Enhancing the rate of the Diels-Alder reaction using CO2 + ethanol and CO2 + n-hexane mixed solvents of different phase regions

The reaction rate of the Diels-Alder reaction between N-ethylmaleimide and 9-hydroxymethylanthrance in CO2 + ethanol and CO2 + hexane mixed solvents of different compositions were determined by in situ UV/vis spectroscopy at 318.15 K and different pressures. The density of the mixed solvents at different pressures was also determined and the isothermal compressibility was calculated using the density data. The activation volume of the reaction was calculated based on the dependence of rate constant (kc) on pressure. It was demonstrated that the kc was very sensitive to the pressure in the mixed solvents near the critical region and the kc increased dramatically as pressure approached dew points, critical point, and bubble points of the mixed solvents. However, the kc in the mixed solvents outside the critical region or in pure CO2 was not sensitive to pressure. At suitable conditions, kc could be 40 times larger than that in acetonitrile. The activation volume of the reaction was nearly independent of pressure as the pressure was much higher than the phase separation pressure of the mixed solvents, while it increased considerably as pressure approached the bubble points, critical point, and dew points from high pressure. The clustering of the solvent molecules with the reactants and the activated complex in the reaction systems near the phase boundary in the critical region may be the main reason for the interesting phenomena observed. This work also shows that, using pure CO2 as the solvent, the reaction cannot be carried out in the critical region of the solvent due to the limitations of the reactants, while it can be conducted in the critical region of mixed solvents of suitable compositions, where the solvents are highly compressible and the reaction rate can be tuned effectively by pressure.     

Solvatochromic behavior of phenol blue in CO2+ethanol and CO2+n-pentane mixtures in the critical region and local composition enhancement

The UV-Vis spectra of probe phenol blue in CO(2)+ethanol and CO(2)+n-pentane binary mixtures were studied at 308.15 K and different pressures. The experiments were conducted in both supercritical region and subcritical region of the mixtures by changing the compositions of the mixed solvents. On the basis of the experimental results the local compositions of the solvents about phenol blue were estimated by neglecting the size difference of CO(2) and the cosolvents. Then the local composition data were corrected by a method proposed in this work, which is mainly based on Lennard-Jones sphere model. It was demonstrated that the local mole fraction of the cosolvents is higher than that in the bulk solution at all the experimental conditions. In the near critical region of the mixed solvents the local composition enhancement, defined as the ratio of cosolvent mole fraction about the solute to that in the bulk solution, increased significantly as pressure approached the phase boundary from high pressure. The local composition enhancement was not considerable as pressure was much higher than the critical pressure. In addition, in subcritical region the degree of composition enhancement was much smaller and was not sensitive to pressure in the entire pressure range as the concentration of the cosolvents in the mixed solvents was much higher than the concentration at the critical point of the mixtures.     

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale (E(T)) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.     

Enthalpy of solution of 1,4-naphthoquinone in CO2 + n-pentane in the critical region of the binary mixture: mechanism of solubility enhancement

The enthalpy of solution (Delta(solv)H(m)) and solubility of 1,4-naphthoquinone in CO(2) + n-pentane were measured at 308.15 K in the critical region of the binary fluid. In order to study the effect of phase behavior of the mixed solvent on Delta(solv)H(m), the experiments were carried out in the supercritical (SC) and subcritical region of the binary solvent. The density of the mixed solvent in different conditions was determined. The isothermal compressibility (K(T)) of the mixed solvent, and the partial molar volume (V(n-pentane)) of n-pentane in the solution were calculated. It was demonstrated that the Delta(solv)H(m) was negative in all conditions. Delta(solv)H(m) is nearly independent of pressure or density in all the solvents in a high-density region, in which compressibility of the solvent is very small; this indicates that the intermolecular interaction between the solvent and the solute is similar to that for liquid solutions. It is very interesting that Delta(solv)H(m) in the mixed SC fluid differs from the Delta(solv)H(m) in mixed subcritical fluids. The absolute value of Delta(solv)H(m) in the mixed SC fluid is close to that in pure SC CO(2) in the high-density region, and is much lower than that in pure SC CO(2) in the low-density region. In the mixed subcritical fluids, the Delta(solv)H(m) is also close to that in the pure CO(2) in the high-density region. However, at the same density, the absolute value of Delta(solv)H(m) in the binary subcritical fluid is larger than that in pure CO(2) in the high-compressible region of the mixed solvent. The main reason for this is that the degree of clustering in the SC solutions is small at the density in which the degree of clustering is large in the subcritical solutions. It can be concluded that solubility enhancement by n-pentane in the mixed SC fluid is entropy driven. In contrast, the solubility enhancement by n-pentane in subcritical fluids is enthalpy driven. The intermolecular interaction in the SC solutions and subcritical solutions can be significantly different even if their densities are the same.     

