Low Mole Fractions Research Articles

Enhanced Chirality Transfer in Self-Assembled Nanocomposites Powered by A Trace Amount of Chiral Dimeric Molecules.

Chiral-selective self-assembly has markedly advanced the development of chiral materials. While the Sergeant and Soldiers principle allows for chirality amplification, it necessitates precise shape-matching between chiral and achiral molecules, leading to a low chirality transfer efficiency-where one chiral molecule influences the chirality of a limited number of achiral molecules. Here, we show that this efficiency can be markedly enhanced by introducing chiral dimeric molecules. In this work, a single chiral molecule can control the chirality of up to 200 achiral molecules and even direct the assembly of inorganic nanoparticles into chiral nanocomposites through a sequential chirality transfer process. Moreover, this approach exhibits remarkable robustness, operating effectively without necessitating a precise match between chiral and achiral molecules. Consequently, using the same chiral molecules at an exceptionally low molar fraction (0.5 mol %) allows for the chiral-selective assembly of achiral molecules over a broad spectrum, regardless of their packing habits, thus facilitating the creation of otherwise inaccessible chiral materials with modulated chiroptical properties. Last but not least, even a trace amount of chiral molecules can enhance the elastic modulus of the self-assembled nanocomposites by a factor of eight.

Enhanced Chirality Transfer in Self‐Assembled Nanocomposites Powered by A Trace Amount of Chiral Dimeric Molecules

Chiral‐selective self‐assembly has markedly advanced the development of chiral materials. While the Sergeant and Soldiers principle allows for chirality amplification, it necessitates precise shape‐matching between chiral and achiral molecules, leading to a low chirality transfer efficiency—where one chiral molecule influences the chirality of a limited number of achiral molecules. Here, we show that this efficiency can be markedly enhanced by introducing chiral dimeric molecules. In this work, a single chiral molecule can control the chirality of up to 200 achiral molecules and even direct the assembly of inorganic nanoparticles into chiral nanocomposites through a sequential chirality transfer process. Moreover, this approach exhibits remarkable robustness, operating effectively without necessitating a precise match between chiral and achiral molecules. Consequently, using the same chiral molecules at an exceptionally low molar fraction (0.5 mol%) allows for the chiral‐selective assembly of achiral molecules over a broad spectrum, regardless of their packing habits, thus facilitating the creation of otherwise inaccessible chiral materials with modulated chiroptical properties. Last but not least, even a trace amount of chiral molecules can enhance the elastic modulus of the self‐assembled nanocomposites by a factor of eight.

Hydrophilicity Dependent Distribution of Water at Ionic Liquids/Metal Interface Monitored by Electrochemical SERS.

The understanding of the interfacial processes is critically important for extending the practical application of ionic liquids, particularly for the role of interfacial water. In the electrochemical system based on ionic liquid electrolytes, small amounts of water at the interface generate a significant change in the electrochemical behaviors of ionic liquids. Therefore, the investigation on the interfacial behavior of water is highly desired in ionic liquids with different anions, water content, and hydrophilicity. Herein, based on the probe strategy, in situ surface enhanced Raman spectroscopy (SERS) combined with electrochemical control (EC-SERS) was developed to investigate the influence of hydrophilicity/hydrophobicity of ionic liquids on the interfacial water. The water-sensitive transformation reaction of 4,4'-dimercaptoazobenzene (DMAB) to para-aminothiophenol (PATP) was employed as a probe reaction for investigating the behavior of interfacial water. The changes of relative SERS intensities of DMAB to PATP served as an indication of the quantity variation of interfacial water. The results show that the transformation reaction efficiencies were critically dependent on the additional water contents, potential, and hydrophilicity of ionic liquids. With a very low molar fraction of additional water (Xw = 0.01), transformation efficiency of DMAB (the amount of interfacial water) followed the sequence of [BMIm]BF4 < [BMIm]PF6 < [BMIm]Tf2N. It was in agreement with the hydrophobicity order of the ionic liquids. With the increase in additional water content, the potential for the full transformation was positively moved, and the efficiency increased significantly. The stronger hydrophobicity allowed more water molecules to migrate to the interface, which was attributed to the difference in interactions between water and the anions of ionic liquids. It demonstrated that the small amount of water tended to gather at the interface in hydrophobic ionic liquids. Compared to traditional cyclic voltammetry, the EC-SERS technique combined with probe reactions is more sensitive to interfacial water. It is anticipated to develop as a promising tool for the investigating water-related issues at interfaces and to provide guidance to screen ionic liquids for practical application.

