A graphical method for locating the end point in potentiometric titration curves

Summary A new graphical method for locating the end point in potentiometric titration curves is described. By moving two glass rods to scan the entire curve, the end point is determined when the difference between the two refracted lines is maximum. The method is particularly useful when the end point is ill-defined.

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Graphisches Verjahren zur Bestimmung des Endpunktes potentiometrischer Titrationskurven

Zusammenfassung Zwei gleich starke Glasstäbe werden senkrecht zur Volumenachse über die Titrationskurve geführt. Der Endpunkt ist durch den maximalen Abstand der durch die Refraktion verzerrten Titrationskurve gekennzeichnet. Das Verfahren eignet sich auch noch bei Titrationskurven mit sonst schlecht definiertem Endpunkt.

     

甘草酸银在几种溶剂中的溶解行为及银量测定

研究了甘草酸银在乙醇、乙醚、丙酮、三氯甲烷、磷酸三丁酯，H2O、HCl、HNO3、H2SO4、氨水、NaOH、Na2CO3等溶剂中的溶解行为，建立了在氨性介质中直接用碘化钾电位滴定测定甘草酸银中银含量的方法。该方法已用于过程控制分析。     

An iodide/anion exchange route to benzimidazolylidene silver complexes from benzimidazolium iodide: Crystal structures of N,N′-dibutylbenzimidazolylidene silver chloride, bromide, cyanide and nitrate

Syntheses of N,N′-dibutylbenzimidazolylidene silver complexes having chloride, nitrate or cyanide as an anion part through an iodide/anion exchange from N,N′-dibutylbenzimidazolium iodide are described, representing a practical route to benzimidazolylidene silver complexes from readily accessible benzimidazolium iodide. The crystal structures of N,N′-dibutylbenzimidazolylidene silver chloride, bromide, cyanide and nitrate have been determined, showing a close ligand-unsupported Ag-Ag interaction in [(NHC)₂]Ag⁺[AgX₂]⁻ and a “T” shape geometry about the silver(I) cation in complexes of chloride, bromide and cyanide, but a nearly linear shape in the bis(N,N′-dibutylbenzimidazolylidene) silver complex [ with non-coordinating nitrate anion.     

The relationship between the inflection point and equivalence point of a potentiometric titration

Attention is drawn to a common textbook error concerning the coincidence of the end-point and equivalence point of potentiometric titration curves.     

Development of a method for estimating an accurate equivalence point in nickel titration of cyanide ions

In a nickel titration of cyanide ions using murexide as indicator, an accurate equivalence point was determined by a non-linear least-squares curve-fitting for a titration curve. This method was developed to establish a standard solution for cyanide ions. In a curve-fitting procedure, a theoretical titration curve was calculated, assuming that nickel ion formed only a 1:4 Ni²⁺:CN⁻ complex with cyanide ions and formed only a 1:1 complex with murexide. Results of the curve-fitting were reasonable at any pH and any indicator concentration studied. The combined standard uncertainty for a concentration of a 1000 mg kg⁻¹ cyanide solution by this method was 0.079%.     

The enthalpimetric determination of mixtures of chloride,bromide and iodide

The individual components of mixtures of chloride (0–1 mmol), bromide and iodide (0–0.1 mmol) may be determined by the use of direct injection enthalpimetry. The heats of reaction of the ions with various reagents have been shown to be additive and the use of non-selective reagents is thus made possible. The amounts of the halides present are calculated by simultaneous equations. The limits of the methods are discussed.     

