Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Sb-Cu alloy cathode with a novel lithiation mechanism of ternary intermetallic formation: Enabling high energy density and superior rate capability of liquid metal battery

Antimony(Sb) is an attractive cathode for liquid metal batteries(LMBs) because of its high theoretical voltage and low cost.The main obstacles associated with the Sb-based cathodes are unsatisfactory energy density and poor rate-capability.Herein,we propose a novel Sb_(64)Cu_(36)cathode that effectively tackles these issues.The Sb_(64)Cu_(36)(melting point:525℃) cathode presents a novel lithiation mechanism involving sequentially the generation of Li_(2)CuSb,the formation of Li_(3)Sb,and the conversion reaction of Li_(2)CuSb to Li_(3)Sb and Cu.The generated intermetallic compounds show a unique microstructure of the upper floated Li_(2)CuSb layer and the below cross-linked structure with interpenetrated Li_(2)CuSb and Li_(3)Sb phases.Compared with Li_(3)Sb,the lower Li migration energy barrier(0.188 eV) of Li_(2)CuSb significantly facilitates the lithium diffusion across the intermediate compounds and accelerates the reaction kinetics.Consequently,the Li‖Sb_(64)Cu_(36)cell delivers a more excellent electrochemical performance(energy density:353 W h kg^(-1)at 0.4 A cm^(-2);rate capability:0.59 V at 2.0 A cm^(-2)),and a much lower energy storage cost of only 38.45 $ kW h^(-1)than other previously reported Sb-based LMBs.This work provides a novel cathode design concept for the development of high-performance LMBs in applications for large-scale energy storage.

Densities and viscosities for ionic liquids [BMIM][BF4] and [BMIM][Cl] and their binary mixtures at various temperatures and atmospheric pressure

The density and viscosity of 1-butyl-3-methylimidazolium tetrafluoroborate[BMIM][BF4]and 1-butyl-3-methylimidazolium chloride[BMIM][Cl]and their binary mixtures within the temperatures from 303.15 K to323.15 K and at ambient pressure were determined in this work.The temperature dependences of density and viscosity were satisfactorily described with the linear model and the Vogel-Tammann-Fulcher type equation,respectively.The molar volume and viscosity of binary IL mixtures were predicted through ideal mixing rules showing that almost null deviations for IL mixtures were observed and their mixing was remarkably close to linear ideal behavior in the molar volumes,while comparatively large errors in viscosity occurred.Additionally,the molar volume of the investigated pure ILs and their mixtures could well be predicted by a predictive model presented by Valderrama et al.(Fluid Phase Equilib.,275(2009)145).

Density Measurement of Liquid Metals Using Dilatometer

The dilatometer method for density measurement of liquid metals was improved to give a high measurement accuracy with simple operation. The density of liquid tin was measured and the results are in agreement with values in literature. The melting point density of liquid Sn was measured to be 6.966×10^3 Kg·m^-3 and the temperature （T） dependence of the density （p） for liquid Sn can be well described by a polynomial equation p（T）=7.406 - 9.94 × 10^-4T ＋ 2.12 × 106-7T2.

Density of Liquid Steel over Temperature Range of 1803-1873K

The density of three kinds of liquid steel was measured by a modified sessile drop method over the temperature range of 1803-1 873 K.It is found that the density of liquid steels decreases with increasing temperature and carbon content in steel.Both of the density and its absolute temperature coefficient of studied steels are smaller than the literature values of pure iron.The molar volume of the steels increases with increasing temperature.

Measurement Method of Compressibility and Thermal Expansion Coefficients for Density Standard Liquid at 2329 kg/m^3 based on Hydrostatic Suspension Principle

The accurate measurement on the compressibility and thermal expansion coefficients of density standard liquid at 2329kg/m3（DSL-2329） plays an important role in the quality control for silicon single crystal manufacturing. A new method is developed based on hydrostatic suspension principle in order to determine the two coefficients with high measurement accuracy. Two silicon single crystal samples with known density are immersed into a sealed vessel full of DSL-2329. The density of liquid is adjusted with varying liquid temperature and static pressure, so that the hydrostatic suspension of two silicon single crystal samples is achieved. The compression and thermal expansion coefficients are then calculated by using the data of temperature and static pressure at the suspension state. One silicon single crystal sample can be suspended at different state, as long as the liquid temperature and static pressure function linearly according to a certain mathematical relationship. A hydrostatic suspension experimental system is devised with the maximal temperature control error ±50 μK; Silicon single crystal samples can be suspended by adapting the pressure following the PID method. By using the method based on hydrostatic suspension principle, the two key coefficients can be measured at the same time, and measurement precision can be improved due to avoiding the influence of liquid surface tension. This method was further validated experimentally, where the mixture of 1, 2, 3-tribromopropane and 1,2-dibromoethane is used as DSL-2329. The compressibility and thermal expansion coefficients were measured, as 8.5′10–4 K–1 and 5.4′10–10 Pa–1, respectively.

