Titrations with Reducing Agents

In analytical chemistry, a redox titration is based on an oxidation-reduction reaction between analyte and titrant. Common analytical oxidants include iodine (I2), permanganate (MnOJ), cerium(IV), and dichromate (Cr207 ). Titrations with reducing agents such as Fe " (ferrous ion) and Sn " (stannous ion) are less common because solutions of most reducing agents need protection from air to prevent reaction with O2. 

This indicator is used for titrations involving iodine. Starch forms a not very reversible complex with I2 that is a very dark-blue color. The color reaction is sensitive to very small amounts of iodine. In titrations of reducing agents with iodine, the solution remains colorless up to the equivalence point. A fraction of a drop of excess titrant turns the solution a definite blue. 

In alkaline solutions when suitable reducing agents are titrated with oxidizing agents such as H2O2 or a hypohalite in the presence of luminol and lucigenin, at the endpoint the redox potential of the solution suddenly moves towards a more positive value and the CL reaction occurs. In acidic solution (pH<3.5), siloxene has been used as a CL redox indicator. An outline of the use of these indicators in redox titrations is presented in Table 4B. 

Andrews deration An important titration for the estimation of reducing agents. The reducing agent is dissolved In concentrated hydrochloric acid and titrated with potassium iodale(V) solution. A drop of carbon tetrachloride is added to the solution and the end point is indicated by the disappearance of the iodine colour from this layer. The reducing agent is oxidized and the iodate reduced to ICl, i.e. a 4-eiectron change. 

Iodide ion, a moderately effective reducing agent, is used extensively for the deterrnination of oxidants. In such appHcations, the iodine Hberated by reaction between the analyte and the unmeasured excess of potassium iodide is ordinarily titrated with a standard solution of sodium thiosulfate. The reaction is as foHows ... 

The hberated iodine, as the complex triiodide ion, may be titrated with standard thiosulfate solution. A general iodometric assay method for organic peroxides has been pubUshed (253). Some peroxyesters may be determined by ferric ion-catalyzed iodometric analysis or by cupric ion catalysis. The latter has become an ASTM Standard procedure (254). Other reducing agents are ferrous, titanous, chromous, staimous, and arsenite ions triphenylphosphine diphenyl sulfide and triphenjiarsine (255,256). 

Chlorate Analysis. Chlorate ion concentration is determined by reaction with a reducing agent. Ferrous sulfate is preferred for quaHty control (111), but other reagents, such as arsenious acid, stannous chloride, and potassium iodide, have also been used (112). When ferrous sulfate is used, a measured excess of the reagent is added to a strong hydrochloric acid solution of the chlorate for reduction, after which the excess ferrous sulfate is titrated with an oxidant, usually potassium permanganate or potassium dichromate. 

The resulting solution has a much lower vapour pressure than a solution of iodine in pure water, and consequently the loss by volatilisation is considerably diminished. Nevertheless, the vapour pressure is still appreciable so that precautions should always be taken to keep vessels containing iodine closed except during the actual titrations. When an iodide solution of iodine is titrated with a reductant, the free iodine reacts with the reducing agent, this displaces the equilibrium to the left, and eventually all the tri-iodide is decomposed the solution therefore behaves as though it were a solution of free iodine. 

With the exception of iron(II) and uranium(IV), the reduced solutions are extremely unstable and readily re-oxidise upon exposure to air. They are best stabilised in a five-fold excess of a solution of 150g of ammonium iron(III) sulphate and 150 mL of concentrated sulphuric acid per litre [approximately 0.3M with respect to iron] contained in the filter flask. The iron(II) formed is then titrated with a standard solution of a suitable oxidising agent. Titanium and chromium are completely oxidised and produce an equivalent amount of iron(II) sulphate molybdenum is re-oxidised to the Mo(V) (red) stage, which is fairly stable in air, and complete oxidation is effected by the permanganate, but the net result is the same, viz. Mo(III)- Mo(VI) vanadium is re-oxidised to the V(IV), condition, which is stable in air, and the final oxidation is completed by slow titration with potassium permanganate solution or with cerium(IV) sulphate solution. 

A common laboratory technique for determining the concentration of a solute is titration (Fig. L.2). Titrations are usually either acid-base titrations, in which an acid reacts with a base, or redox titrations, in which the reaction is between a reducing agent and an oxidizing agent. Titrations are widely used to monitor water purity and blood composition and for quality control in the food industry. 

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