Search results for: ionic imprinting
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 416

Search results for: ionic imprinting

386 Solubility of Carbon Dioxide in Methoxy and Nitrile-Functionalized Ionic Liquids

Authors: D. A. Bruzon, G. Tapang, I. S. Martinez

Abstract:

Global warming and climate change are significant environmental concerns, which require immediate global action in carbon emission mitigation. The capture, sequestration, and conversion of carbon dioxide to other products such as methane or ethanol are ways to control excessive emissions. Ionic liquids have shown great potential among the materials studied as carbon capture solvents and catalysts in the reduction of CO2. In this study, ionic liquids comprising of a methoxy (-OCH3) and cyano (-CN) functionalized imidazolium cation, [MOBMIM] and [CNBMIM] respectively, paired with tris(pentafluoroethyl)trifluorophosphate [FAP] anion were evaluated as effective capture solvents, and organocatalysts in the reduction of CO2. An in-situ electrochemical set-up, which can measure controlled amounts of CO2 both in the gas and in the ionic liquid phase, was used. Initially, reduction potentials of CO2 in the CO2-saturated ionic liquids containing the internal standard cobaltocene were determined using cyclic voltammetry. Chronoamperometric transients were obtained at potentials slightly less negative than the reduction potentials of CO2 in each ionic liquid. The time-dependent current response was measured under a controlled atmosphere. Reduction potentials of CO2 in methoxy and cyano-functionalized [FAP] ionic liquids were observed to occur at ca. -1.0 V (vs. Cc+/Cc), which was significantly lower compared to the non-functionalized analog [PMIM][FAP], with an observed reduction potential of CO2 at -1.6 V (vs. Cc+/Cc). This decrease in the potential required for CO2 reduction in the functionalized ionic liquids shows that the functional groups methoxy and cyano effectively decreased the free energy of formation of the radical anion CO2●⁻, suggesting that these electrolytes may be used as organocatalysts in the reduction of the greenhouse gas. However, upon analyzing the solubility of the gas in each ionic liquid, [PMIM][FAP] showed the highest absorption capacity, at 4.81 mM under saturated conditions, compared to [MOBMIM][FAP] at 1.86 mM, and [CNBMIM][FAP] at 0.76 mM. Also, calculated Henry’s constant determined from the concentration-pressure graph of each functionalized ionic liquid shows that the groups -OCH3 and -CN attached terminal to a C4 alkyl chain do not significantly improve CO2 solubility.

Keywords: carbon capture, CO2 reduction, electrochemistry, ionic liquids

Procedia PDF Downloads 377
385 Study of Bis(Trifluoromethylsulfonyl)Imide Based Ionic Liquids by Gas Chromatography

Authors: F. Mutelet, L. Cesari

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Development of safer and environmentally friendly processes and products is needed to achieve sustainable production and consumption patterns. Ionic liquids, which are of great interest to the chemical and related industries because of their attractive properties as solvents, should be considered. Ionic liquids are comprised of an asymmetric, bulky organic cation and a weakly coordinating organic or inorganic anion. A large number of possible combinations allows for the ability to ‘fine tune’ the solvent properties for a specific purpose. Physical and chemical properties of ionic liquids are not only influenced by the nature of the cation and the nature of cation substituents but also by the polarity and the size of the anion. These features infer to ionic liquids numerous applications, in organic synthesis, separation processes, and electrochemistry. Separation processes required a good knowledge of the behavior of organic compounds with ionic liquids. Gas chromatography is a useful tool to estimate the interactions between organic compounds and ionic liquids. Indeed, retention data may be used to determine infinite dilution thermodynamic properties of volatile organic compounds in ionic liquids. Among others, the activity coefficient at infinite dilution is a direct measure of solute-ionic liquid interaction. In this work, infinite dilution thermodynamic properties of volatile organic compounds in specific bis(trifluoromethylsulfonyl)imide based ionic liquids measured by gas chromatography is presented. It was found that apolar compounds are not miscible in this family of ionic liquids. As expected, the solubility of organic compounds is related to their polarity and hydrogen-bond. Through activity coefficients data, the performance of these ionic liquids was evaluated for different separation processes (benzene/heptane, thiophene/heptane and pyridine/heptane). Results indicate that ionic liquids may be used for the extraction of polar compounds (aromatics, alcohols, pyridine, thiophene, tetrahydrofuran) from aliphatic media. For example, 1-benzylpyridinium bis(trifluoromethylsulfonyl) imide and 1-cyclohexylmethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide are more efficient for the extraction of aromatics or pyridine from aliphatics than classical solvents. Ionic liquids with long alkyl chain length present important capacity values but their selectivity values are low. In conclusion, we have demonstrated that specific bis(trifluoromethylsulfonyl)imide based ILs containing polar chain grafted on the cation (for example benzyl or cyclohexyl) increases considerably their performance in separation processes.

Keywords: interaction organic solvent-ionic liquid, gas chromatography, solvation model, COSMO-RS

Procedia PDF Downloads 80
384 Integrated Two Stage Processing of Biomass Conversion to Hydroxymethylfurfural Esters Using Ionic Liquid as Green Solvent and Catalyst: Synthesis of Mono Esters

