Gaseous catalysts for end-point indication in titrimetric analysis in the microgram range

The method of end-point detection described is very sensitive. In titrations with sodium sulphide, the first drop of titrant in excess cause evolution of hydrogen sulphide which acts as a catalyst for the indicating iodine—azide reaction. The gas formed at the end-point is transferred by a nitrogen stream to the indicator vessel. Microgram amounts of metal ions (Sb, Ni, Fe, Hg⁺ Cd, Pb⁺ Cu, Ag⁺ Cu) and permanganate can be titrated in acidic solution with standard sulphide solution. In a variation of this method, acid-base titrations are possible.     

A conductometric method for colloid titrations

A negative or positive colloid sample solution can be directly titrated, respectively, with a polycationic (poly-N, N-diallyldimethylammonium chloride) or polyanionic (potassium polyvinylsulfate) titrant to a conductometric end-point. With the conventional toluidine blue indicator method a positive colloid solution is titrated directly with a polyanionic titrant, but a negative colloid solution must be treated with an excess of a polycationic titrant, which is back-titrated with the polyanionic titrant. For positive colloid solutions, both indicator and conductometric methods are suitable; for negative colloids the conductometric method is preferable because of its constant titration vlues over a range of pH values.     

Contributions to the basic problems of complexometry-XXVI determination of calcium in the presence of large amounts of magnesium

Two methods for the determination of calcium in the presence of very large amounts of magnesium are proposed. Both are based on back-titration of excess of EGTA, Thymolphthalexone being used as indicator. In the one method the titrant is a zinc solution, in the other a calcium solution is used, with a small amount of zinc present for end-point indication. Both titrations can be performed either visually or spectrophotometrically.     

Titrimetric determination of fluoride in some pharmaceutical products used for fluoridation

Two titrimetric methods were developed for the determination of fluoride contents in some pharmaceutical preparations used for fluoridation. One of the methods is catalytic controlled-current potentiometry involving two identical platinum indicator electrodes and thorium nitrate as titrant. The reaction between hydrogen peroxide and potassium iodide in the presence of acetate buffer (pH 3.6), which is catalysed by the excess of thorium nitrate, served for the end-point indication. The other method is the automatic potentiometric titration involving a fluoride-selective electrode and lanthanum nitrate as titrating agent. In both procedures, special attention was paid to sample pretreatment and to determination of optimal experimental conditions. Fluoride contents in the range 16-32 microg/ml are determined with a relative standard deviation less than 1.34%. The results are compared to those obtained by standard methods described in the United States Pharmacopeia XXI and recommended by the manufacturer of the preparations.     

Tin(II) sulphate as a new reductimetric titrant--direct titration of thallium(III) with use of ion-pair and redox indicators

The use of tin(II) sulphate as a direct reductimetric titrant for thallium(III) has been investigated, with potentiometric and visual detection of the end-point. Some azure dyes are used as redox indicators and Methylene Blue is used as both a redox and an ion-pair indicator.     

Simple instrument for titrimetry without visual indicators. Gasometric titrations: Dichromatometry

Even ions which do not release gases with a certain titrant can be determined by direct gasometric titration. To achive this end, a substance which liberates a gas with the titrant, must be added to the sample solution. The end-point of the main reaction can be read from the gasometric titration curve of this indicator substance.This principle is applied in the present paper to the titration of ferrous and stannous ions by potassium dichromate. Hydrazine sulfate serves as indicator. The results are comparable in precision and accuracy to the values obtained by the conventional visual end-point titrations.     

Total systematic error in redox titrations with visual indicators--I: basic principles

The following factors contribute to the total error in redox titrations with visual indicators: the end-point error (DeltaV(T)), which arises from the difference between the potential of the equivalence point and that of the actual end-point determined by a given indicator ; the indicator consumption error (DeltaV(T)), which arises from the amount of indicator oxidized (or reduced) by the titrant; the irreversibility error, which is in fact a part of the indicator consumption error, arising from the generally uncontrolled processes connected with the irreversibility of the redox processes, decomposition of the reaction products, etc. The first two factors can be evaluated on the basis of the physicochemical characteristics of all the systems involved. They contribute to the total systematic error. The third, being not strictly controlled, in general increases the positive indicator consumption error, depending on such parameters as rate of titrant addition, stirring, effect of decomposition products on the potential, etc.     