Densities and Viscosities of the Ionic Liquid [C4mim][PF6]＋ N,N-dimethylformamide Binary Mixtures at 293.15 K to 318.15 K

为 1-butyl-3-methylimidazolium hexafluorophosphate 的粘性和密度([C4mim ][PF6 ]) 并且 N， N-dimethylformamide (DMF ) 二元混合物从 293.15 K 在温度范围被测量了到 318.15 K。粘性和密度与温度和 DMF 的内容单调地减少，这被显示出。各种各样的对比法包括象 Arrhenius 一样方程， Seddon 等。的方程，有四个参数的 Redlich-Kister，和另外的实验方程被使用评估这些试验数据。一个模型被结合粘性的过量吉布斯自由能模型基于为估计包含离子的液体的混合物的粘性的状态的一个方程建议，它能同时地计算粘性和臼齿的体积。当仅仅一个温度无关的可调节的参数被采用时，结果证明模型为臼齿的卷为 1.05% 的粘性，和偏差给 8.29% 的偏差。当二个参数或参数温度依赖者参数被使用时，关联精确性进一步被改进。

Binary ionic liquid electrolyte design for ultrahigh-energy density graphene-based supercapacitors

Although room temperature ionic liquids(ILs)have emerged as potential next-generation electrolytes for their wide electrochemical stability window(ESW),the trade-off between this window and viscosity has hindered their widespread use in energy storage devices.Here,we present for the first time that such a trade-off can be balanced by mixing two ILs with the common anion([NTf_(2)]^(-))but different cations([EMIM]^(+) and[N1114]^(+))together.The[EMIM]cation-based IL possesses low viscosity while the[N1114]cation-based IL exhibits wide ESW.Since the concentrations of each IL in the mixtures can result in different electrolyte properties,we demonstrate a systematic approach by exploring the properties of various concentration combinations.In addition,the corresponding cell voltage of their resulting graphene supercapacitors(SCs)accompanied based on the interaction between the binary ionic liquid and the electrodes,and the associated electrochemical performance were studied to determine the optimum electrolyte system for the highest SC energy density.The well-balanced viscosity/ESW trade-off is achieved in binary IL consisting 50 vol%[EMIM][NTf_(2)]and 50 vol%[N1114][NTf_(2)]as evident from the extraordinary electrode specific capacitance of 293.1 F g^(-1) and the ultrahigh SC energy density of 177 Wh kg^(-1),which approaches that of a lithium-ion battery.

Densities and surface tensions of ionic liquids/sulfuric acid binary mixtures

The densities and surface tensions of [Bmim][TFO]/H_2SO_4, [Hmim][TFO]/H_2SO_4 and [Omim][TFO]/H_2SO_4 binary mixtures were measured by pycnometer and Wilhelmy plate method respectively. The results show that densities and surface tensions of the mixtures decreased monotonously with increasing temperatures and increasing ionic liquid(IL) molar fraction. IL with longer alkyl side-chain length brings a lower density and a smaller surface tension to the ILs/H_2SO_4 binary mixtures. The densities and surface tensions of the mixtures are fitted well by Jouyban–Acree(JAM) model and LWW model respectively. Redlich-Kister(R–K) equation and modified Redlich-Kister(R–K) equation describe the excess molar volumes and excess surface tensions of the mixtures well respectively. Adding a small amount of ILs(xILb 0.1) into sulfuric acid brings an obvious decrease to the density and the surface tension. The results imply that the densities and surface tensions of ILs/H_2SO_4 binary mixtures can be modulated by changing the IL dosage or tailoring the IL structure.

Seismic response control with density-variable tuned liquid dampers

In this paper, the seismic effectiveness of a density-variable tuned liquid damper （DVTLD） with a sloping bottom is experimentally investigated through a series of shake table tests on a 1/4-scale, 3-story frame structure and numerically simulated by a new semi-analytical model. Special attention was given to reducing the first peak and maximum response under near- and far-field ground motions, and the robustness of a density-variable control system consisting of multiple DVTLDs with closely-spaced frequencies. Adaptable to earthquake excitations, the density-variable control system has been demonstrated to be more effective and more robust than its corresponding traditional tuned liquid damper in suppressing story drift and floor acceleration of the structure. Numerical simulations of the DVTLD-controlled structure agreed very well in phase with experimental results but somewhat overestimated the amplitude of the structural response.