Authors: Komal Kumar, Sreedevi Upadhyayula

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In this study, a two-stage process was established for the synthesis of HMF esters using ionic liquid acid catalyst. Ionic liquid catalyst with different strength of the Bronsted acidity was prepared in the laboratory and characterized using 1H NMR, FT-IR, and 13C NMR spectroscopy. Solid acid catalyst from the ionic liquid catalyst was prepared using the immobilization method. The acidity of the synthesized acid catalyst was measured using Hammett function and titration method. Catalytic performance was evaluated for the biomass conversion to 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) in methyl isobutyl ketone (MIBK)-water biphasic system. A good yield of 5-HMF and LA was found at the different composition of MIBK: Water. In the case of MIBK: Water ratio 10:1, good yield of 5-HMF was observed at ambient temperature 150˚C. Upgrading of 5-HMF into monoesters from the reaction of 5-HMF and reactants using biomass-derived monoacid were performed. Ionic liquid catalyst with -SO₃H functional group was found to be best efficient in comparative of a solid acid catalyst for the esterification reaction and biomass conversion. A good yield of 5-HMF esters with high 5-HMF conversion was found to be at 105˚C using the best active catalyst. In this process, process A was the hydrothermal conversion of cellulose and monomer into 5-HMF and LA using acid catalyst. And the process B was the esterification followed by using similar acid catalyst. All monoesters of 5-HMF synthesized here can be used in chemical, cross linker for adhesive or coatings and pharmaceutical industry. A theoretical density functional theory (DFT) study for the optimization of the ionic liquid structure was performed using the Gaussian 09 program to find out the minimum energy configuration of ionic liquid catalyst.

Keywords: biomass conversion, 5-HMF, Ionic liquid, HMF ester

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383 Preparation, Characterization and Ionic Conductivity of (1‒x) (CdI2‒Ag2CrO4)‒(x) Al2O3 Composite Solid Electrolytes

Authors: Rafiuddin

Abstract:

Composite solid electrolyte of the salt and oxide type is an effective approach to improve the ionic conductivity in low and intermediate temperature regions. The conductivity enhancement in the composites occurs via interfaces. Because of their high ionic conduction, composite electrolytes have wide applications in different electrochemical devices such as solid-state batteries, solid oxide fuel cells, and electrochemical cells. In this work, a series of novel (1‒x) (CdI2‒Ag2CrO4)‒xAl2O3 composite solid electrolytes has been synthesized. The prepared materials were characterized by X‒ray diffraction, differential thermal analysis, and AC impedance spectroscopy. The impedance spectra show single semicircle representing the simultaneous contribution of grain and grain boundary. The conductivity increased with the increase of Al2O3 content and shows the maximum conductivity (σ= 0.0012 S cm‒1) for 30% of Al2O3 content at 30 ℃.

Keywords: composite solid electrolyte, X-ray diffraction, Impedance spectroscopy, ionic conductivity

Procedia PDF Downloads 376
382 Synthesis, Characterization, and Application of Novel Trihexyltetradecyl Phosphonium Chloride for Extractive Desulfurization of Liquid Fuel

Authors: Swapnil A. Dharaskar, Kailas L. Wasewar, Mahesh N. Varma, Diwakar Z. Shende

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Owing to the stringent environmental regulations in many countries for production of ultra low sulfur petroleum fractions intending to reduce sulfur emissions results in enormous interest in this area among the scientific community. The requirement of zero sulfur emissions enhances the prominence for more advanced techniques in desulfurization. Desulfurization by extraction is a promising approach having several advantages over conventional hydrodesulphurization. Present work is dealt with various new approaches for desulfurization of ultra clean gasoline, diesel and other liquid fuels by extraction with ionic liquids. In present paper experimental data on extractive desulfurization of liquid fuel using trihexyl tetradecyl phosphonium chloride has been presented. The FTIR, 1H-NMR, and 13C-NMR have been discussed for the molecular confirmation of synthesized ionic liquid. Further, conductivity, solubility, and viscosity analysis of ionic liquids were carried out. The effects of reaction time, reaction temperature, sulfur compounds, ultrasonication, and recycling of ionic liquid without regeneration on removal of dibenzothiphene from liquid fuel were also investigated. In extractive desulfurization process, the removal of dibenzothiophene in n-dodecane was 84.5% for mass ratio of 1:1 in 30 min at 30OC under the mild reaction conditions. Phosphonium ionic liquids could be reused five times without a significant decrease in activity. Also, the desulfurization of real fuels, multistage extraction was examined. The data and results provided in present paper explore the significant insights of phosphonium based ionic liquids as novel extractant for extractive desulfurization of liquid fuels.

Keywords: ionic liquid, PPIL, desulfurization, liquid fuel, extraction

Procedia PDF Downloads 587
381 Preparation of Carbon Nanofiber Reinforced HDPE Using Dialkylimidazolium as a Dispersing Agent: Effect on Thermal and Rheological Properties

Authors: J. Samuel, S. Al-Enezi, A. Al-Banna

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High-density polyethylene reinforced with carbon nanofibers (HDPE/CNF) have been prepared via melt processing using dialkylimidazolium tetrafluoroborate (ionic liquid) as a dispersion agent. The prepared samples were characterized by thermogravimetric (TGA) and differential scanning calorimetric (DSC) analyses. The samples blended with imidazolium ionic liquid exhibit higher thermal stability. DSC analysis showed clear miscibility of ionic liquid in the HDPE matrix and showed single endothermic peak. The melt rheological analysis of HDPE/CNF composites was performed using an oscillatory rheometer. The influence of CNF and ionic liquid concentration (ranging from 0, 0.5, and 1 wt%) on the viscoelastic parameters was investigated at 200 °C with an angular frequency range of 0.1 to 100 rad/s. The rheological analysis shows the shear-thinning behavior for the composites. An improvement in the viscoelastic properties was observed as the nanofiber concentration increases. The progress in the modulus values was attributed to the structural rigidity imparted by the high aspect ratio CNF. The modulus values and complex viscosity of the composites increased significantly at low frequencies. Composites blended with ionic liquid exhibit slightly lower values of complex viscosity and modulus over the corresponding HDPE/CNF compositions. Therefore, reduction in melt viscosity is an additional benefit for polymer composite processing as a result of wetting effect by polymer-ionic liquid combinations.

