Commenced in January 2007
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Edition: International
Paper Count: 14

Search results for: tetrahydrofuran

14 Heteromolecular Structure Formation in Aqueous Solutions of Ethanol, Tetrahydrofuran and Dimethylformamide

Authors: Sh. Gofurov, O. Ismailova, U. Makhmanov, A. Kokhkharov


The refractometric method has been used to determine optical properties of concentration features of aqueous solutions of ethanol, tetrahydrofuran and dimethylformamide at the room temperature. Changes in dielectric permittivity of aqueous solutions of ethanol, tetrahydrofuran and dimethylformamide in a wide range of concentrations (0÷1.0 molar fraction) have been studied using molecular dynamics method. The curves depending on the concentration of experimental data on excess refractive indices and excess dielectric permittivity were compared. It has been shown that stable heteromolecular complexes in binary solutions are formed in the concentration range of 0.3÷0.4 mole fractions. The real and complex part of dielectric permittivity was obtained from dipole-dipole autocorrelation functions of molecules. At the concentrations of C = 0.3 / 0.4 m.f. the heteromolecular structures with hydrogen bonds are formed. This is confirmed by the extremum values of excessive dielectric permittivity and excessive refractive index of aqueous solutions.

Keywords: refractometric method, aqueous solution, molecular dynamics, dielectric constant

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13 Investigate the Effects of Anionic Surfactant on THF Hydrate

Authors: Salah A. Al-Garyani, Yousef Swesi


Gas hydrates can be hazardous to upstream operations. On the other hand, the high gas storage capacity of hydrate may be utilized for natural gas storage and transport. Research on the promotion of hydrate formation, as related to natural gas storage and transport, has received relatively little attention. The primary objective of this study is to gain a better understanding of the effects of ionic surfactants, particularly their molecular structures and concentration, on the formation of tetrahydrofuran (THF) hydrate, which is often used as a model hydrate former for screening hydrate promoters or inhibitors. The surfactants studied were sodium n-dodecyl sulfate (SDS), sodium n-hexadecyl sulfate (SHS). Our results show that, at concentrations below the solubility limit, the induction time decreases with increasing surfactant concentration. At concentrations near or above the solubility, however, the surfactant concentration no longer has any effect on the induction time. These observations suggest that the effect of surfactant on THF hydrate formation is associated with surfactant monomers, not the formation of micelle as previously reported. The lowest induction time (141.25 ± 21 s, n = 4) was observed in a solution containing 7.5 mM SDS. The induction time decreases by a factor of three at concentrations near or above the solubility, compared to that without surfactant.

Keywords: tetrahydrofuran, hydrate, surfactant, induction time, monomers, micelle

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12 Optical Properties of Tetrahydrofuran Clathrate Hydrates at Terahertz Frequencies

Authors: Hyery Kang, Dong-Yeun Koh, Yun-Ho Ahn, Huen Lee


Terahertz time-domain spectroscopy (THz-TDS) was used to observe the THF clathrate hydrate system with dosage of polyvinylpyrrolidone (PVP) with three different average molecular weights (10,000 g/mol, 40,000 g/mol, 360,000 g/mol). Distinct footprints of phase transition in the THz region (0.4 - 2.2 THz) were analyzed and absorption coefficients and complex refractive indices are obtained and compared in the temperature range of 253 K to 288 K. Along with the optical properties, ring breathing and stretching modes for different molecular weights of PVP in THF hydrate are analyzed by Raman spectroscopy.

Keywords: clathrate hydrate, terahertz, polyvinylpyrrolidone (PVP), THz-TDS, inhibitor

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11 Phase Transition of Aqueous Ternary (THF + Polyvinylpyrrolidone + H2O) System as Revealed by Terahertz Time-Domain Spectroscopy

Authors: Hyery Kang, Dong-Yeun Koh, Yun-Ho Ahn, Huen Lee


Determination of the behavior of clathrate hydrate with inhibitor in the THz region will provide useful information about hydrate plug control in the upstream of the oil and gas industry. In this study, terahertz time-domain spectroscopy (THz-TDS) revealed the inhibition of the THF clathrate hydrate system with dosage of polyvinylpyrrolidone (PVP) with three different molecular weights. Distinct footprints of phase transition in the THz region (0.4–2.2 THz) were analyzed and absorption coefficients and real part of refractive indices are obtained in the temperature range of 253 K to 288 K. Along with the optical properties, ring breathing and stretching modes for different molecular weights of PVP in THF hydrate are analyzed by Raman spectroscopy.

