This article studied experimentally the effect of multi-wall carbon nanotubes (MWCNTs) on the thermo physical properties of ionic liquid-based nanofluids. The nanofluids were composed of ionic liquid, 1-ethyl-3- met...This article studied experimentally the effect of multi-wall carbon nanotubes (MWCNTs) on the thermo physical properties of ionic liquid-based nanofluids. The nanofluids were composed of ionic liquid, 1-ethyl-3- methylimidazolium diethylphosphate [EMIM][DEP], or its aqueous solution[EMIM][DEP](1) + H20(2) and MWCNTs without any surfactants. The thermal conductivity, viscosity and density of the nanofluids were mea- sured experimentally. The effects of the mass fraction of MWCNTs, temperature and the mole fraction of water on the thermo physical properties of nanofluids were studied. Results show that the thermal conductivity of nanofluids increases within the range of 1.3%-9.7% compared to their base liquids, and have a well linear depen- dence on temperature. The viscosity and density of the nanofluids exhibit a remarkable increase compared with those of the base liquids. Finally, the correlation of the effective thermal conductivity and viscosity of the nanofluids was made using the models in the literatures.展开更多
In our previous paper we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. This is a continuation for evaluating TM EOS in predicting PVT properties of heavy n...In our previous paper we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. This is a continuation for evaluating TM EOS in predicting PVT properties of heavy n-alkanes. Liquid density of long-chain n-alkane systems from C 9 to C 20 have been calculated using an analytical equation of state based on the statistical-mechanical perturbation theory. The second virial coefficients of these n-alkanes are scarce and there is no accurate potential energy function for their theoretical calculation. In this work the second virial coefficients are calculated using a corresponding state correlation based on surface tension and liquid density at the freezing point. The deviation of calculated densities of these alkanes is within 0.5% from experimental data. The densities of n-alkanes obtained from the TM EOS are compared with those calculated from Ihm-Song-Mason equation of state and the corresponding-states liquid densities (COSTALD). Our results are in favor of the preference of the TM EOS over other two equations of state.展开更多
Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and N, N-dimethylformamide (DMF) binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. ...Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and N, N-dimethylformamide (DMF) binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.'s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.展开更多
Intradiffusion coefficients of acetylacetone(AcAc) and DMF/DMSO/benzene in binary systems over the entire concentration range at 303.15 K were determined by 1H diffusion-order spectroscopy(DOSY) nuclear magnetic reson...Intradiffusion coefficients of acetylacetone(AcAc) and DMF/DMSO/benzene in binary systems over the entire concentration range at 303.15 K were determined by 1H diffusion-order spectroscopy(DOSY) nuclear magnetic resonance(NMR) method based pulse field gradient(PFG).The densities and viscosities of the above three binary systems at 303.15 K were also studied and employed to calculate the excess molar volumes(V^E) and deviations in viscosity(△η).Besides,experiments were carried out at 333.15 K for the system of AcAc+DMF.The solvent and temperature effect upon the difference in D between enol and keto tautomers,the tautomeric equilibrium and excess properties(V^E and △η) were discussed as well.Isotherms of V^E as a function of mole fraction of AcAc(χ_1) show positive deviations in benzene but negative deviations in DMF and DMSO,whereas isotherms of △ηas a function of χ_1 record positive deviations in DMF but negative in benzene and DMSO.V^E values show more negative and △η values are less positive in the system of AcAc+DMF at 333.15 K compared to 303.15 K.The V^E and △η were fitted to a Redlich-Kister type equation and the measured results were interpreted concerning molecular interactions in the solutions.展开更多
Combining Raman spectroscopy with density functional theory, the populations of the trans- and gaucheethanol conformers are investigated in carbon tetrachloride (CC14) and carbon disulfide (CS2). The spectral cont...Combining Raman spectroscopy with density functional theory, the populations of the trans- and gaucheethanol conformers are investigated in carbon tetrachloride (CC14) and carbon disulfide (CS2). The spectral contributions of two ethanol conformers are identified in OH stretching region. The energy difference between both conformers is estimated with the aid of the calculated Raman cross sections. It can be seen that the trans- ethanol is more stable in CC14 and CS2 solutions. The spectra are also obtained at different temperatures, and it is found the van't Hoff analysis is invalid in these solutions. By taking accounts of the Boltzmann distribution and theoretical Raman cross section, the energy difference is found to be increased with temperature, which shows the weak intermolecular interactions can enhance the population of transethanol.展开更多
