苯乙烯与邻、间、对-二甲苯二元混合液的分子间相互作用

The densities (ρ), ultrasonic speeds (v), and refractive indices (n) of binary mixtures of styrene (STY)with m-, o-, or p-xylene, including those of their pure liquids, were measured over the entire composition range at the temperatures 298.15, 303.15, 308.15, and 313.15 K. The excess volumes (VE), deviations in isentropic compressibilities(△ks), acoustic impedances (△Z), and refractive indices (△n) were calculated from the experimental data. Partial molar volumes (V0φ,2) and partial molar isentropic compressibilities (K0φ,2) of xylenes in styrene have also been calculated. The derived functions, namely, VE, △ks, △Z, △n, V0φ,2, and K0φ,2 were used to have a better understanding of the intermolecular interactions occurring between the component molecules of the present liquid mixtures. The variations of these parameters suggest that the interactions between styrene and o-, m-, or p-xylene molecules follow the sequences: p-xylene＞o-xylene＞m-xylene. Apart from using density data for the calculation of VE, excess molar volumes were also estimated using refractive index data. Furthermore, several refractive index mixing rules have been used to estimate the refractive indices of the studied liquid mixtures theoretically. Overall, the computed and measured data were interpreted in terms of interactions between the mixing components.     

不同温度下α-氨基酸在CTAB溶液中的体积及折光率的变化

Densities(ρ)and refractive indices(nD)of glycine(Gly),DL-alanine(Ala),DL-valine(Val)(0.02,0.04,0.06,0.08,and 0.10 mol·L-1)in 0.005 and 0.008 mol·L-1 aqueous cetyltrimethylammonium bromide(CTAB)have been measured at 298.15,303.15,308.15,and 313.15 K.The density data have been utilized to calculate apparent molar volumes(φv),partial molar volumes(φ0v),at infinite dilution and partial molar volumes of transfer φ0v(tr)of amino acids.The refractive index data have been used to calculate molar refractivity(RD)of amino acids in aqueous cetyltrimethylammonium bromide.It has been observed that φ0v varies linearly with increasing number of carbon atoms in the alkyl chain of amino acids,and hence,was split to get contributions from the zwitterionic end groups(NH 3,COO-)and methylene group(CH2)of the amino acids.The behaviour of these parameters has been used to investigate the solute-solute,solute-solvent interactions and the effect of cetyltrimethylammonium cation on these interactions.     

Physicochemical Properties of Amino Acids in AqueousCaffeine Solution at 25, 30, 35 and 40 ℃

Density, viscosity, and refractive index, for glycine, DL-alanine, L-serine and DL-valine have been determined in aqueous solution of 0.05 mol/kg caffeine as a function of amino acid （AA） concentration at 25, 30, 35, and 40 ℃ The density data have been used to compute apparent molar volume. The partial molar volume （limiting apparent molar volume） was obtained by applying the Masson＇s equation. The viscosity data have been analyzed by means of Jones-Dole equation. The values of Falkenhagen coefficient and Jones-Dole coefficient thus obtained are used to interpret the solute-solute and solute-solvent interactions, respectively. Hydration number was also computed. The transition-state theory was applied to obtain the activation parameters of viscous flow, i.e., free energy of activation per mole of solvent, and solute. The enthalpy and entropy of activation of viscous flow were computed for the system. Refractive index was used to calculate molar refractivity of the mixtures. The results have been interpreted in the light of various interactions occurring between the components of the mixtures under applied experimental conditions.     

Effect of Na＋, K＋ and Ca2＋ Ions on Physico-chemical Properties of Thymine, Cytosine, Thymidine and Cytidine in Aqueous Urea Solution

Experimental determination of density, ultrasonic velocity and viscosity of two pyrimidine bases thymine and cytosine along with their respective nucleosides, thymidine and cytidine has been carried out in aqueous urea solutions in the presence of different concentrations of three salts, viz. NaCl, KCl and CaCl₂. The experimental data have been used for the computation of various thermodynamic parameters, viz. apparent molar volume, apparent molar compressibility, coefficients A and B of the Jones-Dole equation, internal pressure, acoustic impedance, etc. Structural studies of solutions under investigation have also been carried out by ultraviolet spectroscopy, and an attempt has been made to collaborate the findings of ultraviolet spectroscopy with results obtained thermodynamically.     

