Solubility and density measurements of palmitic acid in supercritical carbon dioxide + alcohol mixtures

Solubility data of palmitic acid (hexadecanoic acid) in supercritical carbon dioxide were measured in the pressure range from 10 to 25 MPa at temperatures of 313 and 318 K. Densities for this binary mixture in the homogeneous phase and at saturation conditions were measured in the same range of temperature. The influence of 3 and 6 mol% ethanol and 2-propanol as co-solvent on the solubility and density data for the CO₂ + palmitic acid mixture was also determined at 313 K. Measurements were carried out in a static-synthetic sapphire cell coupled to a vibrating-tube densitometer. The self-consistency of the data was tested according to the density-based models proposed by Mendez-Santiago and Teja.     

Structural features of binary mixtures of supercritical CO2 with polar entrainers by molecular dynamics simulation

Computer simulations of supercritical carbon dioxide and its mixtures with polar cosolvents: water, methanol, and ethanol (concentration, 0.125 mole fractions) at T = 318 K and ρ = 0.7 g/cm³ are performed. Atom-atom radial distribution functions are calculated by classical molecular dynamics, while the probability distributions of relative orientation of CO₂ molecules in the first and second coordination spheres describing the geometry of the nearest environment of CO₂ molecules and the trajectories of cosolvent molecules are found using Car-Parrinello molecular dynamics. Based on the latter, the conclusions regarding structure and interactions of polar entrainers in their mixtures with supercritical CO₂ are made. It is shown that the microstructure of carbon dioxide varies only slightly upon the introduction of cosolvents.     

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.     

Solubility and dissolution thermodynamics of tetranitroglycoluril in organic solvents at 295–318 K

The solubility data of tetranitroglycoluril in acetone, methanol, ethanol, ethyl acetate, nitromethane and chloroform at temperatures ranging from 295–318 K were measured by gravimetric method. The solubility data of tetranitroglycoluril were fitted with Apelblat semiempirical equation. The dissolution enthalpy, entropy and Gibbs energy of tetranitroglycoluril were calculated using the Van’t Hoff and Gibbs equations. The results showed that the Apelblat semiempirical equation was significantly correlated with solubility data. The dissolving process was endothermic, entropy-driven, and nonspontaneous.     

Self-diffusion and molecular association of acetylsalicylic acid and methyl salicylate in methanol-<Emphasis Type="Italic">d</Emphasis>4 in the temperature range 278–318 K

The effect of concentration on the self-diffusion coefficients of acetylsalicylic acid and methyl salicylate in methanol-d4 is investigated in the temperature range of 278–318 K using NMR. It is found that the self-diffusion coefficients increase along with temperature and fall as concentration rises. Within the limit of an infinitely dilute solution, the effective radii of solute molecules, calculated using the Stokes–Einstein equation shrink as the temperature grows. It is shown that the observed reduction of effective radii is associated with an increase in the fraction of solute monomers as the temperature rises. The physicochemical parameters of heteroassociation of acetylsalicylic acid and methyl salicylate with methanol are determined.     

Hydrogen-bonded complexes of serotonin with methanol and ethanol: a DFT study

Density functional theoretical studies on hydrogen-bonded complexes of serotonin with methanol/ethanol have been carried out in a systematic way. The conformational analysis led to ten stable conformers that can be either gauche or anti depending on the dihedral angle values taken by ethylamine side chain and the 5-hydroxyl group. Serotonin-molecules strongly bind with ethanol than methanol. Ethylamine side chain is the most reactive site in both methanol/ethanol complexes and it is responsible for the stability order. The topological parameters, electron density, and Laplacian of electron density show excellent correlation with the hydrogen bond length. Natural bond orbital analysis confirms C–H···O hydrogen bond formed between the serotonin–alcohol complexes to be red shift in nature except for Gph(out)anti complex both with methanol and ethanol to be blue shifted. The energy decomposition analysis reveals that strong interactions between serotonin and ethanol/methanol are due to the attractive contributions from the electrostatic component.     

Time evolution of density fluctuation in the supercritical region. 2. Comparison of hydrogen- and non-hydrogen-bonded fluids

