher concentrations of butyl mercaptan. Fourier transform infrared spectroscopy (FTIR) identified interactions between the mercaptans and the ZN catalyst. Computational analysis further supported these findings, providing insights into the molecular interactions and suggesting possible inhibition mechanisms that could impact the final properties of polypropylene.

Volatile composition of the HD 169142 disk and its embedded planet

Abstract The composition of a planet’s atmosphere is intricately linked to the chemical makeup of the protoplanetary disk in which it formed. Determining the elemental abundances from key volatiles within disks is therefore essential for establishing connections between the composition of disks and planets. The disk around the Herbig Ae star HD 169142 is a compelling target for such a study due to its molecule-rich nature and the presence of a newly-forming planet between two prominent dust rings. In this work, we probe the chemistry of the HD 169142 disk at small spatial scales, drawing links between the composition of the disk and the planet-accreted gas. Using thermochemical models and archival data, we constrain the elemental abundances of volatile carbon, oxygen, and sulfur. Carbon and oxygen are only moderately depleted from the gas phase relative to their interstellar abundances, with the inner ~60 au appearing enriched in volatile oxygen. The C/O ratio is approximately solar within the inner disk (~0.5) and rises above this in the outer disk (>0.5), as expected across the H2O snowline. The gas-phase sulfur abundance is depleted by a factor of ~1000, consistent with a number of other protoplanetary disks. Interestingly, the observed SiS emission near the HD 169142 b protoplanet vastly exceeds chemical model predictions, supporting previous hypotheses suggesting its origin in shocked gas or a localised outflow. We contextualise our findings in terms of the potential atmospheric composition of the embedded planet, and highlight the utility of sulfur-bearing molecules as probes of protoplanetary disk chemistry.

A numerical framework for modeling evaporation and combustion of isolated, spherically-symmetric, multi-component fuel droplets

This paper presents a comprehensive numerical framework for simulating the evaporation and combustion of isolated, spherically-symmetric, multi-component fuel droplets. The framework incorporates a detailed description of chemical reactions in the gaseous phase and is capable of modeling pure evaporation, autoignition, and hot-wire ignition scenarios.The transport equations for mass, species, and energy are solved in both the liquid (droplet) and gaseous (surrounding atmosphere) phases. Diffusion in the liquid phase is described using the Stefan–Maxwell theory, while in the gaseous phase, both molecular and thermal diffusion are considered. The model also includes the thermophoretic effect for carbonaceous particles and accounts for gas radiation through various models, ranging from optically-thin approximations to more complex methods like the P1 and discrete ordinate methods. Non-gray radiative effects are handled using the Weighted-Sum-of-Gray-Gases Model (WSGGM). Liquid/gas interface conditions are evaluated by imposing flux continuity of mass and energy, along with thermodynamic equilibrium for species. Deviations from ideal thermodynamic behavior in the liquid droplet are managed by incorporating a suitable activity coefficient or by using a proper cubic equation of state. Additionally, the presence of supporting fibers is modeled using a simplified one-dimensional approach. The transport equations are solved using the method of lines, with spatial discretization performed via the finite difference method on a body-fitted grid. The resulting system of Differential–Algebraic Equations (DAEs) is then solved using a fully-coupled approach.Thanks to its generality in terms of kinetic and thermodynamic descriptions and the reduced computational time, the proposed framework offers significant potential for advancing our understanding of the complex combustion processes of multi-component liquid fuels and for enhancing the planning and execution of experiments involving isolated fuel droplets.