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1.
A calorimetric study of dissolution of the ionic liquids (ILs) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C2mim][NTf2]), 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C6mim][NTf2]), and 1-hexyl-3-methylimidazolium tris(trifluoromethylsulfonyl)methide ([C6mim][CTf3]) into chloroform (CHCl3) is presented with particular focus on [C2mim][NTf2]. The interpretation of the calorimetric data for [C2mim][NTf2] was aided by additional NMR self-diffusion measurements and viscosity measurements that through the Stokes–Einstein equation provided information about the average size of the species present. It is evident that the main equilibrium species are ion pairs and aggregates. An estimate for the enthalpy contribution from aggregate formation for [C2mim][NTf2] was found to be ?2.09 kJ per mol of added IL at 288.2 K and slightly decreasing in magnitude to ?1.11 kJ·mol?1 at 318.2 K. While all three ILs release heat upon dissolution into CHCl3, different temperature trends are observed demonstrating the fine balance of competing contributions from breaking IL interactions, cavity formation for the solutes to reside in, and the establishment of new solute–solvent interactions.  相似文献   

2.
Tri-n-butylphosphate (TBP) in an ionic liquid (IL) has been proposed as a suitable alternative for the solvent extraction of actinides from nitric acid solutions. This paper reports the detailed investigations on the physicochemical and hydrodynamic properties of the solvent system containing TBP in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) IL. The properties such as density, viscosity, phase separation time (PST), etc., were measured for irradiated and unirradiated solvent phases composed of TBP, [C4mim][NTf2] and 1.1 mol·L–1 TBP in [C4mim][NTf2]. The results are compared with the values obtained in acid-equilibrated IL phases. ATR–FTIR spectroscopy and dynamic light scattering measurement of the IL phase were employed to characterize the interactions among the IL, TBP and nitric acid medium, and the aggregate size of the adduct formed in the IL phase.  相似文献   

3.
1-烷基-3-甲基咪唑双三氟甲基磺酰胺型离子液体(Cnmim][NTf2])被认为是最有希望用于核燃料循环中的分离试剂之一, 虽然其化学结构在辐照过程中变化不大, 但在受到γ辐照后会发生明显的变色, 因此有必要研究该类离子液体的变色原因. 本文以60Co为辐照源, 系统研究了辐照后不同C(1)-烷基链长和咪唑环上C(2)位上的H被甲基取代后离子液体的紫外-可见(UV-Vis)吸收光谱行为, 并结合辐照后离子液体荧光光谱和质谱的变化, 分析了导致该类离子液体辐照后颜色加深的原因. 结果表明, 随着咪唑环上C(1)―烷基链长度和剂量增大, 离子液体颜色加深; 而C(2)位上的H被甲基取代后颜色明显变浅. 辐照后咪唑型离子液体的变色主要来自于辐照后产生的烷基侧链含双键的咪唑阳离子, 咪唑阳离子二聚体和含氟咪唑化合物. 此外, γ辐照引起咪唑阳离子易发生π-π堆积, 而聚集态含量增加也会引起颜色加深.  相似文献   

4.
Heat capacities in a range of temperatures of (5 to 370) K, enthalpies and temperatures of phase transitions for 1-ethyl-3-methylimidazolium bis(triflamide) ([C2mim][NTf2]) and 1-octyl-3-methylimidazolium bis(triflamide) ([C8mim][NTf2]) have been determined by adiabatic calorimetry. [C2mim][NTf2] has been found to form four crystalline phases with different fusion temperatures. Formation of the phases can be controlled by the temperature of annealing during crystallization. [C8mim][NTf2] forms three sequences of crystalline modifications, each including two polymorphs. Based on results of the measurements, thermodynamic functions for the compounds under study have been calculated.A heat-capacity anomaly near T = 230 K reported earlier for [C4mim][NTf2] and [C6mim][NTf2] have been found in some crystalline modifications of both the studied compounds. The position of the anomaly depends on the temperature of annealing of the crystals.  相似文献   