Keywords: high-density polyethylene, carbon nanofibers, ionic liquid, complex viscosity

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380 Ionic Liquid Desiccant for the Dehumidification System

Authors: Chih-Hao Chen, Yu-Heng Fang, Jyi-Ching Perng, Wei-Chih Lee, Yi-Hsiang Chen, Jiun-Jen Chen

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Emerging markets are almost in the high temperature and high humidity area. Regardless of industry or domestic fields, the energy consumption of air conditioning systems in buildings is always significant. Moreover, the proportion of latent heat load is high. A liquid desiccant dehumidification system is one kind of energy-saving air conditioning system. However, traditional absorbents such as lithium chloride are hindered in market promotion because they will crystallized and cause metal corrosion. This study used the commercial ionic liquid to build a liquid desiccant dehumidification system with an air volume of 300 CMH. When the absolute humidity of the inlet air was 15g/kg, the absolute humidity of the outlet air was 10g/kg. The operating condition of a hot water temperature is 45 °C, and the cooling water temperature is 15 °C. The test result proves that the ionic liquid desiccant can completely replace the traditional liquid desiccant.

Keywords: ionic liquid desiccant, dehumidification, heat pump, air conditioning systems

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379 The Role of Long-Chain Ionic Surfactants on Extending Drug Delivery from Contact Lenses

Authors: Cesar Torres, Robert Briber, Nam Sun Wang

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Eye drops are the most commonly used treatment for short-term and long-term ophthalmic diseases. However, eye drops could deliver only about 5% of the functional ingredients contained in a burst dosage. To address the limitations of eye drops, the use of therapeutic contact lenses has been introduced. Drug-loaded contact lenses provide drugs a longer residence time in the tear film and hence, decrease the potential risk of side effects. Nevertheless, a major limitation of contact lenses as drug delivery devices is that most of the drug absorbed is released within the first few hours. This fact limits their use for extended release. The present study demonstrates the application of long-alkyl chain ionic surfactants on extending drug release kinetics from commercially available silicone hydrogel contact lenses. In vitro release experiments were carried by immersing drug-containing contact lenses in phosphate buffer saline at physiological pH. The drug concentration as a function of time was monitored using ultraviolet-visible spectroscopy. The results of the study demonstrate that release kinetics is dependent on the ionic surfactant weight percent in the contact lenses, and on the length of the hydrophobic alkyl chain of the ionic surfactants. The use of ionic surfactants in contact lenses can extend the delivery of drugs from a few hours to a few weeks, depending on the physicochemical properties of the drugs. Contact lenses embedded with ionic surfactants could be potential biomaterials to be used for extended drug delivery and in the treatment of ophthalmic diseases. However, ocular irritation and toxicity studies would be needed to evaluate the safety of the approach.

Keywords: contact lenses, drug delivery, controlled release, ionic surfactant

Procedia PDF Downloads 117
378 Stability Enhancement of Supported Ionic Liquid Membranes Using Ion Gels for Gas Separation

Authors: Y. H. Hwang, J. Won, Y. S. Kang

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Supported ionic liquid membranes (SILMs) have attracted due to the negligible vapor pressure of ionic liquids (ILs) as well as the high gas selectivity for specific gases such as CO2 or olefin. 1-ethyl-3-methylimidazolium tricyanomethanide ([EMIM][TCM]), 1-butyl-3-methylimidazolium tricyanomethanide ([BMIM][TCM]), show high CO2 solubility, CO2 absorption, rapid CO2 absorption rate and negligible vapor pressure, SILMs using these ILs have been good candidates as CO2 separation membranes. However, SILM has to be operated at a low differential pressure to prevent the solvent from being expelled from the pores of supported membranes. In this paper, we improve the mechanical strength by forming ion gels which provide the stability while it retains the diffusion properties of the liquid stage which affects the gas separation properties. The ion gel was created by the addition of tri-block copolymer, poly(styrene-ethylene oxide-b-styrene) in RTIL. SILM using five different RTILs, are investigated with and without ion gels. The gas permeance were measured and the gas performance with and without the SEOS were investigated.

Keywords: ion gel, ionic liquid, membrane, nanostructure

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377 High Efficiency Electrolyte Lithium Battery and RF Characterization

Authors: Wei Quan, Liu Chao, Mohammed N. Afsar

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The dielectric properties and ionic conductivity of novel "ceramic state" polymer electrolytes for high capacity lithium battery are characterized by radio-frequency and Microwave methods in two broad frequency ranges from 50 Hz to 20 KHz and 4 GHz to 40 GHz. This innovative solid polymer electrolyte which is highly ionic conductive (10-3 S/cm at room temperature) from -40 oC to +150 oC and can be used in any battery application. Such polymer exhibits properties more like a ceramic rather than polymer. The various applied measurement methods produced accurate dielectric results for comprehensive analysis of electrochemical properties and ion transportation mechanism of this newly invented polymer electrolyte. Two techniques and instruments employing air gap measurement by capacitance bridge and inwave guide measurement by vector network analyzer are applied to measure the complex dielectric spectra. The complex dielectric spectra are used to determine the complex alternating current electrical conductivity and thus the ionic conductivity.