Oleophilic ion-exchange resins. IV. Swelling of quaternary ammonium polymers in mixed solvents

The swelling characteristics of an oleophilic anion-exchange resin in methanol–benzene and ethanol–chloroform mixed solvent systems were compared with those of a conventional anion-exchange resin. The oleophilic resin was prepared by amination of chloromethylated polystyrene 1% DVB with N,N-dimethyldodecylamine. It showed a large shift of the swelling peak from polar to less polar solution compositions in both methanol–benzene and ethanol–chloroform systems as compared with the swelling of conventional resins. Total solvent uptake and solvent distribution between resin and solvent phases were also determined. The less polar solvent (benzene or chloroform) was sorbed preferentially by the oleophilic resin over a wide range of composition, while preference for the more polar solvent (methanol or ethanol) by the conventional resin was shown over the entire composition of the mixed solvent systems. The Newman-Krigbaum treatment of mixed solvents was applied to swelling data on the ethanol–chloroform–oleophilic resin system, where the volume of the gel network plus the solvent imbibed was relatively constant over the entire range of composition. The result suggests a strong similarity of the liquid–liquid interaction terms in this gel phase compared with those in the pure binary liquid phase.     

超临界二氧化碳二元体系相平衡性质的研究

采用固定体积可视观察法测定了CO₂+甲苯、CO₂+环己烷、CO₂+正丁醛、CO₂+异丁醛、CO₂+甲醇及CO₂+乙醇二元体系的临界点性质,为超临界萃取和化学反应提供基础数据.在对二元体系相行为与单组分超临界相行为进行比较的基础上,对不同化学物质及不同配比的二元体系临界点与二氧化碳临界点之间的关系进行了讨论.     

Relationship between the density of supercritical CO_2 + ethanol binary system and its critical properties

The solvent strength and selectivity of supercritical fluids (SCF) can be greatly enhanced by addition of one or two entrainers into the system. The amount of entrainer added is usually less than 5% (mole fraction). However, even with such slight amount, solubility of organic solutes has been observed to increase by several orders magnitude[1]. Therefore, critical pressure and tem-perature data of these supercritical fluid + cosolvent systems are imperative for the reasonable design of effici…     

Tautomeric reaction equilibrium of ethyl acetoacetate in CO2–n-pentane and CO2–ethanol mixed solvents in the critical region

The tautomeric equilibrium constant K_C of ethyl acetoacetate (EAA) in CO₂–n-pentane and CO₂–ethanol was studied by UV–VIS spectroscopy at 308.2 K over the pressure range from 6.5 to 9.0 MPa. This work focuses on how the tautomeric equilibrium changes with pressure and composition of the mixed solvents in the near critical region. The results showed that the effect of pressure on K_C was very limited at pressures much higher than the phase separation pressures. However, the K_C increased sharply as the pressure approached the critical point or the bubble point of the mixed solvents.     

The gelation rule of the polyol acetal derivatives in binary solvent mixtures

The tendency of a gelator to gel in mixed solvents is strongly correlated with its gelation behaviors in the corresponding single solvents.     

Assessment of the potential models of acetone/CO2 and ethanol/CO2 mixtures by computer simulation and thermodynamic integration in liquid and supercritical states

Binary mixtures of CO(2) with ethanol and with acetone are studied by computer simulation, including extensive free energy calculations done by the method of thermodynamic integration, at 313 K, i.e., above the critical point of CO(2) in the entire composition range. The calculations are repeated with three different models of acetone and ethanol, and two models of CO(2). Comparisons of the molar volume of the different systems as well as of the change of their molar volume accompanying the mixing of the two components with experimental data reveal that, among the model pairs tested, the best results are obtained if both components are described by the Transferable Potentials for Phase Equilibria (TraPPE) force field. Around the ethanol/acetone mole fraction of 0.05 all ethanol/CO(2) and almost all acetone/CO(2) model pairs considered predict the existence of a sharp maximum of the molar volume. Due to the lack of experimental data in this composition range, however, these predictions cannot be verified/falsified yet. Most of the model pairs considered also predict limited miscibility of these compounds, as seen from the positive values of the free energy change accompanying their mixing, and the miscibility gap is located at the same composition range as the aforementioned molar volume maximum.     

