Determination of some halogen osmium-carbonyl derivatives using ion-selective electrodes

Summary The concentrations of certain halogen derivatives of osmium carbonyls were determined potentiometrically by using a silver ion-selective electrode based potentiometric titration technique. In case of the series Os₃(CO)₁₂X₂, X= Cl, Br, I, inflections in the titration curves were at volumes of AgNO₃ corresponding to one halide ion. In contrast, the series Os₃(CO)₁₀X₂ gave inflections equivalent to two X^– ions. The concentrations of trans-Cl₂Os(CO)₄ as well as ClSnPh₃ were also determined by this technique. Standard deviations were in the range of 0.1%–0.37%, recoveries between 98% and 99.7%.

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Bestimmung einiger Halogenosmiumcarbonylverbindungen mit Hilfe von ionenselektiven Elektroden

     

Determination of tetracycline and related compounds using plastic membrane ion-selective electrodes

PVC membrane electrodes selective for hydrochlorides of tetracycline (TC), doxycycline (DC) and oxytetracycline (OTC) are prepared. The electrodes show a linear response with Nernstian slope over the range of 1.6 × 10⁻⁵–10⁻²M, 7.9 × 10⁻⁵–1.9 × 10⁻³M, and 6.3 × 10⁻⁵–6.3 × 10⁻³M for TC, DC, and OTC, respectively. The effects of pH of the test solution and time of soaking on the electrodes' performance are studied. The electrodes exhibit good selectivity for the investigated antibiotics with respect to a large number of inorganic cations and organic substances of biological importance. TC, DC, and OTC are determined successfully in pure solutions and in some pharmaceutical preparations using the standard additions method.     

Determination of sulpha-drugs with ion-selective membrane electrodes

A liquid-membrane mercury(II)-sensitive electrode is used for determination of various sulpha drugs by addition of excess of mercuric nitrate and potentiometric back-titration of the surplus mercury(II) with EDTA. The performance of the electrode is compared with that of an Ag(2)S crystal-membrane electrode. Attempts to prepare a sulphamethoxazole-sensitive electrode failed.     

Micro and semimicro determination of arsenate using ion-selective electrodes

Summary An indirect method for the microestimation of 0.75 to 15 ppm (1–10^–5 to 2·10^–4 M) of As(V) has been described: Arsenate is precipitated with lanthanum nitrate at a pH of 8.65. The excess of lanthanum is titrated with standard fluoride, using a fluoride ion-selective electrode. Equivalence points are located on volume-corrected Gran's plot paper. This method can also be used to estimate the sum of arsenate and phosphate. For larger amounts of arsenate and for increased precision and accuracy, potentiometric titration with lead perchlorate, using a lead ion-selective electrode, is recommended. Other possibilities for determining arsenate and a method for estimating tungstate are suggested.

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Zusammenfassung Eine indirekte Methode zur Mikrobestimmung von 0,75 bis 15 ppm (10^–5 bis 2·10^–4-m) As(V) wurde beschrieben. Arsenat wird bei pH 8,65 mit Lanthannitrat gefällt, dessen Überschuß man mit einer Fluoridstandardlösung unter Verwendung einer fluoridspezifischen Elektrode titriert. Die Äquivalenzpunkte trägt man auf einem volumenkorrigierten Millimeterpapier nach Gran auf. Nach diesem Verfahren kann auch die Summe von Arsenat und Phosphat bestimmt werden. Für größere Arsenatmengen und für erhöhte Anforderungen an Genauigkeit wird die potentiometrische Titration mit Bleiperchlorat gegen eine bleispezifische Elektrode empfohlen. Andere Möglichkeiten der Arsenbestimmung sowie eine Methode zur Wolframbestimmung werden vorgeschlagen.

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

Coated-wire ion-selective electrodes

Coated-wire ion-selective electrodes were first developed in 1971, and comprise a film of polyvinyl chloride or other suitable polymeric matrix substrate containing a dissolved electroactive species, coated on a conducting substrate (generally a metal, although any material with conductivity substantially higher than that of the film can be used). Electrodes of this sort are simple, inexpensive, durable and capable of reliable response in the concentration range of 10^?1 to 10^?6 M for a wide variety of both organic and inorganic cations and anions. The principles on which these electrodes are based, as well as their application to a variety of analytical problems, will be discussed.     

Neutral-carrier-based ion-selective electrodes

Neutral-carrier-based ion-selective electrodes for the assay of alkali and alkaline earth metal cations have advanced to become the most frequently used potentiometric sensors in clinical chemistry. The major developments since the realization of the first potentiometric cell assemblies utilizing electrically neutral complexing agents (valinomycin and the macrotetrolides) in 1966 are presented.     

Direct potentiometric water hardness determination using ion-selective electrodes

Summary The use of ion-selective electrodes for direct potentiometric water hardness determinations is restricted to relatively soft waters if they are to be competitive with other techniques in terms of uncertainty on the water hardness scale. The selectivity factorK _MgCa ^Pot must be within 1.1% of unity if a hardness of 10 degrees on the German scale is to be measured to within 0.1 degrees in the composition rangec _Mg:c _Ca=0.25 to 25. The expressionK _MgNa ^Pot ·a _Na ² / (a _Mg+a _Ca) must be less than 0.001 if freedom from sodium interference is to be achieved. Under these conditions a 1% relative standard deviation can be obtained for an uncertainty of the EMF100V.