Keywords: polymer electrolyte, dielectric permittivity, lithium battery, ionic relaxation, microwave measurement

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376 Liquid-Liquid Extraction of Rare Earths Elements by Use of Ionic Liquids

Authors: C. Lopez, S. Dourdain, G. Arrachart, S. Pellet-Rostaing

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Ionic liquids (ILs) are considered a good alternative for organic solvents in extractive processes; however, the higher or lower extraction efficiency in ILs remains difficult to predict because a lack of understanding of the extraction mechanisms in this class of diluents, making their application difficult to generalize. We have studied the extraction behavior of La(III) and Eu(III) from aqueous solution into n-dodecane and two ionic liquids (ILs), 1-ethyl-1-butylpiperidinium bis (trifluoromethylsulfonyl)imide [EBPip⁺] [NTf₂⁻] and 1-ethyl-1-octylpiperidinium bis (trifluoromethylsulfonyl)imide [EOPip⁺] [NTf₂⁻], at room temperature using N,N’- dimethyl- N,N’-dioctylhexylethoxymalonamide (DMDOHEMA) as extractant. Fe(III) was introduced to the aqueous phase in order to study the selectivity toward La(III) and Eu(III) and the effect of variation of PH was investigated by using of several HNO₃ concentrations. We found that the ionic liquid with shorter alkyl chain [EBPip⁺] [NTf₂⁻] showed a higher extraction ability than [EOPip⁺] [NTf₂⁻] and that the use of ILs as organic solvent instead n-dodecane, greatly enhanced the extraction percentage of the target metals with a good selectivity. Cation ([EBPip⁺] or [EOPip⁺]) and anion ([NTf₂⁻]) concentration in the aqueous phase, has been determined in order to elucidate the extraction mechanism.

Keywords: extraction mechanism, ionic liquids, rare earths elements, solvent extraction

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375 Capture of Co₂ From Natural Gas Using Modified Imidazolium Ionic Liquids

Authors: Alaa A. Ghanem, S. E. M. Desouky

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Natural gas (NG) is considered one of the most essential global energy sources. NG fields are often far away from the market, and a long-distance transporting pipeline usually is required. Production of NG with high content of CO₂ leads to severe problems such as equipment corrosion along with the production line until refinery.in addition to a high level of toxicity and decreasing in calorific value of the NG. So it is recommended to remove or decrease the CO₂ percent to meet transport specifications. This can be reached using different removal techniques such as physical and chemical absorption, pressure swing adsorption, membrane separation, or low-temperature separation. Many solvents and chemicals are being used to capture carbon dioxide on a large scale; among them, Ionic liquids have great potential due to their tunable properties; low vapour pressure, low melting point, and sensible thermal stability. In this research, three modifiedimidazolium ionic liquids will be synthesized and characterized using different tools of analysis such as FT-IR, 1H NMR. Thermal stability and surface activity will be studied. The synthesized compounds will be evaluated as selective solvents for CO₂ removal from natural gas using PVT cell.

Keywords: natural gas, CO₂ capture, imidazolium ionic liquid, PVT cell

Procedia PDF Downloads 153
374 Phase Changing Dicationic Polymeric Ionic Liquid with CO2 Capture Abilities

Authors: Swati Sundararajan, Asit B. Samui, Prashant S. Kulkarni

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Polymeric ionic liquids combine the properties of ionic liquids and polymers into a single material which has gained massive interest in the recent years. These ionic liquids offer several advantages such as high phase change enthalpy, wide temperature range, chemical and thermal stability, non-volatility and the ability to make them task-specific. Separation of CO2 is an area of critical importance due to the concerns over greenhouse gasses leading to global warming. Thermal energy storage materials, also known as phase change materials absorb latent heat during fusion process and release the absorbed energy to the surrounding environment during crystallization. These materials retain this property over a number of cycles and therefore, are useful for bridging the gap between energy requirement and use. In an effort to develop materials, which will help in minimizing the growing energy demand and environmental concerns, a series of dicationic poly(ethylene glycol) based polymeric ionic liquids were synthesized. One part of an acrylate of poly(ethylene glycol) was reacted with imidazolium quarternizing agent and the second part was reacted with triazolium quarternizing agent. These two different monomers were then copolymerized to prepare dicationic polymeric ionic liquid. These materials were characterized for solid-liquid phase transition and the enthalpy by using differential scanning calorimetry. The CO2 capture studies were performed on a fabricated setup with varying pressure range from 1-20 atm. The findings regarding the prepared materials, having potential dual applications in the fields of thermal energy storage and CO2 capture, will be discussed in the presentation.

Keywords: CO2 capture, phase change materials, polyethylene glycol, polymeric ionic liquids, thermal energy storage

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373 PVDF-HFP Based Nanocomposite Gel Polymer Electrolytes Dispersed with Zro2 for Li-Ion Batteries

Authors: R. Sharma, A. Sil, S. Ray

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Nanocomposites gel polymer electrolytes are gaining more and more attention among the researchers worldwide due to their possible applications in various electrochemical devices particularly in solid-state Li-ion batteries. In this work we have investigated the effect of nanofibers on the electrical properties of PVDF-HFP based gel electrolytes. The nanocomposites polymer electrolytes have been synthesized by solution casting technique with 10wt% of ZrO2. By analysis of impedance spectroscopy it has been demonstrated that the incorporation of ZrO2 into PVDF-HFP–(PC+DEC)–LiClO4 gel polymer electrolyte system significantly enhances the ionic conductivity of the electrolyte. The enhancement of ionic conductivity seems to be correlated with the fact that the dispersion of ZrO2 to PVDF-HFP prevents polymer chain reorganization due to the high aspect ratio of ZrO2, resulting in reduction in polymer crystallinity, which gives rise to an increase in ionic conductivity. The decrease of crystallinity of PVDF-HFP due the addition of ZrO2 has been confirmed by XRD. The interaction of ZrO2 with various constituents of polymer electrolytes has been studied by FTIR spectroscopy. TEM results show that the fillers (ZrO2) has distributed uniformly in the polymer electrolytes. Moreover, ZrO2 added gel polymer electrolytes offer better thermal stability as compared to that of ZrO2 free electrolytes as confirmed by TGA analysis.

