Organic Liquid Systems Research Articles

A Study of Correlative Modeling on Viscosity for Some Organic Binary Liquid Systems

In order to systematically investigate the correlating capability of viscosity models, six well-known correlative models of Grunberg-Nissan (GN), Hind (HND), Heric (HRC), Ausländer (AUS) for dynamic viscosity, η, and McAllister 3-body (MAC3) and McAllister 4-body (MAC4) for kinematic viscosity, ν, were employed and tested for viscosity data of 83 organic binary liquid systems consisting of 33 different aromatic hydrocarbons (ArH), alkanes (RH), cycloalkanes (CyRH) and alkanols (ROH). Keeping ArH as a common component and increasing the chain length of other components, the systems were categorized as Category 1: ArH + RH, Category 2: ArH + CyRH, Category 3: ArH + ArH and Category 4: ArH + ROH. For all the models fitting parameters along with the statistical parameters such as SPD σ(%), ASPD σ(%), OASPD σ(%) and GOASPD σ(%) were computed by the Nonlinear Least Squares Minimization (NLSM) technique with the ‘Solver’ add-in package. Among the four categories, Category 3, OASPD, σ(%) values lie between 0.16 and 0.21, indicating that all the models fitted extremely well. However, for dynamic viscosities, the η AUS model demonstrated the best correlating capabilities with GOASPD σ(%) of 0.48, while the HND model performed the poorest with GOASPD σ(%) at 3.8. For the kinematic viscosities, ν in both the MAC3 and MAC4 models yielded satisfactory results with GOASPD σ(%) as < 1.0 %.

Evidence of precipitate formation and byproduct transfer to nonaqueous phase liquids as a result of persulfate exposure

AbstractFor optimal treatment of a source zone using in situ chemical oxidation (ISCO), the oxidant needs to be delivered as close to the nonaqueous phase liquid (NAPL) as possible to enhance the rate of dissolution. However, the interaction between the oxidant and NAPL may result in physical and chemical changes that affect both treatment effectiveness and post‐treatment dissolution behavior from remnant NAPL. Due to a host of favorable attributes, persulfate is frequently selected as the preferred oxidant but little is known about changes that can occur when persulfate interacts with a NAPL. In this study, two series of static batch experiments were conducted. In the first series, NAPL collected from a former manufactured gas plant (FMGP) site was exposed to a persulfate solution for ~60 days, while in the second series, individual and a mixture of pure organic liquids were exposed to a persulfate solution for ~50 days. It was observed that dark‐brown precipitates were formed in almost all the experimental systems. Notably, a layer of precipitates accumulated along the NAPL/water interface in the FMGP NAPL system and inhibited dissolution. In some of the pure organic liquid systems, the aqueous phase appeared yellow and precipitates were formed. Precipitate formation was attributed to the polymerization of aromatic compounds initiated by sulfate and hydroxyl radicals. Although precipitate formation is detrimental to mass transfer, surfactant‐like byproducts which may also be produced could lead to an emulsified aqueous phase, thereby enhancing dissolution and altering NAPL/water surface tension. Several of the organic byproducts that were detected in the aqueous phase were also detected in the NAPL, suggesting that these byproducts which were generated in aqueous phase migrated into the NAPL. Depending on the concentration of these byproducts in the NAPL, they could impact important physical properties (e.g., viscosity and density) and affect NAPL composition, which can affect intra‐NAPL diffusion and post‐treatment dissolution behavior. Although additional investigation is required, the results from this study indicate that the impacts of byproducts generated when using persulfate in ISCO applications need to be considered.