The time evolution of the density fluctuation of molecules is investigated by dynamic light scattering in six neat fluids in supercritical states. This study is the first to compare the dynamics of density inhomogeneity between hydrogen- and non-hydrogen-bonded fluids. Supercritical methanol and ethanol are used as hydrogen-bonded fluids, whereas four non-hydrogen-bonded fluids were used: CHF(3), C(2)H(4), CO(2), and Xe. We measure the time correlation function of the density fluctuation of each fluid at the same reduced temperatures and densities and investigate the relationship between the dynamic and static density inhomogeneities of those supercritical fluids. In all cases, the profile of the time correlation function of the density fluctuation is characterized by a single-exponential function, whose decay is responsible for the dynamics characterized by hydrodynamic conditions. We obtain correlation times from the time correlation function and discuss dynamic and static inhomogeneity using the Kawasaki theory and the Landau-Placzek theory. While the correlation times in the six fluids show noncoincidence, those values agree well with each other except for the supercritical alcohols when scaled to a dimensionless parameter. Although the principle of corresponding state is observed in the non-hydrogen-bonded fluids, both the supercritical methanol and ethanol deviate from that principle. This deviation is attributed to the presence of hydrogen bonding among alcohol molecules at high temperature and low density. The average cluster size of each fluid is estimated under the same thermodynamic conditions, and it is shown that the clusters of supercritical alcohols are on average 1.5-1.7 times larger than those of the four non-hydrogen-bonded fluids. Moreover, the thermal diffusivity of each neat fluid is obtained over wide ranges of density and temperature.     

Conversion of phenylacetonitrile in supercritical alcohols within a system containing small volume of water

The reaction of phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water was studied. The effects of various operating conditions, such as reaction temperature, reaction time, the mole ratio of phenylacetonitrile/water/methanol or ethanol on the product yield were systematically investigated. The optimal yield of methyl phenylacetate for phenylacetonitrile in supercritical methanol in a system containing a small volume of water was 70 % at 583 K and 2.5 h. The optimal yield of ethyl phenylacetate for phenylacetonitrile in supercritical ethanol with a small volume of water was 80 % at 583 K and 1.0 h. At the same time, a feasible mechanism was proposed for phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water.     

Formation of solvate structures by the <Emphasis Type="Italic">ortho</Emphasis>-, <Emphasis Type="Italic">meta</Emphasis>-, and <Emphasis Type="Italic">para</Emphasis>-isomers of hydroxybenzoic acid in supercritical fluid

The solvate structures formed by the ortho-, meta-, and para-isomers of hydroxybenzoic acid (o-HBA, m-HBA, and p-HBA) with a polar co-solvent (methanol at a concentration of 0.030 and 0.035 mole fractions) in supercritical carbon dioxide at a constant density of 0.7 g/cm³ and temperatures of 318 and 328 K have been studied by the classic molecular dynamics. It has been determined that a stable hydrogen-bonded complex with the co-solvent forms via the hydrogen of the carboxyl group for all isomers. The probability of this complex existence is high at all temperatures and concentrations. In the o-HBA molecule, the other functional groups are engaged in the intramolecular hydrogen bond, but not involved in interactions with methanol. It has been found that m-HBA and p-HBA can be involved in hydrogen bonds with methanol via hydroxyl hydrogen and oxygen atoms; they are characterized by the presence of one more co-solvent molecule (rarely, two molecules) in their solvation shell and intermittent formations/breakages of hydrogen bonds via other functional groups. These bonds are far less stable, and their formation is sensitive to change of temperature and co-solvent concentration. It has been concluded that the degree of selective solvation of m-HBA and p-HBA by co-solvent molecules is approximately the same, but the rate of structural rearrangements in the nearest environment of m-HBA is higher than that of p-HBA.     

Peculiar properties of sodium lodide in alcohols,acetone, and alcohol-water mixtures at lower temperatures

The enthalpies of solution of sodium iodide in methanol, ethanol and acetone and in mixtures of methanol and ethanol with water were measured over wide ranges of electrolyte concentration and temperature. Standard enthalpies of solution, transfer enthalpies of NaI from alcohols to alcohol-water mixtures, and temperature coefficients of enthalpies of solution have been calculated. Thermodyanmic characteristics of solution and solvation of the Na⁺ and I^– ions in acetone and ethanol were determined at 243–298 K. It is noted that at lower temperatures the disruption of solvent structure by ions is a local effect. The presence of negative solvation of the Na⁺ and I^– ions in alcohol-water mixtures at lower temperatures is demonstrated.     

水—正己烷—甲醇体系的液液平衡研究

随着国民经济的发展 ,汽油、柴油等发动机燃料的供求关系会日趋紧张 ,寻求代用燃料是今后燃料工业发展的必然趋势 ,而以甲醇、乙醇等作为部分代用燃料成分是今后的一个重要方向[1] 。由于传统的甲醇合成工艺受到传热、传质和化学平衡的限制 ,原料及能源的利用率有待于进一步提高。钟炳等人根据超临界相反应特点 ,向体系中加入适宜溶剂如正己烷 ,在超临界条件下合成甲醇 ,同时克服了现有过程存在的热力学限制和传热限制 ,并将ＣＯ单程转化率提高到 90 %以上[2 ] 。但是 ,正己烷的加入给合成甲醇过程带来了产物分离和溶剂回收问题。反应器流出…     

Solubilities of lactic acid and 2-hydroxyhexanoic acid in supercritical CO2

Solubilities of lactic acid and 2-hydroxyhexanoic acid in supercritical CO₂ have been measured at T=(311 or 313, 318, 328 K) in the pressure range from 50 to 200 bar. The measurements have been performed using a flow-type apparatus. The solute solubility in compressed carbon dioxide increased with pressure at all investigated temperatures. At pressures below 130 bar, a solubility decrease on temperature increase was observed. An accurate correlation method for the solubility of low volatile substances in supercritical CO₂ has been applied for the interpolation of the experimental results.     

