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本文测定了 KClO_3,NaNO_3,NaNO_2三种盐在甲醇-苯,甲醇-甲苯,甲醇-环己烷,甲醇-四氯化碳和甲醇-二氧六环以及 KCl 在甲醇-苯和甲醇-甲苯中的溶解度.它们与非电解质的摩尔分数x_(ne)的关系符合经验公式 log(S_0/S_m)=kX_(ne),其中 S_0和 S_m 分别为盐在纯甲醇和混合溶剂中的溶解度.同时,还得到了经验关系式 log(S_0/S_m)=k_φφ_(ne),其中φ_(ne)为第二组分的体积分数,k_φ称为第二介质常数.盐的溶剂化数近似地符合公式n_++n_-=(2log(S_0/S_m))/(logφ_p)计算得到各种盐的甲醇化数:KClO_3为7.1,NaNO_3为6.4,NaNO_2为5.8.从单纯溶剂化模型出发,应用改进的 Born 公式,推导出第二介质参数 k′的理论计算公式.计算的 k′和实验的 k_φ数值相近,k′对 k_φ有一定的预示. 相似文献
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在303.15 K、313.15 K、323.15 K、333.15 K温度下,0-6 MPa压力范围内测定了甲烷在水-叔丁醇混合溶剂中的溶解度.溶剂中叔丁醇的摩尔分数(x_(TBA))从0到1.结果表明,在温度和溶剂组成一定条件下,甲烷的溶解度随其分区的增加而增大,随x_(TBA)的增加,在富水区内,甲烷的溶解度变化较缓慢,当x_(TBA)超过某值时,甲烷的溶解度随x_(TBA)的增加而增大,并且幅度较大;在x_(TBA)约为0-0.045范围内,甲烷的溶解度随温度增加而减小,x_(TBA)约在0.045-0.15范围内,溶解度随温度增加而增加,x_(TBA)约在0.15~1.0范围内,溶解度随温度增加而减小.根据溶解度与温度和溶剂组成的关系可以推测,在303.15-333.15 K、0-6 MPa范围内,水-叙丁醇混合溶剂中仍存在笼合物结构.根据溶解度与温度、压力的关系讨论了甲烷在此混合溶剂中的亨利常数、偏摩尔体积、标准溶解自由能、标准溶解焓和标准溶解熵. 相似文献
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苯、甲苯、联苯在水-叔丁醇混合溶剂中的溶解度和疏水作用 总被引:1,自引:1,他引:0
在283.15,288.15,293.15,298.15 K温度下,测定了苯、甲苯、联苯在水-叔丁醇混合溶剂中的溶解度,其中混合溶剂中叔丁醇的物质的量分数分别为0.000,0.010,0.020,0.030,0.040,0.045,0.050,0.060,0.080,0.100. 以此为基础计算了苯、甲苯、联苯在不同温度和溶剂组成条件下的标准溶解Gibbs自由能和相关过程的疏水相互作用Gibbs自由能,并从微观上讨论了溶剂结构对溶解度和疏水作用的影响. 相似文献
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高压下气体在混合溶剂中溶解度的测定与研究,无论在理论研究或是实际应用方面均具有重要的意义。但由于进行这类研究,特别是在升温升压下,费时,昂贵和有一定难度,目前这方面的数据十分缺乏。作为本实验室研究系列之一部份,本文将报导文献中尚未见发表的氮气在正庚烷-正辛烷混合溶剂中的溶解度研究结果。实验部份1.试剂氮气纯度99.999%,由北京氧气厂提供;正庚烷,正辛烷由北京化工厂产分析纯试剂,本实验室又进一步精馏纯化。纯化后的试剂用气相色谱分析其纯度高于99.4%.混合溶剂的组成用重量法配制。 相似文献
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高压下氮气在正庚烷-正辛烷混合溶剂中的溶解度研究 总被引:1,自引:0,他引:1
Solubilities of nitrogen in binary mixtures of n-octane and n-heptane have been measured at temperatures from 20 to 70 ℃ and pressures up to 130 atm using a precision gas-liquid solubility apparatus. Experimental results can be expressed by the following equation Inx_(N_2)=A+BP_(N_2)+CP_(N_2)~2+DInP From the results obtained, the partial molar volume of dissolved nitrogen and the Henry's Law constants have also been calculated. 相似文献
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电解质-非电解质混合溶液活度系数的关联及溶解度的推算-(NH~2)~2CO-NaCl-NH~4Cl-H~2O体系的液固平衡热力学 总被引:3,自引:0,他引:3
在浓电解质和非电解质溶液的各种热力学模型基础上,提出了三元,四元溶液活度系数的关联式和溶解度计算方法.只需要少量实验数据即可求出相互作用参数,用此法可以计算在某一未饱和组分浓度下的饱和组分浓度,计算结果和实验相符. 相似文献
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电解质-非电解质混合溶液活度系数的关联及溶解的推算 II:NH3-NaCl-Na2SO4-H2O体系的液固平衡热力学 总被引:1,自引:0,他引:1
由于在研究的体系中, Na2SO4是非对称电解质, 且能生成水合盐, 故推导了由非对称型电解质与非电解质所构成的混合溶液的各组分的活度系数关联通式, 并在此基础上讨论了水合盐液固平衡的计算方法. 相似文献
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The solubilities of potassium fluoride, chloride, and bromide in acetonitrile, N,N-dimethylformamide, and dimethylsulfoxide and in binary mixtures of these solvents were determined at 25°C. The standard molar Gibbs free energies of solution, solnG°, in the neat solvents were related to the polarizabilities and basicities of the anions and the dipole moments and acidities of the solvents. The values of solnG° in the mixtures were fitted by expressions from the quasi-lattice quasi-chemical theory. The mean number of each kind of solvent in the nearest environment of the ions was obtained from these results. 相似文献
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研究了在含不同浓度电子清除剂CCL_4或正穴清除剂吡啶的苯溶液和环己烷溶液中o-Ps强度的变化。结果表明,环己烷中电子和正离子的迁移率是很高的,苯中的迁移率也较高,但比环己烷中的小些。由我们导出的有关正穴清除剂使o-Ps强度增加的关系式表明,o-Ps强度的增强或抑制是电子清除和正穴清除这两个过程竞争的结果。 相似文献
