混合电解质的电导测定

电导测定为研究离子与离子之间的缔合效应、离子与溶剂的相互作用及溶剂结构提供了一个有效手段 .目前 ,电解质水溶液、电解质非水溶剂体系的电导数据却很缺乏 ,而混合电解质体系的电导测定在理论及应用方面都很重要 .作为全面系统地考察金属氯化物的混合电解质的电导性质变化规律 ,前文已测定了 Na Cl- KCl- H2 O体系 [1] 、 Na Cl- Rb Cl- H2 O体系及 KCl- Rb Cl- H2 O体系的电导值 [2 ] ,本文用自行设计的电导池测定了 Ca Cl2 - H2 O,Ca Cl2 - Na Cl- H2 O,Ca Cl2 - KCl- H2 O体系在 2 98.1 5 K时的低浓度电导数据 ,探讨了…     

MeOH-H~2O-NaOAc体系(278.2~318.2K)的电导研究

本文测定了278.2~318.2K间的五个温度下七种浓度的NaOAc分别在10, 20,30, 40, 50, 60, 70, 80, 90及100%MeOH-H~2O体系中的摩尔电导Λ, 并应用FOS,Pitts, L-W, F-78等四个电导方程对实验数据进行了拟合处理, 得到了三个拟合参数Λ~O, K~Λ及R(或α)。最后, 对四个方程与实验的吻合程度, 温度、溶剂组成等对Λ~O、K~Λ的影响规律及溶质-溶剂相互作用进行了讨论。     

四丁基氟化铵在H2O-DMF中的电导研究

测量了298.15~328.15 K温度范围内四丁基氟化铵在20(wt)%~80(wt)%H2O/DMF混合溶液中的电导率,测得的电导率分别通过Kray-Bray方程和Shedlovsky方程分析,推导出了四丁基氟化铵在H2O-DMF混合溶液中的摩尔极限电导、缔合常数和离解常数,并计算出缔合反应的热力学参数(△Ga,△Ha,△Sa);同时探讨了温度和混合溶剂的组成对摩尔极限电导、缔合常数和热力学参数的影响。     

H2O-C2H5OH-MX(NaCl等)体系中离子缔合和活度

用桥式电路测定了H_2O-C_2H_5OH-NaCl体系的摩尔电导, 并用Lee-Wheaton模型回归出H_2O-C_2H_5OH-NaCl(KCl、CsCl、KBr)体系的离子缔合常数、极限摩尔电导和距离参数, 并求出缔合反应标准自由焓。结果表明离子缔合能力的顺序为Cs~+>K~+>Na~+, Cl~->Br~-, 此四种盐在乙醇中都形成溶剂分开型离子对。并用液上空间气相色谱法测定了水-乙醇-(NaCl、KCl、KBr)体系中溶剂的活度, 用改进的Pitzer-Li公式计算了此体系的活度系数, 计算时考虑了盐在低介电常数溶剂中的离子缔合, 结果表明这种处理是合适的。还表明离子缔合程度随着乙醇浓度上升而加大, 以及盐的存在对水呈盐溶效应而对乙醇呈盐析效应。     

电导法检测的过渡金属离子色谱

1980年,James提出了一种具有电导检测器的碱金属和碱土金属单柱阳离子色谱,这种色谱使用了一种特制的交换容量很小的阳离子交换树脂作固定相,很稀的硝酸或乙二胺溶液作流动相。由于巧妙地利用了淋洗离子的当量电导都远大于被淋洗的金属离子,因此在色谱图中,金属离子可以以     

强电解质混合溶剂体系的电导法分析

在生产和科研中经常需要同时测定强电解质浓度和混合溶剂的比例。本文在研究强电解质+水+醇三元溶液电导特性的基础上,建立了两参数经验性电导工作方程,将溶液电导率的测量与电导滴定相结合,可以方便准确地定出此类三元溶液的组成。     

羧酸离子在水中的水合数

本文从溶质分子在水中溶解时会发生水合作用的观点出发,重新审视了四种小分子羧酸在水溶液中的电导数据,解释了其离子迁移速率随羧酸溶液浓度的变化规律,并提出了一种简便方法来计算羧酸离子在水溶液中的离子水合数。     