The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimiza...The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, eight initial EMIM^+-CuCl2^-, and six initial EMIM^+-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I+G (d, p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs, single EMIM^+, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^+-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^+ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^+. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^+, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^+-CuCl2^-, and EMIM^+-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.展开更多
The ultrasonic echo in liquid density measurement often suffers noise,which makes it difficult to obtain the useful echo waveform,resulting in low accuracy of density measurement.A denoising method based on improved v...The ultrasonic echo in liquid density measurement often suffers noise,which makes it difficult to obtain the useful echo waveform,resulting in low accuracy of density measurement.A denoising method based on improved variational mode decomposition(VMD)for noise echo signals is proposed.The number of decomposition layers of the traditional VMD is hard to determine,therefore,the center frequency similarity factor is firstly constructed and used as the judgment criterion to select the number of VMD decomposition layers adaptively;Secondly,VMD algorithm is used to decompose the echo signal into several modal components with a single modal component,and the useful echo components are extracted based on the features of the ultrasonic emission signal;Finally,the liquid density is calculated by extracting the amplitude and time of the echo from the modal components.The simulation results show that using the improved VMD to decompose the echo signal not only can improve the signal-to-noise ratio of the echo signal to 20.64 dB,but also can accurately obtain the echo information such as time and amplitude.Compared with the ensemble empirical mode decomposition(EEMD),this method effectively suppresses the modal aliasing,keeps the details of the signal to the maximum extent while suppressing noise,and improves the accuracy of the liquid density measurement.The density measurement accuracy can reach 0.21%of full scale.展开更多
An equation of state (EOS) for high-pressure liquids, i.e., Tait EOS, is deduced according to isothermal 1 3V compressibility KT= -1/V· (2V/2p)T·.Based on the equation, a generalized EOS for high pressu...An equation of state (EOS) for high-pressure liquids, i.e., Tait EOS, is deduced according to isothermal 1 3V compressibility KT= -1/V· (2V/2p)T·.Based on the equation, a generalized EOS for high pressure-liquids is established by using the reduced state principle and introducing a characteristic parameter-configuration factor ξ. Reasonably satisfactory P-V-T data for many organic compounds, including some polar components, were calculated by using the equation.展开更多
On March 16–17, 2008, a sea fog occurred in Dianbai in the west of Guangdong Province and was accompanied by a high-pressure synoptic system. Using comprehensive observation datasets, this study analyzes the evolutio...On March 16–17, 2008, a sea fog occurred in Dianbai in the west of Guangdong Province and was accompanied by a high-pressure synoptic system. Using comprehensive observation datasets, this study analyzes the evolution of liquid water content during this sea fog and investigates the relationships between liquid water content and the average diameters and count densities of fog droplets, air temperature, wind speed and turbulence exchanges. The main results are presented as follows. (1) The sea fog showed a quasi-periodic oscillation characteristic, i.e., it developed, disappeared and then developed again. (2) During the sea fog, the number of fog droplets changed significantly while the changes in average diameter of the fog droplets were relatively small. The development and disappearance of the sea fog correlated significantly with the fog droplet numbers. (3) The air-cooling mechanism played a significant role in sea fog formation and development. However, the influences of this mechanism were not evident during fog persistence. (4) During sea fog formation, weak turbulence exchanges were helpful for fog formation. During sea fog development and persistence, liquid water content increased when turbulence exchanges weakened, and vice versa. The changes in turbulence exchanges were closely related to the quasi-periodic oscillations observed in sea fog presence.展开更多