5.
Liquid multi‐ion systems made by combining two or more salts can exhibit charge ordering and interactions not found in the parent salts, leading to new sets of properties. This is investigated herein by examining a liquid comprised of a single cation, 1‐ethyl‐3‐methylimidazolium ([C2mim]+), and two anions with different properties, acetate ([OAc]?) and bis(trifluoromethylsulfonyl)imide ([NTf2]?). NMR and IR spectroscopy indicate that the electrostatic interactions are quite different from those in either [C2mim][OAc] or [C2mim][NTf2]. This is attributed to the ability of [OAc]? to form complexes with the [C2mim]+ ions at greater than 1:1 stoichiometries by drawing [C2mim]+ ions away from the less basic [NTf2]? ions. Solubility studies with molecular solvents (ethyl acetate, water) and pharmaceuticals (ibuprofen, diphenhydramine) show nonlinear trends as a function of ion content, which suggests that solubility can be tuned through changes in the ionic compositions.  相似文献   

6.
First, the direct and indirect electrochemical oxidation of ammonia has been studied by cyclic voltammetry at glassy carbon electrodes in propylene carbonate. In the case of the indirect oxidation of ammonia, its analytical utility of indirect for ammonia sensing was examined in the range from 10 and 100 ppm by measuring the peak current of new wave resulting from reaction between ammonia and hydroquinone, as function of ammonia concentration, giving a sensitivity 1.29×10?7 A ppm?1 (r2=0.999) and limit‐of‐detection 5 ppm ammonia. Further, the direct oxidation of ammonia has been investigated in several room temperature ionic liquids (RTILs), namely 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([C4mim] [BF4]), 1‐butyl‐3‐methylimidazolium trifluoromethylsulfonate ([C4mim] [OTf]), 1‐Ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim] [NTf2]), 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim] [NTf2]) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([C4mim] [PF6]) on a 10 μm diameter Pt microdisk electrode. In four of the RTILs studied, the cyclic voltammetric analysis suggests that ammonia is initially oxidized to nitrogen, N2, and protons, which are transferred to an ammonia molecule, forming NH via the protonation of the anion(s) (A?). However, in [C4mim] [PF6], the protonated anion was formed first, followed by NH . In all five RTILs, both HA and NH are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The analytical ability of this work has also been explored further, giving a limit‐of‐detection close to 50 ppm in [C2mim] [NTf2], [C4mim] [OTf], [C4mim] [BF4], with a sensitivity of ca. 6×10?7 A ppm?1 (r2=0.999) for all three ionic liquids, showing that the limit of detection was ca. ten times larger than that in propylene carbonate since ammonia in propylene carbonate might be more soluble in comparison with RTILs when considering the higher viscosity of RTILs.  相似文献   

7.
Lignin is potentially a major renewable, nonfossil source of aromatic and cyclohexyl compounds. In this study, we have investigated the abrasive stripping voltammetry of lignin and four lignin model compounds in the room temperature ionic liquids (RTILs) [C4mim][NTf2], [N6,2,2,2][NTf2] and [C4mim][OTf] (where [C4mim]+=1‐butyl‐3‐methylimidazolium, [N6,2,2,2]+=n‐hexyltriethylammonium, [NTf2]?=bis(trifluoromethanesulfonyl)imide and [OTf]? =trifluoromethanesulfonate) on a gold macrodisk and in 0.1 M H2SO4 and 0.1 M NaOH on a boron‐doped diamond (BDD) macroelectrode, with the hope of using the voltammetry to fingerprint the functional groups within the lignin molecule. The use of RTILs on metal electrodes, or either acidic or basic media in combination with BDD electrodes allows solvent systems with wide electrochemical potential windows, useful for studying voltammetry which may be difficult to observe in systems where early breakdown of the solvent occurs.  相似文献   

