Mercury electrode drop time

Figure 1.7. Current versus time profile for an electrochemical reaction under polarographic conditions at a dropping mercury electrode, drop time 3 s.

Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

Polarography is sampled-current voltammetry at a dropping mercury electrode. The time scale is normally - s. See Sections 7.1 and 7.2. 

Fig. 11. Plots of the diffusion-controlled currents at the dropping mercury electrodes vs. time. Id the instantaneous current (full line), according to Eq. (23) the maximum current (according to Eq. 24) the mean diffusion-limited current (dot-dashed line, according to Eq. (25) Irec the recorded current (dashed curve) (absolute values of currents are considered).

The diffusion current Id depends upon several factors, such as temperature, the viscosity of the medium, the composition of the base electrolyte, the molecular or ionic state of the electro-active species, the dimensions of the capillary, and the pressure on the dropping mercury. The temperature coefficient is about 1.5-2 per cent °C 1 precise measurements of the diffusion current require temperature control to about 0.2 °C, which is generally achieved by immersing the cell in a water thermostat (preferably at 25 °C). A metal ion complex usually yields a different diffusion current from the simple (hydrated) metal ion. The drop time t depends largely upon the pressure on the dropping mercury and to a smaller extent upon the interfacial tension at the mercury-solution interface the latter is dependent upon the potential of the electrode. Fortunately t appears only as the sixth root in the Ilkovib equation, so that variation in this quantity will have a relatively small effect upon the diffusion current. The product m2/3 t1/6 is important because it permits results with different capillaries under otherwise identical conditions to be compared the ratio of the diffusion currents is simply the ratio of the m2/3 r1/6 values. 

Drop time in polarography, 597, 608 Dropping mercury electrode 608, 628 Dry ashing 114 Dry box lOl Drying reagents 99 comparative efficiencies of, (T) 99 Drying of precipitates 119 Duboscq colorimeter 656 Duplication method 701... 

The difference between the various pulse voltammetric techniques is the excitation waveform and the current sampling regime. With both normal-pulse and differential-pulse voltammetry, one potential pulse is applied for each drop of mercury when the DME is used. (Both techniques can also be used at solid electrodes.) By controlling the drop time (with a mechanical knocker), the pulse is synchronized with the maximum growth of the mercury drop. At this point, near the end of the drop lifetime, the faradaic current reaches its maximum value, while the contribution of the charging current is minimal (based on the time dependence of the components). 

Studies in the field of electrochemical kinetics were enhanced considerably with the development of the dropping mercury electrode introduced in 1923 by Jaroslav Heyrovsky (1890-1967 Nobel prize, 1959). This electrode not only had an ideally renewable and reproducible surface but also allowed for the first time a quantitative assessment of diffusion processes near the electrode s surface and so an unambiguous distinction between the influence of diffusion and kinetic factors on the reaction rate. At this period a great number of efectrochemical investigations were performed at the dropping mercury efectrode or at stationary mercury electrodes, often at the expense of other types of electrodes (the mercury boom in electrochemistry). 

The electrodes usually consist of mercury or deposited mercury or occasionally of inert solid material further, they are mainly of a stationary type (in the stripping step as the crucial analytical measurement, but not in the concentration step, where often the solution is stirred or the electrode is rotated). Considering the mercury, only exceptionally has a sessile mercury drop electrode (SMDE)91 or a slowly growing DME(drop time 18 min and phase-selective recording of stripping curve)92 been applied. Most popular are the hanging mercury drop electrode (HMDE) and the mercury film or thin-film electrode (MFE or MTFE). 

This equation is analogous to Eq. (5.4.18) or (5.4.19) for the steady-state current density, although the instantaneous current depends on time. Thus, the results for a stationary polarization curve (Eqs (5.4.18) to (5.4.32)) can also be used as a satisfactory approximation even for electrolysis with the dropping mercury electrode, where the mean current must be considered... 