火试金富集--自动电位滴定法测定粗碲中的银含量

粗碲是由铜、铅、锌冶炼带来的副产品,其中含有大量的金、银等贵金属。快速准确检测粗碲中银含量,具有十分重要的意义。样品预先采用硫酸溶解,还原沉淀金、银,过滤分离大部分的铋、硒、碲等元素,经配料、高温熔融,熔融态的金属铅捕集试料中的贵金属形成铅扣,试料的其他物质与熔剂生成易熔性熔渣。将铅扣灰吹,得金银合粒,清除合粒表面粘附的杂质,经硝酸分金,用硫氰酸钾滴定法测定银量。银的加标回收率在99.5%～101%,相对标准偏差(RSD)小于5%。方法速度快,稳定性好,适用于粗碲中银含量的测定。     

Evaluation of the equivalence point in potentiometric titrations with application to traces of chloride

A mathematical model applicable to the determination of the equivalence point (V_eq) is described. The regression equation is (1 + V/V₀)³E = Σ³_i= _0AiVⁱ, where E is the e.m.f. corresponding to volume V of titrant added, V₀ is the initial volume of titrand, and A_i are the regression coefficients. On the basis of A_i values obtained by the least-squares method, the algorithm for V_eq and the criterion of correctness of results obtained from measurements are presented. The method is applied to titrations of chloride with silver nitrate solutions.     

Catalytic titration of iodide, bromide and thiocyanate by use of the silver catalysed phloxin-persulphate reaction

A method for the catalytic titrimetric determination of iodide, bromide and thiocyanate is described, based on the inhibitory effect of these anions on the silver-catalysed oxidation of phloxin by persulphate in the presence of 2,2'-bipyridyl. The end-point is determined photometrically by measuring the absorbance at 537 nm. Amounts of iodide, bromide and thiocyanate in the 0.01-7.94, 0.11-4.73 and 0.12-3.59mg ranges, respectively, are titrated with a relative error of about 1%.     

Sequential injection analysis of chloride and nitrate in waters with improved accuracy using potentiometric detection

Accurate simultaneous analysis of different anionic species using ion-selective electrodes (ISEs) can be achieved even for non-specific sensors by resorting to an ordinary least squares multiple regression in the vicinity of the predicted concentrations. In this work the potentialities of this approach are evidenced by the determination of nitrate and chloride in synthetic and real water samples in which chloride concentration was significantly higher than nitrate. An AgCl/Ag₂S electrode based on a homogeneous crystalline membrane together with a PVC electrode based on tert-octylammonium bromide dissolved in dibutylphthalate were used as potentiometric detectors for chloride and nitrate, respectively. For the implementation of the procedure, an automatic system based on sequential injection analysis was used. The results obtained by the standard addition method were biased for low concentrations of nitrate and were dependant on the relative proportion of NO₃⁻/Cl⁻. The results obtained by the proposed methodology for chloride determination were slightly better when compared to those obtained by the standard addition method. In relation to nitrate determination, the proposed methodology yielded values with a relative root mean square error of prediction (RRMSEP) of 2.8%, while for standard addition calibration, mean error values were approximately 12.1%.     

Rapid and sustainable process with low toxicity for cyanation of silver nitrate by DC arc-discharge in presence of acetonitrile

Use of Direct current (DC) arc-discharge in the chemistry reactions is very novel method. In this technique, the DC arc-discharge as a high-energy source conducts reaction to cleaving of the C-CN bond in acetonitrile and causes the cyanation of silver nitrate. This process due to non-use of cyanide ion can be proposed as a green and sustainable method. The obtained Silver cyanide from this procedure was characterized by its spectroscopic data (FT-IR and XRD).

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Standard potentials of the silver,silver bromide electrode and the thermodynamic properties of hydrobromic acid in 1,2-dimethoxyethane and its aqueous mixtures

The standard potentials of the silver, silver bromide electrode have been determined in 1,2-dimethoxyethane (DME) and in nineteenDME + water solvents from the e.m.f. measurements of cells of the type Pt|H₂(g, 1 atm)|HBr (m), solvent|AgBr|Ag at intervals of 5°C from 5 to 45°C. The molality of HBr covered the range from 0.01 to 0.1 mol kg^–1. In solvents of highDME content, where the dielectric constant is small, it was necessary to correct for ion-pair formation. The temperature variation of the standard potential has been used to evaluate the standard thermodynamic functions for the cell reaction, and the standard quantities for the transfer of HBr from water to the respective solvents. The results have been discussed both in relation to the acid-base nature of the solvent mixtures and also their structural effects on the transfer process.

