Liquid Alkanes Research Articles

Synthesis of Uniform Alkane-Filled Capsules with a High Under-Cooling Performance and Their Real-Time Optical Properties.

Encapsulating under-cooling materials has been a promising strategy to address the compatibility issue with a surrounding matrix. Herein, we present the synthesis of a uniform alkane-infilled capsule system that shows obvious under-cooling properties. As demonstrating examples, n-hexadecane was selected as a liquid alkane and n-eicosane as a solid in our systems as core materials via in-situ polymerization, respectively. The under-cooling properties of capsules were investigated using differential scanning calorimetry, real-time optical observations with two polarizers, and molecular modeling. The n-hexadecane encapsulated capsules exhibited a large under-cooling temperature range of 20 °C between melt and crystallization, indicating potential applications for structure-transformation energy storage. In addition, molecular modeling calculations confirmed that the solid forms of n-hexadecane and n-eicosane are more stable than their liquid forms. From liquid to solid form, the n-hexadecane and n-eicosane release energies were 4.63 × 103 and 4.95 × 103 J·g−1, respectively.

Facile and Efficient Gas-Phase Pressure-Controlled Thermal Functionalization of Nanocrystalline Porous Silicon with 1-Hexene

Substitution of hydrogen at porous silicon (PSi) surface by organic groups can be done via thermally activated hydrosilylation reactions in which PSi is left for several hours into liquid alkenes at temperatures typically over 100°C. For alkenes whose boiling points are below 100°C (e.g. 1-heptene and shorter molecules), the process suffers from high reagent boiling and evaporation. Gas-phase hydrosilylation is an alternative when using short molecules. It has not been as extensively studied, and was mainly done in plasma reactors with silicon nanocrystals. Here we present a new method for facile gas-phase thermally-activated hydrosilylation in PSi, but using liquid solutions as reagent (1-hexene was used here). PSi and liquid alkene are loaded at room temperature into a chamber which is then closed and heated up to a temperature greater than the alkene boiling point. The effects of process temperature, time and pressure were investigated by means of Fourier transform infrared spectroscopy. The maximum theoretical derivatization efficiency was achieved with optimized parameters. The derivatization was uniform across the PSi layer depth. PSi luminescence was effectively stabilized by the process. The new gas-phase method presented here is facile, requires very small amount of liquid reagent, and is useful for attachment of short molecules to PSi or other materials surface.

Effect of alkane chain length on tribological properties of straight chain alkane liquid film

How to overcome the friction between the micro components has become a key point of the successful operation of the micro/nano-electric mechanical systems. The understanding of the friction mechanism of the alkane liquid film confined between two substrates is important when the friction law on a macro/nano scale is not applicable. In this work, the molecular dynamics simulations are used to study the effect of the chain length on the friction properties of the liquid films that are confined between two golden substrates. There are seven pure alkane liquid films that are composed of one molecule C<sub><i>n</i></sub>H<sub>2<i>n</i> + 2</sub>(<i>n</i> = 6, 8, 10, 12, 14, 16, 18), and six mixed alkane liquid films that are composed of two molecules C<sub>6</sub>H<sub>14</sub>/C<sub><i>n</i></sub>H<sub>2<i>n</i> + 2</sub>(<i>n</i> = 8, 10, 12, 14, 16, 18) with a ratio of 1∶1. The results show that the friction force and the coefficient of friction of pure alkane liquid films both increase as the chain length increases when the carbon atom number is less than 12, whereas the friction property keeps stable when the carbon atom number of the alkane molecule is greater than 10 and the pure hexadecane liquid film has the largest friction force. In the mixed films, the addition of short chain alkane molecules can strengthen the friction, and the hexane/dodecane mixed film has the maximum friction force. The short chain molecule dilutes the C<sub>8</sub>H<sub>18</sub> film and C<sub>10</sub>H<sub>22</sub> film which cause the friction force to decrease. During the sliding progress, the formation of solid-like high density-packet layers is the main reason for the friction reduction. When no solid-like layer or just one solid-like layer is formed at the interface of golden base, the liquid alkane film is liquid-like and its viscosity becomes much larger than that in the normal state, which leads to high friction force. The short chain molecules reduce the density of the solid-like layers, which causes the film to transform from solid-like state to liquid state, thus resulting in the increase of friction. The friction property mainly depends on the layered structure, and the interaction between the golden surface and liquid film contributes to the friction. This study helps to understand the friction mechanism of ultra-thin liquid films.