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Direkte potentiometrische Bestimmung der Wasserhärte mit ionen-selektiven Elektroden

Zusammenfassung Die direkte potentiometrische Bestimmung der Wasserhärte mit ionenselektiven Elektroden kann nur für relativ weiches Wasser verwendet werden, sofern sie mit anderen Methoden konkurrenzfähig sein soll. Der SelektivitätsfaktorK _MgCa ^Pot sollte nicht mehr als 1,1% von 1 abweichen, um eine Messung von 10 deutschen Härtegraden auf 0,1 Grad genau zu ermöglichen, wenn gleichzeitig das Mischungsverhältnisc _Mg:c _Ca im Bereich 0,25 bis 25 schwankt. Der AusdruckK _MgNa ^Pot ·a _Na ² /(a _Mg +a _Ca) sollte 0,001 nicht überschreiten, wenn eine Störung durch Natrium vermieden werden soll. Unter den obigen Bedingungen läßt sich eine Wasserhärte auf 1% genau bestimmen, wenn die Unsicherheit der gemessenen EMK100V.

     

The potentiometric titration of surfactants and soaps using ion-selective electrodes

Summary Several quaternary ammonium halides have been evaluated for the precipitation titration of anionic surfactants and soaps. The titrants were hexadecyltrimethylammonium chloride and bromide, hexadecylpyridinium chloride, and diisobutylphenoxyethoxyethyl(dimethyl)benzylammonium chloride. Hexadecylpyridinium chloride yielded the highest precision and largest potentiometric break. Titrations were monitored with a commercically available fluoroborate ion-selective indicator electrode and a double-junction reference electrode. Commercially available perchlorate, nitrate, and calcium electrodes may also be used for emf monitoring. This obviates the need of preparing special liquid membrane or other electrodes mostly used heretofore in the potentiometric titration of surfactants and soaps. Electrophoresis purity reagent sodium dodecylsulfate is recommended for the standardization of the quaternary ammonium halides. The reverse titration, of cationic surfactants vs. standard sodium dodecylsulfate, is similarly feasible.Work performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore Laboratory under contract number W-7405-ENG-48.     

The determination of microgram amounts of orthophosphate using ion-selective electrodes

Summary The potentiometric titration ofg amounts of orthophosphate with lead perchlorate using a lead ISE, and with silver nitrate using a silver sulfide ISE, was investigated. With 0.001N lead perchlorate the practical limit of the determination is approximately 10g (0.3mol) of phosphorus. Microgram amounts of phosphate require the application of a small polarizing current to the lead ISE to enhance the potential breaks near the endpoint.Previously reported titrimetric methods for orthophosphate with silver nitrate were reinvestigated using a silver sulfide ISE. The borate-buffered system proved superior to the sodium acetate-methanol system when a partially non-aqueous medium of 60–70% methanol was used. With the borate-buffered system, 0.005N silver nitrate can be used, while it cannot be used in the sodium acetate-methanol system. Also, considerably larger amounts of sulfate and fluoride can be tolerated in the borate-buffered system. The sequential determination of halides and phosphate is feasible in this system.

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Zusammenfassung Die potentiometrische Titration von Mikrogrammengen Orthophosphat mit Bleiperchlorat und einer bleispezifischen Elektrode bzw. mit Silbernitrat und einer silberspezifischen Elektrode wurde untersucht. Mit 0,001-n Bleiperchlorat liegt die praktische Grenze der Bestimmbarkeit bei etwa 10g (0,3Mol) Phosphor. Bei Mikrogrammengen Phosphat muß man an die bleispezifische Elektrode einen schwachen Polarisationsstrom anlegen, um den Potential-Knick nahe dem Endpunkt zu verstärken.Früher veröffentlichte Titrationsmethoden für Orthophosphat mit Hilfe von Silbernitrat wurden neuerlich mit einer Silbersulfidelektrode bearbeitet. Ein Boratpuffersystem erwies sich der Pufferung mit Natriumacetat-Methanol überlegen, wenn in 60–70%igem Methanol gearbeitet wird. In boratgepufferter Lösung kann man mit 0,005-n Silbernitrat titrieren im Gegensatz zu acetat-methanolischer Lösung. Auch können wesentlich größere Mengen Sulfat und Fluorid im boratgepufferten System toleriert werden. Halogenide und Phosphat können in diesem Milieu nacheinander bestimmt werden.

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This work was performed under the auspices of the U. S. Atomic Energy Commission.     