Ein einfaches verfahren zum bestimmen von hydrosulfit

When titrating hydrosulphite with a neutral solution of ferric chloride, using a mixture of thiocyanate and ferrocyanide as indicator, a deep red coloration of ferric thiocyanate is observed near the end-point of the titration. At the final end-point the solution rapidly turns blue. By this means it is possible to titrate very rapidly and a slight excess of titrant is easily estimated. A preliminary titration gives the approximate quantity of iron to add in the final solution to which the solid hydrosulphite is to be added; as in the final titration there remain only minimal quantities of hydrosulphite, the error due to aerial oxidation is thus completely eliminated. Without the protection of an inert gas and without back-titration it is possible to obtain results with an error less than 0.1 %.     

Potentiometric back-titration of sulfate ion using a tetraphenylborate derivative as a titrant and a titrant-sensitive plasticized poly(vinyl chloride) membrane electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode without added ion-exchanger is described. A solution of a derivative of tetraphenylborate is used as titrant. The method is based on the ion association between an excess of 2-aminoperimidinium added to the sulfate containing sample and the tetraphenylborate derivative in the titrant. The titration end-point is detected as a sharp potential change due to an increase in the concentration of the free tetraphenylborate derivative at the equivalence point. The sharpness of the titration curve at the end-point is compared for two tetraphenylborate derivatives. Good results are obtained with a solution of sodium tetrakis (4-fluorophenyl) borate.     

Potentiometric determination of potassium ferricyanide

A rapid and accurate electrometric method for the determination of potassium ferricyanide solutions has been investigated. It consists in titrating ferricyanide solutions potentiometrically against standard AgNO₃, using a silver indicator electrode in conjunction with a saturated calomel electrode connected by a KNO₃ bridge. Either of the reagents may be used as the titrant. A marked change in e.m.f is observed at thc end-point corresponding to the formation and precipitation of Ag³[Fe(CN)₆]. The curves have a regular form, a pronounced maximum in dE/dV occurs at the end-point and the results are very accurate and reproducible. The reaction, though simple, affords a quantitative method for the determination of ferricyanide or silver. The effect of neutral salts and ethanol on the accuracy of the end-point has been studied.     

Determination of sulfate ion by potentiometric back-titration using sodium tetrakis (4-fluorophenyl) borate as a titrant and a titrant-sensitive electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode sensitive to a titrant is described. The method is based on ion association between the excess of 2-aminoperimidinium added to the sulfate ion in the sample and sodium tetrakis (4-fluorophenyl) borate (FPB) in the titrant. The titration end-point was detected as a sharp potential change due to an increase in the concentration of the free FPB at the equivalence point. The end-point was detected even in the presence of a 20-fold excess of common cations and anions relative to the concentration of the sulfate ion within approximately 2% of titration error. A linear relationship between the concentration of the sulfate ion and the end-point volume of the titrant exists in the sulfate ion concentration range from 2x10(-4) to 3x10(-3) mol l(-1) using 10(-2) mol l(-1) FPB solutions as the titrant. The present method could be applied to determine sulfate ions in sea water.     

Compleximetric titration of chromium (III) with catalytic end-point detection

Chromium (III) (2–20 mg) is determined by reaction with excess of EDTA and backtitration with a standard copper(II) solution to a catalytic end-point. The indicator reaction is the copper (II) -catalyzed autodecomposition of hydrogen peroxide, which is observed biamperometrically. For 10 mg of chromium (III) , the relative standard deviation was < 0.5 % (n=10).     

