Tetrathiafulvalene esters with high redox potentials and improved solubilities for non-aqueous redox flow battery applications

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.

Measurement of Solubilities of o-Phenylphenol in Petroleum Ether and DDP in Acetone+Water Solution

[（6-oxide-6H-dibenze（c, e）（1, 2）oxaphosphorin-6-yl）methyl]-butanedioic acid （DDP） was prepared and characterized. Solubilities of o-phenylphenol（OPP） in petroleum ether and DDP in acetone ＋ water solution were measured by a gravimetrical method. The solubility data of OPP were well correlated using Francis equation. For the solubility of DDP in acetone aqueous solution, it was found that at each fixed temperature there existed a maximum when the acetone mass fraction in the solvent reached a certain concentration. The experiment shows that the fraction is approximately 0.6. The solubility data would be helpful for their industrial crystallization process.

Experimental determination of solubilities and＇supersolubilities of 2,2＇,4,4＇,6,6＇-hexanitrostilbene in different organic solvents

The laser monitor technique was used to determine solubilities and supersolubilities of HNS in N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone and 1,4-butyrolactone. The experimental solubility values were correlated with λh equation, modified Apelblat equation and NRTL model. Furthermore, the dissolution enthalpy, dissolution entropy and the Gibbs energy of HNS were calculated by the experimental data. The results show that the solubilities of HNS in the above solvents increase with the increasing temperature. Besides, at the same temperature, the order of solubility is N-methyl-2-pyrrolidone > dimethyl sulfoxide > N,N-dimethylformamide > 1,4-butyrolactone > acetonitrile. The temperature dependence of predicted solubility is in agreement with the experimental data.

Measurement and Correlation of Solubilities of C.I. Disperse Red 73,C.I. Disperse Blue 183 and Their Mixture in Supercritical Carbon Dioxide

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology.In this study,solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method.Under the experimental conditions for the binary(C.I.Disperse Red 73+CO2 or C.I.Disperse Blue 183+CO2) and ternary(C.I.Disperse Red 73+C.I.Disperse Blue 183+CO2) systems,the solubilities increase with pressure.The solubility of C.I.Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa,and the trend is opposite when the pressure is higher than 16 MPa.However,there is no crossover pressure for C.I.Disperse Red 73.The solubilities are also affected by molecular polarity of dyes.The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their dissolution in supercritical CO2.The experimental data of solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183,and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.

Solubilities of 1-Methyl-3-（3-sulfopropyl）-imidazolium Hydrogen Sulfate in Selected Solvents

Ionic liquid 1-methyl-3-(3-sulfopropyl) -imidazolium hydrogen sulfate([C3SO3HMIM][HSO4]) was synthesized and characterized by infrared spectroscopy(IR) ,nuclear magnetic resonance(1H and 13C NMR) and ultraviolet-visible(UV-Vis) spectra. Its thermal stability was also examined by thermogravimetric analysis(TGA) and a differential scanning calorimeter(DSC) . The mole fraction solubilities of [C3SO3HMIM][HSO4]) in 12 selected solvents(n-pentane,n-hexane,n-heptane,benzene,toluene,ethylbenzene,acetone,2-butanone,3-methyl-2-butanone,tetrahydrofuran,ethyl acetate and dichloromethane) in the temperature range from 289.15 to 363.15 K were meas-ured using a static analytical method and correlated with an empirical equation.

Solubilities of Isophthalic Acid in Acetic Acid ＋ Water Solvent Mixtures

The solubilities of isophthalic acid （1） in binary acetic acid （2） ＋ water （3） solvent mixtures were determined in a pressurized vessel. The temperature range was from 373.2 to 473.2K and the range of the mole fraction of acetic acid in the solvent mixtures was from x2 = 0 to 1. A new method to measure the solubility was developed, which solved the problem of sampling at high temperature. The experimental results indicated that within the temperature range studied, the solubilities of isophthalic acid in all mixtures showed an increasing trend with increasing tem- perature. The expe^mental solubilities were co .rrelated by the Buchowski equation, and the calculate results showed good agreement with the experimental solubilities. Furthermore, the mixed solvent systems were found to exhibit a maximum solubility effect on the solubility, which may be attributed to the intermolecular association between the solute and the solvent mixture： The maximum solubility effect was well modeled by the modified Wilson equation.

Measurement and Correlation of Solubilities of Adipic Acid in Different Solvents

Using a simple and reliable apparatus, the solubilities of adipic acid in water, ethanol, chloroform, n-butanol and acetone are determined by the analytic method. The results are correlated with λh equation, Apelblat equation, and UNIFAC equation. The solubilities calculated by these models are in good agreement with experi-mental data, so that the models can meet the requirements of engineering design.

