水滑石选择性催化合成三乙二醇单丁醚

The hydrotalcite (n(Mg)/n(Al)=3) calcined at 500 ℃, containing a great number of fine pores (d<3 5 nm, 34% of the all pore volume) and increased BET surface area by about three times (from 75 to 205 m 2/g), has been successfully applied to the selective ethoxylation reaction of a mixture of alcohols. The experimental results showed that the calcined hydrotalcite is an efficient solid base catalyst for synthesis of BuO(EO) 3H with high selectivity of over 90%.     

碱性介质中二(高碘酸根)合铜(Ⅲ)酸根氧化乙二醇独丁醚的反应动力学及机理

在25℃～40℃区间用分光光度法在碱性介质中研究了二(高碘酸根)合铜(Ⅲ)酸根配离子(DPC)氧化乙二醇独丁醚(EGB)的反应动力学。结果表明:反应对DPC为一级,对EGB是1< n_ap< 2(n_ap代表表观反应级数);在保持准一级条件([EGB]₀ 》[Cu(Ⅲ)]₀)下,表观速率常数,k_obs,在弱碱性介质中,随[OH^-]增大而减小,在较强碱性介质中随[OH^-]增大而增大,随着[IO₄^-]增加而减小;无盐效应。提出了含有自由基过程的反应机理,由假设的两种同时进行的反应机理推出的速率方程能很好的解释全部实验现象,进一步求得速控步的速率常数和活化参数。     

Ionic radii in aqueous solutions

The aqueous ionic radii of 35 ions have been calculated from published data of the average distances between the ions and the nearest water molecules, obtained by diffraction and computer simulation methods.     

Acoustic absorption in aqueous potassium phosphate

Measurements of acoustic absorption and velocity as a function of frequency and concentration in KH₂PO₄–K₂HPO₄ buffers at 4°C and pH 5-7 are reported. The dependence of the observed acoustic relaxation parameters on concentration is consistent with that to be expected from perturbation of a monomer-dimer equilibrium with an equilibrium constant [for 2H₂PO ₄ ^– (H₂PO₄)₂ ^2–] of 0.21 M^–1, a bimolecular rate constant of 5×10⁸ M^–1-sec^–1 and a standard volume change of –5 cm³ mole. The equilibrium constant for H₂PO ₄ ^– + HPO₄ ^2–H₃(PO₄)₂ ^3– is estimated to be 0.7 M^–1.     

Ultrasonic absorption spectroscopy between 5 and 3100 MHz on some aqueous polyelectrolyte solutions

The ultrasonic absorption coefficient has been measured as a function of frequency between 5 MHz and 3.1 GHz for aqueous solutions of polyacrylic acid and of its sodium, potassium, and tetraethylammonium salts. Unlike an aqueous solution of propionic acid, all polymer solutions clearly exhibit excess absorption. Within the frequency range under consideration the excess absorption spectra can be analytically represented by two Debye-type relaxation terms. At 25°C the corresponding relaxation times adopt values between 3 and 12.4 ns, and between 0.12 and 0.22ns, respectively. The former process is discussed in accordance with previous models. The relaxation of the polyacrylic acid solutions is assumed to be related to the formation of hydrogen bonds of the polymeric molecules and that of the polyacrylate solutions may be due to interactions of counterions with chain segments. The latter process, the existence of which has been first proven in this study, is likely to reflect rotational motions of carboxyl groups.     

Formation of mercury clusters during pulsed radiolysis of aqueous Hg 2 2+ solutions

Pulsed radiolysis, EPR, and optical spectroscopy were used to investigate the radiation-induced reduction of Hg ₂ ²⁺ ions in aqueous solutions. It was shown that the Hg ₂ ⁺ ions that form as a result of the reduction reaction react rapidly with Hg ₂ ²⁺ with formation of Hg ₄ ³⁺ . Constants of formation and disappearance of these ions were determined. The process of disappearance of this species results in the formation of more complex clusters containing six or more mercury atoms. Further complication of the clusters affords colloidal metal particles.Institute of Physical Chemistry, Russian Academy of Sciences, Moscow 117915. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 9–12, January, 1992.     