The densities and viscosities of ternary systems(Poloxamer 188+ethanol/acetone+water)were meas- ured at 288.15,293.15,298.15,303.15,308.15 K and atmospheric pressure for different mass fractions of Poloxamer 188(0 to ...The densities and viscosities of ternary systems(Poloxamer 188+ethanol/acetone+water)were meas- ured at 288.15,293.15,298.15,303.15,308.15 K and atmospheric pressure for different mass fractions of Poloxamer 188(0 to 0.02)in aqueous solution and different solvent volume fractions of ethanol/acetone(0 to 0.3)in Poloxamer 188 aqueous solution.The densities were measured by a pycnometer,while the viscosities were measured using two Ubbelohde capillary viscometers.The correlations of density and viscosity of these ternary systems are obtained by fitting the experimental data at different temperatures,mass fractions and volume fractions.展开更多
New liquid-liquid equilibrium data for polyethylene glycol (PEG) 3000 + CHO2K + H20 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 cu...New liquid-liquid equilibrium data for polyethylene glycol (PEG) 3000 + CHO2K + H20 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 exam- ined. 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 (△p) increased as the TLL and pH increased. It was found that the TLL and Ap 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.展开更多
A new apparatus was designed with a thick-walled glass capillary, electric heater tube with red copper and heat preservation. The thick-walled glass capillary was used for its advantages of resistance to acid corrosio...A new apparatus was designed with a thick-walled glass capillary, electric heater tube with red copper and heat preservation. The thick-walled glass capillary was used for its advantages of resistance to acid corrosion and pressure, and ease of observation. The experimental densities over the entire range of mole fraction for the binary mixture of p-xylene+acetic acid and o-xylene+acetic acid were measured using the new apparatus at temperatures ranging from 313.15K to 473.15K and pressure ranging from 0.20 to 2,0 MPa. The density values were used in the determination of excess molar volumes, W. The Redlich-Kister equation was used to fit the excess molar volume values, and the coefficients and estimate ot the standard error values were presented. The experimental resuits prove that the density measurement apparatus is successful.展开更多
Saline aquifers are chosen for geological storage of greenhouse gas CO_2 because of their storage potential.In almost all cases of practical interest,CO_2 is present on top of the liquid and CO_2 dissolution leads to ...Saline aquifers are chosen for geological storage of greenhouse gas CO_2 because of their storage potential.In almost all cases of practical interest,CO_2 is present on top of the liquid and CO_2 dissolution leads to a small increase in the density of the aqueous phase.This situation results in the creation of negative buoyancy force for downward density-driven natural convection and consequently enhances CO_2 sequestration.In order to study CO_2 injection at pore-level,an isothermal Lattice Boltzmann Model(LBM) with two distribution functions is adopted to simulate density-driven natural convection in porous media with irregular geometry obtained by image treatment.The present analysis showed that after the onset of natural convection instability,the brine with a high CO_2 concentration infringed into the underlying unaffected brine,in favor of the migration of CO_2 into the pore structure.With low Rayleigh numbers,the instantaneous mass flux and total dissolved CO_2 mass are very close to that derived from penetration theory(diffusion only),but the fluxes are significantly enhanced with high Ra number.The simulated results show that as the time increases,some chaotic and recirculation zones in the flow appear obviously,which promotes the renewal of interfacial liquid,and hence enhances dissolution of CO_2 into brine.This study is focused on the scale of a few pores,but shows implications in enhanced oil/gas recovery with CO_2 sequestration in aquifers.展开更多
Using novel catalyst the pyrolysis of mixed plastics has been considered as an effective way to convert waste plastics into environmental friendly and industrially useful hydrocarbon gas and liquid products. Catalytic...Using novel catalyst the pyrolysis of mixed plastics has been considered as an effective way to convert waste plastics into environmental friendly and industrially useful hydrocarbon gas and liquid products. Catalytic cracking is a promising alternative for plastic wastes recycling. More than 99% of a polymer mixed converted into combustible hydrocarbon in a catalytic converting reaction. The products are mainly middle distillates. In this work equally weighted mixed HDPE (high density polyethylene), LDPE (low density polyethylene) and Polypropylene were degraded. The reaction occurred in a semi batch reactor at several temperatures and catalyst/polymer ratios in search for an optimum operating condition. The products are liquid and gaseous hydrocarbons with minor of residue. The liquid and gas products were in the range of middle distillate cuts of gasoline, kerosene and gas oil. Finally, with a metallic base, yielded 99.5% of given mixed to valuable middle distillate products that include 86% liquid hydrocarbon and 13.5% gas, ranging between C1 and C5 with less percent of residue. The optimum condition for this yield reports at a temperature of 450 ℃ and 10% of catalyst w/w at atmosphere pressure.展开更多