PrOH-H2O混合溶剂中LiCl,NaCl的电导研究

本文设计并制作一套可搅拌U型电导池, 并用其测定了LiCl, NaCl在PrOH-H2O二元混合溶剂中的摩尔电导。应用Fuoss-Onsager电导方程关联得到Λ。, a°及Ka, 并据此探讨了LiCl, NaCl-PrOH-H2O的微观结构及相互作用。     

转化乳剂的离子电导和光电导研究

本文研究了AgBrCl转化乳剂的离子电导和光电导。随着乳剂中溴含量的增高,其离子电导也随之升高,而光电子寿命则降低。AgBrCl乳剂的离子电导主要取决于其组成;AgBrCl转化乳剂的光电子寿命主要受隙间银子浓度的影响,隙间银离子浓度越大,光电子寿命越短。     

JONES型电导池测量的LCR电桥等效电路选择

JONES电导池系统的交流阻抗由电极过程的相关阻抗和电极间溶液的电阻两部分组成,可用适当的等效电路模拟。采用LCR电桥测量JONES电导池中溶液的电阻时需要选择合适的等效电路为模型解析测量的交流阻抗。通过等效电路的分析发现,选择串联电路作为LCR电桥的解析等效电路测量JONES型电导池中溶液的电阻时引入的误差比并联电路小。     

Conductance behaviour of HCl in water-ethylene glycol, water-diethylene glycol and ethylene glycol-diethylene glycol mixtures

The conductance behaviour of HCl in water-ethylene glycol, water-diethylene glycol and ethylene glycol-diethylene glycol mixtures was investigated in the complete range of solvent compositions of 25°C by applying the three-parameter conductance equation. No appreciable association of the acid was observed in any of the mixed solvents. The large decrease ofΛ ₀ andΛ ₀ η ₀ of the acid in the early and end composition region of the mixed solvents has been attributed to the drastic structural changes brought about by the addition of the organic component in the aqueous solvent mixtures and by the addition of diethylene glycol in the case of ethylene glycol-diethylene glycol mixtures.     

高效毛细管电泳电导法快速检测复方维生素B片中的VB1、VB12、VB6和VC

采用高效毛细管电泳电导法同时分离、测定了复方维生素B片中的主要成分VB1, VB12,VB6和VC的含量.研究了运行缓冲溶液的酸度和浓度、电泳电压、进样时间等因素对电泳的影响.在优化的实验条件下40 mmol/L Tris -4 mmol/L H3BO3 (pH 8.0) 的缓冲溶液中加入0.30 mmol/L CTAB(溴化十六烷基三甲基铵),分离电压为15 kV,上述4组分在5 min内得到良好的分离.维生素B1,B12,B6和VC的线性范围分别为5.5～1.0 mg/mL; 15～1.5 mg/mL; 1.0～0.40 mg/mL和6.6～0.80 mg/mL; 检测限分别为0.80 μg/mL, 4.0 μg/mL, 0.50 μg/mL, 2.9 μg/mL; 5次测定峰高的相对标准偏差分别为2.2%, 1.6%, 3.9%, 2.8%.5次测定的平均回收率分别为99%, 94%, 100%, 97%.     

Characterization studies of some bi- and tetradentate bifunctionalSchiff base complexes with Co(II), Ni(II), and Cu(II)

Co(II), Ni(II) and Cu(II) complexes of some bifunctional arylidene-o-phenylenediamineSchiff bases have been prepared. Formation, stoichiometry and stability of the complexes have been tested in solution using electronic spectral measurements. Characterization of the complexes has been accomplished primarily by elemental analysis, molar conductance as well as electronic and IR spectral measurements. It is concluded that theo,o-hydroxy derivative (L ₁) acts as a bivalent ONNO tetradentate ligand while the molecules of the other derivatives (L ₂-L ₅) are coordinated to the metal ions as bidentate NN ligands. The Cu(II)-L ₁ complex is suggested to possess a tetrahedral geometry whereas the other complexes are suggested to exhibit a distarted octahedral geometry. The different bands observed in the electronic spectra of the complexes inDMF solutions have been assigned to the -*,L M CT and d-d electronic transitions.