A quantitative theory for heterogeneous combustion of nonvolatile metal particles in the diffusion-limited regime

The paper presents an analytical theory quantitatively describing the heterogeneous combustion of nonvolatile (metal) particles in the diffusion-limited regime. It is assumed that the particle is suspended in an unconfined, isobaric, quiescent gaseous mixture and the chemisorption of the oxygen takes place evenly on the particle surface. The analytical solution of the particle burn time is derived from the conservation equations of the gas-phase described in a spherical coordinate system with the utilization of constant thermophysical properties, evaluated at a reference film layer. This solution inherently takes the Stefan flow into account. The approximate expression of the time-dependent particle temperature is solved from the conservation of the particle enthalpy by neglecting the higher order terms in the Taylor expansion of the product of the transient particle density and diameter squared. Coupling the solutions for the burn time and time-dependent particle temperature provides quantitative results when initial and boundary conditions are specified. The theory is employed to predict the burn time and temperature of 10–100 μm iron particles, which are then compared with measurements, as the first validation case. The theoretical burn time agrees with the experiments almost perfectly at both low and high oxygen levels. The calculated particle temperature matches the measurements fairly well at relatively low oxygen mole fractions, whereas the theory overpredict the particle peak temperature due to the neglect of evaporation and the possible transition of the combustion regime.Novelty and significance statementFor the first time, we present a comprehensive and quantitative analytical theory elucidating the heterogeneous combustion of nonvolatile (metal) particles in the diffusion-limited regime. This novel theoretical model exhibits a remarkable capacity for quantitative prediction, obviating the need for supplementary information from numerical simulations or experimental data. The derivation process of analytical solutions for burn time and time-dependent particle temperature from conservation equations is elaborated, offering transparency and insight into the model’s foundations. To demonstrate the practical utility of the theory, we apply it to analyze the combustion of iron particles, providing valuable mathematical perspectives on the underlying processes. The model’s predictions for burn time and temperature align closely with experimental results, offering a partial validation of the theory within the realm of its applicable assumptions. This pioneering work contributes a robust and versatile analytical framework, advancing our understanding of diffusion-limited combustion phenomena of nonvolatile particles.

Study of the perturbed hydrogen-bonded water structure of the hydration shell of N-Methyl-Acetamide by Raman multivariate curve resolution spectroscopy

In this work, Raman scattering measurement combined with multivariate curve resolution (Raman-MCR) technique has been used to obtain the solute correlated spectra (SC) of N-methyl-acetamide (NMA) in an aqueous medium. The SC spectra is composed of NMA intramolecular vibrations and NMA induced-perturbations of water OH stretch vibrations. The SC spectra obtained for different mole-fractions of NMA reveal that as the mole-fraction of NMA increases the perturbed water interacting with the amide group is retained whereas it gets depleted from the hydrophobic hydration shell of the methyl group of NMA. The high wavenumber region of the OH spectrum shows that the fraction of the weakly hydrogen-bonded population is higher in the bulk water compared to perturbed water. The Raman spectra of perturbed OH spectral features due to hydration of the hydrophobic methyl group of NMA have been extracted from SC spectra obtained at low mole-fraction of NMA by the MCR technique. Its spectral feature resembles the SC-OH spectra of hydrophobic hydration of the methyl group of methanol.

