Polarography

Linear-scan polarography differs from hydrodynamic voltammetry in two regards 1. There is essentially no convection or migration 2. A dropping mercury electrode (DME) is used as the working electrode Because there is no convection, diffusion alone controls polarographic limiting currents. Compared with hydrodynamic voltammetry, however, polarographic limiting currents are an order of magnitude or more smaller, since convection is absent in polarography. Polarographic currents The current in a cell containing a DME undergoes periodic fluctuations corresponding in frequency to the drop rate. As a drop dislodges from the capillary, the current falls toward zero. As the surface area of the new drop increases, so does the current. The diffusion current is usually taken at the maximum of the current fluctuations. Polarograms (see pg 685) The residual current in polarography is the small current observed in the absence of an electroactive species. Diffusion current is the limiting current observed in polarography when the current is limited only by the rate of diffusion to the DME surface. Residual currents This current has two sources: 1. the reduction of trace impurities that are almost inevitably present in a blank solution 2. Charging or capacitative current flowing from a flow of electrons that charge the mercury droplets with respect to the solution; this current may be positive or negative At potentials more negative than about -0.4V, the mercury tends to be positive with respect to the solution. Thus as each drop is formed, electrons are repelled from the surface toward the bulk of mercury, and a negative current is the result. At about 0.4V the mercury surface is uncharged, and the charging current is zero. The potential is called the potential of zero charge. The charging current is a type of non-faradaic current in a sense that charge is carried across an electrode/solution interface without an accompanying oxidation/reduction process. A faradaic current in an electrochemical cell is the current that results from an oxidation/reduction process. A non-faradaic current is a charging current that results because the mercury drop is expanding and must be charged to the electrode potential. The charging of the double layer is similar to Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

charging a capacitor. Advantages and disadvantages of the DME Advantages 1. The unusually high overvoltage associated with the reduction of hydrogen ions. 1. Metal ions are such as zinc and cadmium can be deposited from acidic solution even though their thermodynamic potentials suggest that deposition of these metals without hydrogen is not possible. 2. A new metal surface is generated continuously, which makes the behaviour of the electrode independent of its past history. 3. Reproducible currents are immediately realized at any given potential whether this potential is approached from lower or higher values. Limitations 1. Ease with which mercury is oxidized; this property severely limits the range of anodic potentials that can be used. At potentials greater than +0.4V, formation of mercury(I) occurs, giving a wave that masks the curves of other oxidizable species. In the presence of ions that form precipitates or complexes with mercury(I), this behaviour occurs at even lower potentials. 2. The non-faradaic residual or charging current, which limits the sensitivity of the classical method to concentrations of about 5 x 10-5M. 1. At low concentrations, the residual current can be greater than the diffusion current, which prohibits accurate diffusion current measurement. 3. The dropping mercury electrode is also cumbersome to use and tends to malfunction as a result of clogging. 4. An additional problem with classical polarography is the existence of peaks on the currentvoltage curves, termed polarographic maxima. Although not entirely understood, polarographic maxima are thought to arise from convection around the expanding mercury drop. 5. Toxicity of mercury

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3