Logarithmic diagrams as an aid in complexometric titrations where 1:2 or 2:1 as well as 1:1 metal-ligand complexes are regarded as principal species

Logarithmic diagrams have earlier been used for theoretical treatment of complexometric titrations where only the 1:1 complex is formed in the main reaction between a metal ion M and a ligand L. This approach has now been extended to include titrations where 1:2 and 2:1 complexes are also formed. Four different types of diagram can be drawn. These diagrams can be used to determine pM (or pL) at the equivalence point, the titration ratio at different pM (or pL) values and the titration error. One of these diagrams is easy to construct and use. The method also has the advantage that it can directly indicate whether the titration is best performed with 1:1 or 2:1 (1:2) stoichiometry. Two typical examples, namely the titration of a manganese solution with triethylenetetraminehexa-acetic acid and of a copper solution with pyridine-2,6-dicarboxylic acid, are discussed. The two titrations proceed with the formation of the complexes Mn(2)L (2: 1) and CuL(2) (1:2) respectively, in addition to the 1:1 complex in each instance.     

Study of Cd2+ complexation by the glutathione fragments Cys-Gly (CG) and gamma-Glu-Cys (gamma-EC) by differential pulse polarography

A differential pulse polarographic study of the Cd2+/gamma-Glu-Cys and Cd2+/Cys-Gly systems assisted by the alternating least-squares multivariate curve resolution (MCR-ALS) method was carried out to obtain a better understanding of the different metal affinities of the complexation sites on glutathione (GSH). The simultaneous analysis of the titration of peptide with metal and of metal with peptide allowed the resolution of the Cd2+/Cys-Gly system, whereas in the analysis of the Cd2+/gamma-Glu-Cys system the analysis of a single titration experiment was sufficient. The analysis of the shape of the resulting pure voltammograms and concentration profiles of the resolved components suggested the presence of two different types of bound Cd2+ in the two systems considered, that could be attributed to Cd2+ bound to one or two sulfur atoms to form complexes of stoichiometry 1:1 and 1:2. respectively.     

A examination of the EDTA titration of manganese(II) taking into consideration formation of 1:1 and 1:2 complexes with Eriochrome Black T indicator

In the EDTA titration of manganese(II) with Eriochrome Black T as indicator, the effect of formation of 1:1 and 1:2 manganese(II)—indicator complexes must be taken into consideration. The titration error can be reduced to less than 0.1%. For comparison purpose the titration of zinc(II) has also been studied.     

Complexation of Hg2+ with α‐Lipoic and Dihydrolipoic Acids: Study by Differential Pulse Voltammetry on Rotating Au‐Disk Electrode and ESI‐MS

The complexation of the natural antioxidants α‐lipoic acid (ALA) and its reduced form dihydrolipoic acid (DHLA) with Hg²⁺ was investigated by a recently proposed differential pulse voltammetric (DPV) method using the rotating Au‐disk electrode. Complexation processes are proposed from the multivariate curve resolution by alternating least squares (MCR‐ALS) analysis of DPV titration data. Main complexes were both 1 : 1 Hg : ALA and Hg : DHLA, although the formation of 1 : 2 complexes can be also deduced. ALA and DHLA show different Hg²⁺‐binding patterns at different pH. Voltammetric findings are completed with the data obtained by electrospray ionization mass‐spectrometry (ESI‐MS), especially in negative mode.     

用小波变换确定电位滴定终点

将小波变换在信号和图象处理过程中边缘检取的思想方法引入到化学中，以确定电位滴定的终点，能直接对测量的数据进行处理，不会引入人为的误差因素。计算精度可达实验精度的下限，且处理结果的判断非常简便，用本方法对实验数据进行处理，获得满意的结果。     

Selective determination of thiamine (vitamin B(1)) in pharmaceutical preparations by direct potentiometric argentometric titration with use of the silver-silver sulphide ion-selective electrode

A simple and selective argentometric titration method is described for determination of thiamine (vitamin B(1)), based on direct potentiometric titration in alkaline media (0.5M) in which a chemical transformation takes place, creating two acidic groups, the protons of which are replaceable by silver ions. The acidimetric and argentometric potentiometric titration curves display two consecutive potential breaks specific for thiamine. The second break is reproducible and corresponds to a 2:1 reaction ratio of silver to thiamine. No interference is caused by other vitamins, active ingredients and inactive excipients normally present in multivitamin preparations. The results obtained for determination of thiamine in pure powders, pharmaceutical tablets and ampoules showed an average recovery of 98.2% of the nominal values and a mean standard deviation of 0.5%, and agreed fairly well with data obtained by the British Pharmacopoeia procedure.     

