Phase equilibria of supercritical C02-ethanol-stearic acid ternary system and hydrogen bonding between ethanol and stearic acid

Solubility of stearic acid in supercritical C0₂ with ethanol cosolvent was determined at 308.15 K in the pressure range from 8 to 16 MPa, and the cosolvent concentration ranges from 0 mol% to 4 mo1%. The corresponding densities of the fluid phases were also measured. It was observed that ethanol enhances the solubility significantly. The solubility increases with pressure noticeably at lower pressure, especially at lower cosolvent concentrations. The effect of pressure on the solubility is very limited at higher pressures or higher cosolvent concentrations. The hydrogen bonding between ethanol and stearic acid in supercritical C0₂ was also studied using FTIR in order to understand the mechanism of the solubility enhancement by ethanol. Project supported by the National Natural Science Foundation of China (Grant No. 29633020).     

Solubility of stearic acid in supercritical CO_2-acetonitrile mixtures

The solubility of stearic acid in supercritical CO2 with acetonitrile (CH3CN) cosolvent was measured at 318.15 K in the pressure range from 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol% . The solubility increases with acetonitrile concentration and pressure, and it also increases with the apparent density of CO2 d1(moles of CO2 in per liter of fluid) at higher cosolvent concentrations. At lower d1, however, the solubility of the acid at lower acetonitrile concentrations is lower than that in pure CO2 provided that d1 is fixed, which is discussed qualitatively based on the clustering of the components in the system.     

FTIR study of hydrogen bonding of stearic acid with ethanol, dimethyl sulfoxide,and acetonitrile in supercritical CO_2

FTIR spectroscopy was used to study the hydrogen bonding of stearic acid with ethanol, dimethyl sulfoxide (DMSO),and acetonitrile in supercritical CO_2 at 318.15 K, and 12.5 and 16.5 MPa. The concentrations of the cosolvents range from 0—0.6 mol·L~(-1). The area percentage of absorption bands for hydrogen-bonded and nonhydrogen-bonded species was obtained from the IR spectra. The acid and the cosolvents can form hydrogen bond even when their concentrations are very low. At fixed solute concentration, the extent of hydrogenbonding increases with cosolvent concentration. At higher ethanol concentrations, it seems that one stearic acid molecule can hydrogen bond with more than one ethanol molecules simultaneously. It is seen that the strength of the hydrogen bond formed by the acid and the cosolvents is in the order: DMSO>ethanol>acetonitrile.     

Phase equilibria of narrowly distributed dextranes in the ternary system dextrane-water-ethanol

Neuchl, C. and Mersmann, A., 1993. Phase equilibria of narrowly distributed dextranes in the ternary system dextrane-water-ethanol. Fluid Phase Equilibria, 90: 389-398.

In this work we consider the phase equilibria of narrowly distributed dextranes with different average molecular masses in the ternary system dextrane-water-ethanol which are of interest in the fractionation of broadly distributed dextranes. It can be emphasized that the degree of polymerization of the dextrane has a great influence on the phase equilibrium in this ternary system. Numerical calculations were performed using the model of Flory and Huggins. The agreement between experimental and theoretical phase equilibria is very good. The interaction parameter of the Flory-Huggins model for the water-dextrane interaction is independent of the molecular mass of the dextrane. The interaction parameters for the water-ethanol and ethanol-dextrane interactions show a dependency on the molecular mass of the dextrane. However, both interaction parameters reach a limiting value for high molecular mass dextrane.     

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…     

二氧化碳-水混合体系的相平衡和汽-液-液三相点研究

在微扰链统计缔合流体理论(PC-SAFT)的基础上建立了适用于二氧化碳-水体系相行为研究的状态方程, 以汽-液平衡和液-液平衡实验数据关联体系的交叉作用参数, 关联结果与实验数据吻合良好. 预测了二氧化碳-水体系存在汽-液-液三相平衡的温度和压力区间, 确定了三相点的汽-液-液三相密度及其与温度和压力的关系.     

Intra and intermolecular hydrogen bonding in formohydroxamic acid

The presence of hydrogen bonding interactions in several tautomeric forms of formohydroxamic acid (FHA) and 1:1 association among the tautomeric forms and water‐coordinated tautomeric forms of FHA is explored theoretically. Out of the seven equilibrium structures, four tautomeric forms have been selected for aggregation with single water molecule and dimer formation. Fifteen aggregates of FHA with H₂O have been optimized at MP2/AUG‐cc‐PVDZ level and analyzed for intramolecular and intermolecular H‐bond interactions. Twenty‐seven dimers of the four tautomeric forms have been obtained at MP2/6‐31+G* level. The stabilization energies associated with dimerization and adduct formation with water are the result of H‐bond interactions and range from very weak to medium. The atomic charges and NBO analysis indicate that the electrostatic and the charge transfer are the important components favoring H‐bond formation. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Statistical theory for hydrogen bonding fluid system of A_aD_d type(II):Properties of hydrogen bonding networks

Making use of the invariant property of the equilibrium size distribution of the hydrogen bonding clus- ters formed in hydrogen bonding system of AaDd type,the analytical expressions of the free energy in pregel and postgel regimes are obtained.Then the gel free energy and the scaling behavior of the number of hydrogen bonds in gel phase near the critical point are investigated to give the corre- sponding scaling exponents and scaling law.Meanwhile,some properties of intermolecular and in- tramolecular hydrogen bonds in the system,sol and gel phases are discussed.As a result,the explicit relationship between the number of intramolecular hydrogen bonds and hydrogen bonding degree is obtained.     