Interactions in aqueous nonelectrolyte systems. Gibbs energy of interaction of the ether group with the hydroxyl group and the amide group

Freezing temperatures of dilute aqueous solutions of equimolar mixtures of 1,3,5-trioxane with myo-inositol, d-mannitol, cyclohexanol, formamide, and acetamide, and 1,4-dioxane with myo-inositol, d-mannitol, formamide, and acetamide have been measured. These data yield pairwise Gibbs energies of interactions between the molecules in an aqueous solution. Using the group additivity principle, the results also yield the pairwise functional group Gibbs energies of interaction for the ether group with the hydroxyl and amide group. These results have been combined with all available data from the literature to yield the Gibbs energy and enthalpy of interaction of amides, ethers, alcohols, and saccharides in aqueous solution.To whom correspondence should be addressed.     

Radiolysis of aqueous solutions of thiamine

The results of the radiolysis of aqueous solutions of thiamine (vitamin B₁) are presented. The yields for decomposition of thiamine and the product of radiolytic products were determined. The G values decrease as the dose increases. Some radiolytic products were identified. Decomposition of thiamine was slightly dependent on the presence of oxygen and on the pH of the solution. At pH 4.4 with a concentration of 2.5 × 10⁻⁴ mol L⁻¹ of thiamine in an oxygen free aqueous solution, the G⁰ value for decomposition is 5.0.     

Experiments and model for the surface tension of carbonated monoethanolamine aqueous solutions

The surface tension of carbonated monoethanolamine aqueous solutions from 293.15 to 323.15 K was measured by using an automatic surface tension-meter.A model applicable for the surface tension of MEA-CO2-water mixtures was proposed and the calculated results agreed well with the experiments.The influences of temperature,MEA concentration and CO2 loading were demonstrated on the basis of experiments and calculations.     

MEA-CO2-水溶液表面张力实验和模型

用全自动表面张力仪测定了293．15-323．15K温度范围内,具有不同C02载荷的乙醇胺（Monoethanolamine,MEA）水溶液的表面张力,提出了计算MEA-CO2-水体系表面张力的半经验模型,计算结果与实验值吻合良好．通过实验和计算相结合,阐明了温度、MEA浓度和C02载荷对MEA-CO2-水体系表面张力的影响规律．     

Impact of carbon dioxide on the surface tension of 1-hexanol aqueous solutions

Effects of carbon dioxide presence on the surface tension and adsorption kinetics of 1-hexanol solutions were investigated. Experiments were performed at a range of carbon dioxide vapor pressures and varying concentrations of 1-hexanol aqueous solution. Both dynamic and steady-state surface tensions of 1-hexanol aqueous solution were found to decrease with carbon dioxide pressure, and a linear relationship was observed between the steady-state surface tension and carbon dioxide pressure. To explain the experiments, adsorption and desorption of the two species (1-hexanol and carbon dioxide) from two sides of the vapor-liquid interface were considered. A modified Langmuir isotherm, the modified Langmuir equation of state and the modified kinetic transfer equation were developed. The resulting steady-state and dynamic surface tension data were modeled using the modified Langmuir equation of state and the modified kinetic transfer equation, respectively. Equilibrium constants and adsorption rate constants of 1-hexanol and carbon dioxide were evaluated through a minimization procedure for CO₂ pressures ranging from 0 to 690 kPa. From the steady-state modeling, the equilibrium parameters for 1-hexanol and carbon dioxide adsorption from vapor phase and liquid phase were found unchanged at different pressures of carbon dioxide. From the dynamic modeling, the adsorption rate constants for 1-hexanol and carbon dioxide from vapor phase and liquid phase were found to decrease with carbon dioxide pressure. Some fluctuations in the fitting parameters of the dynamic modeling (adsorption rate constants) were observed. These fluctuations may be due to experimental errors, or more likely the limitations of the model used. A major limitation of the model is related to large differences in adsorption/desorption between initial and final stages of the process, and a single set of property parameters cannot describe both initial and final states of the system. Variations may occur depending on which set of data, of initial or final states, is used in the model predictions over the entire time range.     

Luminescence kinetics and association equilibria of lanthanide ions in aqueous solutions

Luminescence life time measurement can be used under certain conditions to determine the thermodynamic constants of complex formation between the luminescent (central ion) and ligand. The basic equations correlating the life time and the equilibria constants were derived for two cases: the time for establishing the thermodynamic equilibrium is much shorter than the life time of the excited state of the central ion; and the time for establishing the equilibrium and the life time are of the same order of magnitude.     

