Ferroins reaction

The bromate-ferroin reaction has a quadratic autocatalytic sequence, but in this case the induction period is detennined primarily by the time required for the concentration of the hiliibitor bromide ion to fall to a critical low value tlirough the reactions... 

The first experiment on the relative stability in a bistable multi-variable system is reported in [36]. The apparatus consists of two continuously stirred tank reactors (CSTR), and a different stable stationary state of a bistable bromate-ferroin reaction is established in each CSTR with same set of influx of reactant solutions into the reactors. The reaction solution from each tank is then pumped quickly into a laminar flow reactor (LFR) where the solutions... 

End Point Determination Adding a mediator solves the problem of maintaining 100% current efficiency, but does not solve the problem of determining when the analyte s electrolysis is complete. Using the same example, once all the Fe + has been oxidized current continues to flow as a result of the oxidation of Ce + and, eventually, the oxidation of 1T20. What is needed is a means of indicating when the oxidation of Fe + is complete. In this respect it is convenient to treat a controlled-current coulometric analysis as if electrolysis of the analyte occurs only as a result of its reaction with the mediator. A reaction between an analyte and a mediator, such as that shown in reaction 11.31, is identical to that encountered in a redox titration. Thus, the same end points that are used in redox titrimetry (see Chapter 9), such as visual indicators, and potentiometric and conductometric measurements, may be used to signal the end point of a controlled-current coulometric analysis. For example, ferroin may be used to provide a visual end point for the Ce -mediated coulometric analysis for Fe +. 

Peroxymonosulphuric acid (PMSA, H SO ) proved to be a promising oxidizer in reactions with chemiluminescent substances (luminol) with participation of such ions as Mn(II), Cu(II), Ni(II), Cr(IV), V(V). The literature data show the possibility of utilization PMSA in indicating reaction with ferroin ([Fe(l,10-phenanthrolyne) ] ) which is accelerated by Mn(II) compounds. 

The optimal conditions for accelerating of investigated reaction by ions Fe(III) and Ag(I) ai e the following pH 5,0 (acetic buffer), Cj. . =l,6T0 M, CpMSA=4T0 M, Cpp =2-10 M. Under these conditions, factors of sensitivity for kinetic determination of metals mentioned above were established as a slope s tangent of the calibration curves that is a plot of reaction velocity (change of optical density of ferroin s solution for 4 minutes) versus analyte s concentration. Factors of sensitivity for determination of Mn(II), Fe(III), Ag(I), Pd(II), Co(II) ai-e 5,5-10" 1,1-10" 2,5-10" 2,0-10" 8,0-10", respectively. 

For the titration of colourless or slightly coloured solutions, the use of an indicator is unnecessary, since as little as 0.01 mL of 0.02 M potassium permanganate imparts a pale-pink colour to 100 mL of water. The intensity of the colour in dilute solutions may be enhanced, if desired, by the addition of a redox indicator (such as sodium diphenylamine sulphonate, AT-phenylanthranilic acid, or ferroin) just before the end point of the reaction this is usually not required, but is advantageous if more dilute solutions of permanganate are used. 

Method A Standardisation with arsenic (III) oxide. Discussion. The most trustworthy method for standardising cerium(IV) sulphate solutions is with pure arsenic(III) oxide. The reaction between cerium(IV) sulphate solution and arsenic(III) oxide is very slow at the ambient temperature it is necessary to add a trace of osmium tetroxide as catalyst. The arsenic(III) oxide is dissolved in sodium hydroxide solution, the solution acidified with dilute sulphuric acid, and after adding 2 drops of an osmic acid solution prepared by dissolving 0.1 g osmium tetroxide in 40mL of 0.05M sulphuric acid, and the indicator (1-2 drops ferroin or 0.5 mL /V-phenylanthranilic acid), it is titrated with the cerium(IV) sulphate solution to the first sharp colour change orange-red to very pale blue or yellowish-green to purple respectively. 

