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1.
Compared to conventional molecular solvents, the ionic liquid [b-3C-im][NTf(2)] was found to promote transimination reactions with up to ~100-fold rate enhancement. This rate effect observed at ambient temperature might be explained by the fact that the ionic liquid displays weak Lewis acidity with very low, if any, nucleophilicity and its imidazolium cation is expected to interact by associating with, and thus electrophilically activating, the C=N bond of the starting imine, leading to increased stabilization of the polar, charged intermediate species and ultimately, rapid product formation. Moreover, the presence of 1 mol% Sc(OTf)(3) in [b-3C-im][NTf(2)] further facilitates the transimination reactions studied. 相似文献
2.
The density, refractive index, interfacial tension, and viscosity of ionic liquids (ILs) [EMIM][EtSO 4] (1-ethyl-3-methylimidazolium ethylsulfate), [EMIM][NTf 2] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), [EMIM][N(CN) 2] (1-ethyl-3-methylimidazolium dicyanimide), and [OMA][NTf 2] (trioctylmethylammonium bis(trifluoromethylsulfonyl)imide) were studied in dependence on temperature at atmospheric pressure both by conventional techniques and by surface light scattering (SLS). A vibrating tube densimeter was used for the measurement of density at temperatures from (273.15 to 363.15) K and the results have an expanded uncertainty ( k = 2) of +/-0.02%. Using an Abbe refractometer, the refractive index was measured for temperatures between (283.15 and 313.15) K with an expanded uncertainty ( k = 2) of about +/-0.0005. The interfacial tension was obtained from the pendant drop technique at a temperature of 293.15 K with an expanded uncertainty ( k = 2) of +/-1%. For higher and lower temperatures, the interfacial tension was estimated by an adequate prediction scheme based on the datum at 293.15 K and the temperature dependence of density. For the ILs studied within this work, at a first order approximation, the quantity directly accessible by the SLS technique was the ratio of surface tension to dynamic viscosity. By combining the experimental results of the SLS technique with density and interfacial tension from conventional techniques, the dynamic viscosity could be obtained for temperatures between (273.15 and 333.15) K with an estimated expanded uncertainty ( k = 2) of less than +/-3%. The measured density, refractive index, and viscosity are represented by interpolating expressions with differences between the experimental and calculated values that are comparable with but always smaller than the expanded uncertainties ( k = 2). Besides a comparison with the literature, the influence of structural variations on the thermophysical properties of the ILs is discussed in detail. The viscosities mostly agree with values reported in the literature within the combined estimated expanded uncertainties ( k = 2) of the measurements while our density and interfacial tension data differ by more than +/-1% and +/-5%. 相似文献
3.
Novel quaternary ammonium ionic liquid, ethyl(2-hydroxyethyl)dimethylammonium bis(trifluomethylsulfonyl)imide (C2NTf2), has been prepared from N,N-dimethylethanolamine as a substrate. The paper includes a specific basic characterization of the synthesized compound by NMR and the basic thermophysical properties: the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition determined by the differential scanning calorimetry (DSC), temperature of decomposition, and water content. The density of the new compound was measured. The solid-liquid or liquid-liquid phase equilibria of binary mixtures containing {C2NTf2+water or an alcohol (propan-1-ol, butan-1-ol, hexan-1-ol, octan-1-ol, decan-1-ol), aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (n-hexane, n-octane), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF)} have been measured by a dynamic method in a wide range of temperatures from 230 to 430 K. These data were correlated by means of the nonrandom two-liquid (NRTL) equation utilizing temperature-dependent parameters derived from the solid-liquid or liquid-liquid equilibrium. From the solubility results, the negative value of the partition coefficient of ionic liquid in binary system octan-1-ol/water (log P) at 298.15 K has been calculated. 相似文献
4.
