The thermodynamic dissociation constant of naphazoline by the regression analysis of potentiometric data

The mixed dissociation constant of naphazoline is determined at various ionic strengths I [mol dm⁻³] in the range of 0.01 to 0.26 and at temperatures of 25°C and 37°C using ESAB and HYPERQUAD regression analysis of the potentiometric titration data. A strategy of efficient experimentation is proposed in a protonation constant determination, followed by a computational strategy for the chemical model with a protonation constant determination. Two group parameters, L ₀ and H _T were ill-conditioned in the model and their determination is therefore uncertain. These group parameters, L ₀ and H _T, can significantly influence a systematic error in the estimated common parameter pK_a and they always should be refined together with pK _a. The thermodynamic dissociation constant pK _a^T was estimated by nonlinear regression of {pK _a, I} data at 25°C and 37°C: for naphazoline pK _al^T = 10.41(1) and 10.13(2). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.      

Thermodynamic dissociation constants of risedronate using spectrophotometric and potentiometric pH-titration

Risedronate inhibits bone resorption in diseases like osteoporosis, Paget’s disease, tumor bone diseases or the malfunction of phosphocalcium metabolism. The acid-base properties of risedronate in an aqueous solution have been studied in a pH range from 2 to 12 and can be described in terms of four dissociation steps: pK _a,2, pK _a,4, pK _a,5 (related to the dissociation of POH groups) and pK _a,3 related to the dissociation of protonated amino group NH₃ ⁺. The mixed dissociation constants were determined at different ionic strengths I = 0.02 to 0.20 mol dm⁻³ KCl and of 25°C and 37°C using pH-spectrophotometric and pH-potentiometric titration methods. Determination of group parameters L ₀, H _T might lead to false estimates of common parameters p K _a;therefore, the computational strategy employed is important. A comparison between the two programs ESAB and HYPERQUAD demonstrated that the ESAB program provides a better fit of potentiometric titration curve. The thermodynamic dissociation constants pK _a^T were estimated by a nonlinear regression of (pK _a, I) data and a Debye-Hückel equation at 25°C and 37°C, pK _a,2^T = 2.37(1) and 2.44(1), pK _a,3^T = 6.29(3) and 6.26(1), pK _a,4^T = 7.48(1) and 7.46(2) and pK _a,5^T = 9.31(7) and 8.70(3) at 25°C and 37°C using pH-spectroscopic data and pK _a,2^T = 2.48(3) and 2.43(1), pK _a,3^T= 6.12(2) and 6.10(2), pK _a,4^T = 7.25(2) and 7.23(1) and pK _a,5^T = 12.04(5) and 11.81(2) at 25°C and 37°C. The ascertained estimates of three dissociation constants pK _a,3, pK _a,4, pK _a,5 are in agreement with the predicted values obtained using PALLAS      

Simultaneous determination of equivalence volumes and acid dissociation constants from potentiometric titration data

New iterative methods for analysis of potentiometric titration data of (a) mixtures of weak monoprotic acids with their conjugate bases, (b) solutions of polyprotic (di- and triprotic) acids, and (c) mixtures of two diprotic acids are presented. These methods, using data exclusively resulting from the acidic region of the titration curve permits the accurate determination of the analytical concentration of one or more acids even if the titration is stopped well before the end point of the titration. For the titration of a solution containing a conjugate acid/base pair, the proposed procedure enables the extraction of the initial composition of the mixture, as well as the dissociation constant of the concerned acid. Thus, it is possible by this type of analysis to distinguish whether a weak acid has been contaminated by a strong base and define the extent of the contamination. On the other hand, for the titration of polyprotic acids, the proposed approach enables the extraction of the accurate values of the equivalence volume and the dissociation constants K(i) even when the ionization stages overlap. Finally, for the titration of a mixture of two diprotic acids the proposed procedure enables the determination of the composition of the mixture even if the sum of the concentrations of the acids is not known. This method can be used in the analysis of solutions containing two diastereoisomeric forms of a weak diprotic acid. The test of the proposed procedures by means of ideal and Monte Carlo simulated data revealed that these methods are fairly applicable even when the titration data are considerably obscured by 'noise' or contain an important systematic error. The proposed procedures were also successfully applied to experimental titration data.     