Performance enhancement of hydrogen liquefaction process via absorption refrigeration and organic Rankine cycle-assisted liquid air energy system

This study focuses on the design and analysis of a liquid hydrogen production process integrated with an absorption refrigeration system, a liquid air energy storage system, and an organic Rankine cycle for designing an energy-efficient integrated process. The absorption refrigeration system and liquid air energy storage system facilitate hydrogen pre-cooling, whereas the organic Rankine cycle helps to recover the waste heat generated after air combustion. An ammonia/water-based absorption refrigeration system accompanied by liquid air precools the hydrogen to −180 °C, and the vapor compression refrigeration system liquifies the hydrogen. In this study, an energy-efficient process integration scheme was designed to reduce the overall energy consumption and recover waste heat. The net specific energy consumption of the process was 6.71 kWh/kg. The design variables and composite curve analyses indicate that the most energy-intensive part of the process is the liquefaction section. Moreover, exergy analysis indicates that multi-stream heat exchangers primarily contribute towards exergy destruction. The exergy efficiency of the process was 35.7%. Environmental analysis shows that the refrigeration cycles mainly contribute towards carbon dioxide emissions. Furthermore, according to the economic analysis, compressors and multi-stream heat exchangers accounted for 88.5% of the total capital investment. Overall, these analyses report energy efficient integration and indicate the potential for further improvements, particularly in the refrigeration cycle. This study is expected to provide insights into the design of energy-efficient integrated hydrogen liquefaction processes that exploit the benefits of the absorption refrigeration system, liquid air energy storage system, and organic Rankine cycle.

Low-cost handheld NIR spectroscopy for identification of organic solvents and low-level quantification of water contamination

Quality control of liquid raw materials arriving on an industrial manufacturing site is typically performed in a dedicated laboratory using time- and chemicals-consuming analytical methods. Herein, we report the successful development of a handheld near-infrared spectroscopy method for the rapid, low-cost testing of organic solvents. Our methodology enables the classification of organic solvents with 100% accuracy and the quantification of water in methyl ethyl ketone with a precision of ~0.01 wt% in the 0–0.25 wt% range. The accessory that we have developed for the NIR sensor enables the development of a broad range of sensing applications on organic liquid systems.

Tunable lifetimes and efficiencies of room temperature phosphorescent liquids by modulating the length and number of alkyl chains.

Organic room temperature phosphorescence (RTP) liquid composites exhibit the potential to make innovative changes in large area flexible lighting applications, and it is extremely challenging to achieve high-efficiency RTP in pure organic solvent-free liquid systems. The excited state properties and inner lighting mechanisms of these composites are unclear; therefore, a theoretical perspective to design high efficiency RTP liquids with tunable lifetime is highly desired. Herein, we systematically investigate the photophysical properties of a series of long swallow-tailed bromonaphthalimide (BT unit) molecules by the newly proposed optimally tuned range-separated (RS) functional method, and a state-of-the-art RTP molecule with an absolute quantum yield (ΦRTP) of 57.1% and a lifetime (τ) of 160 ms in solvent-free liquid is obtained. Moreover, theoretical results show that the energy gap between the lowest singlet excited state (S1) and triplet excited state (T1) can be reduced and the non-radiative energy consumption process can be restricted by modulating the length and number of alkyl chains in organic RTP molecules. Thus, a wise molecular design strategy is proposed and five additional efficient RTP molecules with tunable lifetimes (43, 19, 136, 0.11 and 0.005 ms) and efficiencies (11.3%, 6.8%, 5.9%, 0.2% and 0.05%) are theoretically proposed. This study sheds light on the relationship among molecular structure, lifetime and efficiency, and can provide an important prototype to explore high-efficiency RTP by pure organic solvent-free liquid systems.

Nucleation of gas hydrates in multiphase systems with several types of interfaces

Isothermal nucleation of gas hydrates in two-layer water–organic liquid systems was studied with the use of Sapphire Rocking Cell RCS6 with six transparent sapphire cells by thermal analysis under gas pressure. The experiments were conducted at constant supercooling (about 20.2 °C). Decane (both with and without surfactants Surfynol 420 and Span 80) and crude oils were used as organic liquids. It was observed that gas hydrate nucleation occurred at water–stainless steel–gas and water–sapphire–organic liquid three-phase contact lines rather than at water–gas or water–organic liquid interfaces. The empirical survival curves were constructed for the entire set of data. Two series of experiments for the system of water–decane–Surfynol 420–methane with the same sample were also conducted. The series of experiments differed with cell angle relative to the horizontal (45° and 14°). Comparison of the observed thermal effects with data of visual examination for this system allowed nucleation rates of methane hydrate on the different nucleation sites to be determined.