Keywords: polymer electrolytes, ZrO2, ionic conductivity, FTIR

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372 Separation of Copper(II) and Iron(III) by Solvent Extraction and Membrane Processes with Ionic Liquids as Carriers

Authors: Beata Pospiech

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Separation of metal ions from aqueous solutions is important as well as difficult process in hydrometallurgical technology. This process is necessary for obtaining of clean metals. Solvent extraction and membrane processes are well known as separation methods. Recently, ionic liquids (ILs) are very often applied and studied as extractants and carriers of metal ions from aqueous solutions due to their good extractability properties for various metals. This work discusses a method to separate copper(II) and iron(III) from hydrochloric acid solutions by solvent extraction and transport across polymer inclusion membranes (PIM) with the selected ionic liquids as extractants/ion carriers. Cyphos IL 101 (trihexyl(tetradecyl)phosphonium chloride), Cyphos IL 104 (trihexyl(tetradecyl)phosphonium bis(2,4,4 trimethylpentyl)phosphi-nate), trioctylmethylammonium thiosalicylate [A336][TS] and trihexyl(tetradecyl)phosphonium thiosalicylate [PR4][TS] were used for the investigations. Effect of different parameters such as hydrochloric acid concentration in aqueous phase on iron(III) and copper(II) extraction has been investigated. Cellulose triacetate membranes with the selected ionic liquids as carriers have been prepared and applied for transport of iron(IIII) and copper(II) from hydrochloric acid solutions.

Keywords: copper, iron, ionic liquids, solvent extraction

Procedia PDF Downloads 255
371 Nonlinear Porous Diffusion Modeling of Ionic Agrochemicals in Astomatous Plant Cuticle Aqueous Pores: A Mechanistic Approach

Authors: Eloise C. Tredenick, Troy W. Farrell, W. Alison Forster, Steven T. P. Psaltis

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The agriculture industry requires improved efficacy of sprays being applied to crops. More efficacious sprays provide many environmental and financial benefits. The plant leaf cuticle is known to be the main barrier to diffusion of agrochemicals within the leaf. The importance of a mathematical model to simulate uptake of agrochemicals in plant cuticles has been noted, as the results of each uptake experiments are specific to each formulation of active ingredient and plant species. In this work we develop a mathematical model and numerical simulation for the uptake of ionic agrochemicals through aqueous pores in plant cuticles. We propose a nonlinear porous diffusion model of ionic agrochemicals in isolated cuticles, which provides additions to a simple diffusion model through the incorporation of parameters capable of simulating plant species' variations, evaporation of surface droplet solutions and swelling of the aqueous pores with water. The model could feasibly be adapted to other ionic active ingredients diffusing through other plant species' cuticles. We validate our theoretical results against appropriate experimental data, discuss the key sensitivities in the model and relate theoretical predictions to appropriate physical mechanisms.

Keywords: aqueous pores, ionic active ingredient, mathematical model, plant cuticle, porous diffusion

Procedia PDF Downloads 241
370 Solvent Extraction in Ionic Liquids: Structuration and Aggregation Effects on Extraction Mechanisms

Authors: Sandrine Dourdain, Cesar Lopez, Tamir Sukhbaatar, Guilhem Arrachart, Stephane Pellet-Rostaing

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A promising challenge in solvent extraction is to replace the conventional organic solvents, with ionic liquids (IL). Depending on the extraction systems, these new solvents show better efficiency than the conventional ones. Although some assumptions based on ions exchanges have been proposed in the literature, these properties are not predictable because the involved mechanisms are still poorly understood. It is well established that the mechanisms underlying solvent extraction processes are based not only on the molecular chelation of the extractant molecules but also on their ability to form supra-molecular aggregates due to their amphiphilic nature. It is therefore essential to evaluate how IL affects the aggregation properties of the extractant molecules. Our aim is to evaluate the influence of IL structure and polarity on solvent extraction mechanisms, by looking at the aggregation of the extractant molecules in IL. We compare extractant systems that are well characterized in common solvents and show thanks to SAXS and SANS measurements, that in the absence of IL ion exchange mechanisms, extraction properties are related to aggregation.

Keywords: solvent extraction in Ionic liquid, aggregation, Ionic liquids structure, SAXS, SANS

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369 Screening of Ionic Liquids for Hydrogen Sulfide Removal Using COSMO-RS

Authors: Zulaika Mohd Khasiran

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The capability of ionic liquids in various applications makes them attracted by many researchers. They have potential to be developed as “green” solvents for gas separation, especially H2S gas. In this work, it is attempted to predict the solubility of hydrogen sulfide (H2S) in ILs by COSMO-RS method. Since H2S is a toxic pollutant, it is difficult to work on it in the laboratory, therefore an appropriate model will be necessary in prior work. The COSMO-RS method is implemented to predict the Henry’s law constants and activity coefficient of H2S in 140 ILs with various combinations of cations and anions. It is found by the screening that more H2S can be absorbed in ILs with [Cl] and [Ac] anion. The solubility of H2S in ILs with different alkyl chain at the cations not much affected and with different type of cations are slightly influence H2S capture capacities. Even though the cations do not affect much in solubility of H2S, we still need to consider the effectiveness of cation in different way. The prediction results only show their physical absorption ability, but the absorption of H2S need to be consider chemically to get high capacity of absorption of H2S.