Hydrogen‐bonded complexes of nicotine with simple alcohols

Ab initio and density functional theory studies have been performed on the hydrogen‐bonded complexes of neutral and protonated nicotine with ethanol, methanol, and trifluromethanol to explore their relative stability in a systematic way. Among all the hydrogen‐bonded nicotine complexes considered here, protonated forms in nicotine–ethanol and nicotine–methanol, and neutral form in nicotine–trifluromethanol complexes have been found to be the most stable. In the former two complexes, the proton attached to the pyrrolidine nitrogen acts as a strong hydrogen bond donor, whereas the pyrrolidine nitrogen atom acts as a hydrogen bond acceptor in the latter case. Neutral complex of nicotine with trifluromethanol has been found to possess a very short hydrogen bond (1.57 Å) and basis set superposition error corrected hydrogen bond energy value of 19 kcal/mol. The nature of the various hydrogen bonds formed has been investigated through topological aspects using Bader's atoms in molecules theory. From the calculated topological results, excellent linear correlation is shown to exist among the hydrogen bond length, electron density, and its Laplacian at the bond critical points for all the complexes considered. The natural bond orbital analysis has been carried out to investigate the charge transfer in the nicotine alcohol complexes. In contrast to the blue shifting behavior that is generally exhibited by other C? H···O hydrogen bonds involving sp³ carbon atom, the C? H···O hydrogen bond in the protonated nicotine–ethanol and methanol complexes has been found to be proper with red shifting in nature. © 2011 Wiley Periodicals, Inc.     

原位ATR红外光谱研究超临界条件下酯交换反应过程与机理

在温度15℃~300℃和压力0.1MPa~25MPa下,采用原位ATR(Attenuated Total Reflectance)红外光谱技术研究高温高压条件下甲醇、乙醇和丙醇的分子间氢键和分子内化学键随温度和压力的变化及亚/超临界甲醇条件下醇油的混合与酯交换反应过程与机理。纯物质的红外光谱研究表明,在压力高于14MPa时,随温度由15℃升高到250℃,甲醇、乙醇和丙醇的分子间氢键减弱,减弱程度最大的温度为75℃~225℃;但温度升高对甲基的振动没有影响,当温度超过225℃后,甲醇的羟基振动峰发生明显分峰,而乙醇和丙醇的羟基振动峰未发现分峰变化;在整个温度和压力范围内,三油酸甘油酯的红外光谱图未发生明显变化。醇油混合与酯交换反应过程的红外研究表明,在14MPa时,当温度超过185℃后甲醇与三油酸甘油酯完全互溶,两者形成均相;当混合体系温度超过220℃时,甲醇与三油酸甘油酯开始发生酯交换反应。因此,超临界甲醇条件下的酯交换是均相反应,而且氢键变化不是导致酯交换反应的主要原因,高温高压条件下C－OH键振动形式的变化,即出现C⁺…O^-…H⁺振动使小分子醇的亲电性和亲核性均增强是导致超临界无催化酯交换反应快速进行的主要原因。     

色谱保留值法测定碘和硫在超临界流体CO2中的溶解度

用色谱保留值法测定了单质碘和单斜硫在不同温度及压力下在超临界二氧化碳中的溶解度，并用超临界平衡饱和萃取法验证了测定值，结果满意。     

Comparative study on the photophysical properties between carbene-based Fe (II) and Ru (II) complexes

The comparative study on the photophysical properties between cheap metal Fe (II) complexes and noble metal Ru (II) complexes with identical ligand coordination is performed by the combination of density functional theory (DFT) and time-dependent density functional theory (TDDFT) to evaluate the potential alternative applications of Fe (II) complexes. RuBIP (BIP = 2,6-bis (imidazol-2- ylidene)pyridine) is theoretically established that the radiative lifetime of the second lowest triplet state is more consistence with experimental value. However, FeBIP retains nonluminous because of low-lying ³MC originated from weak d orbital splitting. FeBIPC (FeBIP with carboxylic acid groups) has twice longer lifetime than its parent complex FeBIP due to the great decrease of the energy gap between ³MLCT and ³MC. What's more, the lifetimes of Fe (II) complexes detected in the experiments are more accessible to nonradiative decay lifetimes of ³MC. The carboxylic acid groups are beneficial for the improvement of luminescent possibility and controllability of Fe (II) complexes, while there is still a huge challenge for effective material replacement comparing with Ru (II) complexes.     