Experimental and theoretical study of multiple active site-functionalized Spirulina residue-based porous carbon as an economical adsorbent for NH3 and SO2 adsorption: Micro- and macro-mechanistic investigations

Here, we successfully synthesized a cost-effective (7.88 USD/kg) multi-active site (CuCl2, CuO and KCl) functionalized Spirulina residue-based porous carbon (MMBC). This innovative synthesis method utilizes Spirulina residue, a sustainable and low-cost biomass source, making the production of MMBC economically viable and environmentally friendly. Under ambient conditions, MMBC exhibits competitive adsorption capacities for NH3 and SO2 compared to other adsorbents, reaching 3.01 mmol/g (i.e., 51.26 mg/g) and 0.70 mmol/g (i.e., 44.85 mg/g), respectively, and tolerable recoverability. These values are significant improvements over many existing adsorbents, highlighting MMBC's efficiency in removing toxic industrial chemicals (TICs). Additionally, even at low molar fractions of NH3 or SO2, such as 0.001, MMBC demonstrates significant ideal adsorption solution theory (IAST) selectivity for NH3/N2 and SO2/N2, with values of 12.02 and 4.19, respectively. This high selectivity at low concentrations underscores MMBC's potential for applications in environments with trace amounts of pollutants. Furthermore, extensive research has been conducted in this study to elucidate the microscopic and macroscopic adsorption mechanisms of NH3 and SO2 on MMBC. Specifically, investigations in statistical physics models and statistical thermodynamics reveal that the adsorption of NH3 and SO2 on MMBC adhere to a non-aggregative, multilayer, multi-anchorage, and spontaneous exothermic physicochemical behavior. And the adsorption orientation occurs either horizontally or both horizontally and non-horizontally, contingent upon the system and temperature. These findings provide a deeper understanding of the adsorption processes and provide innovative insights into the adsorption mechanisms at the molecular level and at the macroscopic scale. Besides, the material characterization results reveal that the above adsorption process involves both physical interactions (pore diffusion and van der Waals forces) and chemical interactions (CuCl2 with NH3, CuO and KCl with SO2), indicating a physicochemical adsorption mechanism. This dual mechanism of adsorption offers a comprehensive explanation of the high performance of MMBC. In summary, this study developed a cost-effective Spirulina residue-based adsorbent, exhibiting high removal efficiency and selectivity for TICs, and providing deep insights into adsorption mechanisms. The innovative use of Spirulina residue addresses waste management issues and promotes the development of sustainable materials in the field of environmental remediation, contributing to cleaner production.

Long-Term Continuous Gas Diagnostics For Fuel Cell Systems: Development Of An Automatized Raman Metrology

Knowledge of the composition of gas flows in fuel cell systems is crucial for their understanding. In current research, this data is rarely recorded inline and in real-time due to the lack of suitable metrology. Here, we present an optical gas sensor. Green light (532 nm) from a 450 mW laser excites Raman scattering. A spectrometer analyzes the scattered light and a Python software extracts gas composition data automatized and in real-time. We designed a measurement cell that allows optical inline access to gas flow systems and is easy to implement. Therefore, common signal enhancement methods with more complex setups can not be applied. Literature data on scattering cross sections does not offer a reliable basis for calibration what constitutes the need for a gas conditioning system that allows fast preparation of well defined mixtures. We used it to present two principles of calibration. First, calibration based on relative scattering cross sections is the more stable possibility, because it is still valid in cases where laser power and integration time are changed. However, in consequence the results for one species are not independent from the other species. A poor signal, e.g. following from a low mole fraction in a single component, will introduce uncertainty in all components. We avoid that problem through direct linear correlation of signal strength of one species to its partial pressure, which is the second calibration variant. In this case, there is an influence of laser power and integration time. The additional information on overall pressure can be used in model systems, where the presence of undetected components can be ruled out. We can compare that information to pressure measurements to do plausibility checks on the Raman results in real-time. We apply the sensor in fuel cell system research, where measurement intervals of one second yield results of sufficient precision. Increasing integration time can further decrease the uncertainties where favorable. The measurement and data evaluation routines work stable and constant enough to monitor gas compositions in longterm operation. To date, the sensor can measure mixtures of nitrogen, oxygen, hydrogen and water vapor.