EXTENSION OF SOAVE EQUATION OF STATE TO LIQUID DENSITY

On the basis of vapor pressures, volumes of saturated vapor and liquid, both parameters "a" and "b" in Soave equation of state are treated as temperature dependent and an extended Soave equation is proposed in this work. The VLE for 38 pure components including polar substances have been calculated. The comparison of calculated results with experimental data shows the prediction of liquid density is improved over Soave equation without losing the accuracy of prediction in vapor pressure and vapor density.

On the trajectory of nonturbulent liquid jets in subsonic crossflows at different density ratios

Numerical simulations using volume of fluid(VOF)method are performed to study the impact of liquid-to-gas density ratio on the trajectory of nonturbulent liquid jets in gaseous crossflows.In this paper,large eddy simulation(LES)turbulence model is coupled with the VOF method to describe the turbulence effects accurately.In addition,dynamic adaptive mesh refinement method with two refinement levels is applied to refine the size of the cells located at gas-liquid interface.Density ratio is changed from 10 to 5000 while other nondimensional numbers are kept constant.Large density ratios are considered in this paper since they are common in many practical applications such as solution precursor/suspension plasma sprays.Our simulations show that the penetration height,especially in the farfield,increases as the density ratio increases.A general correlation for the jet trajectory,which can be used for a wide range of density ratios,is developed based on our simulation results.

Investigation of vapour-liquid nucleation properties for spherical and chain-like fluids by density functional theory

The excess Helmholtz free energy functional for nonpolar chain-like molecules is formulated in terms of a weighted density approximation （WDA） for short-range interactions and a Weaks Chandler Andersen （WCA） approximation and a Barker Henderson （BH） theory for long-range attraction. Within the framework of density functional theory （DFT）, vapour liquid interracial properties including density profile and surface tension, and vapour-liquid nucleation properties including density profile, work of formation and number of particles are investigated for spherical and chain- like molecules. The obtained vapour liquid surface tension and the number of particles in critical nucleus for Lennard- Jones （L J） fluids are consistent with the simulation results. The influences of supersaturation, temperature and chain length on vapour liquid nucleation properties are discussed.

Establishing a predictive model for fast online determination of relative density and refractive index of e-cigarette liquids using near-infrared spectroscopy

Relative density and refractive index are two fundamental physical properties of e?cigarette liquids to indicate their uniformity and batch stability.These parameters are mainly determined by a density meter and refractometer respectively,which is tedious and the analysis results are not readily available for massive measurements.A rapid determination of the two parameters is important for quality inspection and control of cigarette liquids,and a lot efforts have been devoted to establishing a predictive model for these parameters.In this study,a novel near-infrared spectroscopy(NIR)combined with particle swarm optimization-support vector regression(PSO-SVR)algorithm was applied to build a prediction model.The experimental results showed that comparing with the traditional partial least squares regression(PLSR)model and the principal component regression(PCR)model,the PSO?SVR model had superior prediction performance.

Numerical Simulation on Partially Liquid-Filled Sloshing with Baffle Under Different Density Ratios by the CLSVOF/IB Method

The density and viscosity ratios on partially liquid-filled sloshing with baffle have been investigated numerically in this study.As the key to success in the present simulation,the Coupled Level Set and the Volume of Fluid(CLSVOF)method and the Immersed Boundary(IB)method are used to capture gas/liquid and fluid/structure interfaces,respectively.Within the CLSVOF method,surface normal in weighting factors is calculated by the level set function,resulting in a more accurate solution.Furthermore,the Tangent of Hyperbola for INterface Capturing(THINC)coupled with the Weighted Linear Interface Calculation(WLIC)scheme is used for capturing moving interface.As a standard practice,we first validate the code by comparing it with experimental results of liquid sloshing,which involves large deformation of interface.In addition to the validation study of the present method,the problems of liquid sloshing with baffle are investigated to understand kinematics and dynamics behaviors under different density and viscosity ratios.

A Direct Liquid Fuel Cell with High Power Density Using Reduced Phosphotungstic Acid as Redox Fuel

Direct liquid fuel cells(DLFCs)are proposed to address the problems of high cost and complex storage and transportation of hydrogen in traditional hydrogen-oxygen proton exchange membrane fuel cells.However,present fuels of organic small molecules used in DLFCs are restricted to problems of sluggish electrochemical kinetics and easily poisoning of precious metal catalysts.Herein,we demonstrate reduced phosphotungstic acid as a liquid fuel for DLFCs based on its advantages of high chemical and electrochemical stability,high electrochemical activity on common carbon material electrodes,and low permeability through proton exchange membranes.The application of phosphotungstic acid fuel effectively solves the problems of high cost of anode catalysts and serious fuel permeation loss in traditional DLFCs.A phosphotungstic acid fuel cell achieves a peak power density of466 mW cm^(-2)at a cell voltage of 0.42 V and good stability at current densities in the range from 20 to 200 mA cm^(-2).