Hydrogen peroxide. The diluted solution, which may contain nitric or hydrochloric acid in any concentration between 0.5 and 3M or sulphuric add in the concentration range 0.25 to 1.5M, is titrated directly with standard cerium(IV) sulphate solution, using ferroin or /V-phenylanthranilic acid as indicator. The reaction is ... 

These present an interesting dichotomy in their reductions by tm(l,10-phen-anthroline)iron(ri) (ferroin) °. That of CIO2 to CIOJ is rapid, is first-order in each component ki = 1.86 0.13 l.mole sec at 35 °C) and is independent of acidity. Ferriin is the immediate product and an outer sphere electron-transfer is proposed. The reduction of CIO2 is much slower, proceeding at the same rate as dissociation of ferroin at high chlorite concentrations and a major product is feriin dimer, possibly [(phen)2Fe-0-Fe(phen)2] . Clearly the reaction depends on ligand-displacement followed by an inner-sphere electron transfer. 

This reaction, widely known as the Belousov-Zhabotinskii reaction, can proceed in an oscillatory fashion [68]. For overall slow conversion, the concentrations of intermediates and the catalyst undergo cyclic changes. By this means, many pulselike reaction zones propagate in a spatially distributed system. Ferroin/ferriin can be applied as an optically detectable catalyst... 

One important group of colour indicators is derived from 1 10 phenantholine ortho-phenanthroline) which forms a 3 1 complex with iron(II). The complex known as ferroin undergoes a reversible redox reaction accompanied by a distinct colour change... 

Oxidation-Reduction Titrations. The extent of reduction resulting from reaction of niobium (V) chloride and bromide with pyridine was determined by indirect titration of crude reaction mixtures with standard ammonium tetrasulfato-cerate(IV) solution. Samples were stirred overnight in a stoppered flask with an excess of iron (III) ammonium sulfate. Any iron (II) formed by reaction with the niobium complex mixture was then titrated with the standard tetrasulfato-cerate(IV) solution using ferroin as indicator. Results of these determinations are given in Table III. 

After the digestion is completed, the amount of Cr61 consumed is determined either by titration or by colorimetry. The initial amount of Cr3, and that which is left after the reaction, are determined by titrating against a standard solution of ferrous ammonium sulfate (FAS) using ferroin indicator. The initial amount of Cr6 may also be calculated from the standard grade of K2Cr207 used to prepare the solution. 

Anatol M. Zhabotinsky (b. 1938) is best known as the Zhabotinsky. of the Belousov-Zhabotinsky, or BZ, oscillating reactions. The BZ reactions involve the oxidation of various organic acids and ketones by bromate in the presence of cerium or ferroin ions. Waves of oxidation are easily observed as a color change from red (ferroin) to blue (ferriin). Originally from Moscow, Dr. Zhabotinsky currently does research at the Department of Chemistry of Brandeis University in Waltham, Massachusetts, and that is where we recorded our conversation on July 24,... 

When visual indicators are used, the rate of attainment of equilibrium depends on the type of reaction leading to color development, which may be slow. For simple electron exchange reactions like that of ferroin, the rate of indicator response is usually rapid. If, however, the indicator undergoes a more deep-seated structural change, one can anticipate kinetic complications. The oxidation of diphenylamine, for example, is induced (Section lS-8) by the iron(II)-dichromate reaction. 

Ferroin With the introduction of Ce(IV) as an oxidant and the evaluation of the formal potential of the Ce(rV)-Ce(III) couple, the need for indicators with higher electrode potentials became evident. The indicator ferroin, tris(l,10-phenanthroline)-iron(II), was discovered by Walden, Hammett, and Chapman, and its standard potential was evaluated at 1.14 V. Hume and KolthofiF found that the formal potential was 1.06 V in 1 M hydrochloric or sulfuric acid. The color change, however, occurs at about 1.12 V, because the color of the reduced form (orange-red) is so much more intense than that of the oxidized form (pale blue). From Figure 15-1 it can be seen that ferroin should be ideally suited to titrations of Fe(II) and other reductants with Ce(lV), particularly when sulfuric acid is the titration medium. It has the further advantages of undergoing a reversible oxidation-reduction reaction and of being relatively stable even in the presence of oxidant. 