An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH an...An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH and EMP2 were used for the components CH4 and CO〉 respectively. Then the vapor-liquid equilibria (VLE) of CH4, CO2 and their binary system were calculated via the NVT- and NpT Gibbs Ensemble Monte Carlo Simulations. Meanwhile the traditional method using Equation of State (EoS) to correlate the VLE properties was also investigated. The EoSs considered in this work were three classic cubic RK, SRK, PR and another advanced molecular-based PC-SAFT equations. For pure components, both molecular simulations and the PC-SAFT EoS could obtain satisfactory predictions for all the saturated properties. However, the saturated liquid densities calculated by the cubic EoSs were not so good. It was also observed that the TraPPE-EH force field had a good representation for CH4 molecule, while the EMP2 force field was not enough accurate to represent CO2 molecules. For the mixture CH4 + CO2, SRK and PR showed the best predictions for the saturated pressure-component property, while good results were also obtained via molecular simulations and PC-SAFT EoS. It was suggested that special combining rules or binary interaction parameters were important to obtain enough accurate prediction of the mixed phase behavior. Compared with the cubic EoS, the PC-SAFT and molecular simulation method showed better adaptabilities for both the pure and mixture systems. Besides, the accurate molecular parameters used in the PC-SAFT and molecular simulations could bring about direct and deep understanding about the molecular characteristics.展开更多
Simple synthesis of multifunctional electrocatalysts with plentiful active sites from earth-abundant materials is especially fascinating. Here, N-doped defective carbon with trace Co (1.5 wt%) was prepared via a sca...Simple synthesis of multifunctional electrocatalysts with plentiful active sites from earth-abundant materials is especially fascinating. Here, N-doped defective carbon with trace Co (1.5 wt%) was prepared via a scalable one pot solid pyrolysis process. The sample exhibits efficient bifunctional OER/ORR activiW in alkaline, mainly ascribed to the unique micro-mesoporous structure (1-3 nm), high population of graphitic-N doping (up to 49.0%), abundant defects and the encapsulated Co nanoparticles with graphitized carbon. The according rechargeahle liquid Zn-air batteries showed excellent performance (maximum power density of 154.0 mWcm-2: energy density of 773Wh kg -1 at 5 mAcm 2 and charging-discharging cycling stability over 100 cycles). As a proof-of-concept, the flexible, rechargeable all-solid-state Zn-air batteries were constructed, and displayed a maximum power density as high as 45.9 mW cm 2 among the top level of those reported previously.展开更多
The sloshing of inviscid liquid of stratified density in a rectangular tank is analyzed.As the flow is no longer irrotional,the governing equation is found to be quite different from the Laplace equation used for the ...The sloshing of inviscid liquid of stratified density in a rectangular tank is analyzed.As the flow is no longer irrotional,the governing equation is found to be quite different from the Laplace equation used for the liquid of constant density.In particular it contains terms of mixed temporal and spatial derivatives.The problem is solved based on the variable separation method and Laplace transform for the constant Vaisala-Brunt frequency.It is found that the stratification of density may have small effects on those natural frequencies associated with the constant density,but many new natural frequencies have appeared as a result of its effect.展开更多
Amino acid ionic liquid (AAIL) based on alanine, 1-n-heptyl-3-methylimidazolium alanine ([C7mim][Ala]), has been prepared and characterized. Since the IL can form strong hydrogen bonds with water, trace amount of ...Amino acid ionic liquid (AAIL) based on alanine, 1-n-heptyl-3-methylimidazolium alanine ([C7mim][Ala]), has been prepared and characterized. Since the IL can form strong hydrogen bonds with water, trace amount of water is a problematic impurity in the IL. Using the standard addition method (SAM), the densities were measured in the temperature range from 293.15 to 343.15±0.05 K. On the basis of the experimental data of density, the surface tension y, molar volume, and the molecular vol- ume Vm, molar enthalpy of vaporization AIgHm0, and the thermal expansion coefficients or, for [C7mim][Ala] were estimated using semi-empirical methods. Also the interstice model has been verified with good accordance. Then the [C7mim][Ala] was taken as catalyst in the transesterification reaction with fatty acid, where soybean oil was used as raw material and methanol as reactant. The amount of catalyst, alcohol consumption, reaction time, temperature and other factors of the reaction were inves- tigated. Using GC determination, the conversions were calculated by the internal standard method. The main ingredients of the products were identified by GC-MS as palm methyl ester and linoleic acid methyl ester only, which showed high selectivity in palmitic acid and linoleic acid.展开更多