From nano-emulsions to phase separation: evidence of nano-segregation in (alkane + perfluoroalkane) mixtures using 129Xe NMR Spectroscopy.

In this work we demonstrate that mixtures of (hexane + perfluorohexane) above the upper critical solution temperature segregate by forming domains at the nanometric scale. 129Xe NMR spectra obtained for solutions of xenon in liquid mixtures of (hexane + perfluorohexane) as a function of temperature suggest the existence of domains richer in the hydrogenated component, in which xenon "prefers" to be solvated. The average local concentration within the xenon coordination sphere is at least 0.05 higher in hexane mole fraction than the nominal concentration of the mixture. Atomistic molecular dynamics simulations support this analysis in excellent agreement with the experimental data. Additionally, 129Xe NMR spectra in pure perfluoroalkanes allow a detailed analysis of the liquid structure, continuing that previously reported for the liquid alkanes. It should be emphasised that nano-segregation is here observed in fluids governed exclusively by dispersion interactions, in contrast to other examples in which hydrogen bonding and polarity play important roles. Given its simplicity, this case study is thus prone to have a general impact in understanding the early mechanisms of segregation, phase separation and self-assembly.

Hydration mediated interfacial transitions on mixed hydrophobic/hydrophilic nanodroplet interfaces.

Interfacial phase transitions are of fundamental importance for climate, industry, and biological processes. In this work, we observe a hydration mediated surface transition in supercooled oil nanodroplets in aqueous solutions using second harmonic and sum frequency scattering techniques. Hexadecane nanodroplets dispersed in water freeze at a temperature of ∼15 °C below the melting point of the bulk alkane liquid. Addition of a trimethylammonium bromide (CXTA+) type surfactant with chain length equal to or longer than that of the alkane causes the bulk oil droplet freezing transition to be preceded by a structural interfacial transition that involves water, oil, and the surfactant. Upon cooling, the water loses some of its orientational order with respect to the surface normal, presumably by reorienting more parallel to the oil interface. This is followed by the surface oil and surfactant alkyl chains losing some of their flexibility, and this chain stretching induces alkyl chain ordering in the bulk of the alkane phase, which is then followed by the bulk transition occurring at a 3 °C lower temperature. This behavior is reminiscent of surface freezing observed in planar tertiary alkane/surfactant/water systems but differs distinctively in that it appears to be induced by the interfacial water and requires only a very small amount of surfactant.

On the importance of accounting for nuclear quantum effects in ab initio calibrated force fields in biological simulations

In many important processes in chemistry, physics, and biology the nuclear degrees of freedom cannot be described using the laws of classical mechanics. At the same time, the vast majority of molecular simulations that employ wide-coverage force fields treat atomic motion classically. In light of the increasing desire for and accelerated development of quantum mechanics (QM)-parameterized interaction models, we reexamine whether the classical treatment is sufficient for a simple but crucial chemical species: alkanes. We show that when using an interaction model or force field in excellent agreement with the "gold standard" QM data, even very basic simulated properties of liquid alkanes, such as densities and heats of vaporization, deviate significantly from experimental values. Inclusion of nuclear quantum effects via techniques that treat nuclear degrees of freedom using the laws of classical mechanics brings the simulated properties much closer to reality.