Thermophysical properties of binary mixtures of pentyl acetate with butanol at 298.15 K to 318.15 K: PFP theory, FTB model, and Graph theoretical approach

The measured density (ρ) and refractive index (nD) of binary pentyl acetate (1) + isomers of butanol (2) mixtures were reported at T = 298.15 K to 318.15 K and at 0.1 MPa pressure. Using the experimental ρ, u and nD data, excess molar volume (VmE), excess ultrasonic speed (uE), excess isentropic compressibility (κSE), and excess refractive index (nDE) were calculated and correlated with the Redlich–Kister (RK) equation. The findings suggest that the behavior of a mixture is affected by intermolecular interactions (cohesive forces such as dipole–dipole, H–bonding, dispersive force) and structural aspects of the molecules. The Prigogine–Flory–Patterson (PFP) theory, Flory–Treszczanowicz–Benson (FTB) model, and Graph theoretical approach (GTA) accurately analyzed the VmE values. Both the FTB model and PFP theory predicted the VmE curves not only successfully but also accurately represented their shape and magnitude except GTA at a lower mole fraction of pentyl acetate (xA<0.2). The positive values of VmE values were observed for binary mixtures across all temperatures. The intermolecular interactions were also corroborated by uE, κSE and nDE.

On the Maximum Obtainable Purity and Resultant Maximum Useful Membrane Selectivity of a Membrane Separator.

Design considerations concerning the maximum purity of a membrane separator, and the resultant maximum effective selectivity of the membranes were explored by modeling a binary gas membrane separator (pressure-driven permeance) using a dimensionless form. Although the maximum purity has an analytical solution at the limit of zero recovery or stage cut, this solution over-predicts the obtained purity as the recovery is increased. Furthermore, at combinations of high recovery, low feed mole fraction, and low pressure ratio, the maximum purity becomes independent of selectivity above some critical selectivity. As a consequence of this purity limitation, a maximum selectivity is defined at which further increases in selectivity will result in less than a 1% change in the final purity. An equation is obtained that specifies the region in which a limiting purity is less than unity (indicating the existence of a limiting selectivity); operating at less than the limiting pressure ratio results in a purity limitation less than unity. This regime becomes larger and more significant as the inlet mole fraction decreases (e.g., inlet feed mole fraction of 10% and pressure ratio of 100 results in a maximum useful membrane selectivity of only 130 at 95% recovery). These results suggest that membrane research should focus on increasing permeance rather than selectivity for low-concentration separations. The results found herein can be used to set benchmarks for membrane development in various gas separation applications.

Block Copolymer Self-assembly: Exploitation of Hydrogen Bonding for Nanoparticle Morphology Control via Incorporation of Triazine Based Comonomers by RAFT Polymerization.

Synthesis of polymeric nanoparticles of controlled non-spherical morphology is of profound interest for a wide variety of potential applications. Self-assembly of amphiphilic diblock copolymers is an attractive bottom-up approach to prepare such nanoparticles. In the present work, RAFT polymerization is employed to synthesize a variety of poly(N,N-dimethylacrylamide)-b-poly[butyl acrylate-stat-GCB] copolymers, where GCB represents vinyl monomer containing triazine based Janus guanine-cytosine nucleobase motifs featuring multiple hydrogen bonding arrays. Hydrogen bonding between the hydrophobic blocks exert significant influence on the morphology of the resulting nanoparticles self-assembled in water. The Janus feature of the GCB moieties makes it possible to use a single polymer type in self-assembly, unlike previous work exploiting, e.g., thymine-containing polymer and adenine-containing polymer. Moreover, the strength of the hydrogen bonding interactions enables use of a low molar fraction of GCB units, thereby rendering it possible to use the present approach for copolymers based on common vinyl monomers for the development of advanced nanomaterials.