Developing electrolyte with high electrochemical stability is the most effective way to improve the energy density of double layer capacitors(DLCs), and ionic liquid is a promising choice. Herein, a novel ionic liquid...Developing electrolyte with high electrochemical stability is the most effective way to improve the energy density of double layer capacitors(DLCs), and ionic liquid is a promising choice. Herein, a novel ionic liquid based high potential electrolyte with a stabilizer, succinonitrile, was proposed to improve the high potential stability of the DLC. The electrolyte with 7.5 wt% succinonitrile added has a high ionic conductivity of 41.1 m S cm^(-1) under ambient temperature, and the DLC adopting this electrolyte could be charged to 3.0 V with stable cycle ability even under a discharge current density of 6 A g^(-1). Moreover, the energy density could be increased by 23.4% when the DLC was charged to 3.0 V compared to that charged to 2.7 V.展开更多
基金Supported by the National Natural Science Foundation of China(51376036)
文摘This article studied experimentally the effect of multi-wall carbon nanotubes (MWCNTs) on the thermo physical properties of ionic liquid-based nanofluids. The nanofluids were composed of ionic liquid, 1-ethyl-3- methylimidazolium diethylphosphate [EMIM][DEP], or its aqueous solution[EMIM][DEP](1) + H20(2) and MWCNTs without any surfactants. The thermal conductivity, viscosity and density of the nanofluids were mea- sured experimentally. The effects of the mass fraction of MWCNTs, temperature and the mole fraction of water on the thermo physical properties of nanofluids were studied. Results show that the thermal conductivity of nanofluids increases within the range of 1.3%-9.7% compared to their base liquids, and have a well linear depen- dence on temperature. The viscosity and density of the nanofluids exhibit a remarkable increase compared with those of the base liquids. Finally, the correlation of the effective thermal conductivity and viscosity of the nanofluids was made using the models in the literatures.
基金H. Karimi and F. Yousefi would like to thank Yasouj University for supporting this project
文摘In our previous paper we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. This is a continuation for evaluating TM EOS in predicting PVT properties of heavy n-alkanes. Liquid density of long-chain n-alkane systems from C 9 to C 20 have been calculated using an analytical equation of state based on the statistical-mechanical perturbation theory. The second virial coefficients of these n-alkanes are scarce and there is no accurate potential energy function for their theoretical calculation. In this work the second virial coefficients are calculated using a corresponding state correlation based on surface tension and liquid density at the freezing point. The deviation of calculated densities of these alkanes is within 0.5% from experimental data. The densities of n-alkanes obtained from the TM EOS are compared with those calculated from Ihm-Song-Mason equation of state and the corresponding-states liquid densities (COSTALD). Our results are in favor of the preference of the TM EOS over other two equations of state.
基金Supported by the National Natural Science Foundation of China (20476025, 20776040), Shanghai Municipal Science and Technology Commission of China (05DJ14002) and Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology of China (XLHX2007002).
文摘Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and N, N-dimethylformamide (DMF) binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.'s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.
基金Supported by the National Natural Science Foundation of China(20173074)the Natural Science Foundation of Guangdong Provinces(031583)
文摘Intradiffusion coefficients of acetylacetone(AcAc) and DMF/DMSO/benzene in binary systems over the entire concentration range at 303.15 K were determined by 1H diffusion-order spectroscopy(DOSY) nuclear magnetic resonance(NMR) method based pulse field gradient(PFG).The densities and viscosities of the above three binary systems at 303.15 K were also studied and employed to calculate the excess molar volumes(V^E) and deviations in viscosity(△η).Besides,experiments were carried out at 333.15 K for the system of AcAc+DMF.The solvent and temperature effect upon the difference in D between enol and keto tautomers,the tautomeric equilibrium and excess properties(V^E and △η) were discussed as well.Isotherms of V^E as a function of mole fraction of AcAc(χ_1) show positive deviations in benzene but negative deviations in DMF and DMSO,whereas isotherms of △ηas a function of χ_1 record positive deviations in DMF but negative in benzene and DMSO.V^E values show more negative and △η values are less positive in the system of AcAc+DMF at 333.15 K compared to 303.15 K.The V^E and △η were fitted to a Redlich-Kister type equation and the measured results were interpreted concerning molecular interactions in the solutions.