Solid‐State Sodium Batteries

AbstractRechargeable Na‐ion batteries (NIBs) are attractive large‐scale energy storage systems compared to Li‐ion batteries due to the substantial reserve and low cost of sodium resources. The recent rapid development of NIBs will no doubt accelerate the commercialization process. As one of the indispensable components in current battery systems, organic liquid electrolytes are widely used for their high ionic conductivity and good wettability, but the low thermal stability, especially the easy flammability and leakage make them at risk of safety issues. The booming solid‐state batteries with solid‐state electrolytes (SSEs) show promise as alternatives to organic liquid systems due to their improved safety and higher energy density. However, several challenges including low ionic conductivity, poor wettability, low stability/incompatibility between electrodes and electrolytes, etc., may degrade performance, hindering the development of practical applications. In this review, an overview of Na‐ion SSEs is first outlined according to the classification of solid polymer electrolytes, composite polymer electrolytes, inorganic solid electrolytes, etc. Furthermore, the current challenges and critical perspectives for the potential development of solid‐state sodium batteries are discussed in detail.

Ultrasound-assisted Desorption of CO2 from Carbon Dioxide Binding Organic Liquids

CO2 absorption/desorption performance of 2-tert-Butyl-1,1,3,3-tetramethylguanidine (BTMG) and 1-Hexanol blend, which is a novel carbon dioxide binding organic liquid (CO2BOL) system, was studied in order to investigate the behavior of ultrasound-assisted desorption. Pure CO2 was first absorbed into a 10wt percent BTMG solution in a semi-batch stirred reactor at 303K and at 2 atm until equilibrium was reached, followed by ultrasound-assisted desorption at 353K under nitrogen atmosphere. Experiments were repeated in the absence of ultrasound, keeping everything else the same. The CO2 loading of BTMG:1-Hexanol solvent system was found to be a very favourable ratio of 1.05mol CO2/mol BTMG. When compared with conventional desorption, ultrasound-assisted desorption resulted in enhanced desorption rate so that the solvent regeneration time was significantly shortened. Enhancement of desorption rate was most significant/vigorous at the initial stages of desorption process. Further, regeneration of this CO2BOL was possible at 353K without any phase change. Experimental results clearly show that the ultrasound-assisted desorption is an effective process intensification tool leading to significantly minimised energy consumption for regeneration. To ensure effectiveness of regeneration, reversibility of the solvent system was also investigated by using Fourier transform infrared spectrometry.

Effect of pluronic P123 on the distribution of nanodiamond particles in water–organic liquid systems

The effect adsorption layers of nonionic surfactant (pluronic P123) have on the distribution of nanodiamonds (NDs) between aqueous and organic phases is studied with radioactive tracers using compounds labeled with tritium. The values of reversible and irreversible adsorptions of P123 on NDs are determined. It is shown that the distribution coefficients of NDs modified by irreversibly adsorbed layers of P123 are several times higher than those of raw nanodiamonds. This result is explained by the hydrophobization of an ND’s surface, as is shown by data obtained via interfacial tensiometry and wetting.

UManSysProp v1.0: an online and open-source facility for molecular property prediction and atmospheric aerosol calculations