超临界和近临界条件下Fischer Tropsch合成研究：溶剂的影响

研究了超临界和近临界条件下费托合成过程中溶剂对反应行为的影响。反应在固定床反应器中进行，催化剂为Co/SiO2，所选择的溶剂有两类：纯溶剂（正戊烷和正己烷）和混和溶剂（由正己烷和少量的C5~10烃组成）。结果表明,正己烷分压对CO转化率影响很小，但是产物中1 烯烃含量随正己烷分压增加而增加，超临界条件下1 烯烃含量明显高于非临界条件下。溶剂的种类对CO转化率、CH4和CO2选择性以及产物炭分布影响不大。这一结果表明为了减少溶剂用量，对含有适量轻组分（C5~10）的正己烷溶剂进行循环使用是可行的。结果同时表明与正己烷相比，混和溶剂（25%正己烷和75%正葵烷）具有较高的1 烯烃选择性。     

Spectral Investigations of Preferential Solvation and Solute–Solvent Interactions of Free Base and Protonated 5,10,15,20-Tetrakis(4-trimethyl-ammonio-phenyl)-porphine Tetratosylate in Aqueous Organic Mixed Solvents

The solvatochromic properties of the free base and the protonated 5,10,15,20-tetrakis(4-trimethyl-ammonio-phenyl)-porphine tetratosylate (TTMAPP) were studied in pure water, methanol, ethanol, 2-propanol, and their corresponding aqueous mixtures. The correlation of the empirical solvent polarity scale (E _T) values of TTMAPP with composition of the solvents were analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition effects in preferential solvation of the solute dyes were investigated in terms of both solvent–solvent and solute–solvent interactions and also the local mole fraction of each solvent composition was calculated in the cybotactic region of the probe. The effective mole fraction variation may provide significant physicochemical insights in the microscopic and molecular level of interactions between TTMAPP species and the solvent components and, therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TTMAPP.     

Solubility of Itaconic Acid in Aqueous Ethanol Mixtures from 278.15 K to 333.15 K

Data on corresponding solid?Cliquid equilibrium of itaconic acid in binary aqueous ethanol solutions are essential for industrial design and further theoretical studies. Using the analytical stirred-flask method, the solubility of itaconic acid in pure water solvent and mixed solvents were measured over the temperature range from 278.15 to 333.15 K at atmospheric pressure. The effect of solvent composition and temperature on the solubility is discussed. The solubility data were correlated with the Combined Nearly Ideal Binary Solvent/Redlich (CNIBS/R-K) model. The solubility measured in this study can be used for the itaconic acid purification or optical resolution by the preferential crystallization procedure.     

神华煤直接液化残渣超临界溶剂萃取研究

利用甲苯、苯和乙醇三种溶剂在反应釜中对神华煤直接液化残渣进行了超临界溶剂萃取,考察了压力、温度、萃取时间、溶剂/残渣比等对萃取产物收率和重质液体萃取组成的影响。结果表明,以甲苯为溶剂进行萃取时,萃取时间对重质液体产率及HS和A收率的影响不大,而温度、压力以及溶剂/残渣质量比都会影响萃取产物的产率及组成。溶剂超临界萃取过程中,有其他组分向HS组分转化,提高了HS的收率。三种溶剂中,苯显示了和甲苯相似的萃取性能,而乙醇的萃取性能相比苯和甲苯则较差,但乙醇萃取得到的重质液体中轻质组分含量高于苯和甲苯。萃取过程中,残渣中的灰分和硫分主要富集至萃取残渣中。     

Preferential Solvation in Aqueous–Organic Mixed Solvents Using Solvatochromic Indicators

Solvatochromism of the twisted intramolecular charge-transfer (TICT) fluorescence of 4-(N,N-dimethylamino)benzonitrile (DMABN) in pure water, methanol, ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, and in the corresponding aqueous–organic binary mixed solvents was systematically studied and an empirical solvent polarity scale (F _B) based on the DMABN solvatochromism was defined. The F _B parameters of the explored binary mixed solvents as a function of solvent composition were analyzed by a stepwise solvent-exchange (SSE) model to clarify the preferential solvation (PS) of the probe dye in these binary mixed solvents. Solvation diagrams toward DMABN in the mixed solvents, i.e., the local solvent composition in the solvation shell of DMABN molecules was depicted as a function of bulk solvent composition to visualize the PS in these mixed solvents. For comparison, a similar PS analysis was applied to the solvatochromism of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1- yl)phenolate (ET-30) and pyrene (Py) in these mixed solvents; the responsive PS pattern of the mixed solvents toward the specific indicator dye of DMABN, ET-30, and Py was then discussed in terms of the chemical properties of the probe dye, the properties of the mixed solvents, and the solute–solvent and solvent–solvent interactions.     