不同温度下脯氨酸在非水阴离子、阳离子及非离子型表面活性剂中的相互作用

Density and viscosity data of proline (Pro) in sodium dodecyl sulfate/cetyltrimethylammonium bromide/poly (oxyethylene) isooctyl phenyl ether in formamide were measured at 298.15, 303.15, 308.15, and 313.15K and 0.1MPa. The density data were utilized to evaluate standard partial molar volumes (φ0V) and partial molar isobaric expansibility (φ0E). The viscosity data were used to evaluate A-and B-coefficients, free energy of activation of viscous flow (⊿μ0*1) and (⊿μ0*2), per mole of solvent and solute respectively, enthalpy (⊿H*) and entropy (⊿S*) of activation of viscous flow. The results obtained were utilized in the qualitative elucidation of the Pro-surfactant/formamide and Pro-Pro interactions in the present systems.     

Volumetric and Refractive Index Behaviour of α-Amino Acids in Aqueous CTAB at Different Temperatures

Densities （ρ） and refractive indices （nD） of glycine （Gly）, DL-alanine （Ala）, DL-valine （Val） （0.02, 0.04, 0.06, 0.08, and 0.10 mol·L^-1） in 0.005 and 0.008 mol·L^-1 aqueous cetyltrimethylammonium bromide （CTAB） have been measured at 298.15, 303.15, 308.15, and 313.15 K. The density data have been utilized to calculate apparent molar volumes （φv）, partial molar volumes （φv^0）, at infinite dilution and partial molar volumes of transfer φv^0 （tr） of amino acids. The refractive index data have been used to calculate molar refractivity （Rr,） of amino acids in aqueous cetyltrimethylammonium bromide. It has been observed that φv^0 varies linearly with increasing number of carbon atoms in the alkyl chain of amino acids, and hence, was split to get contributions from the zwitterionic end groups （NH3^＋ COO^-） and methylene group （CH2） of the amino acids. The behaviour of these parameters has been used to investigate the solute-solute, solute-solvent interactions and the effect of cetyltrimethylammoniuln cation on these interactions,     

THEORETICAL ANALYSIS OF REMOTE SENSING OF AEROSOL REFRACTIVE INDEX BY ANGULAR SCATTERING METHOD

This paper introduces the functions representing quantitatively the sensitivity of the volume scattering function to the aerosol refractive index, points out the scattering angle regions where volume scattering function is more sensitive to the real part of refractive index or its imaginary part, and analyzes the correlativity between scattering channels. Furthermore, we have analyzed optimum channels of remote sensing of refractive index, and satisfactory inversion results have been obtained when the optimum channels were used in retrieving refractive index.     

SOLVENT QUALITY AND SOLUTION BEHAVIOR OF NYLON 12

The refractive index increment,dynamic and static laser light scattering,intrinsic viscosity[η]and Huggins constant(K_H)of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃.The intrinsic viscosity,R_H,R_g,A_2,and(~2)~(1/2)(calculated from viscosity data)and"a"values of nylon 12 are found to be higher in m-cresol than in sulphuric acid.All these parameters decrease with the increase in water contents in sulphuric acid.The refractive index increment,K_H and activation energy show an opposite trend to that of[η].The intrinsic viscosity,R_H,R_g,A_2, and(~2)~(1/2) have maximum values around 30-40℃in sulphuric acid/water system,whereas in m-cresol they fall at about 20℃.It has been concluded that the variation in size,interaction parameter(second virial coefficient),[η]and K_H of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents,selective adsorption,hydrogen bonding and conformational transitions.It has also been concluded that the increase in temperature first enhances the quality of the solvent,encourages hydrogen bonding and specific adsorption, and then deteriorates,bringing conformational transitions in the polymer molecules.However,the addition of water to sulphuric acid continuously deteriorates the solvent quality.This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.     

