Potentiometric titration of organic cations with sodium tetraphenylborate and a liquid-membrane tetraphenylborate ion-selective electrode

Simple potentiometric titrations are described for the determination of various organic cations (usually 5–25 μ mol) with 0.01 M sodium tetraphenylborate. A liquid-membrane electrode with tetrapentylammonium tetraphenyiborate dissolved in 4-nitro-m-xylene as liquid ion-exchanger is used successfully in the semi-automatic titration of quaternary ammonium compounds, cationic surfactants, alkaloids and other substances of pharmaceutical importance which are precipitated by tetraphenyiborate. Analysis of pharmaceutical preparations gave satisfactory results.     

Amperometric complex-formation titration of traces of alkaline earths

Alkaline earth metals were determined in microgram quantities by complexometric titration with EDTA, EGTA and DTPA. The end-point was detected by following the anodic wave of the chelating agent at the rotating mercury electrode. All the alkaline earths can be titrated at the microgram level with reasonable accuracy, and calcium may be titrated with EGTA in the presence of a 1000-fold excess of magnesium.     

Determination of tetraphenylborate by two-phase titration with tetraphenylphosphonium salt

A visual indicator method has been developed for the titration of tetraphenylborate (TPB) with a 5 × 10^?5, M tetraphenylphosphonium (TPP) solution. A hydrophobic dye, tetrabromophenolphthalein ethyl ester (TBPE), is used as an indicator in the presence of 1,2-dichloroethane. The organic phase changes from yellow to blue at the endpoint. This method was applied to the determination of solubility product of TPP perchlorate. The extract of ephedrine, homatropine, perchlorate, or thiocyanate with TPB or TPP was titrated.     

Potentiometric titration of organic cations precipitated by tetraphenylborate

Summary Sodium tetraphenylborate has been used for the potentiometric precipitation titration of some water-soluble organic cations, mostly those containing a quaternary ammonium group. Emf's were monitored with a fluoroborate ion-selective indicator electrode and a double-junction reference electrode. Other liquid-membrane electrodes, such as the perchlorate and nitrate, also respond to the cations investigated. The solid-state cyanide electrode responds to those cations yielding potentiometric breaks of > 70 mV with the fluoroborate electrode. The following compounds were examined: procaine, diphenhydramine, chlorpheniramine, methylene blue, dimethyl yellow, benzidine, pyridine, acetylmethylcholine, thiamine.This paper was presented at the International Symposium on Electroanalysis in Cardiff, England, on April 13, 1981     

The enthalpy of precipitation of univalent cations with tetraphenylborate by titration calorimetry

The enthalpy of precipitation of six common univalent cations with the tetraphenylborate anion has been measured at 25.0°C. Reaction entropies range from −8.24kcal/mole for ammonium to −19.7 kcal/mole for silver(I). The entropy of reaction was computed from the above measurements and the corresponding Gibbs free energy changes. A linear relationship exists between ΔF°′ and ΔH°′. The entropy of precipitation of ammonium ions was +5.0 e.u., an unusually large positive value.     

Back titration with mercuric nitrate in alkaline : medium volumetric analysis of binary mixtures of the alkaline earths,magnesium, zinc and cadmium

Mercuric nitiate has proved to be suitable for the back titration of the excess amount of EDTA remaining in solution when this compound has reacted quantitatively either with zinc or cadmium in the presence of one of the three elements barium, strontium and magnesium at pH 8 or 9, or with both cations at pH 11. Advantage is taken of this behaviour for analysing binary mixtures of the above mentioned cations by back titration at lower and higher pH's The end-points are detected potentiometrically, reasonable jumps being obtained; the agreement with the theoretical end-points is satisfactory.     

Oxidations with alkaline permanganate using monovalent thallium for the back titration: Estimation of hydrazine

Oxidation of liydrazine in alkaline solutions with KmnO₄, gives inaccurate results both in the presence of absence of telluric acid. The titration curve is characterized by two inflections.Titration of KmnO₄ with hydrazine gives good results in the presence of Ba⁺² ions and 0.75–1NNaOH (when MnO₄^- gives MnO₂^-) or in the presence of 0.5–2.5N NaOH only (when MnO₄ gives MnO₂).Hydrazine could be estimated by oxidation with KMn0₄ either in the presence of Ba⁺² ions or telluric acid, after which the excess permanganate is back titrated with monovalent thallium. The alkalinity is Kept at 1N NaOH.     