Critical comparison of evaluation methods of potentiometric titration data using a microcomputer-controlled automatic potentiometric titration system

A microcomputer-controlled automatic potentiometric titrator withP controlled intelligent auto-sampler has been built for serial analysis. Controlling and evaluating programs have also been written. In order to use the most powerful evaluating method, a comparison was made between the methods. The data of the titration curves were obtained by the implicit relation characterizing the curve. The different evaluating methods were tested by using these data. The effects of random errors stemming from measurements were also investigated. The methods used were: two point differentiating formula, differentiation of interpolating and smoothing spline functions, the Gran method, and implicit regression with the Gauss-Newton-Marquardt method. Regression is outstanding among the methods, but it needs much more computing time compared with others. The second-best method is the differentiation with smoothing spline function with end point determination based on finding the sign reversal of the second derivative. This method is much faster than regression.     

用紫外分光光度法和电位滴定法测定几种植物激素的电离常数

分别采用紫外分光光度法和电位滴定法测定了脱落酸、3-吲哚乙酸、赤霉素、水杨酸等几种植物激素的电离常数,对比分析了两种测试方法的原理、测试步骤和数据处理方法.结果表明,采用两种方法测定的四种样品的电离常数与文献报道值一致,且测量结果的重现性较好;这表明紫外分光光度法和电位滴定法可方便地用于测定有机化合物的电离常数.     

Determination of EDTA by catalytic amperometric and catalytic potentiometric titration at a small constant current

Summary Amperometric and potentiometric methods at a small constant current were developed to follow the course of catalytic titrations. In ammoniacal medium EDTA was determined by titration with 0.1 M copper(II) chloride in the presence of hydrogen peroxide as the indicator. Amounts of 42.26–126.87 mg of EDTA were determined with a maximal average deviation of 0.55 %. The results obtained are in good agreement with those of comparable methods.

---

Bestimmung von ÄDTA mit Hilfe der katalytischen amperometrischen und der katalytischen potentiometrischen Titration bei kleinem konstantem Strom

Zusammenfassung Die amperometrische und die potentiometrische Methode bei kleinem konstantem Strom wurden für die Verfolgung katalytischer Titrationen ausgearbeitet. ÄDTA wurde in Ammoniakmedium mit 0,1 M Kupfer(II)-chlorid in Anwesenheit von Wasserstoffperoxid als Indicator titriert. Mengen von 42,26–126,87 mg ÄDTA wurden mit einer mittleren Abweichung von 0,55% bestimmt. Die Ergebnisse stimmen gut mit denen vergleichbarer Methoden überein.

The authors thank the SIZ for researchs of SAP Vojvodina for the partial financial support of the present work.     

Determination of uranyl ion by potentiometric titration using an uranyl-selective electrode

Summary A potentiometric titration of uranyl ion is described using an uranyl selective electrode based on a membrane containing a complex of UO₂-bis[di-4-(1,1,3,3-tetra-methylbutyl)phenyl phosphate] as an ion-exchanger and tritolyl phosphate as a solvent mediator. The titrations were carried out with various titrants: sodium hydroxide, potassium fluoride and sodium salts of acetate, oxalate and citrate. The equivalence points were determined by Gran's method. Good results were obtained by using sodium oxalate as a titrant for the determination of uranium in several samples of ammonium diuranate. The results were quite comparable with those obtained by X-ray fluorescence spectrometry.     

Determination of the total acidity in soft drinks using potentiometric sequential injection titration

A potentiometric SI titration system for the determination of total acidity in soft drinks is proposed. The concept is based on the aspiration of the acid soft drink sample between two base zones into a holding coil with the volume of the first base zone twice to that of the second one and channelled by flow reversal through a reaction coil to a potentiometric sensor. A solution of 0.1 mol l⁻¹ sodium chloride is used as ionic strength adjustment buffer in the carrier stream. The system has been applied to the analysis of some South African soft drinks having a total acidity level of about 0.2–0.3% (w/v). The method has a sample frequency of 45 samples per h with a linear range of 0.1 and 0.6% (w/v). It is easy to use, fully computerised, and gives the results that are comparable to both automated batch titration and manual titration.     