Stability constants: comparative study of fitting methods. Determination of second-order complexation constants by (23)Na and (7)Li NMR chemical shift titration

NMR chemical shift titration has been widely used as a method for the determination of stability constants. Systems involving metal-ligand complexation have been investigated using a number of methodologies. There are significant differences in the values reported for stability constants obtained by different experimental methods, such as calorimetry and ion selective electrode (ISE) titrations; nor has NMR chemical shift titration always yielded consistent results. Different researchers have obtained different results for the same system with results differing by as much as an order of magnitude. The chemical shift data are generally plotted against the concentration ratio of the metal and ligand for a set of solutions. A nonlinear least squares fitting method using an analytical solution of the cubic equation for the equilibrium concentration of the free ligand is used in this study and compared with methods used in the literature. Second-order association constants for the LiClO(4):12-crown-4 system in acetonitrile and the NaClO(4):12-crown-4 system in methanol are reported. Formation of both 1:1 and 1:2 metal-ligand complexes are considered. The LiClO(4):12-crown-4 acetonitrile system had been investigated previously by NMR titration but only 1:1 complexation was considered in that study. This study provides convincing evidence that both 1:1 and 1:2 complexes are important, at least, in the lithium system. A Monte Carlo investigation of the propagation of errors from the chemical shifts to the stability constants shows that the choice of data analysis methods may, in part, contribute to discrepancies and that the nonlinear nature of the model can dramatically affect the error limits on the stability constants.     

Extractive indicators in complex-formation titrations: theory and practice

The use of conditional constants to predict the optimum conditions for titration in several complex-formation titrations, in which the end-point is detected by the formation of a coloured extractable complex, is demonstrated. The predictions have been tested by experiment. 2-(2-Pyridylazo)-1-naphthol is shown to be a useful extractive indicator for the copper-EDTA titration; dimethylglyoxine is not recommended as an extractive indicator for the nickel-EDTA titration; the titration of fluoride with aluminium, using 8-hydroxy-quinoline as an extractive indicator, is shown to be undesirable theoretically and experimentally.     

利用滴定曲线方程和Origin精确绘制滴定曲线*

滴定曲线是滴定分析原理的重要内容。它显示了滴定过程中平衡体系性质的变化,可以获知化学计量点和滴定突跃信息,从而指导准确滴定判别或指示剂的选择。滴定曲线方程是滴定过程中体系的某种性质X(例pH)与滴定分数a(或滴定剂体积V)的关系方程,解析方程可获得函数X=f(a)的表达式。对一些较复杂的体系,推导函数X=f(a)较困难,但多数情况下反函数a=g(X)的推导更容易,表达式也更简洁。本文对酸碱、配位、氧化还原和沉淀滴定曲线方程进行了系统总结,并对不同情况下的函数X=f(a)或反函数a=g(X)进行了推导,拓展了教材内容。根据函数关系,在Origin中利用其函数绘图功能可直接绘制出滴定曲线,不用先生成数据点再绘图,方便快捷。用反函数绘图时增加数据点即可获得高精度的滴定曲线,可直接从滴定曲线上查找化学计量点和滴定突跃信息。     

热动力学的滴定量热发研究 I.一级反应的热动力学

用滴定量热法分别建立了滴定期和滴反应期一级反应热动力学的数学模型，根据这两种模型，均可由一次实验的滴定量热曲线同时解析出一级反应的速率常数和摩尔反应焓。用滴定量热法研究了去离子水溶剂中乙酸乙酯皂化反应的热动力学，实验结果验证了本文用滴定量热法研究一级反应热动力学的适用性。     

Constantes de formation des complexes de stoechiometrie 1:1 et 1:2 ainsi que des complexes mixtes formes entre le plutonium(III) et divers acides amino-polyacetiques

Determination of the formation constants of 1:1, 1:2 and mixed complexes between plutonium(III) and various aminopolyacetic acids The complexation of plutonium(III) with various aminopolyacetic acids is investigated by potentiometric titration at 25°C and at a constant ionic strength of 1 (KC1). The formation constants of the 1:1 complexes are reported for NTA, HEDTA, EDTA, DCTA and DTPA. The formation constants of the 1:2 complexes with NTA, HEDTA and EDTA as well as those of the mixed complexes formed between Pu(HEDTA) or Pu(EDTA) and NTA, IMDA or glycine are also reported. Several pK values of the 1:1, 1:2 and mixed complexes have been determined. These results are discussed within the framework of those obtained previously with the lanthanides.     

