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1.
Fakhri Yousefi  Hajir Karimi 《Ionics》2012,18(1-2):135-142
In our previous paper, we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. Here, we predict the equation of state for ionic liquids (ILs). The considered ILs are [Bmim][PF6], [C2mim][NtF2], [C3mim][NtF2], [C6mim][NtF2], [C7mim][NtF2], [C2mim][EtOSO3], [Bmim][MeSO4], [Bmim][OcSO4], and [C4mim][dca]. The equation of state consists of three temperature-dependent parameters: the second virial coefficient, a constant for scaling the softness of repulsive force, and an effective hard-sphere diameter equivalent to the van der Waals co-volume. The second virial coefficients of ILs are scare and there is no accurate potential energy function to allow their theoretical calculation. In this work, the second virial coefficient have been calculated using corresponding states correlation based on temperature and density at normal boiling point. The other two parameters of the equation of state can be calculated using a scaling rule. Analysis of our predicted results shows that the Tao?CMason equation of state is capable of accurately predicting the density of ILs at any temperature and pressure. The overall average absolute deviation densities for 1,633 data points are 2.05%. Also, the density of ILs obtained from the TM EOS has been compared with those calculated from vdW?CCS?C?? and Peng?CRobinson (PR) equation of state. Our results are in favor of the preference of the TM EOS over the two other equations of state. The overall average absolute deviation for 1,633 data points calculated by vdW?CCS?C?? and PR equation of state are 6.63% and 12.19%, respectively.  相似文献   

2.
The electrochemical reduction of benzoic acid (BZA) has been studied at platinum micro‐electrodes (10 and 2 µm diameters) in acetonitrile (MeCN) and six room temperature ionic liquids (RTILs): [C2mim][NTf2], [C4mim][NTf2], [C4mpyrr][NTf2], [C4mim][BF4], [C4mim][NO3] and [C4mim][PF6] (where [Cnmim]+ = 1‐alkyl‐3‐methylimidazolium, [NTf2]? = bis(trifluoromethylsulphonyl)imide, [C4mpyrr]+ = N‐butyl‐N‐methylpyrrolidinium, [BF4]? = tetrafluoroborate, [NO3]? = nitrate and [PF6]? = hexafluorophosphate). Based on the theoretical fitting to experimental chronoamperometric transients in [C4mpyrr][NTf2] and MeCN at several concentrations and on different size electrodes, it is suggested that a fast chemical step preceeds the electron transfer step in a CE mechanism (given below) in both RTILs and MeCN, leading to the appearance of a simple one‐electron transfer mechanism. The six RTIL solvents and MeCN were saturated with BZA, and potential‐step chronoamperometry revealed diffusion coefficients of 170, 4.6, 3.2, 2.7, 1.8, 0.26 and 0.96 × 10?11 m2 s?1 and solubilities of 850, 75, 78, 74, 220, 2850 and 48 mM in MeCN and the six ionic liquids, respectively, at 298 K. The high solubility of BZA in [C4mim][NO3] may suggest a strong interaction of the dissolved proton with the nitrate anion. Although there are relatively few literature reports of solubilities of organic solutes in RTILs at present, these results suggest the need for further studies on the solubilities of organic species (particularly acids) in RTILs, because of the contrasting interaction of dissolved species with the RTIL ions. Chronoamperometry is suggested as a convenient methodology for this purpose. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