Исследование влияния толщины слоя гранулированного пеностекла на горение жидкостей ряда алканов

Показана возможность прекращения горения жидких углеводородов ряда алканов за счет последовательного нанесения на поверхность жидкости легкого носителя (пеностекла) и гелеобразующего состава. Экспериментально определено влияние толщины слоя пеностекла на массовую скорость выгорания жидких гомологов ряда алканов: пентана, гептана, октана, декана и додекана. Установлено, что массовая скорость выгорания алканов уменьшается с ростом толщины слоя пеностекла. Отмечен эффект прекращения горения высококипящих алканов (декан, додекан) при достижении толщины слоя пеностекла 8 и 6 см; для октана необходим слой пеностекла 10 см. Низкокипящие алканы (пентан, гептан) не гаснут при толщине слоя пеностекла 12 см. Нанесение на пеностекло геля в указанных условиях ускоряет тушение и гарантирует невозможность повторного воспламенения.

The aquatic hazard of hydrocarbon liquids and gases and the modulating role of pressure on dissolved gas and oil toxicity

Hydrostatic pressure enhances gas solubility and potentially alters toxicity and risks of oil and gas releases to deep-sea organisms. This study has two primary objectives. First, the aquatic hazard of dissolved hydrocarbon gases is characterized using results of previously published laboratory and field studies and modeling. The target lipid model (TLM) is used to predict effects at ambient pressure, and results are compared to effect concentrations derived from extrapolation of liquid alkane hazard data. Second, existing literature data are used to quantify and predict pressure effects on toxicity using an extension of the TLM framework. Results indicate elevated pressure mitigates narcosis, particularly for sensitive species. A simple adjustment is proposed to allow TLM-based estimates of acute effect and TLM-derived HC5 values (concentrations intended to provide 95% species protection) for oil or gas constituents to be calculated at depth. Future applications, and opportunities and challenges for providing validation, are discussed.

Adsorption Isotherms of Liquid Isomeric Mixtures

To separate linear and branched molecules in a liquid state, adsorption on porous materials is a promising separation method. To calculate the adsorption isotherms, a combination of lattice cluster theory and density functional theory was introduced recently, allowing the prediction of branched molecules’ adsorption isotherms based on the knowledge of the adsorption isotherms of the pure linear substances. However, these models are not practicable for process simulation and optimization because of their high numerical effort. Therefore, a simpler adsorption model based on the lattice cluster theory was developed to provide the results of the density functional theory approach for process development. In addition to the adsorption isotherm calculations, the model also considers the overall mass balance of the adsorption process. The model was validated for the adsorption of two binary, liquid alkane systems on three different adsorbents. Therefore, adsorption isotherms of these mixtures on activated coal, ...

Unique Interfacial Phenomena on Macroscopic and Colloidal Scales Induced by Two-Dimensional Phase Transitions.

This feature article addresses a variety of unique macroscopic-scale and colloidal-scale interfacial phenomena, such as wetting transitions of oil droplets into molecularly thin films, spontaneous merging and splitting of oil droplets at air-water interfaces, solid monolayer and bilayer formation in mixed cationic surfactant/alkane adsorbed films, switching of foam-film thickness, and oil-in-water emulsion stability. All of these phenomena can be observed using commercial cationic surfactants, liquid alkanes, and water.

Selective conversion of butanol into liquid branched olefins over zeolites

The n-butanol to hydrocarbon (BTH) reaction can produce a series of valuable chemicals and clean fuel precursors. The BTH reaction over different zeolite catalysts (ZSM-5, ZSM-22, Meso-ZSM-22, and ZSM-35) with an emphasis on the production of liquid branched olefins which can be used as precursors for clean gasoline was investigated in this paper. It was found that the structure and acidity of zeolite significantly influences the product distribution in BTH reaction. ZSM-5 zeolite with medium micropore size and large intersections, which are not present in ZSM-22, led to aromatic-rich products and had a long lifetime. ZSM-22 and Meso-ZSM-22 zeolites with unidirectional 10-ring structure achieved a high selectivity to isobutylene and C5+ branched hydrocarbons. Moreover, the Meso-ZSM-22 obtained by desilication with a higher acidity density and improved diffusion property resulted in more liquid organic products than the parent ZSM-22. ZSM-35 exhibited a high product-shape-selectivity for producing isobutylene because of its unique irregular sheet structure and is not suitable for liquid olefin production.