Determination of the alkaline earths in glass

The alkaline-earth group was isolated, after removal of silica, by precipitation as sulfates from an alcoholic solution. Those sulfates were reduced and dissolved by treatment with hydriodic acid. The alkaline earths were separated from each other by ion-exchange chromatography. The results are in good agreement with the values reported by the National Bureau of Standards.     

Oxidations with alkaline permanganate using monovalent thallium for the back titration: Estimation of hydrogen peroxide

Owing to the instability of hydrogen peroxide in alkaline solutions, direct oxidation with KmnO₄ did not yield accurate results.The back titration of KmnO₄ in the presence of IN NaOH and Ba⁺² ions also gave inaccurate results. The reaction could not be checked at the manganate state. However, in the presence of 2N NaOH and telluric acid quantitative data were obtained, which is not the case if telluric acid is absent.Another advantageous method is the oxidation of hydrogen peroxide with excess KmnO₄ in the presence of 1N NaOH and telluric acid, followed by back titrating excess oxidant with monovalent thallium.     

Colorimetric titration of vanadium with alkaline ferricyanide

Summary The gradual disappearance of the yellow colour of ferricyanide with the addition of vanadyl ions in alkaline medium has been made the basis of the quantitative determination of both vanadium and ferricyanide. The colorimetric titrations were carried out with the aid of a Hilger Spekker Absorptiometer with a blue filter having maximum transmission in the range of 450–500 m. It is shown that the accuracy of the results compares favourably with those obtained by other standard procedures.     

Estimation of benzidine by non-aqueous titration

Summary It has been shown that the potentiometric titration of benzidine in propyleneglycol: chloroform (13) with hydrochloric acid in propyleneglycol gives two inflexions for the successive neutralisation of the two amino groups, a phenomenon not observed frequently in the case of weak bases. It has also been demonstrated that benzidine can be estimated in glacial acetic acid/chloroform (13) by visual titration.

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Zusammenfassung Benzidin gibt bei der potentiometrischen Titration in Propylenglykol/ Chloroform (13) mit Salzsäure in Propylenglykol zwei getrennte Potentialsprünge für die beiden Aminogruppen, eine Erscheinung, die bei so schwachen Basen selten ist. Visuell kann Benzidin in Eisessig/Chloroform (13) titriert werden.

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Grateful thanks are due to Prof. M. V. C. Sastri for his constant encouragement during the course of the work.     

Palladium-catalyzed hydrophenylation of alkynes with sodium tetraphenylborate under mild conditions

In an aqueous solution of acetic acid, PdCl2(PPh3)2 showed high catalytic activity for the hydrophenylation of both terminal and internal alkynes with sodium tetraphenylborate (NaBPh4) under mild conditions, affording phenyl alkenes in moderate to excellent yields.     

Potentiometric determination of rare earths with sodium ortho-vanadate

Ohne Zusammenfassung     

Potentiometric determination of rare earths with sodium tungstate

Ohne Zusammenfassung     

Microdetermination of chloride and azide by sequential titration

Summary A rapid method for the microdetermination of chloride and azide by sequential titration with silver nitrate in 80%p-dioxane is described. A chloride-selective indicator electrode and a single-junction reference electrode are used with an expanded-scale p_H meter to monitor the emf. For the determination of chloride only (in the presence of azide), the potentiometric titration with mercuric perchlorate is used. A twofold excess of azide does not interfere in this determination.

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Zusammenfassung Ein schnelles Verfahren zur Mikrobestimmung von Chlorid und Azid durch Sequenztitration mit Silbornitrat in 80%igem p-Dioxan wurde beschrieben. Eine chloridspezifische Indikatorelektrode und eine Bezugselektrode mit Einzelverbindung wurden mit einem p_H-Meter mit gedehnter Skala zur Potentialmessung verwendet. Für die Chloridbestimmung allein (in Gegenwart von Azid) wurde potentiometrisch mit Quecksilberperchlorat titriert. Ein zweifacher Überschuß von Azid stört die Bestimmung nicht.