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Standardpotentiale der Silber, Silberbromid-Elektrode und thermodynamische Eigenschaften von H Br in 1,2-Dimethoxyethan und 1,2-Dimethoxyethan—Wasser-Mischungen

Zusammenfassung Die Standardpotentiale der Silber, Silberbromid-Elektrode wurden in 1,2-Dimethoxyethan (DME) und in 19 verschiedenenDME—Wasser-Gemischen aus EMK-Messungen der Zelle Pt|H₂(g,1 atm)|HBr (m), Lsgsm.|AgBr|Ag in Temperaturintervallen von 5°C zwischen 5 und 45°C bestimmt. Die Molalität von HBr deckte den Bereich von 0,01 bis 0,1 mol kg^–1. Bei Lösungen mit höheremDME-Gehalt — und damit niedrigen Dielektrizitätskonstanten —war es nötig, für die Bildung von Ionenpaaren eine Korrektur einzuführen. Über die Temperaturvariation wurden die thermodynamischen Größen für die Zellenreaktion und die Standardgrößen für den Transfer von HBr aus Wasser in das jeweilige Lösungsmittel bestimmt. Die Ergebnisse werden sowohl im Zusammenhang zur Säure-Base-Natur de Lösungsmittelmischungen als auch in bezug auf strukturelle Effekte im Transferprozeß diskutiert.

     

Linear titration plots for the potentiometric titration of partially neutralized weak acids and bases

Summary A linear titration plot method has been derived for the determination of partially neutralized weak acids or weak bases from pH-titration data. A FORTRAN program calculates the total concentration of acid or base in solution as well as the fraction remaining to be neutralized. The program also detects the presence of strong acid with a weak acid or a strong base with a weak base. The weak acid or base may be polyfunctional with overlapping dissociation steps. Activity coefficients are calculated iteratively.

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Lineare Titrationskurven für die potentiometrische Titration von teilweise neutralisierten schwachen Säuren und Basen

Zusammenfassung Lineare Titrationskurven werden für potentiometrische Titrationen von schwachen Säuren und Basen, die bereits teilweise neutralisiert sind, abgeleitet. Eine Fortran-Prozedur berechnet sowohl die Gesamtkonzentration der Säure oder Base als auch den Neutralisationsgrad. Das Rechenprogramm erfaßt auch die Anwesenheit einer starken Säure zusammen mit einer schwachen Säure oder einer starken Base zusammen mit einer schwachen Base. Die schwache Säure oder Base darf mehrere überlappende Dissoziationsstufen aufweisen. Aktivitätskoeffizienten werden mittels eines Iterationsverfahrens berechnet.

     

Determination of gold(III) alone or in some mixtures and alloys by potentiometric titration of iodide

The present work is an application of iodide to the reduction of gold(III), in an attempt to develop new method for gold(III) based on potentiometric back-titration of the excess of iodide with mercury(II). Although it was proved by calculation that the reduction of tetrachloroaurate to the metal should proceed quantitatively to completion, yet our experiments showed that the reduction under ordinary conditions, gave Au(I) in the form of a white precipitate of AuI. We succeeded to push the reduction with iodide to the metal by an excess of ethanol-ether catalyzed iodide at somewhat elevated temperature.With the experimental conditions established a reliable procedure have been developed involving a potentiometric finish which enabled accurate determination of gold(III), either alone or in some of its alloys.     

Photometric titration of arsenate with thorium nitrate on the microgram and milligram scale

Summary A method is described for the photometric titration of arsenate with thorium nitrate using pyrocatechol violet as indicator. The method works at a low pH level and is therefore not subject to the most cationic interferences. Alkali salts do not affect the determination even at high concentrations if present as halides, nitrates or perchlorates. This makes the method particularly suitable for the analysis of arsenic in organic and inorganic compounds after decomposition.