3.
Chen Sun  Wei Zhao  Huanhuan Zhang 《Molecular physics》2019,117(23-24):3957-3967
Structures of ionic liquids (ILs) 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide ([C10mim][TFSA]) and 1-decyl-dimethylimidazolium bis(trifluoromethanesulfonyl)azanide ([C10(mim)2](TFSA)2) in different-sized mica slits have been investigated using molecular dynamics simulations. Ion density and angular distributions for monocationic IL [C10mim][TFSA] were analysed to elucidate the IL structures under different surface charges and especially their changes in the direction perpendicular to the surfaces. [C10mim][TFSA] formes in bilayers, compatible with existing models of ILs with long alkyl chains. For dicationic IL [C10(mim)2](TFSA)2, cations adjacent to the mica surface tend to stay parallel to the surface with both positively charged rings absorbed. While near the centre of the slit, dications show the weak tendency of orientation distribution, more random than [C10mim]+ ions. Structures of [C10(mim)2](TFSA)2 cannot be described by bilayer models. Additionally, the in-plane arrangement of [C10mim][TFSA] is more ordered when K+ ions completely neutralise the negative charge of the mica surface, and [C10mim]+ ions tend to be located in hexagonal mica lattices with two aluminium atoms in replacement of silicon atoms. [TFSA]? ions are constrained by the neighbouring K+ ions absorbed onto mica lattices.  相似文献   

4.
In comparison with the conventional ionic liquids, water-miscible amino acid ionic liquids (AAILs) are considered as more biodegradable and biocompatible, less toxic, and as able to enhance the biomaterials stability. An application of some long-chain ionic liquids in catalysis, extraction, etc. requests the detailed analysis of ionic and water transport properties of their diluted aqueous solutions close to the area of its critical micelle concentration (cmc). In this work, the molecular transport properties of two 1-methyl-3-octylimidazolium-based AAILs, [C8mim][Val], and [C8mim][Leu] (with anions of l-Leucine or l-Valine), in the aqueous solutions were studied by measuring the self-diffusion coefficients and the solution’ viscosities in the temperature ranges 273–343 K at the AAIL’s concentrations below and above its cmc. The data on self-diffusion coefficients of water molecules and cations/anions of AAILs are discussed in terms of activation energies and of hydration effects. Above the cmc, the [C8mim][Val] molecules demonstrate the strengthening effect on the solvent structure, while the molecules of [C8mim][Leu] have structure-destructive effect. The results obtained for the relative dynamic viscosities show a decrease of micellar size with increasing temperature. In addition, it was found that the degrees of counterion binding for both AAILs are higher than for 1-methyl-3-octylimidazolium halides.  相似文献   

5.
The Raman, infrared and proton NMR spectra of the liquid molecules, C2H5-X(X[dbnd]Cl, Br, I) have been recorded. And the molecular structures have been studied on the basis of these spectra. Consequently a non-rigid structure in which a CH2 group rotates freely with respect to the three hydrogen atoms of CH3 group is established.  相似文献   

6.
A detailed chemical kinetic model for oxidation of C2H4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C2H3 + O2 reaction was used to obtain rate coefficients over a wide range of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH2O and HCO, is the dominant product. The experiments, involving C2H4/O2 mixtures diluted in N2, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C2H4 are more complex than those prevailing at higher temperatures and lower pressures. The major differences are the importance of the hydroxyethyl (CH2CH2OH) and 2-hydroperoxyethyl (CH2CH2OOH) radicals, formed from addition of OH and HO2 to C2H4, and vinyl peroxide, formed from C2H3 + O2. Hydroxyethyl is oxidized through the peroxide HOCH2CH2OO (lean conditions) or through ethenol (low O2 concentration), while 2-hydroperoxyethyl is converted through oxirane.  相似文献   

7.
We report temperature-dependent Raman studies on single crystals of [N(CH3)4]2ZnCI4 from 300 to 10 K. The observed spectral features suggest that both the N(CH3)4 + and ZnCl2- 4 ions are distorted from their regular tetrahedral structure and occupy sites of Cs symmetry in the lattice at room temperature. From the variation of line width of some selected Raman bands and other spectral changes as a function of temperature, it is inferred that both the ZnCl2- 4 and—CH3 groups have high motional freedom at room temperature and the different phase transitions up to 160 K are triggered by the gradual freezing-in of orientational freedom of these groups, while the N—C4 tetrahedra do not play any significant role in these phase transitions. The monoclinic to orthorhombic superlattice phase transitions at 159 K is triggered by freezing-in of the orientational motions of both the ZnCl2- 4 and N(CH3)+ 4 groups in the lattice.  相似文献   