Statistical theory for hydrogen bonding fluid system of AaDd type (Ⅱ): Properties of hydrogen bonding networks

Making use of the invariant property of the equilibrium size distribution of the hydrogen bonding clusters formed in hydrogen bonding system of AaDd type, the analytical expressions of the free energy in pregel and postgel regimes are obtained. Then the gel free energy and the scaling behavior of the number of hydrogen bonds in gel phase near the critical point are investigated to give the corresponding scaling exponents and scaling law. Meanwhile, some properties of intermolecular and intramolecular hydrogen bonds in the system, sol and gel phases are discussed. As a result, the explicit relationship between the number of intramolecular hydrogen bonds and hydrogen bonding degree is obtained.     

CO_2-甲醇和CO_2-乙醇体系的交叉缔合模型

在统计缔合流体理论(statistical associating fluid theory,SAFT)的基础上,将二氧化碳(CO2)处理为似缔合分子,考虑醇羟基之间的自缔合作用,以及CO2分子与醇羟基之间的交叉缔合作用,提出了适用于CO2-醇类体系的交叉缔合模型.应用该模型研究了CO2-甲醇和CO2-乙醇体系从低温低压到高温高压的相平衡性质.p-x和p-ρ相图的计算值与实验值吻合良好.研究表明,考虑CO2与甲醇和乙醇分子之间的交叉缔合对Helmholtz自由能的贡献,可显著改善相平衡性质的计算结果,并避免模型对低温区间中三相平衡和三相点的错误预测.     

超临界CO_2溶胀聚合物的研究及其应用

本文介绍超临界CO2 溶胀聚合物的研究及其应用 ,包括聚合物与超临界CO2 相互作用 ,溶胀行为的理论模型以及溶胀后的聚合物的用途 ,如制备微孔聚合物材料、渗透小分子和超临界溶胀聚合等     

水溶性硅油对超临界CO_2介质中丙烯酸聚合反应的影响

：通过对水溶性硅油浓度的改变，研究其对超临界CO2介质中丙烯酸聚合反应的影响。研究表明水溶性硅油可起到分子量调节剂的作用。随着硅油的加入，产物分子量降低，但当硅油浓度过大时，由于硅油在超临界CO2中溶解度的限制，夹带单体聚沉在反应釜底部形成富单体相，分子量有所上升。此外，扫描电镜照片（SEM）显示不同浓度的水溶性硅油对聚丙烯酸分子形态的影响不同，硅油含量越大，聚丙烯酸分子粒径越小，分子量分布越均匀。     

Phase equilibria in the ternary system PbO−P2O5−PbCl2

Journal of Thermal Analysis and Calorimetry - In the ternary system PbO?P2O5?PbCl2, the partial ternary system Pb5Cl2O4?Pb3Cl2O2?Pb10(PO4)6Cl2 was examined by thermal,...     

Solvent and substituent effects on the conformational equilibria and intramolecular hydrogen bonding of 4-substituted-2-hydroxybenzaldehydes

By applying the B3LYP/6-31G(d) method with the SCIPCM model on seven 4X substituted 2-hydroxybenzaldehydes, some structural characteristics related with their conformational equilibria and intramolecular hydrogen bonds have been clarified. The compounds are almost completely under the planar conformation characterized by a strong intramolecular hydrogen bond, which decreases in those solvents that possess a higher hydrogen bond donating capability and polarity. The substituents exert a marked influence on the conformational equilibrium constants and the strength of the IHB. Moreover, the excellent Hammett-type equations obtained support the proposed conformational reactions to quantify the IHB in the o-hydroxybenzaldehydes studied.     