Methylene Volumes in Monoglyceride Bilayers are Larger than in Liquid Alkanes

Abstract The densities as a function of temperature of four fully hydrated saturated monoglycerides with even chain lengths ranging from eight to fourteen were determined by vibrating tube densitometry and their phase transition temperatures were determined by differential scanning calorimetry (DSC). We find the volume of a methylene group in a monoglyceride bilayer is 2% larger than in liquid alkanes at physiological temperatures, similar to the methylene group volumes found in phosphatidylcholine (PC) bilayers. Additionally, we carefully consider the traditional method of calculating component volumes from experimental data and note potential difficulties in this approach. In the literature, the ratio of terminal methyl volume (CH3) to methylene (CH2) volumes is typically assumed to be 2. By analysis of literature alkane data, we find this ratio actually ranges from 1.9 to 2.3 for temperatures ranging from 0 °C to 100 °C. For a rough sense of scale, we note that to effect a 2% reduction in volume requires of order 200 atmospheres of pressure, and pressures of this magnitude are biologically relevant. For instance, this amount of pressure is sufficient to reverse the effect of anesthesia. The component volumes obtained are an important parameter used for determining the structure of lipid bilayers and for molecular dynamics simulations.

Wettability Alteration of Mineral Surface during Low-Salinity Water Flooding: Role of Salt Type, Pure Alkanes, and Model Oils Containing Polar Components

Low-salinity water injection is an emerging enhanced oil recovery technique and an area of active research. According to many researchers, the role of brine salinity has been attributed to its ability to change the reservoir rock wettability. The influence of different parameters such as total dissolved solids, concentration of individual ions, oil composition, lithology, acid and base number, etc., has been tested previously using different combinations of crude oil and reservoir core samples. However, because of the complex nature of crude oil–brine–rock system, there is no clear idea of the mechanism of wettability alteration and the influence of above parameters on this process. In this work, we have investigated the governing factors affecting the wettability of mineral surface using pure alkane liquids and model oils (containing organic acid and base). The wettability studies were performed through contact angle measurements over a wide range of concentration (1 mM to 1M) of monovalent and divalent ...

Comparison of Additive and Polarizable Models with Explicit Treatment of Long-Range Lennard-Jones Interactions Using Alkane Simulations.

Long-range Lennard-Jones (LJ) interactions have a significant impact on the structural and thermodynamic properties of nonpolar systems. While several methods have been introduced for the treatment of long-range LJ interactions in molecular dynamics (MD) simulations, increased accuracy and extended applicability is required for anisotropic systems such as lipid bilayers. The recently refined Lennard-Jones particle-mesh Ewald (LJ-PME) method extends the particle-mesh Ewald (PME) method to long-range LJ interactions and is suitable for use with anisotropic systems. Implementation of LJ-PME with the CHARMM36 (C36) additive and CHARMM Drude polarizable force fields improves agreement with experiment for density, isothermal compressibility, surface tension, viscosity, translational diffusion, and 13C T1 relaxation times of pure alkanes. Trends in the temperature dependence of the density and isothermal compressibility of hexadecane are also improved. While the C36 additive force field with LJ-PME remains a useful model for liquid alkanes, the Drude polarizable force field with LJ-PME is more accurate for nearly all quantities considered. LJ-PME is also preferable to the isotropic long-range correction for hexadecane because the molecular order extends to nearly 20 Å, well beyond the usual 10-12 Å cutoffs used in most simulations.

