Redox reactions titrations

You will recall from Chapter 6 that the Nernst equation relates the electrochemical potential to the concentrations of reactants and products participating in a redox reaction. Consider, for example, a titration in which the analyte in a reduced state, Ared) is titrated with a titrant in an oxidized state, Tox- The titration reaction is... 

In this titration the analyte is oxidized from Fe + to Fe +, and the titrant is reduced from CryOy to Cr +. Oxidation of Fe + requires only a single electron. Reducing CryOy, in which chromium is in the +6 oxidation state, requires a total of six electrons. Conservation of electrons for the redox reaction, therefore, requires that... 

Thus far we have examined titrimetric methods based on acid-base, complexation, and redox reactions. A reaction in which the analyte and titrant form an insoluble precipitate also can form the basis for a titration. We call this type of titration a precipitation titration. 

The amount of sodium hypochlorite in a bleach solution can be determined by using a given volume of bleach to oxidize excess iodide ion to iodine CIO- is reduced to Cl-. The amount of iodine produced by the redox reaction is determined by titration with sodium thiosulfate, Na2S203 I2 is reduced to I-. The sodium thiosulfate is oxidized to sodium tetrathionate, Na2S406. In this analysis, potassium iodide was added in excess to 5.00 ml of bleach d = 1.00 g/cm3). If 25.00 mL of 0.0700 MNa2S203 was required to reduce all the iodine produced by the bleach back to iodide, what is the mass percent of NaCIO in the bleach ... 

Redox reaction (continued) species strength, 506-507q spontaneity of, 489-490,507-508q standard, calculation, 488-489 titration, 92... 

This expression enables us to calculate the exact concentration at the equivalence point in any redox reaction of the general type given above, and therefore the feasibility of a titration in quantitative analysis. 

In the practice of potentiometric titration there are two aspects to be dealt with first the shape of the titration curve, i.e., its qualitative aspect, and second the titration end-point, i.e., its quantitative aspect. In relation to these aspects, an answer should also be given to the questions of analogy and/or mutual differences between the potentiometric curves of the acid-base, precipitation, complex-formation and redox reactions during titration. Excellent guidance is given by the Nernst equation, while the acid-base titration may serve as a basic model. Further, for convenience we start from the following fairly approximate assumptions (1) as titrations usually take place in dilute (0.1 M) solutions we use ion concentrations in the Nernst equation, etc., instead of ion activities and (2) during titration the volume of the reaction solution is considered to remain constant. 

In fact, reaction 4.105 also represents an example of a condensation reaction. A prior redox reaction in non-aqueous medium also often occurs, e.g., in the highly sensitive analysis of peroxides with HI in acetic acid, both under absolutely water-free conditions, where iodine is quantitatively liberated and is subsequently titrated. For much work on non-aqueous redox titrations by Tomicek s school published mainly in the Czech literature, see ref. 17. 

The concept of reduction potential is introduced in Chapter 6. When the reduction potentials of two species differ by 0.1 V or more, the resulting redox reaction will proceed rapidly and stoichiometrically so that it may be used as the basis for a titrimetric procedure. The end point of a redox titration may be observed by following the potential of the titrand with an indicator electrode or with a visual indicator. In two special cases, the reagent (potassium permanganate and iodine) is self-indicating (vide infra). 

Among the most important indirect methods of analysis which employ redox reactions are the bromination procedures for the determination of aromatic amines, phenols, and other compounds which undergo stoichiometric bromine substitution or addition. Bromine may be liberated quantitatively by the acidification of a bromate-bromide solution mixed with the sample. The excess, unreacted bromine can then be determined by reaction with iodide ions to liberate iodine, followed by titration of the iodine with sodium thiosulphate. An interesting extension of the bromination method employs 8-hydroxyquinoline (oxine) to effect a separation of a metal by solvent extraction or precipitation. The metal-oxine complex can then be determined by bromine substitution. 

The course of precipitation and complexometric titrations can also be followed conductometrically, but changes of slope are generally less pronounced. Redox reactions are difficult to follow because of the high... 

In this chapter, you learned about solutions and how to use molarity to express the concentration of solutions. You also learned about electrolytes and nonelectrolytes. Using a set of solubility rules allows you to predict whether or not precipitation will occur if two solutions are mixed. You examined the properties of acids and bases and the neutralization reactions that occur between them. You then learned about redox reactions and how to use an activity table to predict redox reactions. You learned about writing net ionic equations. Finally, you learned how to use the technique of titrations to determine the concentration of an acid or base solution. 

As a number of elements are capable of exhibiting more than one oxidation state, hence volumetric titration methods based on redox reactions are usually employed widely. 