Effect of Mixture Composition on the Photophysics of Indoline Dyes in Imidazolium Ionic Liquid-Molecular Solvent Mixtures: A Femtosecond Transient Absorption Study.

We conducted a study on the photophysics of three indoline dyes, D102, D149, and D205, in binary mixtures of ionic liquids (IL) and polar aprotic molecular solvents (MS). Specifically, we examined the behavior of these dyes in IL-MS mixtures containing four different imidazolium-based ILs and three different polar aprotic MSs. Our investigation involved several techniques, including stationary absorption and emission measurements, as well as femtosecond transient absorption (TA) spectroscopy. Through our analysis, we discovered a peculiar behavior of several photophysical properties at low IL mole fractions (0 < XIL < 0.2). Indeed, in this range of mixture composition, the absorption maximum wavelength decreases noticeably, while the emission maximum wavelength and the Stokes shift, expressed in wavenumbers, reach a maximum. while a minimum occurs in the relative quantum yield and the excited state lifetime. These results indicate that the solvation of dye undergoes a large change in this range of mixture composition. We found that, at high ionic liquid content, the excited relaxation times are correlated with the high viscosity, while at low content, it is the polarity of the solvent that influences the behavior of the excited relaxation times. At a mixture composition of around 0.10, the behavior of the photophysical properties of the studied IL-MS mixtures indicates a crossover between situations where the solvation is dominated by that of ions and that dominated by the solvent.

The Identification of Structural Changes in the Lithium Hexamethyldisilazide-Toluene System via Ultrasonic Relaxation Spectroscopy and Theoretical Calculations.

Ultrasonic absorption measurements were carried out over a wide concentration and temperature range by means of a pulse technique to examine the structural mechanisms and the dynamical properties in lithium hexamethyldisilazide (LiHMDS)-toluene solutions. Acoustic spectra revealed two distinct Debye-type relaxational absorptions attributed to the formation of trimers from dimeric and monomer units and to the formation of aggregates between a LiHMDS dimer and one toluene molecule in low and high frequencies, respectively. The formation of aggregates was clarified by means of molecular docking and DFT methodologies. The aggregation number, the rate constants and the thermodynamic properties of these structural changes were determined by analyzing in detail the concentration-dependent relaxation parameters. The low-frequency relaxation mechanism dominates the acoustic spectra in the high LiHMDS mole fractions, while the high-frequency relaxation influences the spectra in the low LiHMDS mole fractions. In the intermediate mole fraction region (0.25 to 0.46), both relaxations prevail in the spectra. The adiabatic compressibility, the excess adiabatic compressibility and the theoretically estimated mean free length revealed a crossover in the 0.25 to 0.46 LiHMDS mole fractions that signified the transition from one structural mechanism related with the hetero-association of LiHMDS dimers with toluene molecules to the other structural mechanism assigned to the formation of LiHMDS trimers. The combined use of acoustic spectroscopy with theoretical calculations permitted us to disentangle the underlying structural mechanisms and evaluate the volume changes associated with each reaction. The results were compared with the corresponding theoretically predicted volume changes and discussed in the context of the concentration effect on intermolecular bonding.

Colloidal 2D Mo1-xWxS2 nanosheets: an atomic- to ensemble-level spectroscopic study.