Abstract. In this paper we describe the development and application of a new web-based facility, UManSysProp (http://umansysprop.seaes.manchester.ac.uk), for automating predictions of molecular and atmospheric aerosol properties. Current facilities include pure component vapour pressures, critical properties, and sub-cooled densities of organic molecules; activity coefficient predictions for mixed inorganic–organic liquid systems; hygroscopic growth factors and CCN (cloud condensation nuclei) activation potential of mixed inorganic–organic aerosol particles; and absorptive partitioning calculations with/without a treatment of non-ideality. The aim of this new facility is to provide a single point of reference for all properties relevant to atmospheric aerosol that have been checked for applicability to atmospheric compounds where possible. The group contribution approach allows users to upload molecular information in the form of SMILES (Simplified Molecular Input Line Entry System) strings and UManSysProp will automatically extract the relevant information for calculations. Built using open-source chemical informatics, and hosted at the University of Manchester, the facilities are provided via a browser and device-friendly web interface, or can be accessed using the user's own code via a JSON API (application program interface). We also provide the source code for all predictive techniques provided on the site, covered by the GNU GPL (General Public License) license to encourage development of a user community. We have released this via a Github repository (doi:10.5281/zenodo.45143). In this paper we demonstrate its use with specific examples that can be simulated using the web-browser interface.

Toward 5 V Li-Ion Batteries: Quantum Chemical Calculation and Electrochemical Characterization of Sulfone-Based High-Voltage Electrolytes

In seeking new sulfone-based electrolytes to meet the demand of 5 V lithium-ion batteries, we have combined the theoretical quantum chemistry calculation and electrochemical characterization to explore several sulfone/cosolvent systems. Tetramethylene sulfone (TMS), dimethyl sulfite (DMS), and diethyl sulfite (DES) were used as solvents, and three kinds of lithium salts including LiBOB, LiTFSI, and LiPF6 were added into TMS/DMS [1:1, (v)] and TMS/DES [1:1, (v)] to form high-voltage electrolyte composites, respectively. All of these electrolytes display wide electrochemical windows of more than 5.4 V, with the high electrolyte conductivities being more than 3 mS/cm at room temperature. It is indicated that to achieve the best ionic conductivity in TMS/DMS cosolvent, the optimized concentrations of lithium salts LiBOB, LiTFSI, and LiPF6 were 0.8, 1, and 1 M, respectively. Furthermore, the vibrational changes of the molecular functional groups in the cosolvents were evaluated by Fourier transform infrared spectroscopy. It is found that lithium salts show strong interaction with the main functional sulfone groups and sulfonic acid ester group, thus playing a vital role in the enhancement of the ionic conductivity and electrochemical stability of the solvent system. These sulfone-based solvents with high electrochemical stability are expected to become a new generation of a high-voltage organic electrolytic liquid system for lithium-ion batteries.

Aggregation of CO2 and Organic Liquid Molecules at Near Critical and Supercritical Condition of CO2

In order to study the aggregation of CO2 and organic liquid molecules in the binary systems of CO2+ organic liquid at near critical and supercritical condition of CO2, the radial distribution function of CO2-organic liquid molecules and organic liquid–organic liquid molecules in the liquid phase of the CO2+ organic liquid systems is calculated by molecular dynamic simulation in this work and compared with the results of our previous works. The results of the research show that the aggregates of CO2–CO2 molecules, CO2-organic liquid molecules and organic liquid–organic liquid molecules are coexisted in the liquid phase of CO2+ organic liquid system, respectively.

Transmission mechanism of the change in membrane potential by use of organic liquid membrane system

Transmission of the change in potential difference across a liquid membrane was investigated based on the knowledge of voltammetry for the ion transfer at the interface of two immiscible electrolyte solutions by use of a U-shaped liquid membrane cell.Two aqueous phases (W1 and W1′) containing 0.1M KCl were set on two 1,2-dichloroethane solution phases (M1 and M2) containing about 10−5M potassium tetrakis(4-chlorophenyl)borate (K+ TCPB−) and 10−3M tetrabutylammonium tetrakis(4-chlorophenyl)borate (TBA+ TCPB−), respectively. W1 and W1′ were connected via a salt bridge. Then, an aqueous phase (W2) containing 0.1M KCl and 10−3M tetrabutylammonium chloride (TBA+ Cl−) was put in the bottom of the cell, which was in contact with M1 and M2. Under the initial conditions, the potential difference (E) between W1 and W2 (EW1–W2) was identical with EW1′–W2 between W1′ and W2, and then EW1|M1 between W1 and M1 and EM1|W2 between M1 and W2 were also identical with EW1′|M2 between W1′ and M2 and EM2|W2 between M2 and W2, respectively. In this case, the W1|M1 and the W1′|M2 interfaces were depolarized by the distribution of K+, and the M1|W2 and the M2|W2 interfaces were depolarized by the distribution of TBA+. After addition of an adequate volume of 10−3M TBA+ Cl− to W1, EW1–W2 and EW1′–W2 were shifted simultaneously. Since EM1|W2 and EM2|W2 remained unchanged on the addition of TBA+, the change of EW1′|M2 was induced by the change of EW1|M1. This situation can be considered to be a model of the signal transmission.