Solubility and diffusion of CO2 and H2S in the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate
Amir Hossein Jalili Ali Mehdizadeh Mohammad Shokouhi Amir Naser Ahmadi Masih Hosseini-Jenab Fakhrolsadat Fateminassab 《The Journal of chemical thermodynamics》2010,42(10):1298-1303
The solubility and diffusion coefficient were determined for carbon dioxide and hydrogen sulfide gases in the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO4]) at temperatures ranging from (303.15 to 353.15) K and pressures up to 1.6 MPa. The Krichevsky–Kasarnovsky equation was used to correlate solubility data and Henry’s law constants at different temperatures were obtained. The partial molar thermodynamic functions of solution such as Gibbs free energy, enthalpy, and entropy were calculated using the solubility data. A semi-infinite volume approach is used to obtain the diffusion coefficients for CO2 and H2S and a correlation equation with temperature is presented for each gas. Comparison showed that H2S is more soluble than CO2 and its diffusion coefficient is about two orders of magnitude as that of CO2 in the ionic liquid studied in this work. 相似文献
5.
Pinyarat Jindaratsamee Yusuke Shimoyama Hironobu Morizaki Akira Ito 《The Journal of chemical thermodynamics》2011,43(3):311-314
The permeability of carbon dioxide (CO2) through imidazolium-based ionic liquid membranes was measured by a sweep gas method. Six species of ionic liquids were studied in this work as follows: [emim][BF4], [bmim][BF4], [bmim][PF6], [bmim][Tf2N], [bmim][OTf], and [bmim][dca]. The ionic liquids were supported with a polyvinylidene fluoride porous membrane. The measurements were performed at T = (303.15 to 343.15) K. The partial pressure difference between feed and permeate sides was 0.121 MPa. The permeability of the CO2 increases with temperature for the all ionic liquid species. Base on solution diffusion theory, it can be explained that the diffusion coefficient of CO2 in an ionic liquid affects the temperature dependence more strongly than the solubility coefficient. The greatest permeability was obtained with the [bmim][Tf2N] membrane. The membrane of [bmim][PF6] presents the lowest permeability.The separation coefficient between CO2 and N2 through the ionic liquid membranes was also investigated at the volume fraction of CO2 at feed side 0.10. The separation coefficient decreases with the increase of temperature for the all ionic liquid species. The membrane of [emim][BF4] and [bmim][BF4] gives the highest separation coefficient at constant temperature. The lowest separation coefficient was obtained from [bmim][Tf2N] membrane which presents the highest permeability of CO2. 相似文献
6.
Höfft O Bahr S Kempter V 《Langmuir : the ACS journal of surfaces and colloids》2008,24(20):11562-11566
The reflection-absorption infrared (RAIRS) spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]Tf 2N) are presented as a function of temperature between 114 and 292 K. A comparison is made with the corresponding infrared spectra (obtained with transmission spectroscopy) from bulk [EMIM]Tf 2N. The liquid and amorphous films show rather similar spectra, indicating that the film structure is similar in both cases. On the other hand, these spectra differ considerably from those of crystalline films. Characteristic differences seen between the film and bulk spectra are attributed to the different structures of the respective networks. There are, however, indications that under all studied conditions the cation-anion interaction is between the C-H groups of the [EMIM] ring and the SO 2 groups of the anion. 相似文献
7.
Transport properties in ionic liquids and ionic liquid mixtures: the challenges of NMR pulsed field gradient diffusion measurements 总被引:1,自引:0,他引:1
Pulsed field gradient NMR is a powerful method for the measurement of diffusion coefficients in liquids and solids and has begun to attract much attention in the ionic liquids field. However, aspects of the methodology as traditionally applied to solutions may not be uniformly applicable in these more viscous and chemically complex systems. In this paper we present data which shows that the Pulsed Gradient Spin Echo (PGSE) method in particular suffers from intrinsic internal gradients and can produce apparent diffusion coefficients which vary by as much as 20% for different 1H nuclei within a given molecule--an obvious anomaly. In contrast, we show that the Pulsed Gradient Stimulated Echo method does not suffer from this problem to the same extent and produces self-consistent data to a high degree of accuracy (better than 1%). This level of significance has allowed the detection, in this work, of subtle mixing effects in [C(3)mpyr][NTf(2)] and [C(4)mpyr][NTf(2)] mixtures. 相似文献
8.