Keywords: clathrate hydrate, terahertz spectroscopy, tetrahydrofuran, inhibitor

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10 Environmentally Friendly Palm Oil-Based Polymeric Plasticiser for Poly (Vinyl Chloride)

Authors: Nur Zahidah Rozaki, Desmond Ang Teck Chye


Environment-friendly polymeric plasticisers for poly(vinyl chloride), PVC were synthesised using palm oil as the main raw material. The synthesis comprised of 2 steps: (i) transesterification of palm oil, followed by (ii) polycondensation between the products of transesterification with diacids. The synthesis involves four different formulations to produce plasticisers with different average molecular weight. Chemical structures of the plasticiser were studied using FTIR (Fourier-Transformed Infra-Red) and 1H-NMR (Proton-Nuclear Magnetic Resonance).The molecular weights of these palm oil-based polymers were obtained using GPC (Gel Permeation Chromatography). PVC was plasticised with the polymeric plasticisers through solvent casting technique using tetrahydrofuran, THF as the mutual solvent. Some of the tests conducted to evaluate the effectiveness of the plasticiser in the PVC film including thermal stability test using thermogravimetric analyser (TGA), differential scanning calorimetry (DSC) analysis to determine the glass transition temperature, Tg, and mechanical test to determine tensile strength, modulus and elongation at break of plasticised PVC using standard test method ASTM D882.

Keywords: alkyd, palm oil, plasticiser, pvc

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9 Asymmetric Synthesis of Catalponol Using Chiral Iridium Catalyst

Authors: Takeyuki Suzuki, Ismiyarto, Da-Yang Zhou, Kaori Asano, Hiroaki Sasai


The development of catalytic asymmetric reaction is important for the synthesis of natural products. To construct the multiple stereogenic centers, the desymmetrization of meso compounds is powerful strategy for the synthesis of chiral molecules. Oxidative desymmetrization of meso diols using chiral iridium catalyst provides a chiral hydroxyl ketone. The reaction is practical and an environmentally benign method which does not require the use of stoichiometric amount of heavy metals. This time we report here catalytic asymmetric synthesis of catalponol based on tandem coupling of meso-diols and an aldehyde. The tandem reaction includes oxidative desymmetrization of meso-diols, aldol condensation with an aldehyde. The reaction of meso-diol, benzaldehyde in the presence of a catalytic amount of chiral Ir complex and CsOH in tetrahydrofuran afforded the desired benzylidene ketone in 82% yield with 96% ee (enantiomeric excess). Next, we applied this benzylidene ketone derivative to the synthesis of catalponol. The corresponding benzylidene ketone was obtained in 87% yield with 99% ee. Finally, catalponol was synthesized by the regio- and stereo-selective reduction of dienone moiety in good yield.

Keywords: catalponol, desymmetrization, iridium, oxidation

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

Authors: B. Kabane, G. G. Redhi


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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7 Mixture of Polymers and Coating Fullerene Soft Nanoparticles

Authors: L. Bouzina, A. Bensafi, M. Duval, C. Mathis, M. Rawiso


We study the stability and structural properties of mixtures of model nanoparticles and non-adsorbing polymers in the 'protein limit', where the size of polymers exceeds the particle size substantially. We have synthesized in institute (Charles Sadron Strasbourg) model nanoparticles by coating fullerene C60 molecules with low molecular weight polystyrene (PS) chains (6 PS chains with a degree of polymerization close to 25 and 50 are grafted on each fullerene C60 molecule. We will present a Small Angle Neutron scattering (SANS) study of Tetrahydrofuran (THF) solutions involving long polystyrene (PS) chains and fullerene (C60) nanoparticles. Long PS chains and C60 nanoparticles with different arm lengths were synthesized either hydrogenated or deuteriated. They were characterized through Size Exclusion Chromatography (SEC) and Quasielastic Light Scattering (QLS). In this way, the solubility of the C60 nanoparticles in the usual good solvents of PS was controlled. SANS experiments were performed by use of the contrast variation method in order to measure the partial scattering functions related to both components. They allow us to obtain information about the dispersion state of the C60 nanoparticles as well as the average conformation of the long PS chains. Specifically, they show that the addition of long polymer chains leads to the existence of an additional attractive interaction in between soft nanoparticles.