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Untersuchungen zur Charakterisierung einiger zwei- und vierzähniger bifunktionellerSchiffbasen-Komplexe mit Co(II), Ni(II) und Cu(II)

Zusammenfassung Es wurden die Co(II)-, Ni(II)- und Cu(II)-Komplexe einiger bifunktioneller Aryliden-o-phenylendiamin-Schiffbasen hergestellt. Unter Verwendung elektronenspektroskopischer Methoden wurde die Bildung, Stöchiometrie und Stabilität der Komplexe in Lösung untersucht. Die Charakterisierung erfolgte mittels Elementaranalysen, Leitfähigkeitsmessungen und Elektronen- bzw. IR-Spektroskopie. Es wird darauf geschlossen, daß daso,o-HydroxyderivatL ₁ als bivalenter vierzähniger ONNO Ligand wirkt, während die anderen Derivate (L ₂-L ₅) als zweizähnige NN Liganden an die Metallionen koordiniert sind. Für den Cu(II)-L ₁ Komplex wird eine tetraedrische Geometrie vorgeschlagen, währenddessen die anderen Komplexe eine verzerrte octaedrische Geometrie aufweisen. Die in den Elektronenspektren der Komplexe inDMF-Lösung auftretenden Banden werden den -*,L M CT und d-d Elektronenübergängen zugeordnet.

     

Synthesis,identification and study of electrical conductivity of the doped poly aniline

Poly aniline and poly aniline doped with 2,5-dimethyl benzene sulfonic acid (PXSA), 4-hydroxy-m-benzene disulfonic acid (PDSA), 3-chloro-4-hydroxybenzene sulfonic acid (OCPSA) were prepared. The polymers are identified by FT-IR and UV–vis spectroscopy. The ionic conductivities of poly aniline and poly aniline doped with 2,5-dimethyl benzene sulfonic acid (PXSA), 4-hydroxy-m-benzene disulfonic acid (PDSA), 3-chloro-4-hydroxybenzene sulfonic acid (OCPSA) were studied as a function of weight of the dopant compounds. It is noted that an increase of the conductance of poly aniline by doping with OCPSA, and became equal to 0.001321 Ω^?1 for 1 g higher than the conductance for the poly aniline when it is doped with OCPSA.     

Electronic structure and conductance of large molecules and DNA

Using a new technique based on embedding in a local orbital formalism, the electronic structure and electron transmission properties of long biological molecules are calculated, in particular DNA. The electronic structure is found by adding one structural unit at a time to the molecule, and calculating an embedding potential for adding the next structural unit. At present, an extended Hückel scheme is used for the Hamiltonian. The transmission is also calculated within the embedding scheme, taking the molecule–metal contacts into account. The results for transmission depend greatly on the orbitals to which contact is made, and also on energy. The implications of these calculations for conductance are discussed.     

Prediction of the Conductance of Strong Electrolytes and the Calculation of the Ionization Constant of Weak Electrolytes in a Dilute Solution by a New Equation

In order to predict the conductance for dilute 1-1 valent electrolyte solutions,a new conductance equation was proposed based on the Onsager and Onsagar-Fuoss-Chen conductance equation.It has only one parameter A,which can be obtained directly from the data of ionic limiting molar conductivity Λ∞m,and its expression is very simple.The new equation has been verified by the experimental molar conductivities of some single strong electrolyte and mixed electrolyte solutions at 298.15 K reported in literatures.The results are in good agreement with the experimental data.Meanwhile the ionization constants of some weak electrolyte solutions were calculated by a modified equation of this new equation,and it was also found that the calculation results are in good agreement with the data in the literature.     

