Titration of cyanide and hexacyanoferrate(II) with silver nitrate-II Determination of sodium cyanide and sodium hexacyanoferrate(II) in a complexing agent

Cyanide and hexacyanoferrate(II) can be titrated with silver nitrate in the presence of a complexing agent masked with a suitable metal ion. A method for determination of sodium cyanide and sodium hexacyanoferrate(II) in the presence of sodium nitrilotriacetate masked with magnesium ions is given as an example.     

Solid-state ion-selective electrodes for the potentiometric determination of hexacyanoferrate (II)

Hexacyanoferrate(II)-sensing electrodes were prepared by mixing Ag₂S and Ag₄Fe (CN)₆. The 6:1 Ag₂S/Ag₄Fe (CN)₆ provided the best potentiometric response and speed of response. The log concentration vs. potential curves were linear with Nernstian slope (14.8 mV/decade) over the range 10^?1-10^?6 M hexacyanoferrate (II) at pH 7.00 with constant ionic strength. Interferences included iodide, sulfide and bromide. This electrode was used as indicator in potentiometric titrations of hexacyanoferrate (II).     

The potentiometric titration of mercury(II) with cetylpyridinium chloride

Summary New precipitation titrations have been evaluated for the determination of mercury(II) in acid solution and for mercuric cyanide solutions. In acid or neutral solutions the mercuric ion was converted to the bromo complex by addition of excess potassium bromide. Mercuric cyanide was converted to the tetracyano complex by addition of an excess of potassium cyanide. In both cases the complex anions were titrated potentiometrically vs. 0.01M cetyl-pyridinium chloride. Emf's were monitored with a home-made graphite sensor coated with a solution containing poly(vinyl chloride) and dioctylphthalate in tetrahydrofuran and a single-junction reference electrode.

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Über die potentiometrische Titration von Hg(II) mit Cetylpyridiniumchlorid

Zusammenfassung Neue Verfahren zur Fällungstitration von Hg(II) in saurer Lösung sowie von Lösungen von Quecksilbercyanid wurden angegeben. Quecksilberion wird in saurer oder neutraler Lösung durch Zusatz überschüssigen Kalium-bromids in den Brom-Komplex übergeführt. Quecksilbercyanid wird durch Zusatz überschüssigen Kaliumcyanids in den Tetracyanokomplex umgesetzt. In beiden Fällen werden die komplexen Anionen potentiometrisch gegen 0,01M Cetylpyridinium-chlorid titriert. Die EMK wird mit Hilfe eines selbst hergestellten Graphitsensors, der mit einer Lösung von Polyvinylchlorid und Dioctylphthalat in Tetrahydrofuran überzogen ist, sowie einer Single-junction-Bezugselektrode gemessen.

     

Kinetics and mechanism of mercury(II)-catalysed replacement of cyanide in hexacyanoferrate(II) by p-nitrosodiphenylamine

The mercury(II)-catalysed replacement of cyanide in hexacyanoferrate(II) by p-nitrosodiphenylamine (p-NDA) in aqueous solution has been investigated spectrophotometrically by measuring the change in absorbance of the green complex ion, [Fe(CN)(5).p-NDA](3-), at 640 nm. Activation parameters of the catalysed and uncatalysed reactions have been calculated. The effects of the dielectric constant and water content of the medium on reaction rates are used to explain the formation of a polar activated complex and suggest an I(d) mechanism for the catalysed reaction. The varying catalytic activity of Hg(II) as a function of concentration has been discussed.     

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.     

Theory of titration curves : Points of minimum slope on potentiometric strong acid-strong base and precipitation titration curves

Strong acid-strong base and precipitation titration curves, like other kinds of potentiometric titration curves, inherently possess an inflection point where the slope is a minimum as well as one where it is a maximum. In any kind of titration the first of the inflection points can be caused to occur earlier, and can eventually be made to disappear altogether, by adopting certain expedients. For a weak acid-strong base titration, for example, these include decreasing the concentration of the acid titrated and titrating in the presence of an excess of its conjugate base. For strong acid-strong base and precipitation titrations they include decreasing the concentration of the substance titrated and increasing the concentration of the titrant. The conditions under which a physically significant inflection point of minimum slope can exist are defined, and explicit equations are given from which its position can be calculated under various experimental conditions, for strong acid-strong base and for both isovalent and heterovalent precipitation titrations.     

