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固态物质(溶质)从溶液里析出的过程,叫做物质的结晶,简称析晶。这方面的计算是指已知某物质在不同温度下的溶解度和在某温度时的饱和溶液的质量,当饱和溶液从某一温度降低到另一温度时,求能析出的溶质质量。 相似文献
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从理论上阐明了热力学观点所定义的柱相比(即溶质的保留自由能变为零时的κ′值)与溶质种类、柱温、固定相以及溶剂种类的依赖关系。通过研究3种配基链长不同的固定相对7种非极性苯的取代物溶质保留行为的影响,发现柱相比与固定相对溶质吸附力有关;通过对9种正链烷溶质在4种温度下的保留行为的研究,发现了柱相比随温度升高而增大,也发现了柱相比与同系物溶质的碳数无关;通过对3种正链醇同系物,3种正链酸同系物,以及丙酮、乙腈和异丙醇共9种置换剂对9种烷基醇同系物溶质色谱保留行为影响的研究,发现柱相比随溶剂极性增大而减小。 相似文献
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在288.15-318.15 K温度范围内,测定了不同浓度离子液体1-戊基-3-甲基咪唑丙酸盐([C5mim][Pro])水溶液的密度和表面张力,计算了不同温度下不同浓度的溶液热膨胀系数、表观摩尔体积和溶液等张比容;根据密度实验数据计算得到溶质表观膨胀率,并与Harned和Owen提供的理论方程计算结果作了比较,两者计算结果能够很好一致;另外,本文还验证了预测溶液表面张力的经验方程,用其预测溶液的表面张力,不仅与溶液表面张力实验值在误差范围内很好一致,也与用等张比容方法预测的结果一致. 相似文献
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以聚(3-己基噻吩)(P3HT)为电子给体,[6,6]-苯基-C60丁酸甲酯(PCBM)为电子受体材料,制备了不同浓度活性层材料(P3HT:PCBM)的聚合物太阳能电池.通过对比电池性能参数,活性层表面形貌,进一步分析了氯苯溶剂中有机半导体材料的分散规律,并讨论了溶液温度和浓度对溶质粒径的影响,以及粒径大小对器件性能的影响.结果表明,溶液中溶质直径在4000 nm左右的粒子占有较大比例,溶液的浓度和温度对溶液中粒子的粒径有明显的影响,浓度较低时,溶质粒径受温度影响较大.相反,温度对高浓度溶液中的溶质粒径的影响作用减小.溶液浓度为12.67 mg/mL时,分散效果最好,具有最优的填充因子,浓度为19.00 mg/mL时,具有最优的短路电流和能量转换效率. 相似文献
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应用流动式等温精密微量热技术测定了298.15, 303.15, 308.15, 313.15和318.15 K 5个不同温度下L-胱氨酸在一种强酸性和两种强碱性溶剂中的稀释焓. 根据改进的McMillan-Mayer理论对所测数据进行关联, 得到了表观摩尔稀释焓对浓度变化的经验方程和各级焓相互作用系数(h2)和二阶熵相互作用系数(s2), 根据溶质-溶质, 溶质-溶剂等弱相互作用对二阶焓、熵相互作用系数进行了讨论. 结果表明: 对在水相中胱氨酸的二阶相互作用而言, 二价阳离子比二价阴离子具有较强的介质效应; 不同温度下的二阶焓相互作用系数与温度成线性关系, 因而二阶熵相互作用系数在实验温度范围内为一常量. 相似文献
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一种市售汽油添加剂,常温下是半固态。加少量到一定量汽油中,轻摇即可溶解。但当温度降低到10℃,小晶体颗粒陆续开始析出。温度降到0℃时,溶质基本完全析出,且逐渐形成较大的颗粒团,严重影响了此添加剂在低温环境下的使用。为此我们进行了其延时降凝研究。发现溶液中加入少量具有较强极性可与溶质形成氢键、同时具有与溶剂部分相似结构的化合物异丙醇二甲基甲酰胺等,可使溶质在-15℃以下不析出,保持为均匀溶液。1 实验部分此添加剂的主要成份是分子量较大的软脂酸甘油酯,凝固点19℃。据此,在含溶质5%的条件下加入尽可能少的不同溶剂(下… 相似文献
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A theoretical approach for predicting the influence of interparticle interactions on concentration polarization and the ensuing permeate flux decline during cross-flow membrane filtration of charged solute particles is presented. The Ornstein-Zernike integral equation is solved using appropriate closures corresponding to hard-spherical and long-range solute-solute interactions to predict the radial distribution function of the solute particles in a concentrated solution (dispersion). Two properties of the solution, namely the osmotic pressure and the diffusion coefficient, are determined on the basis of the radial distribution function at different solute concentrations. Incorporation of the concentration dependence of these two properties in the concentration polarization model comprising the convective-diffusion equation and the osmotic-pressure governed permeate flux equation leads to the coupled prediction of the solute concentration profile and the local permeate flux. The approach leads to a direct quantitative incorporation of solute-solute interactions in the framework of a standard theory of concentration polarization. The developed model is used to study the effects of ionic strength and electrostatic potential on the variations of solute diffusivity and osmotic pressure. Finally, the combined influence of these two properties on the permeate flux decline behavior during cross-flow membrane filtration of charged solute particles is predicted. Copyright 1999 Academic Press. 相似文献
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BIANLiu-jiao YANGXiao-yan 《高等学校化学研究》2004,20(3):281-284