8.
The volatilisation of ferrocene (Fc), dissolved in the ionic liquid N‐butyl‐N‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C4mpyrr][NTf2], to the gas phase has been indirectly monitored by cyclic voltammetry and chronoamperometry. Simulation of the observed trends in concentration with time using a simple model allowed quantification of the process. Volatilisation of dissolved Fc under flowing wet and dry dinitrogen gas (N2) was found to be kinetically limited with a rate constant in the region of 2×10?7 cm s?1. The activation energy of diffusion for Fc was found to be 28.2±0.7 kJ mol?1, while the activation energy of volatilisation of Fc from [C4mpyrr][NTf2] to dry N2 was found to be 85±2 kJ mol?1.  相似文献   

9.
Song and Mason equation of state (EOS) with a simple modification has been extended to modelling PVT properties of ionic liquids (ILs). The considered ILs are [C1mim][MeSO4], [C1mim][CH3OC2H5SO4], [C1mim][(CH3)2PO4], [C2mim][MeSO4], [C2mim][BF4], [C2mim][SCN], [C2eim][NTf2], [C4mim][C(CN)3], [C4mim][CF3SO3], [C4mim][SCN], [C5mim][NTf2], [C8mim][NTf2], [(C6H13)3P(C14H29)][Cl], [(C6H13)3P(C14H29)][NTf2], [(C6H13)3P(C14H29)][Ac], [C3mpyr][NTf2], [C4mpyr][NTf2] and [Py][C2H5OC2H4SO4]. Three temperature-dependent parameters in the proposed EOS have been scaled as functions of reduced temperature with the use of the law of corresponding states. It is shown that the knowledge of just critical temperature and critical density is sufficient to predict the PVT properties of these ILs. The overall average absolute deviation of calculated densities from literature values for 1347 data points of 18 ILs was found to be 0.58%. The predicted density of ILs from proposed EOS has been compared with those obtained by other literature work. Moreover, we indicate that the Zeno line regularity can well be predicted by proposed model for ILs.  相似文献   

10.
The room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] has various applications in the separation of a range of metal ions replacing volatile and toxic traditional organic solvents in liquid–liquid extraction systems. In this study, the RTIL [C4mim][PF6] was used to separate no-carrier-added (NCA) 109Cd from α-particle irradiated Ag target. A natural Ag foil was bombarded by 30 MeV α-particles to produce 109Cd. After the decay of all co-produced short-lived products, NCA 109Cd was separated from the bulk Ag using [C4mim][PF6] as extractant from HNO3 medium. Ammoniumpyrrolidine dithiocarbamate (APDC) was used as a complexing agent. At the optimum condition, 3 M HNO3, 0.01 M APDC in presence of [C4mim][PF6], ~99 % bulk Ag was extracted to the IL phase, leaving NCA 109Cd in the aqueous phase. The amount of Ag became negligibly small after re-extraction in the same condition. The ionic liquid was recovered by washing it with 1 M HCl.  相似文献   

11.
讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([Cnmim][NTf2],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu3+)和铀酰根离子(UO22+)的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[Cnmim][NTf2]体系萃取性能的影响,并选取CMPO/[C2mim][NTf2]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C2mim][NTf2]体系对Eu3+的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO22+则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu3+的萃取反应是离子交换,而对UO22+的萃取反应则是中性配位;CMPO/[C2mim][NTf2]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。  相似文献   

12.
The radiation effect on a hydrophobic room-temperature ionic liquid (RTIL), 1-butyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide ([C4mim][NTf2]), was studied by γ-irradiation under nitrogen atmosphere. Accompanied by color darkening and increase of light absorbance in a wide wavelength range, a distinct absorption peak at around 290 nm for irradiated [C4mim][NTf2] appeared when acetonitrile was used as solvent, and the intensity of the peak enhanced with increasing dose. The spectrophotometric study on the irradiated RTILs containing 1,3-dialkylimidazolium cations associated with different inorganic anions revealed that the peak is ascribed to the radiolysis products of the [C4mim]+. And the wavelength of the peak was affected by alkyl chain length on imidazolium cation, while the intensity of the peak was influenced by anions. With incorporating a little amounts of oxidants, such as KMnO4 and HNO3 into irradiated [C4mim][NTf2], the intensity of the peak at 290 nm decreased obviously and the decoloration of [C4mim][NTf2] occurred, suggesting that the peak at 290 nm is assigned to the colored species and the species can be oxidized.  相似文献   