Densities,Ultrasonic Speeds,Viscosities and Refractive Indices of Binary Mixtures of Benzene with Benzyl Alcohol,Benzonitrile, Benzoyl Chloride and Chlorobenzene at 303.15 K

Densities,ρ, ultrasonic speeds, u, viscosities,η, and refractive indices, n, of pure benzene, benzyl alcohol (BA), benzonitrile (BN), benzoyl chloride (BC), chlorobenzene (CB) and their thirty six binary mixtures, with benzene as common component, were measured at 303.15 K over the entire mole fraction range. From these experimental data the values of deviations in ultrasonic speed, △u, isentropic compressibility, △k_s,excess acoustic impedance, Z^E, deviation in viscosity, Dh, and excess Gibbs free energy of activation of viscous flow, G^*E, and partial molar isentropic compressibility, Kφ,2⁰ of BA, BN, BC and CB in benzene were computed. The variation of these derived functions with composition of the mixtures suggested the increased cohesion (molecular order) in the solution and that interaction (A-B)＞(A-A) or (B-B).Moreover, theoretical prediction of ultrasonic speed, viscosity and refractive index of all the four binary mixtures was made on the basis of empirical and semi-empirical relations by using the experimental values of the pure components. Comparison of theoretical results with the experimental values was made in order to assess the suitability of these relations in reproducing the experimental values of u, η and n. Also, molecular radii of pure liquids and the average molecular radii of binary mixtures were evaluated using the corresponding refractive indices of pure liquids and binary mixtures. The average molecular radii of binary mixtures were found to be additive with respect to mole fraction of the pure component.     

STUDY ON THE CHARACTERIZATION OF DISTRIBUTION OF SUBSTITUENTS ALONG THE CHAINOF CARBOXYMETHYL CELLULOSE

Four new paranmeters, and , and have been proposed to describe the average length of the sequence of substituted anhydroglucose units and that of unsubstituted ones respectively along the CMC chain. The methods for determining those parameters have also been presented . Six CMC samples have been characterized in terms of intrinsic viscosity, degree of substitution (DS), index of substitution(SI)_ and . It has been proved experimentally that, not only can describe the sequence distribution along the CMC chain, but also can be used for calculating SI and estimating the average degree of substitution in the substituted glucose rings.     

不同温度下α-氨基酸在咖啡碱水溶液中的体积、粘度及折光率特性

Measurements of density(ρ), viscosity(η), and refractive index(n), were carried out on α-amino acids, DL-solution at 298.15, 303.15, 308.15, and 313.15 K. These measurements have been carried out to evaluate some important parameters, viz., apparent molar volume (φv), partial molar volume (φv0), transfer volume (φ0v (tr)), viscosity A and B coefficients of Jones-Dole equation, free energies of activation per mole of solvent (△μ0#1) and solute (△μ0#2),enthalpies (△H*) and entropies (△S*) of activation of viscous flow, variation of B with temperature ((a)B/(a)T)P, and molar refractive index (RD). These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.     

Pt纳米粒子修饰的多孔硅电极的制备及其电催化性能

通过循环伏安法电沉积使直径约为7 nm的Pt纳米粒子均匀地分散于多孔硅表面, 拟用作微型质子交换膜燃料电池的催化电极. 与刷涂法相比较, 电沉积Pt纳米粒子的多孔硅电极(Pt/Si)呈现出高的Pt利用率和增强的电催化活性. 当Pt载量为0.38 mg•cm−2时, 其电化学活性比表面积高达148 cm2•mg−1, 是刷涂相近质量的纳米Pt/C催化剂的多孔硅电极Pt-C/Si的2倍多；该修饰电极对甲醇氧化也呈现了增强的催化性能和好的稳定性, 在0.5 V(vs SCE)极化1 h后电流密度为4.52 mA•cm−2, 而刷涂了相近Pt量的Pt-C/Si电极的电流密度只有0.36 mA•cm−2.     