Lauw Y Horne MD Rodopoulos T Lockett V Akgun B Hamilton WA Nelson AR 《Langmuir : the ACS journal of surfaces and colloids》2012,28(19):7374-7381
The structure of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C(4)mpyr][NTf(2)]) room-temperature ionic liquid at an electrified gold interface was studied using neutron reflectometry, cyclic voltammetry, and differential capacitance measurements. Subtle differences were observed between the reflectivity data collected on a gold electrode at three different applied potentials. Detailed analysis of the fitted reflectivity data reveals an excess of [C(4)mpyr](+) at the interface, with the amount decreasing at increasingly positive potentials. A cation rich interface was found even at a positively charged electrode, which indicates a nonelectrostatic (specific) adsorption of [C(4)mpyr](+) onto the gold electrode. 相似文献
9.
Broder TL Silvester DS Aldous L Hardacre C Compton RG 《The journal of physical chemistry. B》2007,111(27):7778-7785
The electrochemical oxidation of potassium nitrite has been studied in the room temperature ionic liquid (RTIL) [C2mim][NTf2] by cyclic voltammetry at platinum electrodes. A chemically irreversible oxidation peak was observed, and a solubility of 7.5(+/-0.5) mM and diffusion coefficient of 2.0(+/-0.2)x10(-11) m2 s(-1) were calculated from potential step chronoamperometry on the microdisk electrode. A second, and sometimes third, oxidation peak was also observed when the anodic limit was extended, and these were provisionally assigned to the oxidation of nitrogen dioxide (NO2) and nitrate (NO3-), respectively. The electrochemical oxidation of nitrogen dioxide gas (NO2) was also studied by cyclic voltammetry in [C2mim][NTf2] on Pt electrodes of various size, giving a solubility of ca. 51(+/-0.2) mM and diffusion coefficient of 1.6(+/-0.05)x10(-10) m2 s(-1) (at 25 degrees C). It is likely that NO2 exists predominantly as its dimer, N2O4, at room temperature. The oxidation mechanism follows a CE process, which involves the initial dissociation of the dimer to the monomer, followed by a one-electron oxidation. A second, larger oxidation peak was observed at more positive potentials and is thought to be the direct oxidation of N2O4. In addition to understanding the mechanisms of NO2- and NO2 oxidations, this work has implications in the electrochemical detection of nitrite ions and of NO2 gas in RTIL media, the latter which may be of particular use in gas sensing. 相似文献
10.
二氧化碳(CO2)是一种来源丰富的C1资源,在温和条件下实现CO2的资源化利用是当前研究的热点之一。CO2环加成反应制备环状碳酸酯是CO2资源化利用的重要途径之一。环状碳酸酯是电池电解液的优良介质,可承受较恶劣的光、热及化学变化;同时也是聚氨酯、聚碳酸酯等精细化工中间体,广泛应用于医药、化工、纺织、印染等领域。非均相离子液体催化剂具有化学和热稳定性好、合成过程简单和可重复使用等优势。本文重点总结了近年来非均相离子液体催化剂在CO2和环氧化物环加成反应中的应用,并对非均相离子液体催化CO2环加成反应的发展进行展望。 相似文献
11.
The diffusion coefficient of H2S in liquid sulfur is a key kinetic parameter that has been missing in literature. In this paper, a pressure decay method was applied to measure the diffusion coefficients of H2S in liquid sulfur at 403 and 423 K. This pressure decay process was then modeled by taking the simultaneous diffusion and reversible chemical reactions between H2S and liquid sulfur into consideration. The diffusion coefficients and reaction rate constants were numerically determined by fitting theoretical curves to experimental data using Finite Element Method and Genetic Algorithm. The solubility of H2S in liquid sulfur at 403 and 423 K was also calculated and the results agreed with the semi-empirical correlation lately reported in literature. This study further extended the validity of the correlation to higher partial H2S pressure conditions. 相似文献
12.
Qinggong Zhu Jun Ma Xinchen Kang Xiaofu Sun Jiayin Hu Guanying Yang Buxing Han 《中国科学:化学(英文版)》2016,59(5):551-556
Electrochemical reduction of CO2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide (GO), multi-walled carbon nanotube (MWCNT), and GO/MWCNT composites on carbon paper (CP) using electrophoretic deposition (EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical reduction of CO2 to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4)/acetonitrile (MeCN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL (90 wt%)/MeCN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte. 相似文献
13.