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Work performed under the auspices of the U. S. Atomic Energy Commission.     

The flame photometric determination of alkali metals, alkaline earths and copper in nuclear grade uranium

Summary A method, which involves prior chemical separation of uranium from impurities by tributylphosphate extraction, is described for the determination of alkali metals, alkaline earths and copper in nuclear grade uranium. The characteristic emission lines, excited in hydrogen-oxygen flame, are isolated by a small monochromator and recorded photoelectrically.Using 3 g samples 0.005 ppm of Li, 0.001 ppm of Na, 0.05 ppm of K, 1 ppm of Mg, 1.5 ppm of Ba and 2 ppm of Cu can be determined in uranium, with reproducibilities better than ± 3%.Some interelemental interferences are discussed, and the possibilities of their elimination are described.The method can be used without modification for the analysis of uranium containing up to 100ppm of impurities.

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Zusammenfassung Es wird ein Verfahren zur flammenphotometrischen Bestimmung von Alkalien, Erdalkalien und Kupfer in Uran von nuklearem Reinheitsgrad beschrieben, das eine vorherige Extraktion des Urans mit Tributylphosphat verwendet. Die charakteristischen Emissionslinien werden durch eine Wasserstoff-Sauerstoff-Flamme angeregt, durch einen kleinen Monochromator isoliert und photoelektrisch registriert. Mit einer Probe von 3 g können noch 0,005 ppm Li, 0,001 ppm Na, 0,05 ppm K, 1 ppm Mg, 1,5 ppm Ba und 2 ppm Cu mit einer Reproduzierbarkeit von <± 3% bestimmt werden. Störungen durch andere Elemente sowie Möglichkeiten zu ihrer Ausschaltung werden diskutiert. Das Verfahren kann bis zu einem Gehalt von 100 ppm an Verunreinigungen in Uran angewendet werden.

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On leave to the IAEA Vienna, Austria.     

Stability constants of some metal complexes of triethylenetetraminehexa-acetic acid and complexometric titration of rare earths and other metals

The stability constants of some non-protonated 1:1 metal complexes of triethylenetetraminehexa-acetic acid are reported; log K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(III) 24.3, Zn 20.1.     

Ion pairing in solutions of sodium tetraphenylborate

Conductance data are presented for sodium tetraphenylborate (NaBPh₄) in three solvent systems: water-dimethyl sulfoxide, water-acetone, and acetone-dimethyl sulfoxide. These and other data from the literature were first analyzed by the three-parameter equation Λ^′=Λ₀+Aτ²+Bτ³, where $$\Lambda \prime = [\Lambda (obs.) + \beta _0 c^{1/2} (1 + 0.5\tau ln 2\tau )]/[1 - \alpha _0 c^{1/2} + (\tau ^2 /3) ln 2\tau ]$$ Here, β₀ is the Onsager electrophoresis coefficient, α_oc^1/2 the limiting relaxation term, τ=e²κ/2DkT, κ^?1 is the Debye-Hückel distance, andA andB are empirical constants. The fact that three parameters are necessary to reproduce the data shows that ion pairing is not negligible for NaBPh₄ solutions despite the fact that the conductance curve lies above the limiting tangent even in ethanol (D=24.30). The quantity Λ_o is the limit of Λ^′ at zero concentration; the sum Aτ²+Bτ³ represents the part of the observed conductance from which the pairing constantK _Λ and the distance parameterR are derived. Conductance experiments should therefore be designed so that this sum is as large as possible, subject to the restriction that the highest concentration should not exceed 10^?7D³ (where the effects of short-range three-ion interactions are no longer negligible). Pairing constants for NaBPh₄ in the various solvents range from 4.6 in water to 70 in a mixture of Me₂SO and Me₂CO with dielectric constantD=23.80. The dependence ofE _s (the difference in free energy between solvent-separated pairs and contact pairs) on solvent composition is different for aprotic solvents and for mixtures containing water; for the latter, theE _s/kT vs. l/D plot shows a maximum while for the former the curve is monotone descending. The Walden produces (Λ_oη=limiting conductance times viscosity) plotted againstD ^?1 follow the same pattern.