Effect of phase behavior, density, and isothermal compressibility on the constant-volume heat capacity of ethane + n-pentane mixed fluids in different phase regions

The phase behavior, density, and constant-volume molar heat capacity (C_v,m) of ethane + n-pentane binary mixtures have been measured in the supercritical region and subcritical region at T=309.45 K. In addition, the isothermal compressibility (κ_T) has been calculated using the density data determined. For a mixed fluid with a composition close to the critical composition, C_v,m and κ_T increase sharply as the pressure approaches the critical point (CP), the dew point (DP), or the bubble point (BP). However, C_v,m is not sensitive to pressure in the entire pressure range if the composition of the mixed fluid is far from the critical composition. To tune the properties of the binary mixtures effectively by pressure, both the composition and the pressure should be close to the critical point of the mixture. The intermolecular interactions in the mixture are also discussed on the basis of the experimental results.     

Effect of phase behavior and pressure on the constant-volume heat capacity and intermolecular interaction of CO2-ethanol and CO2-n-pentane mixtures in the critical region

Study on the properties of the fluids near the critical point of mixed systems is a key for the development of supercritical (SC) technology and for the further understanding of the features of supercritical fluids (SCFs). The constant-volume molar heat capacity (Cv) of a solution is directly related to the internal energy, intermolecular interaction, and the microstructure of the solution. In this work, the Cv of CO2-n-pentane and CO2-ethanol systems was determined at 308.15 K in different phase regions. This work focuses on how the properties of the mixtures change with pressure, composition, and the structure of the components near the critical point of the mixtures. It was found that at fixed composition, a maximum in Cv versus pressure curve exists (Cv(max)) that occurs at the pressure at which the isothermal compressibility (K(T)) is the largest. We deduced that breaking the "clusters" in the SC mixtures is an endothermic process. It is very interesting that Cv increases sharply as the pressure approaches the critical point (CP) or bubble point (BP), while Cv is nearly independent of pressure and composition at the pressures well above the CP or BP pressure, and that the Cv at CP or BP can be several times larger than that at the high pressures. It can be deduced that at fixed composition the degree of "clustering" changes significantly with pressure near the CP or BP, and is the largest at CP and BP.     

Selection of a nonaqueous two-phase solvent system for fractionation of xylo-oligosaccharide prebiotics using a conductor-like screening model for real solvents

Fractionation of xylo-oligosaccharides (XOS) using a liquid–liquid solvent system can be a difficult endeavor due to the high solubility of XOS in water. Use of a nonaqueous solvent system is a solution for XOS fractionation. XOS are gaining attention as a prebiotic food additive and are abundant in agricultural residues. We describe the use of a molecular modeling approach to determine which solvents and at what volume ratio to use for XOS fractionation. The conductor-like screening model for real solvents was used to predict the partition coefficients of xylose and two major functional XOS—xylobiose and xylotriose, based on the structure of the compounds and the composition of solvents in a panel of nonaqueous biphasic solvent systems. Eleven common solvents used in countercurrent chromatography were used to build 12 biphasic solvents model systems that were then evaluated and compared using shake flask experiments to determine which could fractionate the three XOS from a mixture. The model and experimental results indicate that a heptane/n-butanol/acetonitrile system at a volume ratio of 9:4:5 would result in a partition coefficient close to the region of optimal separation for a countercurrent chromatography fractionation.     

Some Organic Reactions in Supercritical Carbon Dioxide

Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years . ScCO2, as an environmentally friendly reaction medium, may be a substitute for 1 volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive, nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control o…     

Radical polymerization of vinyl acetate in individual and mixed solvents

The kinetics of polymerization of vinyl acetate in individual and mixed solvents was studied. The reaction rate constant and the rate of chain transfer in the mixed solvent were calculated, molecular weights and some adhesive characteristics of poly(vinyl acetate) obtained by the radical polymerization in solution were determined. A comparative analysis of the polymers obtained in the individual and mixed solvents was performed. It is shown that the change in the solvent composition can affect the rate of reaction and the poly-(vinyl acetate) adhesive properties.