新型气体扩散电极体系高效产H2O2的研究

以自制新型石墨/聚四氟乙烯(PTFE)气体扩散电极在无隔膜体系中进行双氧水发生工艺的优化研究, 主要探讨了不同石墨和PTFE质量比、阴极电位、pH值和氧气流速对H2O2产率的影响. 结果表明, 以石墨和PTFE质量比为2:1的气体扩散电极为阴极, 在pH=3, Na2SO4浓度为0.1 mol•L−1, 氧气流速为0.4 L•min−1, 阴极电位为−0.55 V (vs SCE)时, 2 h后H2O2可以达到60 mg•L−1. 该新型体系有较高的H2O2产率和电流效率(可达60%以上), 且pH值适用范围较广, 可望应用于水中污染物的处理.     

Transient species and its properties of melatonin

Reactive oxygen species (ROS) are generated dur- ing radiation, respiratory burst, normal metabolic processes and so on. There are enzymatic and non-enzymatic antioxidants such as superoxide dis- mutase (SOD), glutathione peroxidase (GSH-Px), vi- tamin E (VE) and carotenoids that can either inhibit or repair the ROS-induced damage. ROS is essential to maintain physiological homeostasis. However, exces- sive ROS give rise to oxidative damage to proteins, lipids and DNA which related t…     

Physicochemical Properties, <Superscript>1</Superscript>H-NMR,Ab Initio Calculations and Molecular Interaction in Binary Mixtures of <Emphasis Type="Italic">N</Emphasis>-methylimidazole with Methanol

Over the full molar fraction range, the density, viscosity, refractive index, conductivity and pH at the temperatures (298.15, 308.15, and 318.15) K, mixing enthalpy at T?=?298.15 K, and ¹H-NMR were measured for the binary mixtures of x N-methylimidazole (hereafter abbreviated to N-mim)?+?(1???x) methanol, together with ab initio calculations. The thermodynamic parameters of activation for viscous flow were calculated and analyzed. The excess molar volume, viscosity deviation, deviation for the logarithm of viscosity, refractive index deviation and the excess refractive index, excess Gibbs energy of activation of viscous flow and the molar mixing enthalpy were calculated and fitted with a Redlich–Kister equation. The partial molar mixing enthalpies and the protons’ chemical shift changes of N-mim and methanol were calculated and explained. An increase in temperature leads to the excess molar volume becoming more negative, whereas the deviations for the logarithm of viscosity, viscosity deviation and the excess Gibbs energy of activation of viscous flow become less positive; in contrast the refractive index deviation and the excess refractive index become less positive at first and then become more positive. The activation of the viscous fluid is a more ordered process. The physicochemical properties, ab initio calculations, combined with the ¹H-NMR results reveal that the molecular interactions among unlike molecules is stronger than that between like ones. There is an ionization process and hydrogen bond interaction between N-mim and methanol, the predominant interaction is N-mim:methanol?=?1:1 hydrogen-bonded network, where the methyl groups of methanol and N-mim, respectively, are electron-withdrawing and electron-donating groups.     

Effects of CuCl2��6H2O and ZnCl2��6H2O on the viscosity of aqueous ethanol mixtures

The effects of CuCl₂ and ZnCl₂ on the viscosity in aqueous ethanol mixtures (10%–50% v/v) were studied in the concentration range 1.0×10⁻²–8.0×10⁻² mol·dm⁻³ at different temperatures. It was found that the viscosities increased with an increase in the concentration of the salts and percent composition of ethanol content, whereas it decreased with an increase in temperature. Ion-ion and ion-solvent interactions are determined with the help of A- and B-coefficients of Jones-Dole equation. The values of A- and B-coefficients are irregular and increase with a rise in temperature and also with an increase in ethanol contents for both salts. Negative values of B-coefficients show that ion solvent interactions is comparatively small and suggest that CuCl₂ and ZnCl₂ behave as structure breakers in aqueous ethanol mixtures. Thermodynamic parameters like the energy of activation (E _η ) and change in entropy of activation (ΔS*) were also evaluated which confirm the structure breaker behavior of salts in aqueous ethanol mixtures.     