文摘Combining Raman spectroscopy with density functional theory, the populations of the trans- and gaucheethanol conformers are investigated in carbon tetrachloride (CC14) and carbon disulfide (CS2). The spectral contributions of two ethanol conformers are identified in OH stretching region. The energy difference between both conformers is estimated with the aid of the calculated Raman cross sections. It can be seen that the trans- ethanol is more stable in CC14 and CS2 solutions. The spectra are also obtained at different temperatures, and it is found the van't Hoff analysis is invalid in these solutions. By taking accounts of the Boltzmann distribution and theoretical Raman cross section, the energy difference is found to be increased with temperature, which shows the weak intermolecular interactions can enhance the population of transethanol.
文摘The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, eight initial EMIM^+-CuCl2^-, and six initial EMIM^+-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I+G (d, p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs, single EMIM^+, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^+-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^+ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^+. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^+, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^+-CuCl2^-, and EMIM^+-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.
文摘The ultrasonic echo in liquid density measurement often suffers noise,which makes it difficult to obtain the useful echo waveform,resulting in low accuracy of density measurement.A denoising method based on improved variational mode decomposition(VMD)for noise echo signals is proposed.The number of decomposition layers of the traditional VMD is hard to determine,therefore,the center frequency similarity factor is firstly constructed and used as the judgment criterion to select the number of VMD decomposition layers adaptively;Secondly,VMD algorithm is used to decompose the echo signal into several modal components with a single modal component,and the useful echo components are extracted based on the features of the ultrasonic emission signal;Finally,the liquid density is calculated by extracting the amplitude and time of the echo from the modal components.The simulation results show that using the improved VMD to decompose the echo signal not only can improve the signal-to-noise ratio of the echo signal to 20.64 dB,but also can accurately obtain the echo information such as time and amplitude.Compared with the ensemble empirical mode decomposition(EEMD),this method effectively suppresses the modal aliasing,keeps the details of the signal to the maximum extent while suppressing noise,and improves the accuracy of the liquid density measurement.The density measurement accuracy can reach 0.21%of full scale.
文摘An equation of state (EOS) for high-pressure liquids, i.e., Tait EOS, is deduced according to isothermal 1 3V compressibility KT= -1/V· (2V/2p)T·.Based on the equation, a generalized EOS for high pressure-liquids is established by using the reduced state principle and introducing a characteristic parameter-configuration factor ξ. Reasonably satisfactory P-V-T data for many organic compounds, including some polar components, were calculated by using the equation.
基金Natural Science Foundation of China (40675013)Foundation project of Nanjing University of Information Science & TechnologyProject on natural science for universities and colleges in Jiangsu province
文摘On March 16–17, 2008, a sea fog occurred in Dianbai in the west of Guangdong Province and was accompanied by a high-pressure synoptic system. Using comprehensive observation datasets, this study analyzes the evolution of liquid water content during this sea fog and investigates the relationships between liquid water content and the average diameters and count densities of fog droplets, air temperature, wind speed and turbulence exchanges. The main results are presented as follows. (1) The sea fog showed a quasi-periodic oscillation characteristic, i.e., it developed, disappeared and then developed again. (2) During the sea fog, the number of fog droplets changed significantly while the changes in average diameter of the fog droplets were relatively small. The development and disappearance of the sea fog correlated significantly with the fog droplet numbers. (3) The air-cooling mechanism played a significant role in sea fog formation and development. However, the influences of this mechanism were not evident during fog persistence. (4) During sea fog formation, weak turbulence exchanges were helpful for fog formation. During sea fog development and persistence, liquid water content increased when turbulence exchanges weakened, and vice versa. The changes in turbulence exchanges were closely related to the quasi-periodic oscillations observed in sea fog presence.
基金Supported by the National Natural Science Foundation of China(20606031)
文摘The densities and viscosities of ternary systems(Poloxamer 188+ethanol/acetone+water)were meas- ured at 288.15,293.15,298.15,303.15,308.15 K and atmospheric pressure for different mass fractions of Poloxamer 188(0 to 0.02)in aqueous solution and different solvent volume fractions of ethanol/acetone(0 to 0.3)in Poloxamer 188 aqueous solution.The densities were measured by a pycnometer,while the viscosities were measured using two Ubbelohde capillary viscometers.The correlations of density and viscosity of these ternary systems are obtained by fitting the experimental data at different temperatures,mass fractions and volume fractions.
文摘New liquid-liquid equilibrium data for polyethylene glycol (PEG) 3000 + CHO2K + H20 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 exam- ined. 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 (△p) increased as the TLL and pH increased. It was found that the TLL and Ap 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.