Composition dependent tuning of electronic and optical properties in semiconducting two-dimensional (2D) transition metal dichalcogenide (TMDC) alloys is promising for tailoring the materials for optoelectronics. Here, we report a solution-based synthesis suitable to obtain predominantly monolayered 2D semiconducting Mo1-xWxS2 nanosheets (NSs) with controlled composition as substrate-free colloidal inks. Atomic-level structural analysis by high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDXS) depicts the distribution of individual atoms within the Mo1-xWxS2 NSs and reveals the tendency for domain formation, especially at low molar tungsten fractions. These domains cause a broadening in the associated ensemble-level Raman spectra, confirming the extrapolation of the structural information from the microscopic scale to the properties of the entire sample. A characterization of the Mo1-xWxS2 NSs by steady-state optical spectroscopy shows that a band gap tuning in the range of 1.89-2.02 eV (614-655 nm) and a spin-orbit coupling-related exciton splitting of 0.16-0.38 eV can be achieved, which renders colloidal methods viable for upscaling low cost synthetic approaches toward application-taylored colloidal TMDCs.

Aβ Amyloid Fibers Drastically Alter the Topography and Mechanical Properties of Lipid Membranes.

Alzheimer's disease (AD) is related to the fibrillation of the Aβ peptides at neuronal membranes, a process that depends on the lipid composition and may impart different physical states to the membrane. In the present work, we study the properties of the Aβ peptide when mixed with a zwitterionic lipid (DMPC), using the Langmuir monolayer technique as an approach to control membrane physical conditions. First, we build on previous characterizations of pure Aβ monolayers and observe that, in addition to high shear, these films present a pronounced compressional hysteresis. When Aβ is assembled with DMPC in a binary film, the resulting membranes become heterogeneous, with a peptide-enriched phase distributed in a network-like pattern, and they exhibit a lateral transition that depends on the Aβ content. At lower peptide proportions, the films segregate into two well-defined phases: one consisting of lipids and another enriched with peptides. The reflectivity of these phases differs from that obtained for pure Aβ films. Thus, the formed fibers effectively cover most of the interface area and remain stable at higher pressures (from 20 to 30 mN m-1 depending on Aβ content) compared to pure peptide films (17 mN m-1). Furthermore, such structures induce a compressional hysteresis in the film, similar to that of pure peptide films (which is nonexistent in the pure lipid monolayer), even at low peptide proportions. We claim that the mechanical properties at the interface are governed by the size of the fibril-like structures. Based on the low molar fractions and surface packing at which these phenomena were observed, we postulate that as a consequence of peptide intermolecular interactions, Aβ may have drastic effects on the molecular arrangement and mechanical properties of a lipid membrane.

Density and viscosity of multicomponent diluent/bitumen mixtures with application to in-situ bitumen recovery and diluted bitumen transportation

The extraction of bitumen relies on energy-intensive methods, and its transportation necessitates dilution due to its high viscosity. Hence, there is a growing demand to explore alternative approaches that are cost-effective and energy-efficient to enhance the extraction and transportation processes. While there is ample thermophysical data available in the literature regarding the individual performance of pure solvents and bitumen systems, there is a significant gap in data concerning density and viscosity measurements for multicomponent solvents and their interaction with bitumen. This study presents new measurements by investigating the effect of varying multicomponent diluent concentrations (7 to 70 wt%) on the density and viscosity of multicomponent diluent/Mackay River bitumen system in a pressure range of 1.291–8.769 MPa and a temperature range of 295–389 K. These thermophysical data are essential in the design, optimization, and reservoir simulation of solvent-based and solvent-aided recovery processes, as well as the surface processing and transportation of diluted bitumen. The findings demonstrated that the addition of the diluent, even at a lower mole fraction, has a notable impact on reducing both the density and viscosity of the bitumen. As part of this study, we have also obtained empirical correlations based on well-established relationships that can be employed as predictive tools for estimating the density and viscosity of a multicomponent diluent/bitumen system. The obtained correlations estimate the density and viscosity of mixtures of bitumen and diluent with average absolute relative deviations (AARD) of 0.4 % and 16.29 %, respectively. The new experimental data are then used to perform zeroth-order energy, greenhouse gas emission, and carbon tax recovery analyses of solvent-aided viscosity reduction. The results reveal that the utilization of natural gas condensate as a diluent leads to significant energy reductions and greenhouse gas emissions. The results find applications in solvent-based and solvent-aided bitumen recovery processes, surface processing, and the transportation of diluted bitumen.