Effect of current density on distribution coefficient of solute at solid-liquid interface

When current passes through the solid-liquid interface, the growth rate of crystal, solid-liquid interface energy and radius of curvature at dendritic tip will change. Based on this fact, the theoretical relation between the distribution of solute at solid-liquid interface and current density was established, and the effect of current on the distribution coefficient of solute through effecting the rate of crystal growth, the solid-liquid interface energy and the radius of curvature at the dendritic tip was discussed. The results show that as the current density increases, the distribution coefficient of solute tends to rise in a whole, and when the former is larger than about 400 A/cm 2, the latter varies significantly.

Density,refractive index and liquid–liquid equilibrium data of polyethylene glycol 3000 + potassium formate + water at different pH values

New liquid–liquid equilibrium data for polyethylene glycol(PEG) 3000 + CHO_2K + H_2O systems were measured at 298.15 K and pH values of 7.95, 8.40 and 9.98. It was found that an increase in pH caused the binodal curve to be displaced downward and the two-phase region to expand. Accordingly, the binodal curve was adjusted to the Pirdashti equation and the tie-line compositions were correlated using the Othmer–Tobias, Bancroft and Hand equations. The study measured the refractive index and densities of several homogeneous binary and ternary solutions. The solutions were used for calibration within a range of 0% to 30% of the mass of the PEG and potassium formate. The density and refractive index data show a linear variation with the mass fraction of the polymer and the salt. The effect of pH on the binodal, tie-line lengths(TLL) and slope of the tie-line(STL) in the systems was examined. It was found that an increase in pH increased the TLL and decreased the STL. It was observed that the density of the aqueous two-phase system was influenced by the TLL. The difference in density between phases(Δρ) increased as the TLL and pH increased. It was found that the TLL and Δρ showed a linear relationship. The effective excluded volume(EEV) of the PEG was obtained and it was found that EEV also increased as the pH increased.

Density of liquid NiCoAlCr quartemary alloys measured by modified sessile drop method

The densities of liquid NiCoAlCr quaternary alloys with a fixed molar ratio of Ni to Co to Al (x(Ni):x(Co):x(Al)≈73:12.15) which is close to the average value of the commercial Ni-based superalloys TMS75, INCO713, CM247LC and CMSX-4, and the mass fraction of chromium changes from 0 to 9% were measured by a modified sessile drop method. It is found that with increasing temperature and chromium concentration in the alloys, the densities of the liquid NiCoAlCr quaternary alloys decrease, whereas the molar volume of the liquid NiCoAlCr quaternary alloys increases. And the liquid densities of NiCoAlCr quaternary alloys calculated from the partial molar volumes of nickel, cobalt, aluminum and chromium in the corresponding Ni-bases binary alloys are in good agreement with the experimental ones, i.e. within the error tolerance range the densities of the liquid Ni-based multi-component alloys can be predicted from the partial volumes of elements in Ni-based binary alloys in liquid state. The molar volume of liquid NiCoAlCr binary alloy shows a negative deviation from the ideal linear mixing and the deviation changes small with the increase of chromium concentration at the same temperature.

Density Calculation for NaCl-H_2O Solutions in the Liquid-Solid TwoPhase Field in NaCI-H_2O Three-Phase Inclusions

Three-phase NaCl-H_2O fluid inclusions featuring halite dissolution temperature（Tm）higher than vapor bubble disappearance temperature（T_h） are commonly observed in porphyry copper/molybdenum deposits,skarn-type deposits and other magmatic- hydrothermal ore deposits.Based on ｜ΔV_1｜（the absolute value of volume variation of NaCl-H_2O solution in a heating or cooling process of inclusions）= ｜ΔV_s｜（the absolute value of volume variation of the halite crystal in a heating or cooling process of inclusions） and on the principle of conservation of the mass of NaCl and H_2O,we systematically calculated the densities of NaCl-H_2O solutions in the solid-liquid two-phase field for temperatures（T_h） from 0.1℃ to 800℃ and salinities from 26.3 wt%to 99.2wt%.Consequently for the first time we obtained the upper limit of the density of NaCI-H_2O solutions in the solid-liquid twophase field for T_b〈T_m inclusions with variant salinities.The results indicate that for inclusions of the T_h〈T_m type with the same T_h,the higher the T_m or salinity is,the higher the density of the NaClsaturated solution will be.If a group of fluid inclusions were homogeneously trapped,they must have the same T_h value and the same T_m or salinity value.This may be used to distinguish homogeneous,inhomogeneous,and multiple entrapments of fluid inclusions.