A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium--VII. Photometric titration of vanadium(IV) and of cerium(III) alone and in mixtures with iroN(II)

Vanadium(IV) can be accurately titrated with potassium dichromate in media containing phosphoric acid of 3-12M concentration: the change in absorption of vanadium(IV) is followed in the region 660 mmicro using a red filter. It is more convenient to carry out the titration in 3M phosphoric acid because at higher concentrations chloride, nitrate, cerium(III) and manganese(II) may interfere. Photoelcetric titration is more convenient than potentiometric because the former can be made in a 3M phosphoric acid medium, whereas the latter is possible only in 12M phosphoric acid. The simultaneous differential photometric titration of iron(II) and vanadium(IV) is also possible. Conditions have been found for the photometric titration of cerium(III) and of cerium(III) plus iron(II). The titration is carried out (at 450 mmicro or with a blue filter) in about 10.5M phosphoric acid. Application of the method to a cerium mineral is considered.     

Dosage du plutonium par potentiometrie a intensite constante: Application au combustible de rapsodie

A new method is proposed for the determination of plutonium in the UO₂PuO₂ pellets for Rapsodie. The sample is dissolved in a mixture of II N nitric acid and 0.l N hydrofluoric acid, and the plutonium is oxidized with silver(II) oxide. Plutonium(VI) is reduced in the presence of sulphamic acid with an excess of iron(II) which is back-titrated with cerium(IV) solution to a constant-current potentiometric end-point. Uranium and iron do not interfere and no separation is required. In routine work, the method gives a precision of 0.5%.     

High-precision analysis of nuclear materials by constant-current coulometry: Part I Determination of uranium

Work is described on the application of constant-current coulometry for the highly precise and accurate assay of uranium and its compounds. Uranium is reduced to the tetravalent state by titanium(III) in nitric acid solution containing sulphamate and reacted with excess of iron(III) to give an equivalent amount of iron(II) which is titrated with electrogenerated cerium(IV). Factors governing the overall titration efficiency are discussed and results for the assay of a number of standard uranium materials presented. The procedure gives a standard deviation of 0.004% at the 40-mg level and an accuracy exceeding 0.01 %.     

Voltammetric behavior of the iron(II)-(III) and cerium(III)-(IV) couples in potentiometric titrations at constant current and amperometric titrations with two indicator electrodes

The voltammetric behavior at the rotated platinum electrode of the iron(II)-(lII) and cerium (III)-(IV) couples in sulfuric and hydrochloric acids has been investigated The iron and cerium couples are not reversible at a platinum electrode when current flows in the system, and the current-potential curves deviate considerably from those predicted on the basis of reversibility Titration curves for potentiometric titrations at constant current using one and two indicator electrodes are predicted from the current-potential curves and compared with the experimental curves.The degree of reversibility of the iron couple depends greatly on the pretreatment of the electrode The current-potential curves of the iron couple at a platinum electrode coated with a monomolecular film of platinum oxide approach reversibility while those at a clean electrode are highly irreversible Experimental and calculated titration lines for amperometric titrations using two indicator electrodes are compared, and the effects of medium and applied e.m.f. upon the characteristics of the titration curves are considered.     

Chemical determination of some major constituents in rocks and minerals

Macro-analytical schemes are described for the determination of aluminium, total iron and iron(II), as part of the complete analysis of silicate rocks and minerals Solvent extraction eliminates interferences before titration of aluminium with DCTA Iron(III) is extracted with MIBK and determined indirectly with EDTA Iron(II) is determined by potentiometric titration under an inert atmosphere. Interferences are removed with 2,4-pentanedione and carbon tetrachloride before the determination of calcium and magnesium.     

Potentiometric flow titration of iron(II) and chromium(VI) based on flow rate ratio of a titrant to a sample

A new potentiometric flow titration has been proposed based on the relationship of the flow rates between titrant and sample solutions. A sample solution is pumped at a constant flow rate. The flow rate of the titrant solution is gradually increased at regular time intervals and a flow rate for the titrant solution in the vicinity of the equivalence point is obtained. The concentration of the sample is calculated by C(S) (mol l(-1))=(R(T) (ml min(-1))xC(T) (mol l(-1)))/R(S) (ml min(-1)), where C(S), C(T), R(S), and R(T) denote the unknown sample concentration, titrant concentration in the reservoir, the flow rate of the sample solution which is a constant rate, and the flow rate of the titrant solution at an inflection point, respectively. The potentiometric flow titration of iron(II) with cerium(IV) and of chromium(VI) with iron(II) has been presented. The titration time of the proposed method is about 10 min per sample. An R.S.D. of the method is 0.77% for seven determinations of 1x10(-3) mol l(-1) iron(II). Similarly, the flow titration of chromium(VI) with iron(II) is carried out over the range 1x10(-4)-1x10(-3) mol l(-1) chromium(VI) and is successfully applied to the determination of chromium in high carbon ferrochromium.     