8.
CdS-TiO2 and CdS-C60/TiO2 were prepared using C60, cadmium acetate dehydrate [(CH3COO)2Cd·2H2O], sodium sulfide (Na2S·5H2O) and titanium (IV) n-butoxide by a sol-gel method. The prepared sonocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and transmission electron microscopy (TEM). A rhodamine B (RhB) solution under ultrasonic irradiation was used to determine the catalytic activity. Excellent catalytic degradation of an RhB solution was observed using the CdS-C60/TiO2 composites under ultrasonic irradiation. C60 coupled CdS-TiO2 can enhance the Brunauer-Emmett-Teller (BET) surface area and increase the decolorization rate for rhodamine B solution. The results also shows that increase the content of CdS can enhance the catalytic activity.  相似文献   

9.
To understand the molecular interactions between newly synthesized ammonium ionic liquids (ILs) and highly polar solvent dimethylsulfoxide (DMSO), precise measurements such as densities (ρ), ultrasonic sound velocities (u) and viscosities (η) have been performed over the whole composition range at temperature ranging from 298.15 to 308.15 K and at atmospheric pressure. The ILs investigated in the present study included diethyl ammonium acetate ([Et2NH][CH3COO], DEAA) and triethyl ammonium acetate ([Et3NH][CH3COO], TEAA). Further, to gain some insight into the nature of molecular interactions in these mixed solvents, we predicted the excess molar volume (VE), the deviation in isentropic compressibilities (ΔKs) and deviation in viscosity (Δη) as a function of the concentration of IL using the measured properties of ρ, u and η, respectively. Redlich-Kister polynomial was used to correlate the results. The intermolecular interactions and structural effects were analyzed on the basis of the measured and the derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and DMSO molecules and their structural factors.  相似文献   

10.
Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C2H3F, C2H3Cl, C2H3Br, C2H5F, C2H3CN, CH2CF2, HCOOH and CH3Br with a CO2 laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.  相似文献   

11.
The ferrodistortive phase transition in the bis-tetramethylammonium tetrabromide crystals below room temperature is studied within the framework of the Landau theory. The specific heats of [N(CH3)4]2MnBr4 and [N(CH3)4]2ZnBr4 are correctly described down to 40°C below the transition temperature. The phenomenological parameters are determined from calorimetric results, elastic constants and thermal expansion data. Using these coefficients, the monoclinic angle in the ferrodistortive phases is obtained. The anharmonic quantities, such as the isothermal compressibility, calculated from the specific heat data, are in good agreement with the values derived from the elastic measurements.  相似文献   

12.
Eu activated Sr5(PO4)3F phosphor powders have been subjected to the electron bombardment at 2 keV (10 μA) at an oxygen pressure of 1×10−6 Torr. The synthesized Sr5(PO4)3F phosphor was identical to the hexagonal apatite structure, with the Sr present at two different sites Cs (S1) and C3 (S2) in the Sr5(PO4)3F host, as inferred from the crystallographic study. Cathodoluminescence (CL) and Auger electron spectroscopy of the phosphor excited by the same electron beam were used to monitor changes in the surface state during prolonged electron bombardment. A direct correlation between the surface reactions and the degradation of the CL brightness was observed. Both C and F were depleted from the surface during electron bombardment. The postulated mechanism for the electron stimulated chemical reactions on the phosphor surface is electron beam dissociation of molecular species to atomic species, which subsequently react with C to form volatile compounds CO2, CH4, etc. and with Sr5(PO4)3F to form a non luminescence layer of metal oxides of Sr and P.  相似文献   

13.
The structures and energetics of the chemisorbed CO2, CHx species and H as well as C2H4 on the α-Mo2C(0 0 0 1) surface have been computed at the GGA-RPBE level of density functional theory. It is found that CO2 adsorbs dissociately into CO and O, in agreement with the experimental finding. The adsorbed O, CHx and H species prefer the site of three surface molybdenum atoms over a second layer carbon atom (VC site). On the basis of the calculated adsorption energies of CHx and H, the sequential dehydrogenation of CH4 and the C/C coupling reaction of CHx have been discussed.  相似文献   