Performance analysis of PEMEC with non-uniform deformation based on a comprehensive numerical framework coupling image recognition and CFD

Proton exchange membrane electrolysis cell (PEMEC) is widely regarded as an efficient device for producing green hydrogen. Proper clamping pressure during cell assembly can reduce contact resistance while ensuring sealing and safety. Meanwhile, the clamping pressure will cause deformation of the cell components, resulting in increasing mass transfer resistance. However, the evolution law of multi-physical parameters under different clamping pressures has not been fully studied. In this study, a comprehensive numerical framework is proposed for non-uniform deformation and performance analysis of PEMEC. The framework includes three parts: non-uniform deformation model, data transmission based on image recognition, and three-dimensional (3D) multi-phase and multi-physical model. The effects of cell component non-uniform deformation on heat and mass transfer, and electrochemical characteristics are studied. The purity of hydrogen production is also fully taken into consideration. Results show that high clamping pressure causes severe deformation of liquid and gas diffusion layers under the land and a significant decrease in porosity and permeability. In addition, the accumulation of oxygen in the flow channel will weaken the liquid water supply rate and form a high oxygen covered region on the membrane. The current density inhomogeneity in this region will increase significantly with clamping pressure. Although high clamping pressure can obtain low contact resistance and high output hydrogen molar fraction, it also increases mass transfer resistance. An appropriate clamping pressure of 3 MPa is recommended with a lower cell voltage of 2.12 V at 2A/cm2 after considering the physical and chemical properties. The present study can provide helpful guidelines on the design of large-scale electrolyzers.

A numerical study to determine proper steam-to-fuel ratio in a biogas-fueled solid oxide fuel cell for different levels of biogas methane content

It is vital to find the optimal quantity of water added to the fuel in a biogas-fueled Solid Oxide Fuel Cell (SOFC). An under-optimal water quantity can impede steam reforming reactions, while an over-optimal quantity of water (which is equivalent to reduced biogas portion) may reduce the performance of the fuel cell due to a shortage of fuel. Water production in electrochemical reactions and the carbon deposition constraint add to the complexity of water quantity optimization. The present work develops a 3D numerical model to simulate a direct biogas-fueled SOFC to find the optimal steam/biogas (S/C) ratio. Several biogas mixtures (CH4/CO2 ratios) are analyzed. For each mixture, a wide range of S/C ratios is evaluated in a wide range of voltages. It is found that the polarization curves corresponding to different S/C ratios intersect each other for a given biogas mixture. In other words, an S/C ratio can be optimal at some voltages and non-optimal at others. Based on power density maximization as an explicit criterion, the optimal S/C ratio is found to be 0.75 at low CH4 molar fractions (~50%) and 1.25 at high CH4 molar fractions (~75%).

Gradation control in the hydrodynamic diameters of mixed glycan-aglycan glycovesicles

Abstract Glycovesicles mimic synthetic cell membrane surfaces and aid to delineate intricate, weak carbohydrate–protein interactions. In this report, the dependence of the hydrodynamic diameters in relation to the molar fractions of carbohydrate moieties in the mixed polydiacetylene (PDA) glycovesicles is evaluated. The glycovesicles are constituted with diacetylene monomers of varying molar fractions of carbohydrate moieties and the hydrodynamic diameters are assessed without and with polymerization of the vesicles. A strong dependence of the hydrodynamic diameter of glycovesicles is seen as a function of the molar fractions and the nature of the sugar moiety being either mono- or disaccharide. A monotonous increase in the hydrodynamic diameters of the glycovesicles occurs with the increase in mole fractions of the sugar monomer lipids. Upon polymerization, the hydrodynamic diameters reduce for the vesicles with lower mole fractions of sugar monomer, whereas the reverse occurs for glycovesicles possessing higher mole fractions. Disaccharide glycovesicles possess higher hydrodynamic diameters than monosaccharide-containing vesicles. Ligand–lectin interactions were probed with lactose disaccharide-containing glycovesicles with tetrameric peanut agglutinin lectin, from which an increase in the hydrodynamic diameters is observed, as the mole fraction of sugar monomer is increased in the PDA-glycovesicles.