Mercury electrodes require far less maintenance than solid metal electrodes. Especially for the dropping mercury electrode, a noticeable amount of impurities present in the solution at low concentrations (<10-5mol dm-3) cannot appreciably reach the surface of the electrode through diffusion during the drop-time (see Section 5.7.2). 

Fig. 5.46 The dependence on time of the instantaneous current / at a dropping mercury electrode in a solution of 0.08 m Co(NH3)6C13 + 0.1 m H2SO4 + 0.5m K2S04 at the electrode potential where -7 -/d (i.e. the influence of diffusion of the electroactive substance is negligible) (1) in the absence of surfactant (2) after addition of 0.08% polyvinyl alcohol. The dashed curve has been calculated according to Eq. (5.7.23). (According to J. Kuta and I.

Lopez-Fonseca et al. [11] discussed the theory of reverse pulse polarography and the technique was applied in the determination of penicillamine electrochemically coated on a dropping-mercury electrode. Using long drop times and short pulses, the drug can be determined at levels as low as 50 nM in the presence of Cu(II), and the technique compares well with normal-pulse and differential-pulse polarography. 

The dropping mercury electrode had a drop time of 3-4s under an open head of 50 cm Hg. A saturated calomel electrode was the reference electrode. Before recording, the solutions were shaken well. After recording, the electrodes were well rinsed with distilled water and wiped dry. A starting potential of 0.2 V was used and the solutions were degassed with dry nitrogen for 2 min prior to recording. A full-scale sensitivity of 10 pA was used. 

Bond et al. [791 ] studied strategies for trace metal determination in seawater by ASV using a computerised multi-time domain measurement method. A microcomputer-based system allowed the reliability of the determination of trace amounts of metals to be estimated. Peak height, width, and potential were measured as a function of time and concentration to construct the database. Measurements were made with a potentiostat polarographic analyser connected to the microcomputer and a hanging drop mercury electrode. The presence of surfactants, which presented a matrix problem, was detected via time domain dependent results and nonlinearity of the calibration. A decision to pretreat the samples could then be made. In the presence of surfactants, neither a direct calibration mode nor a linear standard addition method yielded precise data. Alternative ways to eliminate the interferences based either on theoretical considerations or destruction of the matrix needed to be considered. 

Electro Capillarity and the dropping Mercury Electrode. The term electro capillarity derives from the early application of measurements of interfacial tension at the Hg-electrolyte interface. The interfacial tension, y, can be measured readily with a dropping mercury electrode. E.g., the life time of a drop, tmax. is directly proportional to the interfacial tension y. Thus, y is measured as a function of y in presence and absence of a solute that is adsorbed at the Hg-water interface this kind of data is amenable to thermodynamic interpretation of the surface chemical properties of the electrode-water interface. 

Fig. 1.5 Barker square-wave polarogram of electrode reaction (1.1) on dropping mercury electrode. P = frequency = 225 Hz, amplitude = 30 mV, drop life time = 1 s,...

Recently, Darowicki [29, 30] has presented a new mode of electrochemical impedance measurements. This method employed a short time Fourier transformation to impedance evaluation. The digital harmonic analysis of cadmium-ion reduction on mercury electrode was presented [31]. A modern concept in nonstationary electrochemical impedance spectroscopy theory and experimental approach was described [32]. The new investigation method allows determination of the dependence of complex impedance versus potential [32] and time [33]. The reduction of cadmium on DM E was chosen to present the possibility of these techniques. Figure 2 illustrates the change of impedance for the Cd(II) reduction on the hanging drop mercury electrode obtained for the scan rate 10 mV s k... 

Sander and Henze [50] have performed ac investigations of the adsorption potential of metal complexes at Hg electrode. Later, Sander etal. [51] have studied electrosorption of chromium - diethylenetriaminepentaacetic acid (DTPA) on mercury in 0.1 M acetate buffer at pH 6.2 using a drop-time method. The changes in the interfacial activity of the Cr(III)-DTPA complex with the bulk concentration obeyed the Frumkin adsorption isotherm. 

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