Keywords: fulleren nanoparticles, polymer, small angle neutron scattering, solubility

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6 Synthesis of Rare-Earth Pyrazolate Compounds

Authors: Nazli Eslamirad, Peter C. Junk, Jun Wang, Glen B. Deacon


Since coordination behavior of pyrazoles and pyrazolate ions are widely versatile towards a great range of metals such as d-block, f-block as well as main group elements; they attract interest as ligands for preparing compounds. A variety of rare-earth pyrazolate complexes have been synthesized by redox transmetalation/protolysis (RTP) previously, therefore, a variety of rare-earth pyrazolate complexes using two pyrazoles, 3,5-dimethylpyrazole (Me₂pzH) and 3,5-di-tert -butylpyrazolate (t-Bu₂pzH), in which the structures span the whole La-Lu array beside Sc and Y has been synthesized by RTP reaction. There have been further developments in this study: Synthesizing structure of [Tb(Me₂pz)₃(thf)]₂ which is isomorphous with those of the previously reported [Dy(Me₂pz)₃(thf)]₂ and [Lu(Me₂pz)₃(thf)]₂ analogous that has two µ-1(N):2(Nʹ)-Me2pz ligands (the most common pyrazolate ligation for non-rare-earth complexes). Previously most of the reported compounds using t-Bu2pzH were monomeric compounds however the lanthanum derivative [La(Me₂pz)₃thf₂] ,which has been reported previously without crystal structure, has now been structurally characterized, along with cerium and lutetium analogue. Also a polymeric structure with samarium has now been synthesized which the neodymium analogue has been reported previously and comparing these polymeric structures can support the idea that the geometry of Sm(tBu₂pz)₃ affect the coordination of the solvent. Also, by using 1,2-dimethoxyethane (DME) instead of tetrahydrofuran (THF) new [Er(tBu₂pz)₃ (dme)₂] has now been reported.

Keywords: lanthanoid complexes, pyrazolate, redox transmetalation/protolysis, x-ray crystal structures

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5 Quality Control of 99mTc-Labeled Radiopharmaceuticals Using the Chromatography Strips

Authors: Yasuyuki Takahashi, Akemi Yoshida, Hirotaka Shimada


99mTc-2-methoxy-isobutyl-isonitrile (MIBI) and 99mTcmercaptoacetylgylcylglycyl-glycine (MAG3 ) are heat to 368-372K and are labeled with 99mTc-pertechnetate. Quality control (QC) of 99mTc-labeled radiopharmaceuticals is performed at hospitals, using liquid chromatography, which is difficult to perform in general hospitals. We used chromatography strips to simplify QC and investigated the effects of the test procedures on quality control. In this study is 99mTc- MAG3. Solvent using chloroform + acetone + tetrahydrofuran, and the gamma counter was ARC-380CL. The changed conditions are as follows; heating temperature, resting time after labeled, and expiration year for use: which were 293, 313, 333, 353 and 372K; 15 min (293K and 372K) and 1 hour (293K); and 2011, 2012, 2013, 2014 and 2015 respectively were tested. Measurement time using the gamma counter was one minute. A nuclear medical clinician decided the quality of the preparation in judging the usability of the retest agent. Two people conducted the test procedure twice, in order to compare reproducibility. The percentage of radiochemical purity (% RCP) was approximately 50% under insufficient heat treatment, which improved as the temperature and heating time increased. Moreover, the % RCP improved with time even under low temperatures. Furthermore, there was no deterioration with time after the expiration date. The objective of these tests was to determine soluble 99mTc impurities, including 99mTc-pertechnetate and the hydrolyzed-reduced 99mTc. Therefore, we assumed that insufficient heating and heating to operational errors in the labeling. It is concluded that quality control is a necessary procedure in nuclear medicine to ensure safe scanning. It is suggested that labeling is necessary to identify specifications.