Titration of vanadium(IV) with cerium(IV) sulphate, with ferroin as indicator, in aqueous acetone as facile reaction medium An analytical and mechanistic study

A new procedure for the titration of vanadium(IV) with cerium(IV) sulphate, with ferroin as indicator, in aqueous acetone medium is reported. A differential determination of iron(II) and vanadium(IV) is also possible. A probable mechanism for the fast ferriin-vanadium(IV) reaction in acetone medium is given.     

Titration of vanadium(IV) with cerium(IV) sulphate, with ferroin as indicator, in aqueous alcohol as a facile reaction medium

A new procedure for the titration of vanadium(IV) with cerium(IV) sulphate, with ferroin as indicator, in aqueous alcohol medium, is reported. The visual titration gives accurate results but potentiometric titration fails in this medium; this failure is attributed to the sluggish indicator electrode behaviour. Experimental conditions for preliminary quantitative photochemical reduction of vanadium(V) with alcohol have been established.     

Sequential titration of iron(II), antimony(III) and arsenic(III) in binary or ternary mixture

A simple titrimetric procedure for the determination of iron(II), antimony(III) and arsenic-(III) in a mixture, with cerium(IV) sulphate as titrant, is proposed. The end-points can all be detected with ferroin or potentiometrically. Phosphoric acid medium is used for titration of the iron(II), then acetic acid medium for the titration of antimony(III), and finally the arsenic(III) is titrated in presence of iodine as catalyst. The procedure utilizes a single portion of test solution; it can be adopted for the analysis of binary mixtures.     

Sequential titration of iron(II) and vanadium(IV) mixtures with cerium(IV) sulphate, with ferroins as indicators

The titration of vanadium(IV) with cerium(IV) sulphate, with nitroferroin as indicator, is proposed. Unlike ferroin, the indicator does not need a catalyst in this system. By suitable choice of experimental conditions iron(II) can be titrated first to a ferroin end-point and then vanadium(IV) to a nitroferroin end-point.     

The determination of molybdenum in high-nickel alloys by potentiometric titration with cerium(IV) solutions

A combination of ion-exchange separation and potentiometric titration is used in the determination of the molybdenum content of various high-nickel alloys that contain more than 4% molybdenum. The molybdenum(VI) fraction of a sample separated by ion exchange is reduced with tin(II) chloride and titrated with cerium(IV) sulfate. The method facilitates accurate, routine determinations without the extreme care that is required by the standard photometric method or the length and complexity of the gravimetric method. By suitable adjustment of the sample size or the strength of the titration solution, effective titrations can be conducted on samples containing up to 100% molybdenum.     

2-Nitrodiphenylamine as a versatile high-potential reversible oxidation-reduction indicator

The use of 2-nitrodiphenylamine as a reversible indicator has been investigated in the titration of iron(II) with cerium(IV) sulphate, potassium dichromate and sodium vanadate in sulphuric acid media. Accurate results can be obtained with cerium(IV) sulphate in 0.5–5.0 M acid, with potassium dichromate in 5.0–7.0 M acid, and with sodium vanadate in 5.0–7.5 M acid. With cerium(IV) sulphate the titrations are preferably conducted in 2.0 M sulphuric acid or in a 1.0 M. sulphuric acid-1.0 M pechloric acid medium. Tungstic acid, acetic acid, arsenic(III) and manganese(II) do not interfere. In titrations of iron(II) with dichromate and vanadate, the colour changes at the end-point are much more vivid with 2-nitrodiphenylamine than with ferroin.     

Macro and semimicro determination of inorganic bromide by cerium(IV) oxidimetry

Aqueous solutions containing 1-200 mg of inorganic bromide in 25-100 ml of solution are quantitatively analysed at room temperature by direct titration with ammonium hexanitratocerate(IV) in 2M perchloric acid. The titration medium is perchloric acid at a concentration of at least 4M. End-points are determined from potentiometric (Pt vs. S.C.E. electrodes) titration plots, the potential break at the end-point being 300 mV. Iodide up to at least 0.02N and sulphate up to 0.01N do not interfere. Chloride depresses the end-point potential break but a satisfactory titration curve is still obtained in the presence of 0.04N chloride. Standard deviations are +/- 0.068 mg of bromide in the 1- to 20-mg range [0.02M cerium(IV) titrant] and +/- 0.45 mg of bromide in the 20- to 200-mg range [0.1M cerium(IV) titrant].     