Solubility and Dissolution Thermodynamics of Cefmetazole Acid in Four Neat Solvents and Preferential Solvation in Co-Solvent Mixtures of (Methanol,Ethanol or Isopropanol) + Water

The solubilities of cefmetazole acid in methanol, ethanol, isopropanol and water were determined experimentally by using the saturation shake-flask method within the temperature range from (278.15 to 303.15) K under pressure p?=?101.1 kPa. At a fixed temperature, the cefmetazole acid solubility falls in the order methanol?>?ethanol?>?isopropanol?>?water. The apparent dissolution enthalpy, dissolution entropy and Gibbs energy change were calculated. The acquired solubilities were correlated with Apelblat’s equation. The largest value of relative average deviation for mole fraction solubility was 0.45 × 10^?2, and of root-mean-square deviation, 0.747 × 10^?5. The type and extent and direction of solute–solvent interactions were identified using the concept of Linear Solvation Energy Relationship. In addition, the preferential solvation parameters (δx_1,3) of cefmetazole acid in co-solvent mixtures of methanol (1)?+?water (2), ethanol (1)?+?water (2) and isopropanol (1)?+?water (2) were derived via the inverse Kirkwood–Buff integrals method. At 298.15 K, the magnitude of preferential solvation of cefmetazole acid by the co-solvent is highest in methanol mixtures, followed by ethanol mixtures, and finally by isopropanol mixtures.     

Single‐Crystal X‐ray Diffraction Structure of the Stable Enol Tautomer Polymorph of Barbituric Acid at 224 and 95 K

The thermodynamically stable enol crystal form of barbituric acid, previously prepared as powder by grinding or slurry methods, has been obtained as single crystals by slow cooling from methanol solution. The selection of the enol crystal was facilitated by a density‐gradient method. The structure at 224 and 95 K confirms the enol inferred on the basis of powder data. The enol has bond lengths that are consistent with the expected bond order and with DFT calculations that include treatment of hydrogen bonding. In isolation, the enol is higher in energy than the tri‐keto form by 50 kJ mol^?1 which must be more than compensated by enhanced hydrogen bonding. Both crystal forms have four normal H‐bonds; the enol has two additional H‐bonds with O–O distances of 2.49 Å. Conversion into the enol form occurs spontaneously in the solid state upon prolonged storage of the commercial tri‐keto material. Slurry conversion of tri‐one to enol in ethanol is reversed in direction in ethanol‐D₁.     

Why do co-solvents enhance the solubility of solutes in supercritical fluids? New evidence and opinion

The effects of two polar co-solvents, chlorodifluoromethane and acetone, on the solubility and enthalpy of a solution of 1,4-naphthoquinone in supercritical (SC) CO2 were studied. We found that the dissolution process becomes less exothermic in the presence of the co-solvents relative to that in pure CO2, although the solubility is enhanced significantly by the co-solvents. This indicates that the increase in the solubility by adding co-solvents results from the increase of the entropy of solution. On the basis of the unexpected results we propose a new mechanism for the solubility enhancement of the solute by the co-solvents in supercritical fluids (SCF); this should be applicable to cases in which the local density of the SC solvent around the solute and the co-solvent is larger, and the co-solvent associates preferentially with the solute. The results are also very important for the understanding of other fundamental questions of SCF science, such as the effect of co-solvents on the thermodynamic and kinetic properties of the reactions in SCFs.     

Kinetic analysis for hydrothermal depolymerization of nylon 6

We investigated the influences of reaction temperature, time and water density. We also investigated the reaction rate and reaction scheme which is necessary to industrialize this process from the result of hydrolysis of nylon 6 in sub- and supercritical water. The reactions were carried out at temperatures between 573 and 673 K under the estimated pressures of up to 35 MPa (water amount charged in a reactor 0.83-3.79 g/5 cm³ - reactor) for reaction times of 5-60 min. The main products of hydrolysis of nylon 6 by sub- and supercritical water are ?-caprolactam and ?-aminocaproic acid. Based on our experimental results, the reaction scheme of nylon 6 decomposition is represented. Nylon 6 was decomposed into ?-aminocaproic acid by hydrolysis followed by cyclodehydration to ?-caprolactam or decomposition further to lower molecules. At each reaction conditions, the k₁ and k₂ values were determined and the activation energy was calculated.