Determination of dissociation constants for coordination compounds of Cr(III) and Co(III) using potentiometric and spectrophotometric methods

The acid–base properties of analogous complex ions of chromium(III) and cobalt(III) in aqueous solution have been studied. The equilibrium constants for all metal complexes were determined by using potentiometric and spectrophotometric titration methods. First, dissociation constants for the studied complexes of Cr(III) and Co(III) were determined by means of the potentiometric titration method and using the STOICHIO computer programme. Then, pH-spectrophotometric titrations were performed and the OriginPro 7.5 computer programme was used to calculate the same constants. The measurements using both methods were carried out under the same conditions of temperature, T = 298.15 K, and over the same pH range 2.00–10.00, respectively. It turned out that the two methods used enabled us to obtain acidity constants in very good agreement.     

Statistical adjustment of parameters for potentiometric titration data

The paper deals with the statistical problem of adjusting parameters to the experimental data from potentiometric titrations. The parameters to be refined are, first, the value of the stability constant of the titration reaction, and, second, the equivalence volume. The paper discusses the selection of the error variable and the need for weighting in the optimization procedure. The case where both parameters are refined at the same time is also considered. Special reference is made to linearized titration curves for the determination of the equivalence volume.     

Gran电位滴定法测定乳酸环丙沙星

介绍了乳酸环丙沙星测定的Gran电位滴定法。采用Gran线性函数进行电位滴定,经图解外推或线性回归处理求出计量点,可直接用于测定乳酸环丙沙星原料药的含量。该法用于多批原料药的测定,结果与药典法基本一致。     

The thermodynamic dissociation constants of methotrexate by the nonlinear regression and factor analysis of multiwavelength spectrophotometric pH-titration data

The mixed dissociation constants of methotrexate — chemically (2S)-2-[(4-{[(2,4-diamino-7,8-dihydropteridin-6-yl)methyl] (methyl)amino}phenyl)formamido]pentanedioic acid (the cas number 59-05-2) at various ionic strengths I of range 0.01–0.4, and at temperatures of 25°C and 37°C, were determined with the use of two different multiwavelength and multivariate treatments of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis according to a general rule of first, determining the number of components, and then calculating the spectral responses and concentrations of the components. Concurrently, the experimental determination of the thermodynamic dissociation constants was in agreement with its computational prediction of the PALLAS programme based on knowledge of the chemical structures of the drug. The factor analysis in the INDICES programme predicts the correct number of light-absorbing components when the data quality is high and the instrumental error is known. Three thermodynamic dissociation constants were estimated by nonlinear regression of {pK _a , I} data: for methotrexate pK_a1^T= 2.895(13), pK_a2^T= 4.410(14), pK_a3^T= 5.726(15) at 25°C and pK_a1^T= 3.089(15), pK_a2^T= 4.392(12), pK_a3^T= 5.585(11) at 37°C, where the figure in brackets is the standard deviation in last significant digits. The reliability of the dissociation constants of the drug were proven by conducting goodness-of-fit tests of the multiwavelength spectrophotometric pH-titration data.      

Macroscopic and microscopic acid dissociation constants of diprotic acids--a potentiometric and spectrophotometric study

A state-of-the-art survey of the determination of acid dissociation microconstants of diprotic acids is presented. It is shown that potentiometric and spectrophotometric titration data can yield macroscopic constants but are not sufficient to completely resolve the microconstant system unless some sort of assumption is made, which may not always be warranted. Such an estimative deduction procedure is applied to 2,6-di(methylthiomethyl)-3-hydroxypyridine chloride.     

A nonaqueous potentiometric titration study of the dissociation of t-butyl methacrylate-methacrylic acid copolymers.

The dissociation of t-butyl methacrylate-methacrylic acid copolymers in dimethyl sulfoxide was analyzed by a nonaqueous potentiometric titration technique. The negative logarithm of the dissociation constant of the monomer unit of a methacrylic acid (MAA) monotonously increased with the increasing degree of dissociation corresponding to the titrant/MAA amount ratio, and was highly influenced by the copolymerization ratio. The results are discussed in terms of the suppression of the dissociation of MAA by a neighboring charged methacrylate anion unit.     

Determination of equivalence points of sigmoidal potentiometric titration curves

The equivalence point of potentiometric titration curves coinciding with the point of inflection is calculated from the maximum of the first derivative or the zero of the second derivative. The approximation of the curve is carried out by means of cubicB-splines. The quality of the fitted curve depends on the number and position (proportionally spaced or equidistant) of knots. Series of simulated and measured titration curves were evaluated. Optimum fits were obtained with knot numbers about 20–35% of the number of data points. Only proportionally spaced splines are applicable for all types of curves and produce results of high accuracy.     

