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  • polarography: basics and Principle

    In polarography the substance to be analyzed undergoes electrolysis under the

    influence of potential difference  result in generation of current in electrolytic cell.

    Polarograph: An electrical apparatus used for supplying voltage for electrolysis of an

    electrolyte is called polarograph – it consist of potentiometer, an electrolyte cell or

    polarographic cell and galvanometer.

    Polarographic wave –voltage relationship of  polarogram

    • initially very small gradual increases in current known as residual current (ir)
    • Residual current ((ir) is sum of the faradic current (if) and condenser current (ic)  i.e. ir = if  + ic
    • Current increases rapidly because more number of ions moves towards the electrode surface of DME from the solution carries current. At the half wave potential E1/2 à concentration of oxidized and reduced form of electrode surface is equal à this potential is the characteristic of the reducing substance.
    • Diffusion current (id) or limiting current (il) gives straight line in absence or presence of electrolyte used à depending upon the concentration of reducing substance.

    Ilkovic equation  

    id = 607 n D1/2 c m2/3 t1/6

    id             =          diffusion current during life of drop (amperes)

    607      =          constant generated from π, faraday constant and density of mercury

    n          =          the number of electrons involved

    D         =          the diffusion coefficient in cm2 s-1

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