Keywords: H2S, hydrogen sulfide, ionic liquids, COSMO-RS

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368 Ionic Liquid 1-Butyl-3-Methylimidazolium Bromide as Reaction Medium for the Synthesis of Flavanones under Solvent-Free Conditions

Authors: Cecilia Espindola, Juan Carlos Palacios

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Flavonoids are a large group of natural compounds which are found in many fruits and vegetables. A subgroup of these called flavanones display a wide range of biological activities, and they also have an important physiological role in plants. The ionic liquid (ILs) are compounds consisting of an organic cation with an organic or inorganic anion. Due to its unique properties such as high electrical conductivity, wide temperature range of the liquid state, thermal and electrochemical stability, high ionic density and low volatility and flammability, are considered as ecological solvents in organic synthesis, catalysis, electrolytes in accumulators, and electrochemistry, non-volatile plasticizers, and chemical separation. It was synthesized ionic liquid IL 1-butyl-3-methylimidazolium bromide free-solvent and used as reaction medium for flavanones synthesis, under several reaction conditions of temperature, time and production. The obtained compounds were analyzed by melting point, elemental analysis, IR and UV-vis spectroscopy.

Keywords: 1-butyl-3-methylimidazolium bromide, flavonoids, free-solvent, IR spectroscopy

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367 Effect of Anion Variation on the CO2 Capture Performance of Pyridinium Containing Poly(ionic liquid)s

Authors: Sonia Zulfiqar, Daniele Mantione, Muhammad Ilyas Sarwar, Alexander Rothenberger, David Mecerreyes

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Climate change due to escalating carbon dioxide concentration in the atmosphere is an issue of paramount importance that needs immediate attention. CO2 capture and sequestration (CCS) is a promising route to mitigate climate change and adsorption is the most widely recognized technology owing to possible energy savings relative to the conventional absorption techniques. In this conference, the potential of a new family of solid sorbents for CO2 capture and separation will be presented. Novel pyridinium containing poly(ionic liquid)s (PILs) were synthesized with varying anions i.e bis(trifluoromethylsulfonyl)imide and hexafluorophosphate. The resulting polymers were characterized using NMR, XRD, TGA, BET surface area and microscopic techniques. Furthermore, CO2 adsorption measurements at two different temperatures were also carried out and revealed great potential of these PILs as CO2 scavengers.

Keywords: climate change, CO2 capture, poly(ionic liquid)s, CO2/N2 selectivity

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366 The “Buffer Layer” An Improved Electrode-Electrolyte Interface For Solid-State Batteries

Authors: Gregory Schmidt

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Solid-state lithium batteries are broadly accepted as promising candidates for application in the next generation of EVs as they should offer safer and higher-energy-density batteries. Nonetheless, their development is impeded by many challenges, including the resistive electrode–electrolyte interface originating from the removal of the liquid electrolyte that normally permeates through the porous cathode and ensures efficient ionic conductivity through the cell. One way to tackle this challenge is by formulating composite cathodes containing solid ionic conductors in their structure, but this approach will require the conductors to exhibit chemical stability, electrochemical stability, flexibility, and adhesion and is, therefore, limited to some materials. Recently, Arkema developed a technology called buffering layer which allows the transformation of any conventional porous electrode into a catholyte. This organic layer has a very high ionic conductivity at room temperature, is compatible with all active materials, and can be processed with conventional Gigafactory equipment. Moreover, this layer helps protect the solid ionic conductor from the cathode and anode materials. During this presentation, the manufacture and the electrochemical performance of this layer for different systems of cathode and anode will be discussed.

Keywords: electrochemistry, all solid state battery, materials, interface

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365 Extraction of Strontium Ions through Ligand Assisted Ionic Liquids

Authors: Pradeep Kumar, Abhishek Kumar Chandra, Ashok Khanna

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Extraction of Strontium by crown ether (DCH18C6) hasbeen investigated in [BMIM][TF2N] Ionic Liquid (IL) giving higher extraction ~98% and distribution ratio as compared to other organic solvents (Dodecane, Hexane, & Isodecyl alcohol + Dodecane). Distribution ratio of Sr in IL at 0.15M DCH18C6 indicates an enhancement of 20000, 2000, 500 times over Dodecane, Hexane and 5% Isodecyl Alcohol + 95 % Dodecane at 0.01M aqueous acidity respectively. In presence of IL, Sr extraction decreases with increase in HNO3 concentration in aqueous phase whereas opposite trend was observed with organic solvents.Extraction of Sr initially increases with increase in DCH18C6 concentration in IL, finally reaching an asymptotic constant.

Keywords: distribution ratio, ionic liquid, ligand, organic solvent, stripping

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364 Improving Gas Separation Performance of Poly(Vinylidene Fluoride) Based Membranes Containing Ionic Liquid

Authors: S. Al-Enezi, J. Samuel, A. Al-Banna

Abstract:

Polymer based membranes are one of the low-cost technologies available for the gas separation. Three major elements required for a commercial gas separating membrane are high permeability, high selectivity, and good mechanical strength. Poly(vinylidene fluoride) (PVDF) is a commercially available fluoropolymer and a widely used membrane material in gas separation devices since it possesses remarkable thermal, chemical stability, and excellent mechanical strength. The PVDF membrane was chemically modified by soaking in different ionic liquids and dried. The thermal behavior of modified membranes was investigated by differential scanning calorimetry (DSC), and thermogravimetry (TGA), and the results clearly show the best affinity between the ionic liquid and the polymer support. The porous structure of the PVDF membranes was clearly seen in the scanning electron microscopy (SEM) images. The CO₂ permeability of blended membranes was explored in comparison with the unmodified matrix. The ionic liquid immobilized in the hydrophobic PVDF support exhibited good performance for separations of CO₂/N₂. The improved permeability of modified membrane (PVDF-IL) is attributed to the high concentration of nitrogen rich imidazolium moieties.