The thermodynamic dissociation constants of losartan, paracetamol, phenylephrine and quinine by the regression analysis of spectrophotometric data

The mixed dissociation constants of four drug acids - losartan, paracetamol, phenylephrine and quinine - at various ionic strengths I of range 0.01 and 1.0 and at temperatures of 25 and 37 °C were determined using SPECFIT32 and SQUAD(84) regression analysis of the pH-spectrophotometric titration data. A proposed strategy of efficient experimentation in a dissociation constants determination, followed by a computational strategy for the chemical model with a dissociation constants determination, is presented on the protonation equilibria of losartan. Indices of precise methods predict the correct number of components, and even the presence of minor ones when the data quality is high and the instrumental error is known. Improved identification of the number of species uses the second or third derivative function for some indices, namely when the number of species in the mixture is higher than 3 and when, due to large variations in the indicator values even at logarithmic scale, the indicator curve does not reach an obvious point where the slope changes. The thermodynamic dissociation constant was estimated by nonlinear regression of {pK_a, I} data at 25 and 37 °C: for losartan and 3.57(3), and 4.80(3), for paracetamol and 9.65(1), for phenylephrine and 8.95(1), and 10.22(1), for quinine and 4.12(1), and 8.46(2). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.     

Determination of phosphorous in titanium bearing minerals by potentiometric titration using Pb-ion selective electrode

A method for phosphorous determination in titanium bearing minerals by potentiometric titration using a Pb-ion selective electrode has been developed. Sample decomposition is achieved by means of K(2)CO(3) fusion in a platinum crucible at 800 degrees C for 30 min in a muffle furnace, and subsequent leaching with water of the fused melt. The aqueous leachate is neutralised with HClO(4) and subsequent boiling. The obtained solution is used for titration with Pb(ClO(4))(2), and the Pb-ion selective electrode detects the end point. The lowest concentration determinable is 0.02% P(2)O(5) in a solid sample. The method was applied on in-house titanium bearing mineral samples and on IGS-31 ilmenite sample (British Geological Survey, UK). Synthetic samples were prepared and analysed, and phosphorous recovery is in the range 98-106%. The recovery and accuracy of the present method have been validated by spiking experiments and by comparing with the spectrophotometric values, respectively. The precision of the proposed method in terms of relative standard deviation is 2.0%.     

Determination of plutonium and uranium in the same aliquot by potentiometric titration

A potentiometric titration method was developed for the determination of plutonium and uranium in the same aliquot in nitric acid medium. Plutonium was first determined by oxidation to Pu/VI/ by fuming with conc. HClO₄. Pu/VI/ formed was reduced to Pu/IV/ with known excess of Fe/II/ and the excess Fe/II/ was titrated with standard K₂Cr₂O₇ to a potentiometric end point. Uranium in the same solution was determined by reduction to U/IV/ with Fe/II/ in conc. H₃PO₄ medium and titrating U/IV/ formed with standard K₂Cr₂O₇ using the potentiometric end point detection technique. For the quantity of plutonium and uranium each in the range of 3–5 mg per aliquot a precision of ±0.2% and ±0.4%, respectively, was obtained.     

Determination of traces of chloride and bromide ions by potentiometric titration

Summary A method is presented for the determination of chloride and bromide in the range of 10^–3 to 10^–6 M by potentiometric titration in nonaqueous medium using a commercial type platinum indicator electrode. ThisF procedure is more convenient and more accurate than the conventional method which uses silver electrode.

---

Zusammenfassung Ein Verfahren zur Bestimmung von 10^–3 bis 10^–6 Mol Chlorid und Bromid durch potentiometrische Titration in nichtwäßrigem Medium mit Hilfe einer handelsüblichen Platin-Indikator-Elektrode wurde vorgeschlagen. Es ist einfacher und genauer als die übliche Methode mit einer Silberelektrode.

     

Determination of chloride in sulphuric acid by potentiometric mercurometric titration

The chloride content of concentrated sulphuric acid is determined by mercurometric titration in 80% v/v methanol medium, with a mercury pool as indicator electrode. The method is simple, fast, accurate and reasonably sensitive (limit of detection 4.5 μg/ml), and suitable for routine application.