In consideration of the adsorption of solvent, diluent and solute molecules on the surface of a stationaryphase, a new equation for solute retention in liquid chromatography is presented. This equation includesthree parameters: the displacement equilibrium constant (Ksd) between the solvent and diluent molecules onthe surface of the stationary phase, the total number(N) of the solvent and diluent molecules released fromthe stationary phase after one solute molecule being adsorbed, and the parameter (I) related to the thermody-namic equilibrium constant for the solute adsorption on the stationary phase. Over the whole concentrationrange of the solvent in the mobile phase, the experimental retention data can be well described by this equa-tion, parameters K~, N and I can be obtained by the regression analysis of the experimental retention data,and consequently the number of the solvent and the diluent molecules displaced by one solute molecule fromthe stationary phase can also be derived at different solvent concentrations in the mobile phase, 相似文献
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Ravi Sharma R. C. Thakur Balwinder Sani Harsh Kumar 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(12):2389-2396
Using density and sound velocity partial molar volumes, partial molar adiabatic compressibilities, partial molar expansibilities and structure of L-ascorbic acid have been determined in water and aqueous mixtures of D-glucose and D-fructose at different concentrations and temperatures. Masson’s equation was used to analyze the measured data. The obtained parameters have been interpreted in terms of solute–solute and solute–solvent interactions. It is found that the L-ascorbic acid acts as structure breaker in water as well in binary studied mixtures. 相似文献
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从气-固吸附体系中推导出的Langmuir方程,近一世纪来只能经验性地描述液相吸附。本研究以液-固界面上的溶质计量置换模型为基础,考虑到液-固吸附体系中各组分之间的相互作用,从理论上推导出了在液-固体系中描述在不同溶剂浓度条件下的溶质吸附的扩展的Langmuir公式,并称其为扩展的Langmuir公式。将Langmuir公式中经验参数与液相色谱中的计量置换平衡中的参相关联,还将其扩展到在不同溶剂浓度条件下的溶质定量吸附的描述,为Langmuir方程在描述不同溶剂浓度条件下的组分吸附奠定了理论基础,扩大了Langmuir公式的应用。以不同溶剂浓度条件下所得到的吸附等温线数据对理论推导出的扩展的Langmuir公式进行了验证,并与计算置平衡中的参数相关联,表现用吸附等温线法计算的计量置换参数Z与用高效液相色谱法得到的Z值符合程度很好。 相似文献
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陈丽 《理化检验(化学分册)》2007,43(4):287-289
考虑到气相中溶质分子和其它成分在固定相上的竞争吸附作用,提出了一个描述溶质在气相色谱中进样量和保留值的关系式.由此方程可以获得两个描述色谱体系特征的重要参数:溶质和其它成分在固定相表面竞争吸附的热力学平衡常数Ka和单位体积固定相所能吸附溶质的量NmS.当其它参数给定时,Ka的大小直接决定溶质进样量与保留值关系式的性质.通过试验对此方程进行了初步验证. 相似文献
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The volumetric and viscometric study of three allopathic drugs (sodium valporate, benzalkonium chloride, and losartan potassium) in ethanol solvent is reported here. This study was carried out at four different temperatures that is, from 288.15 to 318.15 K. The accurately measured density values were used to calculate partial molar volume at infinite dilution, solute–solute interaction parameter, Hepler's constant, partial molar expansivity constant, and isobaric thermal expansion coefficient. The viscosity measurements were carried out for the calculation of constants of Jones–Dole equation and to calculate different thermodynamic parameters of viscous flow which include standard free energy change, standard enthalpy change, and standard entropy change of viscous flow. All these viscometric and volumetric parameters are useful for understanding the different types of interactions of drugs in solution and to study the drug action in body. The results of both volumetric and viscometric studies showed that all drugs had structure promoting effect on solvent, existing of strong solute–solvent interaction, and very weak solute–solute interaction. For all these drugs, solvophobic interaction was found to be dominant over electrostriction. Viscometric studies also showed the existing of stronger solute–solvent interaction in ground state as compared to that in transition state. 相似文献