Solubilities of CO_2, CH_4,H_2,CO and N_2 in choline chloride/urea

Solubilities of CO_2, CH_4, H_2, CO and N_2 in choline chloride/urea(ChCl/Urea) were investigated at temperatures ranging from 308.2 to328.2 K and pressures ranging from 0.6 to 4.6 MPa. The results show that the solubilities of gases increase with increasing pressure and decreasing temperature. The solubility of CO_2 is higher than that of CH_4, H_2, CO and N_2, which indicates that ChCl/Urea may be used as a potential solvent for CO_2 capture from the gas mixture. Solubility of CO_2 in ChCl/Urea was fitted by Non-Random Two-Liquid and Redlich-Kwong(NRTL-RK) model, and solubility of CH_4, H_2, CO or N_2 in ChCl/Urea was fitted by Henry's Law. The standard enthalpy, standard Gibbs energy and standard entropy of gases were calculated. Additionally, the CO_2/CH_4 selectivities in water, dry ChCl/Urea and aqueous ChCl/Urea were further discussed.

DETERMINATION OF THE SOLUBILITIES OF 2,4-DICHLOROBENZALDEHYDE IN ORGANIC SOLVENTS

Solubilities of 2,4-dichlorobenzaldehyde in five single organic solvents,namely,n-propanol,n-butanol.cyclohexane,chloroform and dichloromethane as well as in two mixed solvents,namely,cyclohexane-acetone and cyclohexane n-butanol,have been measured.These data are correlated withWilson,NRTL and UNIQUAC activity coefficient models and can be used for the process design inthe purification of 2,4-dichlorobenzaldehyde.

Solubilities,Densities,Refractive Indices of Aqueous Ternary Systems PEG400-NaCl/KCl-H2O at 298 K

Phase equilibria for the NaCl/KCl-PEG400-H2O aqueous ternary systems at 298 K were studied using an isothermal dissolution method.In addition,the densities and refractive indices were determined.The corresponding phase diagrams,as well as the density vs.composition and refractive index vs.composition diagrams,were plotted.Results revealed that over the entire PEG400 composition range studied at 298 K only 1 liquid phase was obtained,without the formation of a biphase region.The phase diagrams of these 2 systems consist of 1 homogeneous area with unsaturated liquid (L) and an equilibrium area containing the solid phase of NaCl/KCl and the saturated liquid phase (S+L).The solubility of NaCl/KCl decreases with the addition of PEG400 at 298 K.

Solubilities of Cimaterol and Mabuterol in SF-CO_2

The solubilities of two β-agonists, cimaterol and mabuterol, in supercritical carbon dioxide (SF-CO2) were measured by a recirculating method at temperatures of 40℃ and 60℃ and pressures between 9 MPa to 49 MPa.The compounds exhibit very limited solubilities in the range of 10^-5 to 10^-7 (mole fraction). Cimaterol has a higher solubility than that of mabuterol. The experimental data of solubility were correlated by four density-based models.The correlation accuracy highly depends on the system investigated, which is mainly determined by the density ranges and temperature.

Correlating and Predicting the Solubilities of Solid n-Alkanes in Supercritical Ethane Using Carnahan-Starling-van der Waals Model

The solubilities of some solid n-alkanes in supercritical ethane were correlated and predicted in this paper using the Carnahan-Starling-van der Waals model with a density-dependent parameter of a12.At a given temperature,the linear fit of the parameter of a12and the density of the supercritical solvent was used for solubility correlation,resulting in an average absolute average relative deviation(AARD)of 8.68%,which was between the values of the semiempirical models and the other compressed gas models used in this article.In the linear fit of the parameter of a12and the density of the solvent,the regressed slope m and intercept n of the linear fit can be correlated with the carbon atom number of solid n-alkanes and then the solubilities of solid n-alkanes in supercritical ethane can be predicted with the intercept n and slope m.The average AARD in solubility prediction was 26.99%.

Prediction of the Aqueous Solubilities of Polychlorinated Biphenyls

Using the molecular electronegativity distance vector descriptors derived directly from the molecular topological structures, the aqueous solubilities of polychlorinated biphenyls (PCBs) were predicted. A three-variable regression equation with correlation coefficient of 0.9739 and the root mean square errors of 0.26 was developed. The descriptors included in the equation represent three interactions between three pairs of atomic types, i.e., atom -C= and >C=, -C= and -Cl, and -Cl and -Cl. It has been proved that the aqueous solubilities of 137 PCB congeners can be accurately predicted as long as there are more than 65 calibration compounds.