The diffusion of liquid crystal 4‐n‐pentyl‐4′‐cyanobiphenyl (5CB) into a poly(butyl methacrylate) (PBMA) matrix has been studied using fast FTIR imaging. The concentration profiles were obtained as a function of time at several temperatures above and below the nematic to isotropic transition temperature (TNI) of 5CB and the Tg of PBMA. The time‐dependent progression of the diffusion front position, when fitted to a power law model, exhibited exponential values between 0.40 and 0.52. This, along with the observed progression of a sharp 5CB‐diffusion front into the PBMA matrix, indicates the presence of an anomalous diffusion process. It was shown that fast FTIR was able to correctly identify the diffusion process as anomalous, whereas a simple mass uptake analysis would have led to the conclusion that the process proceeded according to Fick's second law. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2261–2268, 1999 相似文献
14.
《The Journal of chemical thermodynamics》2006,38(11):1396-1401
New experimental results are presented for the total pressure above liquid mixtures of carbon dioxide and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]). The series of experiments were performed at preset temperature and liquid phase composition by means of a very precise high-pressure view-cell technique based on the synthetic method. A temperature range from (293.15 to 413.2) K was investigated where the maximum pressure reached approximately 10 MPa. Gas molalities in [hmim][Tf2N] ranged up to about 4.7 mol · kg−1. The (extended) Henry’s law is successfully applied to correlate the solubility pressures. 相似文献
15.
CO(2) capture by a task-specific ionic liquid 总被引:20,自引:0,他引:20
Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function. 相似文献
16.
17.
Akon Higuchi Tadashi Nakajima Atsushi Morisato Michiaki Ando Kazukiyo Nagai Tsutomu Nakagawa 《Journal of Polymer Science.Polymer Physics》1996,34(13):2153-2160
Infrared spectra of CO2 sorbed in rubbery and glassy polymeric membranes were measured to examine the relationships between the spectroscopic data and the physical properties of the membranes. The two peaks observed in the spectra of CO2 were attributed to the R branch and P branch of CO2 sorbed in the membranes based on the consideration that both peaks were observed at a temperature above the glass transition temperature of the membranes. Apparent diffusion coefficients of CO2 in the membranes were measured from the desorption kinetics of CO2 detected by FTIR spectroscopy. The solubility coefficients of CO2 were also estimated from absorbance spectra of CO2 sorbed in the membranes using Lambert-Beer's rule. The permeability, solubility, and diffusion coefficients estimated by the FTIR method were found to correlate well with the coefficients obtained by conventional methods such as vacuum-pressure or sorption isotherm methods. © 1996 John Wiley & Sons, Inc. 相似文献
18.
In this study emission-based ratiometric response of ion pair form of 1-hydroxy-3,6,8-pyrenetrisulfonate (HPTS) to gaseous CO(2) has been evaluated in ionic liquid (IL) containing ethyl cellulose (EC) matrix. The ionic liquid: 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF(4)); provided longer storage time and highly stable microenvironment for the HPTS molecule due to the buffering effect. The utilization of ionic liquid in ethyl cellulose matrix resulted with superior spectral characteristics. The excitation spectra of HPTS exhibited an atypical isoemmissive point in modified EC matrix at 418 nm which allows ratiometric processing of the signal intensities. EMIMBF(4)-doped sensor films exhibited enhanced linear working range between 0 and 100% pCO(2). The signal changes were fully reversible and the shelf life of the EMIMBF(4)-doped films was extended from 15 to 95 days. 相似文献
19.
20.
Y. U. Pavlechko G. Ya. Kabo 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2008,82(8):1412-1414
The 1-ethyl-3-methylimidazolium bistriflamide + 1-hexyl-3-methylimidazolium bistriflamide ([C2mim]NTf2 + [C6mim]NTf2) system was investigated by adiabatic calorimetry over the temperature range 80–370 K. It was found that, at T < 250 K, the system formed several solid phases of different compositions. 相似文献