Potentiometric back-titration of sulfate ion using a tetraphenylborate derivative as a titrant and a titrant-sensitive plasticized poly(vinyl chloride) membrane electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode without added ion-exchanger is described. A solution of a derivative of tetraphenylborate is used as titrant. The method is based on the ion association between an excess of 2-aminoperimidinium added to the sulfate containing sample and the tetraphenylborate derivative in the titrant. The titration end-point is detected as a sharp potential change due to an increase in the concentration of the free tetraphenylborate derivative at the equivalence point. The sharpness of the titration curve at the end-point is compared for two tetraphenylborate derivatives. Good results are obtained with a solution of sodium tetrakis (4-fluorophenyl) borate. Received: 9 March 1998 / Revised: 21 April 1998 / Accepted: 25 April 1998     

Use of a Tensammetric Wave for the End-Point Detection in Chelatometry

Abstract

A new method for the end-point detection in complexometric titration using a tensammetric wave of organic reagents such as oxine and alizarin complexone (ALC) was studied. The tensammetric wave of these reagents disappears by their chelate formation and reappears by the liberation of free indicator during the exchange reaction between indicator chelate and EDTA. This mechanism is utilized for the end-point detection in complexometric titration of metals. Since the sensitivity of tensammetric wave is extremely high, very sharp end-point can be obtained for the titration of metals even in the concentration of 10^?5M.     

Catalytic end-point indication in redox titrations

The applicability of catalytic end-point indication to redox titrations is demonstrated by the determination of 3–30 μmol of ascorbic acid (in 22.5 ml of solution) with standard dichromate solution; the chromium(VI)-catalyzed oxidation of o-dianisidine with hydrogen peroxide serves as indicator reaction. Oxidizing substances, such as vanadium(V), thallium(III) or cerium(IV) can be determined by addition of excess of ascorbic acid and back-titration.     

Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator

The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5×10⁻⁵ eq. mol dm⁻³ for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined.     

An automatic back titration method for microchemical analysis

An automatic back titration method for microchemical analysis is introduced, which is based on conventional volumetric analysis's principle and the use of flow injection analysis apparatus for the automation and microminiaturization of the process. The sample and a known, but excess amount of a calibrated reagent solution are injected and propelled into a titration cell, where their reaction takes place. The excess of the reagent is then titrated with a titrant containing an indicator and the end point is monitored photometrically. Since homogeneous mixing in the titration cell is obtained magnetically in the whole process, there is a linear relationship between the analyte's concentration and the volume of the titrant consumed. Nickel in the range of 10-70 g 1(-1) is determined by the above method, in which 30 microl of sample and 500 microl of EDTA are injected and the excess of EDTA is titrated with a standard zinc salt solution containing xylenol orange which could be blocked by nickel ion in a direct titration. This method is characteristic of low sample and reagent consumption, high sampling rate as high as 45 samples h(-1), negligible effect of sample's viscosity, small carry-over effect (lower than 0.14%), and very good precision, whose relative standard deviations are as small as 0.24%.     

Titration of methylene blue with chloromolybdate(III)

The reaction of Methylene Blue with aquomolybdenum(III) chloride and chloromolyb-date(III) in hydrochloric acid media has been investigated. Chloromolybdate(III) can be satisfactorily used as a reductometric titrant for Methylene Blue in 6-8M hydrochloric acid medium. The end-point can be detected either potentiometrically or visually. Aquomolybdenum(III) chloride is not useful as a titrant for this estimation.     

Gaseous catalysts for end-point indication in titrimetric analysis in the microgram range with iodide and bromide as catalysts

A new technique for end-point detection in titrations with bromate is described. The first drop in excess causes evolution of bromine which is swept by nitrogen into an indicator vessel. There, the bromine reacts with iodide to form iodine which catalyzes the cerium(IV)—arsenic(III) reaction or with sulfite to form bromide which catalyzes the permanganate—iodine reaction. Microgram amounts of antimony(III) or arsenic(III) can be determined.     

Amperometric titration of copper with tetraethylenepentamine

Tetraethylenepentamine is a very selective titrant for the determination of copper in acidic medium. With amperometric end-point detection as little as 0.1 mg copper in a volume of 25 ml can, be determined with an accuracy of ± 1%. When the titration is performed in acetic acid/ ammonium acetate buffer of pH 4.1, only mercury causes significant interference.