基金Supported by China Petrochemical Corporation(X505012)
文摘A new apparatus was designed with a thick-walled glass capillary, electric heater tube with red copper and heat preservation. The thick-walled glass capillary was used for its advantages of resistance to acid corrosion and pressure, and ease of observation. The experimental densities over the entire range of mole fraction for the binary mixture of p-xylene+acetic acid and o-xylene+acetic acid were measured using the new apparatus at temperatures ranging from 313.15K to 473.15K and pressure ranging from 0.20 to 2,0 MPa. The density values were used in the determination of excess molar volumes, W. The Redlich-Kister equation was used to fit the excess molar volume values, and the coefficients and estimate ot the standard error values were presented. The experimental resuits prove that the density measurement apparatus is successful.
文摘Saline aquifers are chosen for geological storage of greenhouse gas CO_2 because of their storage potential.In almost all cases of practical interest,CO_2 is present on top of the liquid and CO_2 dissolution leads to a small increase in the density of the aqueous phase.This situation results in the creation of negative buoyancy force for downward density-driven natural convection and consequently enhances CO_2 sequestration.In order to study CO_2 injection at pore-level,an isothermal Lattice Boltzmann Model(LBM) with two distribution functions is adopted to simulate density-driven natural convection in porous media with irregular geometry obtained by image treatment.The present analysis showed that after the onset of natural convection instability,the brine with a high CO_2 concentration infringed into the underlying unaffected brine,in favor of the migration of CO_2 into the pore structure.With low Rayleigh numbers,the instantaneous mass flux and total dissolved CO_2 mass are very close to that derived from penetration theory(diffusion only),but the fluxes are significantly enhanced with high Ra number.The simulated results show that as the time increases,some chaotic and recirculation zones in the flow appear obviously,which promotes the renewal of interfacial liquid,and hence enhances dissolution of CO_2 into brine.This study is focused on the scale of a few pores,but shows implications in enhanced oil/gas recovery with CO_2 sequestration in aquifers.
文摘Using novel catalyst the pyrolysis of mixed plastics has been considered as an effective way to convert waste plastics into environmental friendly and industrially useful hydrocarbon gas and liquid products. Catalytic cracking is a promising alternative for plastic wastes recycling. More than 99% of a polymer mixed converted into combustible hydrocarbon in a catalytic converting reaction. The products are mainly middle distillates. In this work equally weighted mixed HDPE (high density polyethylene), LDPE (low density polyethylene) and Polypropylene were degraded. The reaction occurred in a semi batch reactor at several temperatures and catalyst/polymer ratios in search for an optimum operating condition. The products are liquid and gaseous hydrocarbons with minor of residue. The liquid and gas products were in the range of middle distillate cuts of gasoline, kerosene and gas oil. Finally, with a metallic base, yielded 99.5% of given mixed to valuable middle distillate products that include 86% liquid hydrocarbon and 13.5% gas, ranging between C1 and C5 with less percent of residue. The optimum condition for this yield reports at a temperature of 450 ℃ and 10% of catalyst w/w at atmosphere pressure.
基金The National Natural Science Foundation of China(Grant No.51376188)The National Basic Research Program of China("973"Project)(Grant No.2011CB710701)
文摘An accurate knowledge about phase behaviors of CH4, CO2 and their binary mixture is crucial in fields of natural gas liquefaction and refrigeration applications. In this work, two all-atom force fields of TraPPE-EH and EMP2 were used for the components CH4 and CO〉 respectively. Then the vapor-liquid equilibria (VLE) of CH4, CO2 and their binary system were calculated via the NVT- and NpT Gibbs Ensemble Monte Carlo Simulations. Meanwhile the traditional method using Equation of State (EoS) to correlate the VLE properties was also investigated. The EoSs considered in this work were three classic cubic RK, SRK, PR and another advanced molecular-based PC-SAFT equations. For pure components, both molecular simulations and the PC-SAFT EoS could obtain satisfactory predictions for all the saturated properties. However, the saturated liquid densities calculated by the cubic EoSs were not so good. It was also observed that the TraPPE-EH force field had a good representation for CH4 molecule, while the EMP2 force field was not enough accurate to represent CO2 molecules. For the mixture CH4 + CO2, SRK and PR showed the best predictions for the saturated pressure-component property, while good results were also obtained via molecular simulations and PC-SAFT EoS. It was suggested that special combining rules or binary interaction parameters were important to obtain enough accurate prediction of the mixed phase behavior. Compared with the cubic EoS, the PC-SAFT and molecular simulation method showed better adaptabilities for both the pure and mixture systems. Besides, the accurate molecular parameters used in the PC-SAFT and molecular simulations could bring about direct and deep understanding about the molecular characteristics.