Review of the theory of electrolytic conductance

The Ostwald dilution law, based on the Arrhenius hypothesis of electrolytic dissociation, was the first theoretical formulation of the dependence of conductance on concentration. While it adequately described the conductance of weak electrolytes, it could not account for the observation by Kohlrausch that, at low concentrations, the equivalent conductance of strong electrolytes approached linearity inc ^1/2, the square root of concentration. Debye and Hückel (1923) assumed complete dissociation and calculated the theoretical behavior of rigid charged spheres moving in a continuum (the primitive model); the result was prediction of the Kohlrausch result. Onsager (1927) predicted the exact numerical value of the limiting slope for the vs.c ^1/2 curves. Bjerrum (1926) suggested association of ions to pairs which would not contribute to the long-range interionic effects considered by Debye and Hückel. Fuoss and Kraus (1933) corrected the Ostwald dilution law for the DHO square-root terms and obtained a (c) function which satisfactorily accounted for conductance curves which lay below the limiting tangent. Investigations of the effects of higher terms which had been neglected in the classical DHO treatment of the primitive model led to (c) functions which lay above the limiting tangent for completely dissociated electrolytes. By combining these higher-term equations with Bjerrum pairing, a generally useful conductance function was obtained (Fuoss-Hsia, 1957). In order to eliminate a number of inconsistencies between the properties of real systems and those of the primitive model, a new model (Fuoss, 1975) was proposed: Ion pairs are defined as those whose center-to-center distance lies in the rangearR, whereR is the diameter of the Gurney cosphere. Later (1977) the paired ions were divided into two categories: ions which have only solvent molecules as nearest neighbors, and ions which have one ion of opposite charge as a member of the inner shell. The latter contribute only to charging current.Presented at the Symposium on Electrolytes, University of Reading, September 13, 1977.     

Synthesis,characterization and biological studies of some Co(II), Ni(II) and Cu(II) complexes derived from indole-3-carboxaldehyde and glycylglycine as Schiff base ligand

The Schiff base ligand derived from indole-3-carboxaldehyde(indal) and glycylglycine(glygly) were synthesized and characterized by elemental analysis, IR, electronic spectrum, ¹H NMR and mass spectrum. Co(II), Ni(II) and Cu(II)–indal-glygly Schiff base complexes were synthesized and characterized by elemental analysis, molar conductance, IR, electronic spectra, magnetic measurements, ESR, electrochemical studies, TGA, DSC analysis, XRD and SEM. Conductance measurements indicate that the above complexes are 1:1 electrolytes. IR spectral data show that the ligand is tridentate and the binding sites are azomethine nitrogen, peptide nitrogen and carboxylato oxygen atoms. Electronic spectral measurements indicate tetrahedral geometry for Co(II) and Ni(II) complexes and square planar geometry for Cu(II) complex. Magnetic measurements show weak ferromagnetic behaviour for Co(II) and Ni(II) complexes and paramagnetic behaviour for Cu(II) complex. ESR spectral data shows the ionic link between metal and the Schiff base ligand. The metal complexes are found to be stabilized in the unusual oxidation states of the metal ion during electrolysis. Thermal analysis of the complex indicates that the decomposition takes place in three steps. IR and thermal studies indicate that the fourth position would be occupied by a water molecule in complexes. XRD shows that the complexes have the crystallite size of 31, 40 and 67 nm, respectively. The surface morphology of the complexes was studied by SEM. The antimicrobial activity of the ligand and its complexes were screened by Kirby Bayer Disc Diffusion method. DNA cleavage studies were performed for metal–Schiff base complexes in presence of hydrogen peroxide as oxidant.     

高效毛细管电泳-电导检测对四环素衍生物分离测定的研究

运用毛细管电泳-电导检测方法对4种四环素衍生物——土霉素(OTC)、金霉素(CTC)、强力霉素(DOC)和四环素(TC)的分离进行了研究。在3．5mmol/L三羟基氨基甲烷(Tris)-7．5mmol/L柠檬酸(Cit)pH4．0的运行缓冲液中，4种四环素衍生物在15min内获得完全分离。四环素衍生物的线性范围分别为5．0-500μg/mL OTC，3．6-420μg/mL CTC，4.5-470μg/mL DOC和2.5-400μg/mL TC。检测限(S／N＝3)分别为OTC2．0μg/mL，CTC 1．8μg／mL，DOC2．5μg/mL和TC1．0μg/mL。采用本法对实际样品强力霉素片中强力霉素和土霉素片中土霉素进行测定，回收率分别为97．2％和96.4％。     

The conductance of tetrabutylammonium lodide in toluene-acetonitrile mixtures at 15, 25, and 35°C

Association constants and the limiting molar conductances have been evaluated for Bu ₄ NI in acetonitrile-toluene mixtures at 15, 25 and 35°C. The experimental data were analyzed by means of the Lee-Wheaton equation. The thermodynamic parameters for the noncoulombic interactions were evaluated.