Keywords: quality control, tc-99m labeled radio-pharmaceutical, chromatography strip, nuclear medicine

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4 Exploring the Bifunctional Organocatalysts for Asymmetric Synthesis of 3-Substituted-3-Aminooxindoles

Authors: Jasneet Kaur, Swapandeep Singh Chimni


The unfavorable use of metal-based catalysts that are often extortionate and toxic can be overcome by using small organic molecules known as organocatalysts. A variety of small organic molecules, including Brønsted/Lewis bases and acids, based on sulfonic acids, phosphoric acids, amines, phosphines or carbenes, Cinchona alkaloids, have been used as organocatalysts. One of the key reasons for using organocatalysis is their ability to be effectively removed from the final product in comparison to the metallic counterparts, which are exceedingly difficult to remove. The present investigation seeks to explore the catalytic nature of Cinchona alkaloids as an organocatalyst for enantioselective synthesis of 3-substituted-3-aminooxindole, which is known to exhibit a variety of biological activities and pharmacological activities. In this context, an organocatalytic asymmetric route for the synthesis of 3-aminooxindoles via reaction of isatin imine with α-acetoxy-β-ketoesters has been developed. The bifunctional Cinchona derived thiourea catalyzed the reaction of α-acetoxy-β-ketoesters derivatives with isatin imine to afford 3-substituted-aminooxindole derivatives in up to 93% yield, 95% enantiomeric excess and >20:1 diastereomeric ratio. The reaction was performed at room temperature for two hours using 10 mol% of catalyst, in the presence of 4Å molecular sieves in tetrahydrofuran as a solvent at ambient temperature. After the completion of the reaction, the pure product could be easily separated by using column chromatography using hexane and ethyl acetate as solvents. In conclusion, the catalytic potential of Cinchona derived chiral thiourea-tertiary amine catalyst was explored for an organocatalytic enantioselective Mannich reaction of β-ketoester derivatives with various isatin imine derivatives under mild conditions.

Keywords: asymmetric synthesis, aminooxindoles, enantioselective, isatin imine

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3 Indoor Air Assessment and Health Risk of Volatile Organic Compounds in Secondary School Classrooms in Benin City, Edo State, Nigeria

Authors: Osayomwanbor E. Oghama, John O. Olomukoro


The school environment, apart from home, is probably the most important indoor environment for children. Children spend as much as 80-90% of their indoor time either at school or at home; an average of 35 - 40 hours per week in schools, hence are at the risk of indoor air pollutants such as volatile organic compounds (VOCs). Concentrations of VOCs vary widely but are generally higher indoors than outdoors. This research was, therefore, carried out to evaluate the levels of VOCs in secondary school classrooms in Benin City, Edo State. Samples were obtained from a total of 18 classrooms in 6 secondary schools. Samples were collected 3 times from each school and from 3 different classrooms in each school using Draeger ORSA 5 tubes. Samplers were left to stay for a school-week (5 days). The VOCs detected and analyzed were benzene, ethlybenzene, isopropylbenzene, naphthalene, n-butylbenzene, n-propylbenzene, toluene, m-xylene, p-xylene, o-xylene, styrene, chlorobenzene, chloroform, 1,2-dichloropropane, 2,2-dichloropropane, tetrachloroethane, tetrahydrofuran, isopropyl acetate, α-pinene, and camphene. The results showed that chloroform, o-xylene, and styrene were the most abundant while α-pinene and camphene were the least abundant. The health risk assessment was done in terms of carcinogenic (CRI) and non-carcinogenic risks (THR). The CRI values of the schools ranged from 1.03 × 10-5 to 1.36 × 10-5 μg/m³ (a mean of 1.16 × 10-5 μg/m³) with School 6 and School 3 having the highest and lowest values respectively. The THR values of the study schools ranged from 0.071-0.086 μg/m³ (a mean of 0.078 μg/m³) with School 3 and School 2 having the highest and lowest values respectively. The results show that all the schools pose a potential carcinogenic risks having CRI values greater than the recommended limit of 1 × 10-6 µg/m³ and no non-carcinogenic risk having THR values less than the USEPA hazard quotient of 1 µg/m³. It is recommended that school authorities should ensure adequate ventilation in their schools, supplementing natural ventilation with mechanical sources, where necessary. In addition, indoor air quality should be taken into consideration in the design and construction of classrooms.