High-performance anion-exchange chromatographic study of desialylated human alpha 1-acid glycoprotein variants. Development of a fractionation method for the protein slow variants

The three main desialylated variants (F1, S and A) of human alpha 1-acid glycoprotein (AAG), a serum acute-phase reactant, were analysed by high-performance anion-exchange chromatography in order to determine their optimum separation conditions. The analysis consisted of three steps, as follows: (1) A desialylated commercial AAG was separated into one "fast"- and one "slow"-migrating fraction by preparative isoelectrofocusing. The "fast" and "slow" fractions were shown to contain the F1 variant and a mixture of the S and A variants, respectively. (2) The pH titration curves of these two fractions were then measured by strong anion-exchange chromatography with several buffer systems of increasing pH. From the data obtained, it was not possible to select the optimum conditions to separate the "fast" variant F1 from the "slow" variants A and S. However, the S and A variants were shown to ionize very differently. (3) The specific fractionation of the S and A variants was therefore carried out by anion-exchange chromatography under operating conditions based on the data obtained from the study of their pH titration curves. This was performed both with the "slow"-migrating fraction obtained by preparative isoelectrofocusing of commercial AAG and with an AAG (containing only variants S and A) purified from an individual serum on immobilized Cibacron Blue F3G-A. Identification of the fractionated proteins was achieved by analytical isoelectrofocusing.     

Synthesis of a fluorescein–porphyrin hybrid and its supramolecular self-assembly with amino-porphyrinatocopper(II) by hydrogen bonding

A fluorescein–porphyrin hybrid (Fl-PTPP) has been synthesized and characterized by UV/Vis, IR, ¹H NMR, ES-MS and elemental analysis. The supramolecular self-assembly of Fl-PTPP with the copper(II) complex of 5-(p-amino-phenyl)-10,15,20-triphenylporphyrin, (CuAPTPP), by hydoxyl-amino type hydrogen bonding was studied using vapor pressure osmometry (VPO) measurements, ES-MS, UV/Vis, ¹H NMR and fluorescence spectroscopic titration. The data indicate formation of a (Fl-PTPP)–CuAPTPP supramolecular complex. Fluorescence strengthening character was observed in a spectroscopic titration experiment for the Fl-PTPP/CuAPTPP system. The association constant of the supramolecular complex was calculated from the fluorescence titration data, and found to be less than that of a carboxyl–carboxyl type hydrogen-bonding system.     

Capillary electrophoretic separation of binaphthyl enantiomers with two polymeric chiral surfactants: 1H-nuclear magnetic resonance and fluorescence spectroscopy study

The use of the water-soluble polymeric chiral surfactants (PCS), sodium N-undecanoyl-L-valinate (poly-L-SUV) and sodium undecanoyl-L-isoleucinate (poly-L-SUI) as buffer additives in electrokinetic chromatography (EKC) afforded the separation of racemic mixtures of 2,2'-dihydroxy-1,1'-binaphthyl (BOH) and 1,1'-binaphthyl-2,2'-diyl hydrogen phosphate (BNP). The apparent binding constants of the PCS to the enantiomers of BNP and BOH were obtained through 1H-nuclear magnetic resonance (1H-NMR) titrations and fluorescence spectroscopy, respectively. The 1H-NMR titration studies show that the BNP enantiomers are localized in the hydrophobic micellar pockets of PCS and form complexes of a 1:1 stoichiometry. The binding constants of PCS of BOH were determined from a Benesi-Hildebrand treatment of the fluorescence data. The EKC data corroborate those of the binding constants, supporting the formation of inclusion complexes. A model rationalizing the chiral discrimination of the enantiomers of BNP is proposed based on the intermolecular interactions observed in 1H-NMR data.     

