Effect of pressure on the solubilities ofo-,m- andp-xylene in water

The solubilities of o-, m- and p-xylene in water were measured at 25.0°C up to 250, 385, and 50 MPa, respectively. The solubility increased with increasing pressure up to 120 MPa (50 MPa for p-xylene) and then decreased. The reaction volumes, V^o accompanying the dissolution at 0.1 MPa were estimated as –3.6±0.5, –3.4±0.5, and –4.1±0.5 cm³-mol^–1 for o-, m-, and p-xylene, respectively, from the pressure dependences of the solubilities. The limiting partial molar volumes, of p- and o-xylene in water under high pressure were estimated from V^o and the molar volume of the xylene. The partial molar volumes decreased with increasing pressure. The reaction volume for the formation of intra-molecular pairwise hydrophobic interaction between the methyl groups, as proposed by Ben-Naim, is discussed for the V^o of p- and o-xylene at 0.1 MPa.     

Effects of pressure and solvent on the diffusion of aromatic compounds through polymers

The diffusion of six azo and five anthraquinone derivatives through nylon 6, poly(ethylene terephthalate) and secondary cellulose acetate films were studied under high hydrostatic pressures of up to 3000 bar and at temperatures 80–130 °C, by analyzing the diffusion profiles yielded in a stacked multiple film, placed in the solution of the diffusant. It was found that the diffusion coefficient,D, of the diffusant decreased with increasing pressure, giving a linear relationship between InD and the pressure, the slope of which gave the activation volume for the diffusion,V . It was revealedV increased linearly with increasing intrinsic molecular volume of the diffusant,V _w , the slopes being different between the azo and the anthraquinone derivatives. The ratio ofV toV _w (V /V _w ) ranged from 0.13 to 0.93, depending in a sensitive manner on the degree of swelling of the polymer matrix which in turn was varied by the solvent. The overall results could be explained in accordance with the formulation,V _{f, local} +V =V _w , whereV _{f, local} represents the free volume contribution. It was proposed thatV _w is increased by solvation when the solvent is good for the diffusant.     

Application of a chemical equilibrium model to thermodynamic functions of transfer of alcohols from water to aqueous surfactants

In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.     

A calorimetric study of the glass transition kinetics in polyisoprene

The connection between the dielectric and calorimetric relaxation behaviours of synthetic polyisoprene Cariflex IR 305 is studied. A similar comparison of dielectric and dilatometric results was described in [1]. The heat capacity was measured during heating of samples prepared with different thermal history. Experimental results were compared with the heat capacity curves calculated for a model based on the multiparameter theory of Kovacs et al. [4]. The model considers the relaxation system as being composed of a set of subsystems characterized by different relaxation times. The distribution of relaxation times and their temperature dependence were taken from the diclectric measurement. The relaxation time of a subsystem from posed to depend, not only on the actual, temperature of the sample, but also on the deviation of this subsystem from equilibrium, or alternatively, on the deviation of the system as a whole. The comparison between the measured and modeled curves shows that both influences must be taken into account in order to explain the experimental results.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday.     

Coordination around thorium(IV) in aqueous perchlorate,chloride and nitrate solutions

The coordination around the thorium(IV) ion in aqueous perchlorate, chloride and nitrate solutions has been determined from large angle X-ray scattering measurements. In perchlorate solutions, where inner-sphere complexes are not formed, the first coordination sphere contains 8.0±0.5 water molecules with Th-H₂O bond lengths of 2.48₅ Å. In chloride solutions inner-sphere complexes are formed, which lead to an increase in the coordination number. In nitrate solutions the nitrate ions are bonded as bidentate ligands to the thorium ion. The bond lengths are similar to those found in crystalline hydrates of thorium nitrate. The coordination numbers found for thorium(IV) in solution are compared with previously reported values for lower charged ions of similar size.On leave from Department of Inorganic Chemistry Royal Institute of Technology S-10044 Stockholm Sweden     

Headspace-gas chromatography: The influence of sample volume on analytical results

Summary The role of the volume of the sample and the sample vial in equilibrium headspace-gas chromatography is discussed. A new term, thesample phase fraction (_S) is introduced. It is shown that if the value of _S is kept constant, the vial's volume has no influence on the sensitivity of the headspace analysis (which is proportional to the concentration of the analyte in the headspace). In a given headspace sampling system, concentration of the compound of interest in the headspace (c _G ^* ) at equilibrium is related to the value of _S: a higher _S will increase c _G ^* . However, the influence is important only in the case of low distribution coefficients: in the case of higher distribution coefficients this influence is negligible. This conclusion is also true for small changes in the sample volume in duplicate analyses: exact reproducibility of the sample volume is important only in the case of low distribution coefficient values.     

Topological investigations of molar excess volumes of quinoline with alkanols

Excess volumes V ^E of binary liquid mixtures of quinoline with alkanols have been determined from densities at 30°C as a function of composition. The excess volumes are negative over the whole mole fraction range for all the mixtures and decrease with increasing length of alkanol (C₁–C₁₀). The V^E data have been analyzed in terms of an approach which uses graph theoretical connectivity parameters of the third degrees for two components. The analysis gives information regarding associated species in the pure state and in the mixture. It is suggested that, in the mixture state, no change occurs in the association of alkanols.     

反相液体色谱中饱和醇保留行为的研究 Ⅰ.低碳醇保留行为与溶质分子结构的关系

本文从吸附-疏溶剂理论出发,根据热力学平衡观点,导出了一定固定相和流动相时,描述溶质保留行为与其分子结构关系的理论模型,并用之预测了饱和醇的保留值,获满意结果。从而表明本模型不但能用于同系物,而且亦可用于同分异构体及立体异构体保留行为的预测。     

DCE-MRI定量参数对子宫内膜癌的诊断价值及与临床病理因素的相关性

本文选取了子宫内膜癌患者108例作为观察组,另选取子宫内膜良性病变患者105例作为对照组,均行DCE-MRI检查后发现,观察组容量转移常数(Ktrans)、速率常数(Kep)、血管外细胞外间隙容积比值(Ve)高于对照组(P＜0.05);Ktrans、Kep、Ve值联合诊断子宫内膜癌的曲线下面积(AUC)为0.841;K...     

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