Keywords: PVDF, polymer membrane, gas permeability, CO₂ separation, nanotubes

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363 Genomic Imprinting as a Possible Epigenetic Cause of Esophageal Atresia

Authors: M. Błoch, P. Karpiński, P. Gasperowicz, R. Płoski, A. Lebioda, P. Skiba, A. Rozensztrauch, D. Patkowski, R. Śmigiel

Abstract:

Introduction: The cause of the isolated form of esophageal atresia has been yet unknown. Objectives: The primary objective of this study was to indicate epigenetic factors which may play an important role in the etiopathogenesis of esophageal atresia. Methods: We recruited a group of 6 pairs of twins, among whom one of the twins developed EA. The selection of such a group for testing allows for excluding external factors (e.g., infections, drugs, toxins) as the cause of the birth defect. The analyzes were performed with the use of genetic material isolated from the whole blood and esophagus tissue of a patient with EA. The reduced representation bisulphite sequencing (RRBS) technique was used to study the change in the genomic imprinting -a change in the expression of genes, which may be the epigenetic cause of EA. Results: In the course of the analyzes, significant hypomethylation and hypermethylation regions were identified. 65 genes with probably increased expression and 65 with decreased expression were selected. These genes have not been marked in literature as possibly pathogenic in esophageal atresia. However, their participation in the pathogenesis of esophageal atresia cannot be clearly excluded. Conclusion: We suggest a role of hypomethylation or hypermethylation of selected genes as one of the possible epigenetic factors in EA pathogenesis. The use of the RRBS technique in the search for the cause of EA is pioneer research; therefore, it seems necessary to extend the research group to new patients with EA. Acknowledgment: The work was supported by the National Science Centre, Poland, under research project 2016/21/N/NZ5/01927.

Keywords: esophageal atresia, epigenetics, embryonic development, surgery, genes expression, twins

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362 Useful Effects of Silica Nanoparticles in Ionic Liquid Electrolyte for Energy Storage

Authors: Dong Won Kim, Hye Ji Kim, Hyun Young Jung

Abstract:

Improved energy storage is inevitably needed to improve energy efficiency and to be environmentally friendly to chemical processes. Ionic liquids (ILs) can play a crucial role in addressing these needs due to inherent adjustable properties including low volatility, low flammability, inherent conductivity, wide liquid range, broad electrochemical window, high thermal stability, and recyclability. Here, binary mixtures of ILs were prepared with fumed silica nanoparticles and characterized to obtain ILs with conductivity and electrochemical properties optimized for use in energy storage devices. The solutes were prepared by varying the size and the weight percent concentration of the nanoparticles and made up 10 % of the binary mixture by weight. We report on the physical and electrochemical properties of the individual ILs and their binary mixtures.

Keywords: ionic liquid, silica nanoparticle, energy storage, electrochemical properties

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361 Methyltrioctylammonium Chloride as a Separation Solvent for Binary Mixtures: Evaluation Based on Experimental Activity Coefficients

Authors: B. Kabane, G. G. Redhi

Abstract:

An ammonium based ionic liquid (methyltrioctylammonium chloride) [N8 8 8 1] [Cl] was investigated as an extraction potential solvent for volatile organic solvents (in this regard, solutes), which includes alkenes, alkanes, ketones, alkynes, aromatic hydrocarbons, tetrahydrofuran (THF), alcohols, thiophene, water and acetonitrile based on the experimental activity coefficients at infinite THF measurements were conducted by the use of gas-liquid chromatography at four different temperatures (313.15 to 343.15) K. Experimental data of activity coefficients obtained across the examined temperatures were used in order to calculate the physicochemical properties at infinite dilution such as partial molar excess enthalpy, Gibbs free energy and entropy term. Capacity and selectivity data for selected petrochemical extraction problems (heptane/thiophene, heptane/benzene, cyclohaxane/cyclohexene, hexane/toluene, hexane/hexene) were computed from activity coefficients data and compared to the literature values with other ionic liquids. Evaluation of activity coefficients at infinite dilution expands the knowledge and provides a good understanding related to the interactions between the ionic liquid and the investigated compounds.

Keywords: separation, activity coefficients, methyltrioctylammonium chloride, ionic liquid, capacity

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360 Metal Extraction into Ionic Liquids and Hydrophobic Deep Eutectic Mixtures

Authors: E. E. Tereshatov, M. Yu. Boltoeva, V. Mazan, M. F. Volia, C. M. Folden III

Abstract:

Room temperature ionic liquids (RTILs) are a class of liquid organic salts with melting points below 20 °C that are considered to be environmentally friendly ‘designers’ solvents. Pure hydrophobic ILs are known to extract metallic species from aqueous solutions. The closest analogues of ionic liquids are deep eutectic solvents (DESs), which are a eutectic mixture of at least two compounds with a melting point lower than that of each individual component. DESs are acknowledged to be attractive for organic synthesis and metal processing. Thus, these non-volatile and less toxic compounds are of interest for critical metal extraction. The US Department of Energy and the European Commission consider indium as a key metal. Its chemical homologue, thallium, is also an important material for some applications and environmental safety. The aim of this work is to systematically investigate In and Tl extraction from aqueous solutions into pure fluorinated ILs and hydrophobic DESs. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. The extraction efficiency of the TlXz3–z anionic species (where X = Cl– and/or Br–) is greater for ionic liquids with more hydrophobic cations. Unexpectedly high distribution ratios (> 103) of Tl(III) were determined even by applying a pure ionic liquid as receiving phase. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the co-extraction of two different anionic species, and the relative contributions of each mechanism have been determined. The first evidence of indium extraction into new quaternary ammonium- and menthol-based hydrophobic DESs from hydrochloric and oxalic acid solutions with distribution ratios up to 103 will be provided. Data obtained allow us to interpret the mechanism of thallium and indium extraction into ILs and DESs media. The understanding of Tl and In chemical behavior in these new media is imperative for the further improvement of separation and purification of these elements.