Dispersion Property of CO2 in Oil. 2: Volume Expansion of CO2 + Organic Liquid at Near-Critical and Supercritical Conditions of CO2

To investigate the effect of polarity of organic liquids and the dispersion state of CO2 in organic liquids on the volume expansion of CO2 + organic liquid systems, the solubility of CO2 in methylbenzene and ethanol and the volume of CO2 + methylbenzene and ethanol at different temperatures and pressures were measured with a PVT apparatus. The results imply that the microscopic dispersion state of CO2 molecules in organic liquids under near-critical or supercritical conditions play a dominant role for increasing the volume of the CO2 + organic liquid systems. The microscopic dispersion state and the solubility of CO2 in the organic liquids and the volume expansion of the CO2 + organic liquid systems are affected by the polarity and the structure of the organic liquid molecule obviously. When pressure and temperature are fixed, the intermolecular force between CO2 molecule and the organic liquids and the intermolecular force operating within the organic liquids play a dominate role in the volume expansion of the CO2 + organic liquid systems.

Surface charge density model for predicting the permittivity of liquid mixtures and composites materials

The case “cube inside cube” for the recent predictive equivalent capacitance model (ECM) is resolved into three different analytic equations expressing the relative permittivity of a composite in terms of constituent relative permittivities and inclusion volume fraction, and they are averaged analytically (ECM-average). Although ECM represents an advance, it requires a specific calculation for each inclusion shape. Sharing the same assumptions and basic physics with ECM an alternative numerical model, named surface charge density model (SCDM), is developed. Using this model it is shown that ECM is an approximation in any of the three solutions mentioned above. Since the approach “cube inside cube” leads to isotropic systems where the volume fraction of the inclusion can be varied from zero to one, an attempt is made to apply SCDM and ECM to binary liquid mixtures. Literature values for relative permittivities of some organic–organic liquid systems are used to test values predicted by SCDM and ECM, as well as by four classic predictive mixing equations. It is concluded that ECM-average and SCDM can be applied to binary liquid mixtures with dissimilar molar volumes, when the component of bigger molar volume is considered as inclusion, and that ECM-average is generally an acceptable approximation to the numerical SCDM. Present results suggest that the SCDM performs better when bigger molar volume is associated with higher permittivity. Finally, using an example in 2D for an anisotropic inclusion it is shown that the assumption of non-reflecting boundary potential, which has been used by different authors, is satisfied only for highly symmetric inclusion distributions.

Heat transport in structured packings with two-phase co-current downflow

In this work structured packings such as OCFS (open cross flow structure), CCFS (closed cross flow structure), Knitted wire packing, and Aluminium Foams were characterized with respect to their heat transport performance in gas–liquid down flow covering all important flow regimes. A dedicated set-up was built to measure radial temperature profiles at different axial and azimuthal positions for a gas–organic liquid system flowing co-currently downwards in a cooled column with constant wall temperature. The effective bed conductivity and the wall heat transfer coefficient for various structured packings were estimated from a 2-D pseudo-homogeneous plug flow model used to correlate the measured temperature profiles. The measured heat transfer parameters can be explained with the different flow patterns of the packings. The structured packings – especially OCFS and CCFS – show heat transport parameters (up to 1000W/(m2K)) that are superior over those of packed beds of Glass beads and at much lower energy dissipation. Due to the high radial transport in these structured packings, overall heat transfer is only limited by the wall heat transfer coefficient and therefore depends strongly on the turbulence generated between packing and wall.