A potentiometric detector for hydrogen cyanide gas using silver dicyano complex

A sensitive method capable of detecting Hydrogen cyanide gas in atmosphere at its TLV is being presented. This method makes use of two silver electrodes kept in two separate compartments which are in contact with a solution of constant concentration of Silver dicyano complex at a pH 11.5. One of the electrodes used as reference is concealed and the other used for sensing is exposed to the incoming air. In the absence of Hydrogen cyanide gas the potential difference between the two electrodes is zero, but when hydrogen cyanide gas is passed into the cell, the activity of Ag(+) ions nearer to the sensing electrode changes, there by generating a potential difference between the two electrodes. The plot between the potential vs. log of Concentration of Hydrogen cyanide gas is linear, in the concentration range 0.66-42.3 mg/m(3) with a slope nearer to 120mV and regression coefficient around 0.997. The standard deviation is 6% (n=4). Minimum detectable limit is 0.66 mg/m(3). Various concentrations of Silver dicyano complex used gave similar plots.     

The potentiometric titration of iron(II)/HCl solutions with permanganate

Summary Reagents other than the Zimmerman-Reinhardt reagent have been used to minimize the errors incurred when Fe(II)/HCl systems are titrated with MnO₄ ^–. Potentiometric studies made of the effect of these additives on the initial and equivalence point potentials show that salts whose anions stabilize the Mn(III) state affect the equivalence point potential more than those containing Mn(II). The cation also affects the result, e.g., H₂SO₄ ^– and Na₂SO₄-containing solutions show a greater equivalence potential change than do those containing (NH₄)₂SO₄ and K₂SO₄. Ce₂(SO₄)₃, reportedly an effective inhibitor, does not affect the equivalence point potential. Less titrant is required for 6 M HCl-containing Fe(II) solutions than for 1 M HCl-containing solutions-a result opposite to that expected and only partially explained by a more rapid air-oxidation of Fe(II) in 6 M HCl. The Pt electrode is not inert in this system.

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Zusammenfassung Bei einer Untersuchung der potentiometrischen Titration salzsaurer Eisen(II)-lösungen mit Permanganat wurde die Wirkung der verschiedenen für diese Bestimmung zur Verhinderung von Störungen empfohlenen ZusÄtze geprüft. Dabei ergab sich, da\ Salze, deren Anionen das dreiwertige Mangan stabilisieren, das Potential im Äquivalenzpunkt stÄrker beinflussen als solche, die zweiwertiges Mangan enthalten. Da\ auch das Kation das Ergebnis beeinflu\t ergab sich daraus, da\ bei H₂SO₄ und Na₂SO₄ eine grö\ere PotentialÄnderung im Äquivalenzpunkt beobachtet wurde als bei (NH₄)₂SO₄ und K₂SO₄. Bei Ce₂(SO₄)₃ wurde keine Wirkung auf die PotentialÄnderung festgestellt. Für 6 M salzsaure Fe(II)-Lösungen wurde weniger Titrationsmittel verbraucht als für 1 M salzsaure, was nur zum Teil mit der schnelleren Luftoxydation des zweiwertigen Eisens im 6 M HCl-Lösung erklÄrt werden kann. Die Platinelektrode erwies sich in diesem System nicht als inert.

     

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.

     

Natural pyrite as an electrochemical sensor for potentiometric titrations with EDTA, mercury(II) and silver(I)

The results obtained in potentiometric titrations of copper(II), mercury(II) and iron(III) with standard EDTA solutions are presented. The titration of copper(II) at pH values in the range from 8.11 to 10.99 (ammonia buffer) and the titration of mercury(II) and iron(III) at pH values from 3.59 to 5.65 (acetate buffer) were performed. The titration end-point (TEP) was detected with an indicator electrode made from natural crystalline pyrite as an electrochemical sensor. The results obtained in potentiometric titration with the pyrite electrode were compared with those obtained using a platinum electrode (Fe³⁺), a Cu ion selective electrode (Cu²⁺) and a Hg electrode (Hg²⁺). Accurate and reproducible results with good agreement were obtained, but higher potential changes at the TEP were obtained using the pyrite electrode. In the course of the titration the potential was established within less than 1 min, whereas at the TEP it was within about 2–3 min. The potential changes at the TEP were in the range from 60 to 200 mV per 0.1 ml EDTA, according to the stability constant of the complex formed. The highest potential changes, ranging from 160 to 200 mV, were obtained in the titration of iron(III) at pH 3.59. Reverse titration was also performed and accurate and reproducible results were obtained. Moreover, titration of halogenide and thiocyanate with standard mercury(II) solutions, as well as cyanide with silver(I) solution, were performed and accurate and reproducible results were again obtained. Received: 20 February 1998 / Accepted: 19 November 1999     