14.
In the present study, the adsorption behaviour of methanol (CH3OH) and ethanol (C2H5OH) molecules over heterofullerene C59B surface is studied by density functional theory calculations. This heterofullerene is obtained from C60 by substituting a carbon atom with a boron atom and relaxing self-consistently the structure to the local minimum. The adsorption of CH3OH and C2H5OH on the C59B is exothermic and the relaxed geometries are stable. The CH3OH and C2H5OH adsorption can also induce a change in the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy gap of the nanocage. The dehydrogenation pathways of CH3OH and C2H5OH via O–H and C–H bonds scission are also examined. The results indicate that O–H bond scission is the most favourable pathway on the C59B surface.  相似文献   

15.
Abstract

The electron spin resonance of γ-irradiated single crystals of methoxycarbonylcholine picrate hemihydrate, C7H16NO3 + · C6H2N3O7 ? · ½ H2O has been observed and analyzed for different orientations of the crystal in the magnetic field. The crystals have been investigated between 70 and 350 K. The spectra were found to be temperature independent and the radiation damage centers are attributed to – ?[Obar]OCH3 and –CH2CH2O? radicals. The g and hyperfine coupling constants were found to be almost isotropic with an average, g = 2.0060, a H1 = 4.4G for –CH2CH2O?, g = 2.0050, a H2 = 3.5G for –CH2CH2O? and g = 2.0045, a H = 3.5 G for –?[Obar]OCH3. These values indicate a long-range coupling between the unpaired electron and H protons.  相似文献   

16.
In order to examine the effects of polymer matrix substituting crystalline solvents and photoisomerization of azobenzene in photo-modulation of AC susceptibility discovered recently, we have compared various quantum magnetic properties of new organic/inorganic hybrid materials composed of Mn12-acetate (a typical single-molecule magnet, [Mn12(CH3COO)16(H2O)4O12]·2CH3COOH·4H2O) containing or not containing azobenzene casted into polymethylmethacrylate (PMMA) films on Polyvinylalchol (PVA) films. The M-H hysteresis loops below blocking temperature for both materials exhibited distinct differences of the dM/dH vs. H plots, which suggested azobenzene as well as crystalline solvents resulted in tuning of magnetic properties. Moreover, the AC susceptibility at 0.1-1000 Hz frequencies provided activation energy Ueff=87 K from Arrhenius law for both materials, albeit Cole-Cole plots indicated perturbation of quantum magnetization for both hybrid materials in polymer matrix.  相似文献   

17.
It is important to study the interaction of ionic liquids (ILs) with protein for the applications of ILs in biochemical process, and help the researchers to choose and design the better ILs to serve as a solvent. In this work, the interaction between 1-alkyl-3-methylimidazolium bromide [Cnmim]Br (n=4, 6, 8, 10) and bovine serum albumin (BSA) was systematically investigated for the first time by multi-spectroscopic approach (fluorescence, UV–vis and FT-IR spectroscopy) and density functional theory (DFT). [Cnmim]Br (n=4, 6, 8, 10) can bind to BSA by H-bond interaction between their cationic headgroups and Asp/Glu amino acid residue at the surface of BSA, and hydrophobic interaction between their hydrocarbon chains and the hydrophobic amino acid residues in the interior of BSA. On the basis of thermodynamic parameters and the similar structure of [Cnmim]Br (n=4, 6, 8, 10), it can be inferred that the hydrophobic interaction plays a major role in the interaction of [C10mim]Br with BSA, while the hydrogen bond and van der Waals force play a major role in the interaction of [Cnmim]Br (n=4, 6, 8) with BSA. Synchronous fluorescence and FT-IR spectra indicate that [C10mim]Br could markedly change the secondary structure of BSA, while [Cnmim]Br (n=4, 6, 8) could slightly change the secondary structure of BSA. The results allowed us to understand (i) the effect of the alkyl chain length of the cation on the mechanism of ILs–protein interaction and (ii) the effect of the alkyl chain length of the cation on the protein secondary structure.  相似文献   