Phase equilibria in the system NiO-V2O5-Fe2O3 in subsolidus area

Reactivity of FeVO₄ towards Ni₂V₂O₇ and Ni₃V₂O₈ in the solid state was investigated. On the base of XRD and DTA results, phase diagrams in subsolidus area of the FeVO₄-Ni₂V₂O₇ and FeVO₄-Ni₃V₂O₈ intersections of the ternary system NiO-V₂O₅-Fe₂O₃ have been worked out and the phase diagram of this ternary system in subsolidus area in the whole component concentration range has been verified. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reaction dynamics and statistical theory for the growth of hydrogen bonding clusters

The similarities between the formation of hydrogen bonds and polycondensation reactions are stated from the statistical viewpoint, and then taking the hydrogen bonding system of AaDd type as an example, the growing process of hydrogen bonding clusters is investigated in terms of the theory of reaction dynamics and statistical theory for polymeric reactions. The two methods lead to the same conclusions, stating that the statistical theory for polymerization is applicable to the hydrogen bonding systems. Based on this consideration, the explicit relationship between the conversions of proton-donors and proton-acceptors and the Gibbs free energy of the system under study is given. Furthermore, the sol-gel phase transition is predicted to take place in some hydrogen bonding systems, and the corresponding generalized scaling laws describing this kind of phase transition are obtained.     

Temperature-dependent Crystallization and Phase Transition of Poly(L-lactic acid)/CO_2 Complex Crystals

Semicrystalline polymers can crystallize in the unique crystalline polymorph and show different phase behaviors under the highpressure CO_2 treatment. Understanding such unique crystallization and phase transition behavior is of fundamental importance for the CO_2-assisited processing of semicrystalline polymers. Herein, we investigated the polymorphic crystalline structure, phase transition, and structureproperty relationships of poly(L-lactic acid)(PLLA) treated by CO_2 at different pressures(1-13 MPa) and crystallization temperatures(T_c's, 10-110 °C). PLLA crystallized in the PLLA/CO_2 complex crystals under 7-13 MPa CO_2 at T_c≤50 °C but the common α crystals under the high-pressure CO_2 at T_c≥70 °C. Solid-state nuclear magnetic resonance analysis indicated that the PLLA/CO_2 complex crystals possessed weaker interactions between the PLLA chains than the common α crystals. The PLLA/CO_2 complex crystals were metastable and transformed into the thermally stableα crystals via the solid-to-solid route during heating or annealing at the temperature above 50 °C. The complex crystals of PLLA produced at low T_c was more ductile than the α crystals due to the lower crystallinity and the plasticizing effect of CO_2.     

Statistical theory for hydrogen bonding fluid system of AaDd type (Ⅱ): Properties of hydrogen bonding networks

Making use of the invariant property of the equilibrium size distribution of the hydrogen bonding clusters formed in hydrogen bonding system of A_aD_d type, the analytical expressions of the free energy in pregel and postgel regimes are obtained. Then the gel free energy and the scaling behavior of the number of hydrogen bonds in gel phase near the critical point are investigated to give the corresponding scaling exponents and scaling law. Meanwhile, some properties of intermolecular and intramolecular hydrogen bonds in the system, sol and gel phases are discussed. As a result, the explicit relationship between the number of intramolecular hydrogen bonds and hydrogen bonding degree is obtained. Supported by the National Natural Science Foundation of China (Grant Nos. 20303006 and 20574016), the Natural Science Foundation of Hebei Province (Grant Nos. B2006000959 and B2004000093) and the Natural Science Foundation of Education Committee of Hebei Province (Grant No. 2003101)     

受限狭缝中CO_2-CH_4体系的汽液相平衡性质

受限条件下CO2-CH4体系的相平衡性质对化工工艺过程的设计具有非常重要的意义.采用Gibbs系综Monte Carlo模拟,对220K下CO2-CH4体系在主体相和受限狭缝中的相平衡性质进行了系统地研究.通过主体相模拟与实验结果比较,验证了流体分子势能参数的合理性;通过改变狭缝壁面原子的能量参数,研究了受限环境对CO2-CH4体系汽液相平衡性质的影响.与主体相相比,在硬壁狭缝中,CO2-CH4体系的露点压力增加,泡点压力降低,压力-组成相图变窄,且体系更容易达到超临界状态;在吸引狭缝中,随壁面原子能量参数的增大,CO2-CH4体系的压力-组成相图上移,临界点处CH4的摩尔分数减小,相图变窄.在体系汽液相总组成相同情况下,硬壁狭缝内体系的汽液相密度均比主体相中小;随壁面原子能量参数增大,气相密度变大、液相密度在CH4的摩尔分数较小时变大而当CH4的摩尔分数达到一定值后反而减小.在体系汽液相总组成相同时,受限环境下的汽化热比主体相的汽化热小且随壁面吸引势的增强越来越小;在主体相和硬壁狭缝中体系的汽化热随CH4含量的增加单调减小,而当壁面势能参数较大时汽化热随CH4含量增加先增大后减小.     

1,2,3-三氮杂苯-水簇复合物氢键结构与性质的理论研究

在B3LYP/6-31 G**水平上对1,2,3-三氮杂苯和水形成1∶1,1∶2和1∶3复合物的基态氢键结构进行几何优化和性质计算,结果表明复合物之间存在较强的氢键作用。氢键的形成使水分子中H-O键振动频率减小(红移)。NBO分析表明,最稳定的1∶1,1∶2和1∶3复合物发生分子间电荷转移总量分别为0.0222e,0.0261e和0.0273e。