Auto-ignition and knocking combustion characteristics of iso-octane-ammonia fuel blends in a rapid compression machine

Ammonia has attracted much attention because of its carbon-free nature. Ammonia also has a high research octane number (RON), making it a promising anti-knock additive for conventional engine fuels. In this study, to investigate the effects of ammonia addition on the knocking combustion of iso-octane, a series of spark ignition experiments were conducted in an optical rapid compression machine. And compression ignition experiments were also carried out to measure the ignition delay times. The molar fractions of ammonia in iso-octane-ammonia blends were set as 80% (A80), 40% (A40), and 0% (A0), and the initial thermodynamic conditions were 630–840 K and 8–25 bar. Chemical kinetics analysis of the end-gas was also performed with a blended reaction mechanism obtained by directly merging the LLNL iso-octane mechanism and the Glarborg ammonia mechanism. The experimental results showed that the ignition delay time increased with increasing ammonia fraction, but this trend could only be qualitatively predicted by the blended mechanism. At the same initial pressure and temperature conditions, the knock intensity (KI) decreased with increasing ammonia fraction, but the inhibitory effect was less pronounced at high initial temperature conditions. At the same initial energy density and high-temperature conditions, the KI of A40 and A80 was higher than A0, which was ascribed to the higher pressure requirement for the blended fuels with higher ammonia fractions to achieve the same energy density as those with lower ammonia fractions. At low temperature and pressure conditions, the auto-ignition showed a two-stage characteristic. With the increasing fraction of ammonia, the first-stage auto-ignition shifted from supersonic to subsonic, and the second-stage detonative auto-ignition gradually disappeared. The weakened auto-ignition with increasing ammonia fraction was attributed to the less reactive end-gas, as evidenced by the lower mole fraction of OH radical and lower heat release rate in the end-gas at the auto-ignition timing. When using the ε- ξ diagram to examine the auto-ignition mode, the experimental detonation cases were well distributed in the detonation peninsula, but the non-detonation and critical detonation cases were scattered irregularly.

Some features of heat capacity changes in aqueous solutions of low molecular weight alkanols at T = 298.15 K and ambient pressure

The specific (cp) and molar (Cp) heat capacities of dilute aqueous solutions of methanol (MeOH), ethanol (EtOH), 1-propanol (n-PrOH) and 2-propanol (i-PrOH) were measured using an adiabatic calorimetry at T = 298.15 K and ambient pressure. Based on the obtained results, the excess molar heat capacities, CpE, as well as the apparent molar heat capacities of each of components, Cp,∅,12, of the system {water (1) + alkanol (2)} were calculated. The standard (at infinite dilution) Cp,2o values were also estimated. All the CpE values are positive and pass through maxima, which shift to the range of a lower mole fraction of alcohol, x2, when the molecular weight of the latter increases. The same goes for the Cp,∅,1max values, too. In turn, the order of changing Cp,∅,2max within the narrow high-diluted range of (∼0.01 <x2 < 0.035) m.f. is oppositely directed. It is established that the x2 value at dCpE/dx2 = 0 is approximately half of the sum of the x2 values at Cp,∅,1max and Cp,∅,2max, a fact indicating the parity contribution of both interacting components of the solution to the structure-energy transformations occurring in it.