Desulfurization by MOFs as Sorbents for Thiophene Sulfides

Metal-organic frameworks UMCM-150 [Cu3(BHTC)2] and its heterobimetallic analogue Co1Cu2(BHTC)2 based on an asymmetrical ligand, biphenyl-3,4’,5-tricarboxylate (H3BHTC), were studied for desulfurization of model oils. The adsorption experiments were conducted under room temperature and atmospheric pressure. The total sulfur concentration of model oils was 250 ppmw determined by WK-2D coulomb integrated micro-analyzer through adding benzothiophene (BT) and dibenzothiophene (DBT) into liquid alkanes. Adsorptive desulfurization experiments were conducted in a consecutive fixed bed adsorption system. The results indicate that Cu3(BHTC)2 has a higher sulfur-capacity than Co1Cu2(BHTC)2. Taking DBT as an example, Cu3(BHTC)2 and Co1Cu2(BHTC)2 have breakthrough adsorption capacities of 10.6 and 5.8 g S/kg of sorbent for model oils.

Directional freeze-cast hybrid-backbone meso-macroporous bodies as micromonolith catalysts for gas-to-liquid processes

Directional freeze casting enables the assembly of bimodally porous micronomolith Fischer–Tropsch catalyst bodies with enhanced effective thermal conductivity and pore molecular transport rates, leading to a high selectivity to liquid olefin products.

BOCS: Bottom-up Open-source Coarse-graining Software.

We present the BOCS toolkit as a suite of open source software tools for parametrizing bottom-up coarse-grained (CG) models to accurately reproduce structural and thermodynamic properties of high-resolution models. The BOCS toolkit complements available software packages by providing robust implementations of both the multiscale coarse-graining (MS-CG) force-matching method and also the generalized-Yvon-Born-Green (g-YBG) method. The g-YBG method allows one to analyze and to calculate MS-CG potentials in terms of structural correlations. Additionally, the BOCS toolkit implements an extended ensemble framework for optimizing the transferability of bottom-up potentials, as well as a self-consistent pressure-matching method for accurately modeling the pressure equation of state for homogeneous systems. We illustrate these capabilities by parametrizing transferable potentials for CG models that accurately model the structure, pressure, and compressibility of liquid alkane systems and by quantifying the role of many-body correlations in determining the calculated pair potential for a one-site CG model of liquid methanol.

Angelica Lactones: From Biomass‐Derived Platform Chemicals to Value‐Added Products

The upgrading of biomass-derived compounds has arisen in recent years as a very promising research field in both academia and industry. In this sense, a lot of new processes and products have been developed, often involving levulinic acid as a starting material or intermediate. In the last few years, though, other scaffolds have been receiving growing attention, especially, angelica lactones. Considering these facts and the emergent applications of said molecules, in this review we will discuss their preparation and applications; the use of these frameworks as starting materials in organic synthesis to produce potential bioactive compounds will be covered, as will their use as a foundation to highly regarded compounds such as liquid alkanes with prospective use as fuels and polymers.

Synthesis of Renewable Lubricant Alkanes from Biomass-Derived Platform Chemicals.

The catalytic synthesis of liquid alkanes from renewable biomass has received tremendous attention in recent years. However, bio-based platform chemicals have not to date been exploited for the synthesis of highly branched lubricant alkanes, which are currently produced by hydrocracking and hydroisomerization of long-chain n-paraffins. A selective catalytic synthetic route has been developed for the production of highly branched C23 alkanes as lubricant base oil components from biomass-derived furfural and acetone through a sequential four-step process, including aldol condensation of furfural with acetone to produce a C13 double adduct, selective hydrogenation of the adduct to a C13 ketone, followed by a second condensation of the C13 ketone with furfural to generate a C23 aldol adduct, and finally hydrodeoxygenation to give highly branched C23 alkanes in 50.6 % overall yield from furfural. This work opens a general strategy for the synthesis of high-quality lubricant alkanes from renewable biomass.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd\u2013Mo catalyst

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.