18.
《光谱学快报》2013,46(3):267-277
The bridged ruthenium cluster-polypyridine dimer [Ru3O(CH3COO)6(py)2(tmbpy)Ru(bpy)2(Cl)](PF6)2 (py = pyridine, = 2, 2′-bipyridine and tmbpy = 4, 4′-trimethylenedipyridine) has been synthesized and structurally characterized based on 1H and 13C NMR spectroscopy. This species exhibits a complex pattern of NMR signals due to the presence of a paramagnetic [Ru3O] core and seven non-equivalent aromatic rings. 2D NMR (COSY, HMQC and HMBC) correlation techniques have been required for the total assignment of the 1H and 13C NMR spectra.  相似文献   

19.
Structures of several premixed ethylene-oxygen-argon rich flat flames burning at 50 mbar have been established by using molecular beam mass spectrometry in order to investigate the effect of CO2, or NH3, or H2O addition on species concentration profiles. The aim of this study is to examine the eventual changes of profiles of detected hydrocarbon intermediates which could be considered as soot precursors (C2H2, C4H2, C5H4, C5H6, C6H2, C6H4, C6H6, C7H8, C6H6O, C8H6, C8H8, C9H8 and C10H8). The comparative study has been achieved on four flames with an equivalence ratio (f) of 2.50: one without any additive (F2.50), one with 15% of CO2 replacing the same quantity of argon (F2.50C), one with 3.3% of NH3 in partial replacement of argon (F2.50N) and one with 13% of H2O in replacement of the same quantity of argon (F2.50H). The four flat flames have similar final flame temperatures (1800 K).CO2, or NH3, or H2O addition to the fresh gas inlet causes a shift downstream of the flame front and thus flame inhibition. Endothermic processes CO2 + H = CO + OH and H2O + H = H2 + OH are responsible of the reduction of the hydrocarbon intermediates in the CO2 and H2O added flames through the supplementary formation of hydroxyl radicals. It has been demonstrated that such processes begin to play at the end of the flame front and becomes more efficient in the burnt gases region.The replacement of some Ar by NH3 is responsible only for a slight decrease of the maximum mole fraction of C2H2, but NH3 becomes much more efficient for C4H2 and C5 to C10 species. Moreover, the efficiency of NH3 as a reducing agent of C5 to C10 intermediates is larger than that of CO2 and H2O for equal quantities added.  相似文献   

20.
In this article, the isomerisation mechanisms of HN(NO2)2 to O2NNN(O)OH without and with catalyst X (X = H2O, (H2O)2, (H2O)3, HCOOH, H2SO4, CH3CH2COOH and HN(NO2)2) have been investigated theoretically at the CBS-QB3 level of theory. Our results show that the catalyst X (X = H2O, (H2O)2, (H2O)3, HCOOH, H2SO4 and CH3CH2COOH) shows different positive catalytic effects on reducing the apparent activation energy of the isomerisation reaction processes. Such different catalytic effects are mainly related to the number of hydrogen bonds and the size of the ring structure in X (X = H2O, (H2O)2 and (H2O)3)-assisted transition states, as well as different values of pKa for H2SO4, HCOOH and CH3CH2COOH. Very interesting is also the fact that H2SO4-assisted reaction is the most favourable for the hydrogen transfer from HN(NO2)2 to O2NNN(O)OH, due to the smallest pKa (?3.0) value of H2SO4 than H2O, HCOOH, H2SO4 and CH3CH2COOH, and also because of the largest ∠X???H???Y (the angle between the hydrogen bond donor and acceptor) involved in H2SO4-assisted transition state. Compared to the self-catalysis of the isomerisation mechanisms of HN(NO2)2 to O2NNN(O)OH, the apparent activation energy of H2SO4-assisted channel also reduces by 9.6 kcal?mol?1, indicating that H2SO4 can affect the isomerisation of HN(NO2)2 to O2NNN(O)OH, most obvious among all the catalysts H2O, (H2O)2, (H2O)3, HCOOH, H2SO4, CH3CH2COOH and HN(NO2)2.  相似文献   

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