Keywords: deep eutectic solvents, indium, ionic liquids, thallium

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359 Effect of Non-Ionic Surfactants on in vitro Release of Ketorolactromethamine

Authors: Ajay Aggarwal, Kamal Saroha, Sanju Nanda

Abstract:

Niosomes or non-ionic surfactant vesicles are microscopic lamellar structures formed on admixture of non-ionic surfactant of the alkyl or dialkyl polyglycerol ether class and cholesterol with subsequent hydration in aqueous media. They are vesicular systems similar to liposomes that can be used as carriers of amphiphilic and lipophilic drugs. Entrapment efficiency was found to be higher in case of niosome prepared with span60 than niosome prepared with tween. The amount of release was found to be in order of Span20>Tween60>Tween20>Span60. As the concentration of surfactant is increased in vitro release was increased due to high entrapment. The stability study of optimized batch revealed that particle size was increased after 3months on increasing the temperature. On the other hand entrapment efficiency was decreased on increasing the temperature.

Keywords: niosomes, vesicles, span, tween, in vitro release

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358 Improving Binding Selectivity in Molecularly Imprinted Polymers from Templates of Higher Biomolecular Weight: An Application in Cancer Targeting and Drug Delivery

Authors: Ben Otange, Wolfgang Parak, Florian Schulz, Michael Alexander Rubhausen

Abstract:

The feasibility of extending the usage of molecular imprinting technique in complex biomolecules is demonstrated in this research. This technique is promising in diverse applications in areas such as drug delivery, diagnosis of diseases, catalysts, and impurities detection as well as treatment of various complications. While molecularly imprinted polymers MIP remain robust in the synthesis of molecules with remarkable binding sites that have high affinities to specific molecules of interest, extending the usage to complex biomolecules remains futile. This work reports on the successful synthesis of MIP from complex proteins: BSA, Transferrin, and MUC1. We show in this research that despite the heterogeneous binding sites and higher conformational flexibility of the chosen proteins, relying on their respective epitopes and motifs rather than the whole template produces highly sensitive and selective MIPs for specific molecular binding. Introduction: Proteins are vital in most biological processes, ranging from cell structure and structural integrity to complex functions such as transport and immunity in biological systems. Unlike other imprinting templates, proteins have heterogeneous binding sites in their complex long-chain structure, which makes their imprinting to be marred by challenges. In addressing this challenge, our attention is inclined toward the targeted delivery, which will use molecular imprinting on the particle surface so that these particles may recognize overexpressed proteins on the target cells. Our goal is thus to make surfaces of nanoparticles that specifically bind to the target cells. Results and Discussions: Using epitopes of BSA and MUC1 proteins and motifs with conserved receptors of transferrin as the respective templates for MIPs, significant improvement in the MIP sensitivity to the binding of complex protein templates was noted. Through the Fluorescence Correlation Spectroscopy FCS measurements on the size of protein corona after incubation of the synthesized nanoparticles with proteins, we noted a high affinity of MIPs to the binding of their respective complex proteins. In addition, quantitative analysis of hard corona using SDS-PAGE showed that only a specific protein was strongly bound on the respective MIPs when incubated with similar concentrations of the protein mixture. Conclusion: Our findings have shown that the merits of MIPs can be extended to complex molecules of higher biomolecular mass. As such, the unique merits of the technique, including high sensitivity and selectivity, relative ease of synthesis, production of materials with higher physical robustness, and higher stability, can be extended to more templates that were previously not suitable candidates despite their abundance and usage within the body.

Keywords: molecularly imprinted polymers, specific binding, drug delivery, high biomolecular mass-templates

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357 Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte

Authors: Manuel Salado, Mikel Rincón, Arkaitz Fidalgo, Roberto Fernandez, Senentxu Lanceros-Méndez

Abstract:

Lithium-ion batteries (LIBs) are a promising technology for energy storage, but they suffer from safety concerns due to the use of flammable organic solvents in their liquid electrolytes. Solid-state electrolytes (SSEs) offer a potential solution to this problem, but they have their own limitations, such as poor ionic conductivity and high interfacial resistance. The aim of this research was to develop a new type of SSE based on metal-organic frameworks (MOFs) and ionic liquids (ILs). MOFs are porous materials with high surface area and tunable electronic properties, making them ideal for use in SSEs. ILs are liquid electrolytes that are non-flammable and have high ionic conductivity. A series of MOFs were synthesized, and their electrochemical properties were evaluated. The MOFs were then infiltrated with ILs to form a quasi-solid gel and solid xerogel SSEs. The ionic conductivity, interfacial resistance, and electrochemical performance of the SSEs were characterized. The results showed that the MOF-IL SSEs had significantly higher ionic conductivity and lower interfacial resistance than conventional SSEs. The SSEs also exhibited excellent electrochemical performance, with high discharge capacity and long cycle life. The development of MOF-IL SSEs represents a significant advance in the field of solid-state electrolytes. The high ionic conductivity and low interfacial resistance of the SSEs make them promising candidates for use in next-generation LIBs. The data for this research was collected using a variety of methods, including X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy. The data was analyzed using a variety of statistical and computational methods, including principal component analysis, density functional theory, and molecular dynamics simulations. The main question addressed by this research was whether MOF-IL SSEs could be developed that have high ionic conductivity, low interfacial resistance, and excellent electrochemical performance. The results of this research demonstrate that MOF-IL SSEs are a promising new type of solid-state electrolyte for use in LIBs. The SSEs have high ionic conductivity, low interfacial resistance, and excellent electrochemical performance. These properties make them promising candidates for use in next-generation LIBs that are safer and have higher energy densities.

Keywords: energy storage, solid-electrolyte, ionic liquid, metal-organic-framework, electrochemistry, organic inorganic plastic crystal

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