Keywords: carcinogenic risk indicator, health risk, indoor air, non-carcinogenic risk indicator, secondary schools, volatile organic compounds

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2 Study of Bis(Trifluoromethylsulfonyl)Imide Based Ionic Liquids by Gas Chromatography

Authors: F. Mutelet, L. Cesari


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

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1 Oxidative Dehydrogenation and Hydrogenation of Malic Acid over Transition Metal Oxides

Authors: Gheorghiţa Mitran, Adriana Urdă, Mihaela Florea, Octavian Dumitru Pavel, Florentina Neaţu


Oxidative dehydrogenation and hydrogenation reactions of L-malic acid are interesting ways for its transformation into valuable products, including oxaloacetic, pyruvic and malonic acids but also 1,4-butanediol and 1,2,4-butanetriol. Keto acids have a range of applicationsin many chemical syntheses as pharmaceuticals, food additives and cosmetics. 3-Hydroxybutyrolactone and 1,2,4-butanetriol are used for the synthesis of chiral pharmaceuticals and other fine chemicals, while 1,4-butanediol can be used for organic syntheses, such as polybutylene succinate (PBS), polybutylene terephthalate (PBT), and for production of tetrahydrofuran (THF). L-malic acid is a non-toxic and natural organic acid present in fruits, and it is the main component of wine alongside tartaric acid representing about 90% of the wine total acidity. Iron oxides dopped with cobalt (CoxFe3-xO4; x= 0; 0.05; 0.1; 0.15) were studied as catalysts in these reactions. There is no mention in the literature of non-noble transition metal catalysts for these reactions. The method used for catalysts preparation was coprecipitation, whileBET XRD, XPS, FTIR and UV-VIS spectroscopy were used for the physicochemical properties evaluation.TheXRD patterns revealed the presence of α-Fe2O3 rhombohedral hematite structure, with cobalt atoms well dispersed and embedded in this structure. The studied samples are highly crystalline, with a crystallite size ranged from 58 to 65 nm. The optical absorption properties were investigated using UV-Vis spectroscopy, emphasizing the presence of bands that correspond with the reported hematite nanoparticle. Likewise, the presence of bands corresponding to lattice vibration of hexagonal hematite structurehas been evidenced in DRIFT spectra. Oxidative dehydrogenation of malic acid was studied using as solvents for malic acid ethanol or water(2, 5 and 10% malic acid in 5 mL solvent)at room temperature, while the hydrogenation reaction was evaluated in water as solvent (5%), in the presence of 1% catalyst. The oxidation of malic acid into oxaloacetic acid is the first step, after that, oxaloacetic acid is rapidly decarboxylated to malonic acid or pyruvic acid, depending on the active site. The concentration of malic acid in solution, it, in turn, has an influence on conversionthis decreases when the concentration of malic acid in the solution is high. The spent catalysts after the oxidative dehydrogenation of malic acid in ethanol were characterized by DRIFT spectroscopy and the presence of oxaloacetic, pyruvic and malonicacids, along with unreacted malic acidwere observed on the surface. The increase of the ratio of Co/Fe on the surface has an influence on the malic acid conversion and on the pyruvic acid yield, while the yield of malonic acid is influenced by the percentage of iron on the surface (determined from XPS). Oxaloacetic acid yield reaches a maximumat one hour of reaction, being higher when ethanol is used as a solvent, after which it suddenly decreases. The hydrogenation of malic acid occurs by consecutive reactions with the production of 3-hydroxy-butyrolactone, 1,2,4-butanetriol and 1,4-butanediol. Malic acid conversion increases with cobalt loading increasing up to Co/Fe ratio of 0.1, after which it has a slight decrease, while the yield in 1,4-butanediol is directly proportional to the cobalt content.

Keywords: malic acid, oxidative dehydrogenation, hydrogenation, oxaloacetic acid

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