Screen-printed copper ion-selective electrodes

A simple, low-cost and reproducible method for the mass production of potentiometric ion-selective electrodes for copper ions is presented. These planar, strip sensors were obtained by screen-printing. The application of pastes cured at low temperature allows printing of the sensors on low-cost, plastic substrates. The pastes for printing of ion-sensitive thick-film membranes were based on copper (1) and copper (II) sulfides. The analytical characteristics of the thick-film electrodes were compared. The analytical properties (range of determination, sensitivity, selectivity, response time) of the copper (I) sulfide-based sensors were comparable with those for conventional ion-selective electrodes.     

Theory and applications of ion-selective electrodes. Part 8

This review on ion-selective electrodes (ISEs) is arranged in the same way as earlier reviews of this series. The whole subject continues to grow. As in the preceding review, the most discussed field is that of analysis for body-fluid cations, particularly with automatic devices. Almost 800 papers published between Spring 1987 and Spring 1989 are mentioned, including some omitted in the preceding review. They cover the theory of membrane processes, technology (including ISFETs and electrolysis at liquid/liquid interfaces), fixed-site electrodes, potentiometric biosensors and miscellaneous systems.     

Screen-printed copper ion-selective electrodes

A simple, low-cost and reproducible method for the mass production of potentiometric ion-selective electrodes for copper ions is presented. These planar, strip sensors were obtained by screen-printing. The application of pastes cured at low temperature allows printing of the sensors on low-cost, plastic substrates. The pastes for printing of ion-sensitive thick-film membranes were based on copper (I) and copper (II) sulfides. The analytical characteristics of the thick-film electrodes were compared. The analytical properties (range of determination, sensitivity, selectivity, response time) of the copper (I) sulfide-based sensors were comparable with those for conventional ion-selective electrodes. Received: 12 January 2000 / Revised: 13 March 2000 / Accepted: 16 March 2000     

Determination of K+ in diluted and undiluted urine with ion-selective electrodes

Summary Polyvinylchloride liquid membrane electrodes based on valinomycin lead to low readings in the determination of K⁺ in undiluted urine because of anion interference. This interference is eliminated by instead incorporating valinomycin into silicone rubber. When K⁺-concentrations, as determined in undiluted urine by ion selective electrodes, are correlated with those obtained for the same samples by flame photometry, the residual standard deviation is found to be ±1.5 mM over the 20 to 170 mM K⁺ range.

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Bestimmung von K⁺ in verdünntem und unverdünntem Harn mit ionen-selektiven Elektroden

Zusammenfassung Bestimmungen von K⁺ in unverdünntem Harn mit auf Valinomycin beruhenden Polyvinylchlorid-Flüssigmembranelektroden ergeben systematisch zu tiefe Werte. Diese Abweichungen sind durch Anioneninterferenz bedingt und können durch den Einsatz von Silikongummi als Membranmatrix eliminiert werden. Die Korrelation der mit K⁺-selektiven Silikongummimembranen in unverdünntem Harn ermittelten Meßwerte mit Ergebnissen der Flammenphotometrie ergibt eine Standardabweichung um die Regressionsgerade von ±1,5 mM über den K⁺-Konzentrationsbereich von 20 bis 170 mM.

     

Determination of selectivity coefficients of ion-selective electrodes by a matched-potential method

A new method is proposed for the determination of selectivity coefficients of ion-selective electrodes. A reference solution of the primary ion is used and potential changes are measured after adding either the primary ion or secondary ion. Increasing concentrations of the secondary ion are added to provide the same potential change as obtained for a fixed added concentration of the primary ion. The ratio of the primary-to-secondary ion concentrations for this potential change represents the selectivity coefficient. This method is illustrated by the use of a sodium glass electrode and a potassium valinomycin electrode. Results obtained are compared with those from conventional determinations of selectivity coefficients. The advantages of this method are discussed.     

Properties of naproxen ion-selective electrodes

Naproxen membrane electrodes based on different plasticizers and the quaternary ammonium salts (QASs) dimethyldidecylammonium bromide, methyltrioctylammonium chloride, or tetraoctylammonium chloride, were prepared. The following basic parameters were investigated for the optimal electrode: measurement range (10⁻⁴ − 10⁻¹ mol L⁻¹), slope of the linear range of the calibration curve (−58.3 mV decade⁻¹), limit of detection (6.0 × 10⁻⁵ mol L⁻¹), lifetime (2.5 months), dependence of the electrode potential on pH (5.5 − 9.0), reproducibility of potential (1.2 mV) and selectivity coefficients in relation to selected organic and inorganic anions. The electrode was utilized for determination of naproxen in tablets by the calibration curve method and the standard addition method.      

A dilutional microassay for serum ionized calcium using ion-selective electrodes

A microassay for serum ionized calcium was developed and characterized with commercially available instrumentation that employs conventional electrochemical, ion-selective electrode, methodology. The microassay consists of diluting serum with an appropriate concentration and volume of tris(hydroxymethyl)aminomethane at physiological pH and ionic strength. The diluent was capable of buffering serum throughout the normal and pathologic ranges of pH and the performance characteristics of the microassay were independent of serum protein concentration. An application of the method is provided and the results support the view that calcium may be involved in cysteamine-induced attenuation of episodic growth hormone secretion in male rats.