水-环己烷-二乙二醇丁醚三元体系的三液相相平衡

用改进的相体积法测定了水-环己烷-二乙二醇丁醚三元体系的相平衡, 给出了不同温度下平衡共存三液相的体积分数及平衡共存三液相的相密度的共存曲线. 实验结果表明, 在平衡共存三液相中, 水、环己烷和二乙二醇丁醚的体积分数随温度改变的变化曲线分别是倒“S”型, 正“S”型, “结”型; 将共存三液相的体积分数转化为对应的相密度后, 相密度随温度改变的变化曲线也是规整的倒“S”型; 而且, 3条“S”曲线形状均表现出不对称的特性. 因此, 密度也可以用作描述体系的相平衡, 而且在描述体系临界标度率时, 密度可能是一个很好的序参量.     

The aromatic amino acid behaviour in aqueous amide solutions

The enthalpies of solution of L-phenylalanine in the mixtures of water with the protein denaturant urea have been measured in the temperature range of 288.15–318.15 K. Using the results of the present research and literature data of free energies, the standard thermodynamic functions of the solute transfer from water to aqueous urea solutions have been estimated in a wide temperature range. The enthalpic, heat capacity, entropic and free energy parameters of the solute-urea pair and triplet interactions have been computed. The amino acid — amide pair interaction was found to be attractive in the temperature range studied due to the favourable enthalpic term. The triplet interaction being slightly repulsive reveals the enthalpic origin also. The examination of the Savage and Wood additivity-of-groups approach does indicate the inapplicability of this scheme to enthalpies and entropies of interaction. It has been found for the first time that the heat capacity of interaction changes its sign at 303 K, i.e. the temperature dependence of enthalpic and entropic parameters passes through the pronounced extrema near the temperature of the minimum of the heat capacity of pure water.     

Thermochemical behavior of 18-crown-6 in aqueous solutions of some monosaccharides

Enthalpies of solution of 18-crown-6 in water-monosaccharide mixtures have been measured at 298.15 K. The values of standard enthalpies of solution of the crown ether are negative for all studied systems but the shape of the solution enthalpy curves differs from one mixed solvent to another. Measurements performed in this work demonstrate the influence of the stereochemical structure of the monosaccharides and their hydration on the enthalpies solution of the crown ether.     

焙烧的水滑石上醇类选择性乙氧基化合成三乙二醇单乙醚 Selective Ethoxylation of Alcohols to Triethylene Glycol Monoethyl Ether over Calcined Hydrotalcite Catalyst

 以焙烧的水滑石(Mg/Al摩尔比为3)为催化剂,通过二乙二醇单乙醚和环氧乙烷(二者摩尔比为5)的乙氧基化反应合成了三乙二醇单乙醚. 在500 ℃焙烧2 h的水滑石上三乙二醇单乙醚的选择性可达94.6%. 焙烧后的水滑石碱性增强,比表面积增大,并含有大量的微孔,对串联式乙氧基化反应具有选择性催化作用. 催化剂经回收处理后可重复使用6次以上.     

Effects of pressure on the kinetics of the dehydration of carbonic acid and the hydrolysis of CO2 in aqueous solution

The pressure dependence of the dehydration reaction of H₂CO₃ was measured in acidic aqueous solution for pressures up to 1 kbar using a high-pressure stopped-flow instrument. The corresponding volume of activation was found to be 6.4±0.4 cm³-mol^–1 at 25°C and 0.5 ionic strength. Volume equation calculations result in a value of –9.9±1.9cm³-mol^–1 for the volume of activation for the hydrolysis of CO₂ under the same conditions. For the first time, the reaction mechanism can be interpreted in terms of dissociative and associative modes, respectively. These data are used to construct an overall reaction volume profile.     

Enthalpies of solution of glycine in aqueous solutions of 1,2-diols and glycerol at 25°C

Dissolution enthalpies of glycine in mixtures of water with 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,3-propanediol and glycerol have been measured at 25°C. The enthalpic pair interaction coefficients of the glycine zwitterion with the polyalcohol molecule have been determined by using the standard solution enthalpies of glycine in water and in aqueous solutions of the polyalcohols. The values of the resultant enthalpic interaction coefficients are interpreted assuming a criterion in the form of the effect of hydrophobic alkyl radicals on the interactions between the hydroxyl groups of polyalcohols and the zwitterion of glycine.