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现场扫描隧道显微镜研究有机相中的蛋白质结构 总被引:1,自引:0,他引:1
本文用现场扫描隧道显微镜(STM)研究了血红蛋白(Hb)分子在二类不同性质的有机溶剂中的结构变化。结果表明: 在疏水性有机溶剂CCl4中Hb分子结构几乎与其在水溶液中的结构一样, 保持天然的结构; 而在亲水性有机溶剂DMF中,组成Hb分子的两个二聚体分离, 肽链部分舒展, 表明其二、三级结构和四级结构遭到不同程度的破坏。 相似文献
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间对二氯苯在盐水溶液中活度系数的研究 总被引:1,自引:0,他引:1
本文用紫外可见分光度法测定了25℃下间位和对位二氯苯在NaF,NaCI,KBr,Na~2CO~3,K~2So~4,Et~4NBr水溶液中的活度系数,Logf-c~5关系符合Setschenow 盐效应经验公式,盐效应次序为,Na~2CO~3>K~2So~4>NaF>NaCi>NaBr>Et~4NBr. 通过比较发现:二氯苯的偶极矩对盐效应几乎没有影响,本文选取Debye-Mcaulay( DMT)和Conway-Desnoyers-smith(CDST)静电作用理论,定表标粒子理论(SPT)及改进前后的内压力理论IPT和XIPT),计算出理论值,与实验值进行比较, 证实的内压力理论计算值更接近实际. 相似文献
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The enthalpies of solution of uracil and its alkylated derivatives in water, methanol, N,N-dimethylformamide (DMF) and water+DMF mixtures were measured at 25°C. The enthalpies of solvation were determined. The enthalpies of cavity formation, corresponding to the enthalpies of solvent-solvent interactions were calculated and the enthalpies of solute-solvent interactions were obtained. The presence of the alkyl groups was found to have different effects on the enthalpy of interaction depending on the position and size of the substitution. The effect of alkylation at the nonpolar side of the uracil ring was found to arise mostly from the enhancement of the van der Waals interactions. The alkyl substitutions at the polar side resulted also in the removal of the solvent molecules interacting specifically with the polar groups of uracil. The enthalpy of those specific interactions was determined and found to be stronger in methanol and DMF than in water. Enthalpies of solvation in the binary water+DMF solvent were found to depend in a nonlinear way on the solvent composition. The nonlinearities in the water-rich region were found to arise from the decay of the hydrophobic hydration of the solutes with the increasing DMF content. The substitution of two methyl groups caused the uracil molecule to bahave as a predominantly hydrophobic solute. The nonlinearities in the DMF-rich region were found only for those solutes which can form hydrogen bonds with DMF. 相似文献
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A. A. Chernenko 《Russian Journal of Electrochemistry》2007,43(3):251-260
A “solvionic” model of a multicomponent electrochemical system (mixed electrolyte) is considered. An ion in the solution is considered as a point charge rigidly fixed inside its solvation shell. The corresponding equations for the diffuse layer on an ideally polarizable electrode are derived, and an effective method of their numerical solution is formulated. The calculations are performed in order to follow the changes in the diffuse layer structure with variations in the electrode charge and electrolyte composition. Far from the zerocharge potential of solution, the dependences of distributions of solution components over the diffuse layer on the electrode charge radically differ from those within the classic Gouy-Chapman theory. Analytical equations (asymptotics at large electrode charges) for concentrations of solvated ions in the plane of their maximum approach and for their “surface excesses” (diffuse adsorption) are determined. Results of numerical calculations for a 0.2 M LiCl + 0.05 M BaCl2 solution are plotted. 相似文献