13.
Heat capacities of crystalline 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][NTf2] and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C6mim][NTf2] in the range 80 K-Tfus were measured in an adiabatic calorimeter. Anomalies in the heat-capacity curves for the both compounds occurred near 240 K. Positions of the anomalies depended on thermal history of the samples. More stable crystals had higher heat capacities in the range 220-260 K. Below 200 K heat capacities of all the crystals of the same compound were indistinguishable.  相似文献   

14.
This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [C2mim]+ cation. [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] single gas separation performance towards CO2, N2, and CH4 at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO2 permeation results, [C2mim][CF3BF3] showed an undermined value of 710 Barrer at 293.15 K and 1 bar of feed pressure when compared to [C2mim][BF4], whereas for the [C2mim][CF3SO2C(CN)2] IL an unexpected CO2 permeability of 1095 Barrer was attained at the same experimental conditions, overcoming the results for the remaining ILs used for comparison. The prepared membranes exhibited diverse permselectivities, varying from 16.9 to 22.2 for CO2/CH4 and 37.0 to 44.4 for CO2/N2 gas pairs. The thermophysical properties of the [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] ILs were also determined in the range of T = 293.15 K up to T = 353.15 K at atmospheric pressure and compared with those for other ILs with the same cation and anion’s with similar chemical moieties.  相似文献   

15.
This paper reports on the electrodeposition of aluminium on several substrates from the air‐ and water‐stable ionic liquids 1‐propyl‐1‐methylpiperidinium bis(trifluoromethylsulfonyl)amide ([C3mpip][NTf2]) and 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([C4mpyr][NTf2]), which contain anhydrous AlCl3. At an AlCl3 concentration of 0.75 molal, no evidence for aluminium electrodeposition was observed in either system at room temperature. However, aluminium electrodeposition becomes feasible upon heating the samples to 80 °C. Aluminium electrodeposition from bis(trifluoromethylsulfonyl)amide‐based ionic liquids that contain AlCl3 has previously been shown to be very dependent upon the AlCl3 concentration and has not been demonstrated at AlCl3 concentrations below 1.13 molal. The dissolution of AlCl3 in [C3mpip][NTf2] and [C4mpyr][NTf2] was studied by variable‐temperature 27Al NMR spectroscopy to gain insights on the electroactive species responsible for aluminium electrodeposition. A similar change in the aluminium speciation with temperature was observed in both ionic liquids, thereby indicating that the chemistry was similar in both. The electrodeposition of aluminium was shown to coincide with the formation of an asymmetric four‐coordinate aluminium‐containing species with an 27Al chemical shift of δ=94 and 92 ppm in the [C3mpip][NTf2]–AlCl3 and [C4mpyr][NTf2]–AlCl3 systems, respectively. It was concluded that the aluminium‐containing species that give rise to these resonances corresponds to the electroactive species and was assigned to [AlCl3(NTf2)]?.  相似文献   

16.
讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_nmim][NTf_2],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu~(3+))和铀酰根离子(UO_2~(2+))的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[C_nmim][NTf_2]体系萃取性能的影响,并选取CMPO/[C_2mim][NTf_2]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C3+2mim][NTf_2]体系对Eu的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO_2~(2+)则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu~(3+)的萃取反应是离子交换,而对UO_2~(2+)的萃取反应则是中性配位;CMPO/[C_2mim][NTf_2]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。  相似文献   