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Zur photometrischen Titration von Arsenat mit Thoriumnitrat im Mikrogramm- und Milligrammbereich

Zusammenfassung Ein Verfahren zur photometrischen Titration von Arsenat mit Thoriumnitrat gegen Brenzcatechinviolett als Indicator wird beschrieben. Die Titration erfolgt bei niedrigem pH-Wert und wird deshalb von den meisten Kationen nicht beeinflußt. Außerdem stören auch hohe Konzentrationen an Alkalisalzen nicht, wenn diese als Halogenide, Nitrate oder Perchlorate vorliegen. Deshalb ist das Verfahren insbesondere zur Analyse von anorganischen und organischen Arsenverbindungen nach Aufschlüssen geeignet.

     

Species formed in the potentiometric titration of fluoride with thorium or lanthanum nitrate and functions suitable for the evaluation of the equivalence points

Calculations by means of SILLÉN's HALTAFALL program have been performed on experimental curves by LINGANE for the potentiometric titration of fluoride with thorium and lanthanum in different media. After adjusting the stability constants for some of the main species formed during the titration a good fit was obtained between the experimental data and the calculated titration curves. In the cases where the solution was buffered with acetate it was necessary to consider the formation of mixed fluoride-acetate complexes. Suitable functions for the evaluation of the equivalence point could be derived from the calculations. If the functions: F₁=(v₀+v)[F^-] and F₃=(v₀+v)[F^-]^-3 are used before and after the equivalence point, respectively, it ought to be possible to determine fluoride very accurately by titration with lanthanum nitrate in an unbuffered solution. A value proportional to [F^-] is obtained from 10 exp (—EF/RT In 10), the Nernst e.m.f. equation.     

Construction and evaluation of tubular potentiometric detectors sensitive to chloride, bromide, and iodide and based on homogeneous crystalline membranes

Summary The construction of tubular potentiometric detectors is described, without an inner reference solution, sensitive to chloride, bromide, and iodide. They are based on homogeneous crystalline membranes obtained by high-pressure pressing of AgX/Ag₂S powdered mixtures (X = Cl, Br and I). The respective operating characteristics are evaluated by comparison with conventionally-shaped electrodes with the same sensor. In general, the detectors showed similar operating characteristics as those of the corresponding conventional electrodes, namely the concentration range, in which they presented a Nernstian response, an excellent reproducibility, and an extremely rapid response rate which in some cases enabled the FIA manifolds to attain sampling rates of 360 samples/h.     

Titrimetric determination of silver,chloride and bromide in glasses

Titrimetric methods are described for the determination of total silver, free silver or free halide (Cl, Br and I), and bromide (or iodide) in glasses. Total silver is titrated potentiometrically with standard bromide solution after hydrofluoric—sulfuric acid sample decomposition followed by sodium hydrogensulfate fusion for volatilizing hydrogen halide. Free silver is determined similarly on a separate sample without the fusion step. For glasses containing excess of halide, free halide is titrated potentiometrically with standard silver(I) solution after dissolution of the sample in ice-cold hydrofluoric—nitric acid. Total bromide (or iodide) is determined by iodometric titration after oxidation to bromate (or iodate) with hypochlorite solution. The methods have been applied to a wide range of complex glass compositions and results are compared with values obtained by controlled-potential coulometry and x-ray fluorescence analysis.     

Room temperature synthesis of silver nanowires from tabular silver bromide crystals in the presence of gelatin

Long silver nanowires were synthesized at room temperature by a simple and fast process derived from the development of photographic films. A film consisting of an emulsion of tabular silver bromide grains in gelatin was treated with a photographic developer (4-(methylamino)phenol sulfate (metol), citric acid) in the presence of additional aqueous silver nitrate. The silver nanowires have lengths of more than 50 μm, some even more than 100 μm, and average diameters of about 80 nm. Approximately, 70% of the metallic silver formed in the reduction consists of silver nanowires. Selected area electron diffraction (SAED) results indicate that the silver nanowires grow along the [111] direction. It was found that the presence of gelatin, tabular silver bromide crystals and silver ions in solution are essential for the formation of the silver nanowires. The nanowires appear to originate from the edges of the silver bromide crystals. They were characterized by transmission electron microscopy (TEM), SAED, scanning electron microscopy (SEM), and powder X-ray diffraction (XRD).