Chlorobenzylidine-herring sperm DNA interaction: binding mode and thermodynamic studies

The interaction of chlorobenzylidine with herring sperm DNA has been investigated by fluorescence, absorption, DNA melting experiment and differential scanning calorimetry (DSC). When bound to DNA, chlorobenzylidine shows hypochromism and red shift in absorption spectra, fluorescence quenching and polarization increasing in fluorescence spectra and increasing in DNA melting temperature. These spectral characteristics strongly support intercalation of chlorobenzylidine into herring sperm DNA. Scatchard plots constructed from fluorescence titration data give a binding constant of 3.2 x 10(4) M(-1) and a binding site size of six base pairs per bound drug molecule. The intercalative interaction is exothermic with a van't Hoff enthalpy of -30.6 kJ mol(-1). This result is obtained from DSC experiment. In addition, DeltaG degrees =-28.5 kJ mol(-1), and DeltaS degrees =-7.1 J mol(-1) K(-1). These results show that the binding of chlorobenzylidine to herring sperm DNA is exothermic.     

Theory of the surface acoustic wave/impedance sensor system and its application to the end-point determination in titrimetry

Theory and characteristics of the surface acoustic wave (SAW)/impedance sensor system in electrolyte solution are reported. This kind of sensor was constructed by a 62-MHz SAW resonator and a pair of conductive electrodes in series. By using the circuit network analysis theory, two oscillation equations were derived and used to explain the frequency-shift response to solution conductance. Results showed that the sensor possesses high sensitivity to the solution conductivity and can be applied to conductivity measurements in solution. Its sensitivity and accuracy could be improved in the presence of a large amount of unreacting foreign electrolytes. The sensor was successfully applied to four types of titration (acid-base, precipitation, oxidation-reduction and compleximetric titration) by monitoring the frequency-shift response. Factors influencing the frequencimetric titration curve were also investigated. Analytes at levels down to 1 × 10⁻⁵ M could be determined by the proposed titration technique. The total acidity in several food samples was determined and the results were consistent with those obtained by conventional methods.     

滴定量热法研究连串一级反应热动力学

本文用滴定量热法分别建立了滴定期和停滴反应期1-1级连串反应热动力学的数学模型。根据这两种模型,由非线性最小二乘法原理直接拟合单次实验结果可同时求得1-1级连串反应的速率常数（ k ₁和 k ₂）和摩尔反应焓。并用滴定量热法研究了丁二酸二乙酯皂化反应的热动力学,实验结果验证了两种数学模型的正确性。     

Simulation of titration curves indicated with two indicator electrodes (biamperometry)

A rigorous method to simulate titration curves with indication using two indicator electrodes (biamperometry) is presented. Computer simulations can be carried out for reversible as well as for irreversible systems. The different parameters like the area of the individual electrodes, applied potential difference, heterogeneous rate constant, and the kinetic parameter were varied and investigated as to their influence upon the shape of the titration curves. The theoretically derived effects match with the effects obtained by experiment. Considering the effects described here, it is possible to tailor the shape of the titration curve by the experimental conditions for specific applications in order to get an optimum shape at the end point of the titration.     

针对理论-实验教学相融合的微助教辅助实验教学实践——以滴定分析实验教学为例

为了促进滴定分析理论-实验教学的融合,在借鉴疫情期间线上教学模式经验的基础上,我们在滴定分析内容教学中实践了微助教辅助的实验课堂教学模式。该教学模式灵活机动,不受行政班级划分与理论实验教学先后顺序的制约,能够有效地提高实验课教学效果,促进理论-实验教学相互融合,提升教学质量。     

High frequency titrations involving chelation with ethylenediaminetetraacetic acid: Determination of uranyl ion

It has been shown that for the pH range of 3.5 to 4.0, ethylenediaminetetraacetic acid reacts with uranyl ion to form a stable salt. The reacting ratio was found to be 2 : 1 (metal to addendum) which is in contrast to the usual reacting ratio of 1 : 1 obtained with ethylenediaminetetraacetic acid and other heavy metals. The chelate obtained with uranyl ion is probably a pseudo salt.A high frequency titration employing tri-sodium ethylenediaminetetraacetate is suggested for the determination of uranyl ion.