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Carrott PJ Mourão PA Ribeiro Carrott MM Gonçalves EM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11863-11869
A modified form of the Freundlich equation in which the solute equilibrium concentration is normalized with respect to the solute solubility is analyzed and applied to adsorption isotherms of phenol, 4-nitrophenol, 4-chlorophenol, and 2-chlorophenol at different values of pH on commercial activated carbon before and after oxidation. The analysis confirms the importance of normalizing the solute equilibrium concentration when analyzing the adsorption isotherms, and it is suggested that a parameter, K(F10), obtained by taking 10% solubility as the reference point when applying the Freundlich equation, is probably the best comparative estimate of the relative adsorption capacity of the carbon for different phenolic compounds. In combination with the Freundlich exponent, n(F), estimates of the adsorption capacity at any other reference point can then be obtained. Analysis of the experimental results also indicates a need to distinguish between two regimes of adsorption, characterized by an adsorption energy, E(ads), greater than or less than a critical value, E(ca). When E(ads) > E(ca), the shape of the adsorption isotherm is determined by solute-solid interactions. On the other hand, when E(ads) < E(ca), solute-solution interactions become more important. 相似文献
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以计量置换吸附理论(SDT A)为基础,从理论上推导出计量吸附模型中表征溶质对固定相亲合势大小的参数βa值与流动相中强置换剂浓度的对数呈线性关系。计量置换模型中的参数n和q(n和q分别代表1摩尔溶剂化溶质被吸附时,从吸附剂表面和从溶质分子表面所释放出的溶剂的物质的量)是计量置换参数Z值的分量,是两个非常有用的参数,可以从这个定量关系中直接获得。推导出的方程用苯的衍生物进行了实验验证,获得了较满意的结果。将这种方法计算得到的分量值与SDT A与计量置换保留模型(SDT R)相结合的方法得到的分量值进行了比较。 相似文献
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Zhi-Chang Wang 《Journal of solution chemistry》2018,47(3):484-497
Zdanovskii’s rule is the simplest isopiestic molality relation of mixed electrolyte aqueous solutions and the McKay–Perring equation is a differentio-integral equation particularly suitable for calculating solute activity coefficients from isopiestic measurements. However, they have two unsolved problems, which have puzzled solution chemists for several decades: (1) Zdanovskii’s rule has been verified by precise isopiestic measurements. But, several scientists suggested that the rule contradicts the Debye–Hückel limiting law for extremely dilute unsymmetrical mixtures. (2) In the McKay–Perring equation, a solute activity coefficient is multiplied by a solute composition variable. Different scientists have suggested that the composition variable may be the total ionic strength, common ion concentration, total ionic concentration, or an additive function with arbitrary proportionality constants. But, the different choices of the composition variable may lead to different activity coefficient results. Here, I derive a modified McKay–Perring equation in which the composition variable has the exclusive physical meaning of total ionic concentration for mixed electrolyte solutions (or of total solute particle concentration for the mixed solutions containing nonelectrolyte solutes). I also demonstrate that Zdanovskii’s rule is consistent with the Debye–Hückel limiting law for extremely dilute unsymmetrical mixtures. I derive two particular solutions of the modified McKay–Perring equation: one for the systems obeying Zdanovskii’s rule and another for the systems obeying a limiting linear concentration rule. These theoretical results have been verified with literature experiments and model calculations. 相似文献