Physical–chemical properties of nickel analogs ionic liquid based on choline chloride

In this paper, a homogeneous, green analogs ionic liquid containing choline chloride and nickel chloride hexahydrate is formed. The structure of the analogs ionic liquid is preliminary investigated by Fourier transform infrared spectroscopy. It is shown that the nickel chloride hexahydrate bond via hydrogen bonds with choline chloride and urea. The physico-chemical properties of the analogs ionic liquid such as viscosity, conductivity, density, and thermal stability are measured as a function of temperature and composition. The thermal expansion coefficients (r), the molar Gibbs energy of activation (ΔG*) for viscous flow, the molar enthalpy of activation (ΔH*), and the molar entropy of activation (ΔS*) for viscous flow have been calculated. A straight-line equation is used to fit the density data while the Arrhenius equation is used to fit both viscosity and conductivity. Thermal stability of analogs ionic liquid was carried out from room temperature to 973.15 K. It indicates that analogs ionic liquid is stable from room temperature to 488.2 K.     

磷酸三丁酯与醇二元混合体系的热力学性质

用量热法测定了298.15 K时, 磷酸三丁酯(TBP)+甲醇/乙醇/正丁醇/正丙醇四个二元混合体系的超额混合焓及293.15 K和303.15 K时部分组成下的超额混合焓, 其值均在−0.3 − 0.3 kJ•mol−1之间, 且基本不受温度的影响. 用无热溶液模型计算了各体系的超额熵、超额Gibbs自由能及各组分的活度系数. 热力学分析表明, TBP+甲醇/乙醇/正丙醇二元体系能较好地符合无热溶液模型, 而TBP+正丁醇体系则不符合无热溶液模型.     

Viscous synergy and antagonism,excess molar volume,isoentropic compressibility and excess molar refraction of ternary mixtures containing tetrahydrofuran,methanol and six membered cyclic compounds at 298.15 K

The densities (ρ), viscosities (η), sound speeds (u) and refractive indices (n _D) of seven ternary mixtures of cyclic ether (tetrahydrofuran), methanoland cyclic compounds; benzene, toluene, chlorobenzene, nitrobenzene, anisole, cyclohexane and cyclohexanone are determined over the entire range of composition at 298.15?K. From the experimental observations, viscosity deviation (Δη), the viscous synergy and antagonism, synergic and antagonic index are derived by the equations developed by Kalentunc-Gencer and Peleg [G. Kalentunc-Gencer and M. Peleg, J. Texture Stud. 17, 61 (1986)] and Howell [N.K. Howell, Presented at the Proceedings of the Seventh International Conference, Wales, 1993], respectively. Excess molar volume (V ^E), excess isoentropic compressibility (ΔK _S) and excess molar refraction (ΔR) have been calculated from the experimentally measured density, sound speed and refractive index values. The excess Gibb's free energy of activation (ΔG ^E) has also been calculated. The results are discussed and interpreted in terms of molecular package and specific interaction predominated by hydrogen bonding.     

Study of molecular interactions in binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol at varying temperatures

The thermophysical properties of binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol have been investigated in this article. Densities, refractive index, ultrasonic velocity and viscosity for the two binary mixtures viz. formamide with 2-methoxyethanol and 2-ethoxyethanol have been measured over the entire composition range at 293, 303 and 313 K and at atmospheric pressure. The excess molar volume, the molar refraction deviation, excess Gibb's free energy of activation for viscous flow, excess isentropic compressibility, deviation in viscosity, excess free volume and excess molar enthalpy have been computed using experimental data. These excess parameters have been correlated with Redlich–Kister polynomial equation. The results have been interpreted on the basis of strength of intermolecular interaction occurring in these mixtures. Densities, refractive index and ultrasonic velocity were correlated with second-order polynomial equation. The molar volume and excess partial molar volume at infinite dilution have also been calculated for both the mixtures.