In the foregoing discussion the indicator has tacitly been assumed to come rapidly to equilibrium at each point of the titration curve. That this is an over-simplihcation is evident from a number of experimental observations. Kolthoflf and Sarver found that the oxidation of diphenylamine with dichromate is induced by the Fe(II)-dichromate reaction. The direct oxidation is so slow that the indicator blank is best determined by comparison of the visual with the potentiometric end point. With ferroin. Smith and Brandt and Stockdale foimd that the reverse titration, dichromate with iron, gave satisfactory results at sufficiently high acidities, whereas the direct titration failed because the indicator could not be oxidized. Here the oxidation seems to be slow and the reduction rapid because of the irreversible nature of the oxidant and the reversible nature of the reductant. 

With As(III) as the reductant and Ce(IV) as the oxidant in sulfuric acid, the situation is reversed. The oxidized indicator, ferriin, is reduced hardly at all by excess As(III) even in the presence of osmium tetroxide as a catalyst. If a drop of Ce(IV) solution is added, however, the red color of ferroin is rapidly developed, evidently because of an induced reaction. In hydrochloric acid the induced reaction does not occur, ferroin is oxidized by the first drop of Ce(IV), and so the titration fails. A small amount of chloride (for example, 0.1 Af hydrochloric acid in 0.5 Af sulfuric acid) does not interfere. Addition of excess Hg(II) perchlorate prevents the interference by complexation of the chloride, ... 

In sulfuric acid solution the reaction is rapid and quantitative. Phosphoric acid usually is added to decolorize the Fe(III) by formation of a colorless complex. The complex Fe(HP04), of formation constant 2.3 x 10 , has been found to be the species involved. Permanganate may be used as its own indicator, or ferroin may be added to provide a more sensitive end point. Whether phosphoric acid is present or not, the end point may be detected potentiometrically. 

Sodium oxalate has been used as a primary standard substance for Ce(IV) in sulfuric acid. In the absence of a catalyst a temperature of 70 to 75°C is necessary. Smith and Getz found that in 1 to 2 M perchloric acid solution, sodium oxalate can be titrated at room temperature with Ce(IV) perchlorate or nitrate but not with sulfate. Rao, Rao, and Rao carried out the titration at room temperature in the presence of barium chloride to remove sulfate, which retards the reaction between oxalate and Ce(IV) and between oxalate and oxidized ferroin. Alternatively, some Fe(III) was added, and the trace of Fe(II) produced photochemically then reacted with the indicator. Rao, Rao, and Murty carried out the titration in 0.5 M HNOj with ammonium hexanitratocerate(IV) instead of the sulfate. With a small amount of KI and KIO3, a satisfactory end point was obtained at room temperature with ferroin as indicator. 

The complexed iron in the ferroin undergoes a reversible oxidation/reduction reaction that can be written... 

The cyanide ion can displace Ag from its associates with phen and Bromopyrogallol Red [23], and eosin [24]. Cyanide ions liberate coloured ferroin from the solid [Fe(phen)3 " ][l3 ]2. A method based on displacement of IO3 from the sparingly soluble Pb(I03)2, with subsequent reaction of the IO3 with iodide added, and determining the liberated I2 as the coloured starch complex has also been proposed [26]. 

The titration of excess standard ceric ammonium nitrate solution after addition of azide either as a slurry, solution, or as distilled hydrazoic acid gives precise and accurate results. The ferroin endpoint is sharp and virtually instantaneous. Loss of hydrazoic acid in the distillation is apparently nil, and the reaction of hydrazoic acid with ceric ion is extremely rapid. 

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