Part 5 draws upon the skills and concepts you learned in Unit 5. You will use your understanding of redox reactions to design a titration for vitamin C, an antioxidant... 

O 3n> If you titrate orange juice that has been exposed to the air for a week, will the vitamin C concentration be different from the vitamin C concentration in fresh juice If so, will it decrease or increase Explain your prediction, in terms of redox reactions. 

Consistent with the two-electron donor nature of H2, the reaction behaved as an n=2 Nernst redox reaction. It showed a pH dependence of 66mV per pH unit, so again one proton was taken up for each electron. It is not known where all incoming protons are localized in the enzyme. The reaction shows that in addition to the light-sensitive hydrogen species bound to the active site in the Nia-C " state, a second hydrogen can react at the active site and deliver its two electrons to the enzyme. We hence proposed that the active site of the A. vinosum enzyme has two sites where hydrogen can bind. If H2 is completely removed, the Nia-C state persists for hours this is unlike the situation in redox titrations in the presence of redox mediators. As the active site in the Nig-SR state has one electron more than that in the Nia-C state, an Fe-S cluster has to be involved in this reaction with H2. 

Figure 4.1 Schematic diagram of the apparatus required when monitoring a redox reaction via a potentiometric titration while a burette is depicted here, the apparatus may be contained within an autotitrator.

Consider the redox reaction shown in equation (4.1). From a potentiometric titration, it is found that 12.5 cm of 06 + (0.01 moi dm ) will completely oxidize 25.0 cm of Fe + soiution. What is the concentration of the ferrous iron (Hint - remember the equation, Ci / =CtV2, from acid-base titrations.)... 

There is no redox couple in solution at the start of the ferrous-ceric titration because the solution contains only Fe ". The oxidation of ferrous to ferric occurs as soon as an aliquot of ceric ions enter the solution to effect the redox reaction shown in equation (4.1). The bulk of the initially present ferrous ions remain, with the ferric products of the redox reaction residing in the same solution, i.e. a Fe " ", Fe + redox couple is formed. This couple has the electrode potential Epf + pg2+. 

During a redox reaction, a potentiometric titration can be employed to determine a concentration of analyte rather than an activity, since we are only using the emf as a reaction variable in the accurate determination of an end point volume. For this reason, an absolute value of reference electrode need not be known, as we are only concerned with changes in emf. It is, however, advisable to titrate at high ionic strength levels in order to minimize fluctuations in the mean ionic activity coefficients. 

Elemental composition H 9.15%, N 42.41%, O 48.44%. Hydroxylamine may be measured by coulometric titration to a potentiometric end point using a coulometric titration cell. A standard solution of bromine may be used as oxidizer in the redox reaction. (Skoog, D. A., D. M. West, and F. J. HoUer. 1992. Fundamentals of Analytical Chemistry, 6th ed. pp. 467, Orlando Saunders College Publishing)... 

Elemental composition K 23.41%, Br 47.85%, O 28.74%. Aqueous solution of the salt after sufficient dilution may be analyzed for its potassium content by AA, ICP, or flame photometry (see Potassium) and for bromate anion by ion chromatography. Also, bromate content can be measured by iodometric titration using a standard solution of sodium thiosulfate and starch as indicator. The redox reactions are as follows ... 

This chapter deals with the fundamental aspects of redox reactions in non-aque-ous solutions. In Section 4.1, we discuss solvent effects on the potentials of various types of redox couples and on reaction mechanisms. Solvent effects on redox potentials are important in connection with the electrochemical studies of such basic problems as ion solvation and electronic properties of chemical species. We then consider solvent effects on reaction kinetics, paying attention to the role of dynamical solvent properties in electron transfer processes. In Section 4.2, we deal with the potential windows in various solvents, in order to show the advantages of non-aqueous solvents as media for redox reactions. In Section 4.3, we describe some examples of practical redox titrations in non-aqueous solvents. Because many of the redox reactions are realized as electrode reactions, the subjects covered in this chapter will also appear in Part II in connection with electrochemical measurements. 

The characteristics of redox reactions in non-aqueous solutions were discussed in Chapter 4. Potentiometry is a powerful tool for studying redox reactions, although polarography and voltammetry are more popular. The indicator electrode is a platinum wire or other inert electrode. We can accurately determine the standard potential of a redox couple by measuring the electrode potential in the solution containing both the reduced and the oxidized forms of known concentrations. Poten-tiometric redox titrations are also useful to elucidate redox reaction mechanisms and to obtain standard redox potentials. In some solvents, the measurable potential range is much wider than in aqueous solutions and various redox reactions that are impossible in aqueous solutions are possible. 

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