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Additional resources for Qualitative inorganic analysis; a new physico-chemical approach

Sample text

OXIDATION-REDUCTION POTENTIAL OF OXIDIZING AND REDUCING SOLUTIONS In the system: Oxidant E =E we have 4- ^ ne 0-058 -j reductant I , log B n : | Ox Red | I Let us vary the ratio of Ox |/| Red from per cent oxidant and 100 per cent reductant to 100 per cent oxidant and per cent reductant, the sum of the two remaining constant. We obtain the curve shown in fig. 4, which is of the form | | y = a + b log x c Potential of a solution containing conjugate oxidants and reductants. Buffer solutions. The potential is given by the preceding formula.

An oxidant is the stronger the more easily it can take up electrons. The more energetically the oxidant takes up electrons, the less easily the conjugate reductant gives them up, or, put differently, the more easy the oxidant is to reduce, the more difficult its conjugate reductant is to oxidize, or again, the stronger the oxidant, the weaker the conjugate reductant. In the system: Ce 4+ -f e ^ Ce 3+ , Ce 4+ is a strong oxidant, and Ce 3+ is a weak reductant. In the system: Ti 4+ -f e ^ Ti 3 +, Ti 3+ is a strong reductant, it reduces numerous oxidants; Ti 4 "^ is a weak oxidant, and cannot be reduced by many substances.

This | | varies. | property is frequently utilized in analysis in order to mask a given ion. Applications. (1) Detection ofPe 3+ by thiocyanate. If to a solution of ferric iron of about M/100 concentration an equal amount of M/100 thiocyanate be added, the rather unstable but very intense red-coloured 2 complex FeCNS + is formed : Fe 3 + + CNS- ^ FeCNS 2 +; pK = 2-9 The intensity of the red coloration is a measure of the concentration of the complex. If we continue to add dilute CNS~, then CNS~ saturated, the concentration of FeCNS 2 * increases.

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