Determination of the subcooled liquid solubilities of PAHs in partitioning batch experiments

Subcooled liquid solubility is the water solubility for a hypothetical state of liquid. It is an important parameter for multicomponent nonaqueous phase liquids （NAPLs） containing polycyclic aromatic hydrocarbons （PAHs）, which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature. So far, subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and （subcooled） liquid phase, but rarely derived from experi- mental data. In our study, partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system. For selected PAH, a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/ water volume ratio. The equilibrium aqueous PAH concentrations were measured with HPLC and/or GC- MS. The suhcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity. With the derived subcooled liquid solubility, the fugacity ratio and enthalpy of fusion of the solute were also estimated. Our results show a good agreement between the experimentally determined and published data.

SOLUBILITIES OF CARBON DIOXIDE IN MIXTURES OF n-DECANE-n-HEXADECANE AND n-HEPTANE-TOLUENE

Solubilities of CO2 in binary mixtures of n-decane-n-hexadecane and n-heptane-toluenewere measured in a glass apparatus by a synthetic method.Henry’s constants at several temperaturesand solvent compositions were reported.While the Henry’s constants of CO2 in mixtures of decaneand hexadecane can be satisfactorily predicted by a simple linear interpolation,prediction of Henry’sconstants for CO2 in mixtures of heptane and toluene requires excess Gibbs energy of the solvent mix-tures.The standard thermodynamic functions of solution（ΔH0,ΔG0,and ΔS0）were reported.

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF_6^- in Six Alcohols

Four novel benzothiazolium ionic liquids with 6PF?([C1Bth][PF6], [C4Bth][PF6], [C5Bth][PF6] and [C6Bth][PF6]) were synthesized, and the rang of their melting points were determined between 358.35 K-424.05 K. The relationship of their melting points and the length of the straight alkyl chain on cation reflected ‘S' type ten-dency. Then, the solubilities of the four ionic liquids in six lower alcohols(methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-1-propanol) were measured in the temperature rang of 253.15-383.15 K at at-mospheric pressure with static analytical method, respectively. It was found that [C6Bth][PF6] in all investigated ionic liquids had the largest solubility in six alcohols and the solubility of [C4Bth][PF6] in methanol was very sensi-tive for temperature in 313.15-333.15 K, which was so-called "temperature-sensitivity". This feature is of great significance to their application of catalyzing reaction or extraction process, and makes the recovery and reuse of ionic liquids(ILs) become easier. Moreover, the experimental solubility data were correlated with the modified Apelblat equation and λh equation, respectively. It was found that the result of correlation using two divided tem-perature ranges was better than that of using the whole temperature range.

SOLUBILITIES OF VINYL CHLORIDE IN EMULSIFIER SOLUTIONS

1 INTRODUCTIONVinyl chloride（VC）is a slightly water-soluble monomer.But its solubility in water(～10g·L-1)is much higher than that of olefins(0.1～1g·L-1).The solubilityof VC is an important parameter in suspension,emulsion and miniemulsionpolymerizations.The presence of emulsifier in aqueous medium will enhance the solubil-ity of VC.The solubility of VC depends not only on the types and concentration of theemulsifier,but also on the temperature and pressure.Unfortunately,the solubilities ofVC in emulsifier solutions are rarely reported in literatures.

SOLUBILITIES OF Ce,Nd AND Y IN α-Fe

The solubilities of Ce,Nd and Y in α-Fe at 873 to 1153 K have been deter mined by means of electron microprobe quantitative analyses.The temperature dependences of the solubilities were obtained from the experimental data.The results have been compared with those deter- mined by three other technigues,very good agreement was obtained between the results of all these techniques.

Effects of High Hydrostatic Pressure on the Solubilities and Structures of Alaska Pollock Protein

Alaska pollock is an important protein source which is extensively used in the food industry. Pollock protein isolates(PPI) with significantly enriched protein contents could be prepared using isoelectric solubilization/precipitation(ISP) processing; however, the functional properties of this process is limited by the large amount of water-insoluble proteins. In this study, we investigated the influence of high hydrostatic pressure(HHP) treatment on the solubility and structural changes of PPI. PPI obtained using ISP is treated with hydrostatic pressures of 200, 300, 400, and 500 MPa for up to 15 min, and the HHP-treated samples were observed to exhibit significantly improved solubilities. Further biochemical assays reveal that the continuous HHP treatments reduce the contents of free sulfhydryl groups and promote the formation of macromolecules with better water solubilities, which may induce the solubility improvements of the HHP-treated PPI. Our results indicate that HHP can be utilized to effectively prepare highly water-soluble Alaska pollock protein in food processing.

FACTORS INFLUENCING SOLID SOLUBILITIES OFRARE-EARTHS IN Pd

A parameter describing the solid solubilities of mre-earths in Pd, Nf/aX(TR - rPd),was proposed, where N is the fshell filled electron nutnben △X the electronegativity dtherence between Palladium and rare-earths, rR the atotnic radii of rare-earth elementand rPd of Pd. The marimum solid solubilities are linear relation to this parnmeterexcept La, Nd and Ce.