基金support from the Research Project of National University of Defense Technology(ZK16-03-32)National University Student Innovation Programthe support form Research Foundation of Education Bureau of Hunan Province(16K102)
文摘Simple synthesis of multifunctional electrocatalysts with plentiful active sites from earth-abundant materials is especially fascinating. Here, N-doped defective carbon with trace Co (1.5 wt%) was prepared via a scalable one pot solid pyrolysis process. The sample exhibits efficient bifunctional OER/ORR activiW in alkaline, mainly ascribed to the unique micro-mesoporous structure (1-3 nm), high population of graphitic-N doping (up to 49.0%), abundant defects and the encapsulated Co nanoparticles with graphitized carbon. The according rechargeahle liquid Zn-air batteries showed excellent performance (maximum power density of 154.0 mWcm-2: energy density of 773Wh kg -1 at 5 mAcm 2 and charging-discharging cycling stability over 100 cycles). As a proof-of-concept, the flexible, rechargeable all-solid-state Zn-air batteries were constructed, and displayed a maximum power density as high as 45.9 mW cm 2 among the top level of those reported previously.
基金the State Key Laboratory of Ocean Engineering for its support (Grant No. GP010818)
文摘The sloshing of inviscid liquid of stratified density in a rectangular tank is analyzed.As the flow is no longer irrotional,the governing equation is found to be quite different from the Laplace equation used for the liquid of constant density.In particular it contains terms of mixed temporal and spatial derivatives.The problem is solved based on the variable separation method and Laplace transform for the constant Vaisala-Brunt frequency.It is found that the stratification of density may have small effects on those natural frequencies associated with the constant density,but many new natural frequencies have appeared as a result of its effect.
基金financially supported by the National Natural Science Foundation of China (21003068, 21073189, 21071073)China Postdoctoral Science Foundation (20110491546)+1 种基金Key Projects in the National Science & Technology Pillar Program (2012BAF03B02)Liaoning University Research Funding
文摘Amino acid ionic liquid (AAIL) based on alanine, 1-n-heptyl-3-methylimidazolium alanine ([C7mim][Ala]), has been prepared and characterized. Since the IL can form strong hydrogen bonds with water, trace amount of water is a problematic impurity in the IL. Using the standard addition method (SAM), the densities were measured in the temperature range from 293.15 to 343.15±0.05 K. On the basis of the experimental data of density, the surface tension y, molar volume, and the molecular vol- ume Vm, molar enthalpy of vaporization AIgHm0, and the thermal expansion coefficients or, for [C7mim][Ala] were estimated using semi-empirical methods. Also the interstice model has been verified with good accordance. Then the [C7mim][Ala] was taken as catalyst in the transesterification reaction with fatty acid, where soybean oil was used as raw material and methanol as reactant. The amount of catalyst, alcohol consumption, reaction time, temperature and other factors of the reaction were inves- tigated. Using GC determination, the conversions were calculated by the internal standard method. The main ingredients of the products were identified by GC-MS as palm methyl ester and linoleic acid methyl ester only, which showed high selectivity in palmitic acid and linoleic acid.
基金supported by the International S&T Cooperation Program of China (2014DFA61670)the Key Program of National Natural Science Foundation of China (91434203)+1 种基金the International Cooperation and Exchange of the National Natural Science Foundation of China (51561145020)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09010103)
文摘Developing electrolyte with high electrochemical stability is the most effective way to improve the energy density of double layer capacitors(DLCs), and ionic liquid is a promising choice. Herein, a novel ionic liquid based high potential electrolyte with a stabilizer, succinonitrile, was proposed to improve the high potential stability of the DLC. The electrolyte with 7.5 wt% succinonitrile added has a high ionic conductivity of 41.1 m S cm^(-1) under ambient temperature, and the DLC adopting this electrolyte could be charged to 3.0 V with stable cycle ability even under a discharge current density of 6 A g^(-1). Moreover, the energy density could be increased by 23.4% when the DLC was charged to 3.0 V compared to that charged to 2.7 V.