Catalytic amperometric and catalytic constant-current potentiometric titrations of silver(I), palladium(II) and mercury(II)

Amperometry and constant-current potentiometry were used to follow the course of catalytic titrations of silver(I), palladium(II), and mercury(II) with potassium iodide. The Ce(IV)As(III) and Ce(IV)Sb(III) systems in the presence of sulphuric acid were used as indicator reactions. The possibilities of application of platinum, palladium, gold, graphite, and glassy-carbon indicator electrodes were investigated. Graphite appeared to be somewhat more advantageous than the other electrode materials. The effect of concentration of the components of the indicator reactions, the presence of organic solvents and acids on the shape of the catalytic titration curves was studied. Amounts of 30-3000 mug of silver(I) nitrate, 90-900 mug of palladium(II) chloride, 130-1300 mug of mercury(II) chloride, and 150-1500 mug of mercury(II) nitrate were determined with a relative standard deviation less than 1.0%. The results obtained were in good agreement with those of comparable methods. The catalytic titration method developed was applied to determination of mercury in Unguentum Hydrargyri.     

Determination of Fe(II)-Fe(III) and Fe(III)-Ni(II) by the two-component potentiometric complexometric titration

Summary The two-component complexometric potentiometric titration has been applied to the simultaneous determination of Fe(III) and Fe(II), and of Fe(III) and Ni(II) in solution. In each case the two analytes were determined by reading the end-points directly from the titration curve. The end-points are determined in a sense arbitrarily, but they are repeatable and easy to be detected precisely. However, the apparent (found) analytical results are biased. They are effectively corrected with the use of a set of two calibration equations (uncomplete second degree polynomials), which approximate the relationship between found endpoints and true concentrations of analytes in solution. The regression coefficients in the equations are determined on the basis of titration data obtained for standard solutions whose compositions correspond to a 2² factorial. Permanent address: Department of Analytical Chemistry, Jagiellonian University, Krakow     

Approximation of potentiometric titration curves by logarithmic functions: Factors affecting the accuracy of redox titration

The influence of random errors in measuring the potential and dosing the titrant volume on the reliability of the parameters of redox titration calculated using logarithmic relationships has been studied. It is found that the propagation of measurement errors in this case mostly depends on the difference between the real potentials of the reacting redox couples, on the number and distribution of points in the titration curve, and on the stoichiometry of the reaction.     

Titration curves in complexometric titrations with the redox system Fe(III)/Fe(II)

Potentiometric titrations of metal ions with EDTA have been carried out with a platinum or graphite electrode and the Fe(III)/Fe(II) redox system. In the absence of oxygen and for pH < 2 the titration curves may be described by an equation similar to that given previously for titrations with silver and mercury electrodes. Titration curves for bismuth and indium, which are more strongly complexed than iron, are asymmetrical and useful for analytical purposes. When the titrated ions are complexed less strongly than iron(III) ions the kinetics of metal complexation have a pronounced effect. The titration curves of thorium and copper, which react more rapidly than iron, are analytically useful. The curves recorded rapidly after titrant additions have a better end-point break than those which correspond to thermodynamic equilibrium. When a metal, e.g., nickel, is weakly bound by EDTA, and reacts more slowly than iron, a very small end-point break or none at all is observed.     

Regioselective 1,4-conjugate hydrocyanation of dienones using potassium hexacyanoferrate(II) as an eco-friendly cyanide source

A highly regioselective 1,4-conjugate hydrocyanation of dienones using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source, benzoyl chloride as a promoter and potassium carbonate as a catalyst is described. This protocol has advantages of non-toxic cyanating agent, high regioselectivity, high yield, and simple work-up procedure.     

Effect of the concentration of solutions being titrated on the shape of conductometric titration curves

The influence exerted by the concentration of solution being titrated on the shape of the theoretical curves of conductometric titration was studied. The concentrations at which the equivalence points are clearly observed in the conductometric titration curves were determined.