17.
[C12mim][BF4], [C8mim][BF4], and [C4mim][BF4] were first applied as reaction media for atom transfer radical polymerization using activators regenerated by electron transfer (ARGET ATRP) of acrylonitrile (AN) with 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) as both ligand and reducing agent in the presence of air. The rate of polymerization in [C12mim][BF4] was considerably faster than in [C8mim][BF4] and [C4mim][BF4]. ARGET ATRP of AN in [C12mim][BF4] were better controlled than in [C8mim][BF4] and [C4mim][BF4] under the same experimental conditions. With an increase in the content of PMDETA, the polymerization provided an accelerated reaction rate and a broader polymer molecular weight distribution. A slow polymerization rate and a broad polydispersity index were observed using TMEDA instead of PMDETA as both ligand and reducing agent. There was an obvious induction period with CuCl2 instead of CuBr2 as catalyst. Well‐defined PAN‐b‐PMMA with higher molecular weight at 104,560 and relatively broader distribution at 1.35 was successfully prepared with PAN as macroinitiator via ARGET ATRP in [C12mim][BF4] in the presence of air. The resultant fibers were obtained with the fineness at 1.17dtex and the tenacity at 6.03cN · dtex?1. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

18.
The iron‐containing ionic liquids 1‐butyl‐3‐methylimidazolium tetrachloroferrate(III) [C4mim][FeCl4] and 1‐dodecyl‐3‐methylimidazolium tetrachloroferrate(III) [C12mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 °C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35 % in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow‐brown liquid phase recovered after phase separation is the starting IL [C4mim][FeCl4] and [C12mim][FeCl4], respectively. Photometry and ICP‐OES show that about 40 % of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal‐containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction.  相似文献   

19.
Absalan G  Akhond M  Sheikhian L 《Talanta》2008,77(1):407-411
In this paper, imidazolium-based ionic liquids [C4mim][PF6], [C6mim][PF6], [C8mim][PF6], [C6mim][BF4] and [C8mim][BF4] were tested as extracting solvents for removal of 3-indole butyric acid (IBA) from aqueous media with subsequent determination using HPLC. Percent extraction of IBA was strongly affected by pH of aqueous phases and the chemical structures of ionic liquids (ILs). Extraction of IBA was quantitative in the pH values lower than pKa of IBA. Considering both extraction and stripping efficiencies of IBA, [C4mim][PF6] was found to act more efficient than other studied ILs. Capacity of [C4mim][PF6] was 17.6 × 10−4 mmol IBA per 1.0 mL of IL. Ionic strength of aqueous phase and temperature had shown no serious effects on extraction efficiency of IBA. A preconcentration factor of 100 and a relative standard deviation of 1.16% were obtained. It was found that ionic liquid phase was reusable almost five times for extraction/stripping purposes. 3-Indole acetic acid showed interferential effect in the extraction step. In order to assess the applicability of the method, extraction and stripping of IBA from pea plants and some other samples were studied.  相似文献   

20.
An electrochromic liquid crystal (ECLC) material composed of only liquid crystal (LC) and ionic liquid (IL) was developed. The LC containing the substituted diphenylacetylene serves as electrochromic (EC) material to realise transmittance and colour change under the direct current (DC) field, while the IL with the designable cation and anion served as electrolyte. Herein, a series of IL electrolytes was screened to investigate how IL tunes the electro-optic performance of the ECLC cell. By testing the electrochemistry window of ILs in EC cells, IL with the [NTf2]? anion shows adequate electrochemical stability when the EC material undergoes oxidation and reduction. The electro-optic performance of ECLC containing 1-ethoxy-4-[2-(4-pentylphenyl) ethynyl]-benzene (PEB) and IL was then evaluated by UV-vis spectrometry under the control of an electrochemical work station. Compared with other PEB-IL, PEB-[Bmim][NTf2] with [Bmim][NTf2] electrolyte shows a satisfactory transmittance at low operating voltage. Furthermore, Pd NPs in situ formed in [Bmim][NTf2] reduced the EC potential and improved the light scattering of the ECLC cell. In this work, we also designed a bifunctional device based on polymer dispersed liquid crystal (PDLC) that hosts electrochromic guest molecules, and analysed the electro-optical and electrochromic properties of LC electrolyte mixtures, in order to gain control of the incident daylight and glare in building and automotive applications.  相似文献   

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