Characterizing Pore‐Scale Configuration of Organic Immiscible Liquid in Multiphase Systems With Synchrotron X‐Ray Microtomography

The objective of this study was to examine the pore‐scale distribution and morphology of organic immiscible liquid in natural porous media containing three immiscible fluids. High‐resolution, three‐dimensional images of an organic liquid (tetrachloroethene) in both three‐phase (water–air–organic liquid) and two‐phase (water–organic liquid) systems were obtained using synchrotron X‐ray microtomography. These data were used to quantitatively characterize the morphology of the organic liquid residing within columns packed with one of three natural, sandy porous media. Organic‐liquid blobs varied greatly in both size and shape, ranging from small, single spheres (≥0.03 mm in diameter) to large, amorphous ganglia with mean lengths of 4 to 5 mm. Singlets comprised the greatest number of blobs, whereas the large ganglia, while much fewer in number, comprised the majority of the organic‐liquid surface area and volume. A significant portion of the organic liquid in the three‐phase systems was observed to exist as lenses and films in contact with air. These features were not observed in the two‐phase water–organic liquid systems. The median of the blob‐frequency distributions was smaller and the variance larger for the three‐phase systems. In addition, the global specific surface areas of the organic liquid were greater for the three‐phase systems. These differences are attributed to the presence of the organic‐liquid lenses and films for the three‐phase systems.

Near edge X-ray absorption fine structure spectroscopy as a tool to probe electronic and structural properties of thin organic films and liquids

Synchrotron-based spectroscopic techniques have contributed significantly to a better understanding of the properties of materials on the macroscopic and microscopic scale over the last decades. They can be applied to samples from a diversity of fields, including Biology, Life Sciences, Chemistry and Materials. One of these techniques is Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy, revealing electronic structure and information on the orientation of adsorbed molecules. The present article describes the basics of the technique and the progress it has made over the last three decades, and summarizes some of its more recent developments and applications. This tutorial review article should be accessible for novices to the field from Physics, Chemistry, Biology, Materials, and the Life Sciences, interested in thin organic films and liquid systems.

Thermomorphic phase separation in ionic liquid–organic liquid systems—conductivity and spectroscopic characterization

Electrical conductivity, FT-Raman and NMR measurements are demonstrated as useful tools to probe and determine phase behavior of thermomorphic ionic liquid-organic liquid systems. To illustrate the methods, consecutive conductivity measurements of a thermomorphic methoxyethoxyethyl-imidazolium ionic liquid/1-hexanol system are performed in the temperature interval 25-80 degrees C using a specially constructed double-electrode cell. In addition, FT-Raman and 1H-NMR spectroscopic studies performed on the phase-separable system in the same temperature interval confirm the mutual solubility of the components in the system, the liquid-liquid equilibrium phase diagram of the binary mixture, and signify the importance of hydrogen bonding between the ionic liquid and the hydroxyl group of the alcohol.

Electrochemical Separation and Concentration of

Low energy separations for <1% gases would benefit gas treatment and sequestration. Theoretically, electrochemical pumping can separate and concentrate from the atmosphere or other gases with <1% at significantly lower energy cost than current systems. Principles of electrochemical pumping for separations are discussed and results for both organic solvent and ionic liquid working fluid systems are presented. Due to the large quantities of gases requiring processing during the separation/concentration of <1% gases, this work looked at solvents with negligible vapor pressures, specifically propylene carbonate and the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. Other important parameters, as illustrated by the data and models presented, are low solubility in the solvent, high carrier solubility, binding constants, and the carrier’s electrochemistry. Reported is the electrochemical pumping of from 0.5% (in nitrogen) to 100%, a 200-fold increase in partial pressure, using the carrier 2,6-di-tert-butyl-1,4-benzoquinone in a propylene carbonate solution. The ratio of moles pumped per electron mole was 0.43. The models determined the optimal solubility in the solvent and the required redox swing in the binding constants of the carrier. © 2003 The Electrochemical Society. All rights reserved.