Titrimetric determination of U(iv) alone and in mixtures with V(IV), Mn(II), Ce(III) and Fe(II)

Summary A rapid and accurate method is described for the potentiometric determination of uranium(IV) with permanganate at room temperature using trace amounts of ortho-phosphoric acid as a catalyst. The procedure has been extended for the differential potentiometric determination of mixtures with vanadium, manganese or cerium. The methods are easy, non-time consuming and free from interference by a large number of foreign ions. Conditions are also developed for the differential photometric determination of uranium and iron in mixtures.Based on these procedures, a differential titrimetric procedure has been developed for determination of iron(III), vanadium(V), chromium(VI) and manganese(VII) [or cerium(IV)] in a single solution at room temperature. This procedure has also been tested on Bureau of Standard samples.

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Titrimetrische Bestimmung von U(IV) allein und in Mischungen mit V(IV), Mn(II), Ce(III) und Fe(II)Anwendung auf die Analyse von Stählen und Legierungen

Zusammenfassung Eine schnelle und genaue Methode wird beschrieben zur potentiometrischen Bestimmung von Uran(IV) mit Permanganat bei Raumtemperatur unter Verwendung von Spuren Orthophosphorsäure als Katalysator. Das Verfahren wurde auf die differentialpotentiometrische Bestimmung im Gemisch mit V, Mn und Ce ausgedehnt. Die rasch und einfach ausführbare Methode wird durch zahlreiche Fremdionen nicht gestört. Eine differentialphotometrische Bestimmung von U(IV) und Fe(II) im Gemisch wird ebenfalls angegeben, außerdem eine differentialtitrimetrische Bestimmung von Fe(III), V(V), Cr(VI), Mn(VII) [oder Ce(IV)] in einer Lösung. Anwendungsbeispiele für Stähle und Legierungen werden beschrieben.

     

Potentiometric titration of milligram quantities of uranium in the presence of iron

A method is described for the potentiometric titration of milligram quantities of the uranium(IV) ion in the presence of iron. This is accomplished by complexing the iron with 1.10-phcnanthroline. The uranium can then be titrated with standard ceric sulfate without interference from the iron.     

镧系元素光化学 Ⅳ 铁和铈对光还原分离铕的影响

本文在水溶液中以1:1HCOOH～HCOONa做自由基清除剂,Na_2SO_4做光还原产物Eu~(2+)沉淀剂,研究了杂质铁和含量变化对光还原分离铕的影响,并用紫外光谱证明了体系中是光反应生成的Fe和Ce~(4+)对发生氧化,致使Eu~(2+)光还原生成Eu~(2+)速度减慢,铕的收率下降。     

Coulometric determination of serum iron

The iron in 500 μl of serum is determined by a coulometric titration developed for ferroin. The titration step is preceded by chloroform extraction from a protein-free filtrate of serum iron as ferroin perchlorate. Evaporation of chloroform in the presence of an acetate buffer of pH 4.6 causes the ferroin perchlorate to back-extract into the aqueous layer. The ferroin is introduced into a titration cell and titrated with electrogenerated cerium(IV), a modified amperometric end-point detection system being used.     

Electrometric end points in the oxidation of thiocyanate by permanganate. Determination of cerium

Summary Oxidation of thiocyanate by standard permanganate using electrometric end points is shown to be quantitative in 1.5–2.5N HCl medium and in the presence of ICl as catalyst. A method of estimating cerium(IV), based upon its reduction to cerium(III) by excess KSCN and potentiometric titration of the excess against KMnO₄, is also described.Sincere thanks of the author are due to Prof. S. S. Joshi for research facilities.     

Microtitrimetry by controlled current potentiometric titration

The classical methods of titration require large volumes of chemicals. Microtritimetry is the method of choice since it utilizes small quantities of chemicals and yields less waste compared to other conventional methods. Thus it benefits both the analytical chemists and the environment. In this communication, microtitrimetry is performed by employing the technique of differential electrolytic potentiometry for the location of the end point. Oxidation-reduction titration using platinum electrodes is described. For the first time the endpoint for a sample of 1.0 μL of 0.10 M Fe(II) has been located by titration using a solution of Ce(IV). The optimum conditions such as volume of cerium ammonium sulfate added, current applied to polarize the electrodes in case of dc controlled current potentiometric titration (CCPT). The effect of changing the percentage bias of the square wave used to polarize the electrodes on the differential peak in case of ac CCPT has been investigated. The precision of this microtitrimetric method is also reported.     

Micro-fusion and spectrophotometric determination of iron(II) and iron(III) in chrome spinels and other refractories

Spectrophotometric determination of FeO in milligram samples of chrome spinels and related refractory minerals after high-frequency micro-fusion with lithium tetraborate in an inert atmosphere is described. Anomalous responses (apparent reduction or oxidation of FeO depending on the ferroïn-type reagent)_rendered the procedure highly unreliable. All the fluxes containing structural oxygen, as well as phosphoric acid, acted as oxidants even when atmospheric oxidation was rigorously excluded. However, the method is suitable for micro-determination of total iron in spinels. Spectrophotometric measurements gave an average relative standard deviation of 0.73%.