A method for the improvement of the signal‐to‐noise ratio in square‐wave (SW) voltammetry is proposed. It is based on the modification of a square‐wave waveform. This method is applied to cathodic stripping voltammetric (CSV) determination of selenium(IV) in nitric acid solutions. Hanging mercury drop electrode (HMDE) was used in the presence of Cu(II) ions. The optimal conditions were chosen: square‐wave waveform mode, pH, time and potential of electrodeposition. Kinetic processes of copper selenide reduction with the use of SWCSV, applying different square‐wave waveforms, are studied. Quasi‐reversible processes are observed. The standard reaction rate constants are evaluated for different square‐wave waveforms. It is shown that the determination of Se(IV) by this modified SWCSV technique is possible with an excellent sensitivity (the detection limit 8×10−12 mol L−1 only for 5 min of electrodeposition) and good reproducibility (Sr<8%) in a wide range of concentration (1×10−11−1×10−6 mol L−1) of Se(IV). The presence of Mo(VI), Pb(II), Ni(II), Zn(II), Cr(VI) metal ions with molar excess around 1000 do not prevent the detection of Se(IV) signals.
In order to understand the complex reduction mechanism of pertechnetate ions on mercury electrode we have developed electrochemical techniques which use an additional time parameter to the classical methods applied on mercury microelectrode: 3 Dimensional polarography and 3D differential capacity measurements have been investigated in addition with coulometry, cyclic voltammetry, and radioactivity determinations. We have concluded that the first VII -> III reduction wave, which has been described in literature, has to be associated with the successive VII -> V reactions followed by the disproportionation of Tc(V) and formation of Tc(VI) and insoluble tetravalent species which are adsorbed on the electrode and reduced to trivalent ions. Then, reduction of Tc(III) to Tc(0) is reached through Tc(II) and Tc(I) intermediate species. The intermediates are characterised depending on the time window of observation.
59 hot particles were collected in Kiev, Ukraine, in 1987. All but one were prepared from a moss carpet of 360 cm2 area. Radionuclide composition of the hot particles was investigated by gamma-spectrometry and beta absorption method. Pure beta emitters 90Sr and 147Pm were determined in 25 hot particles measuring the beta absorption curves of the hot particles with an end-window Geiger-Müller counter and decomposing the curves in order to obtain the contributions of 90Sr and 147Pm to the total beta counting rate. All but one of the hot particles were found to be the debris of the fuel. The activity ratio 90Sr:l44Ce was 0.052 in good agreement with theoretical calculations on core inventories. This means that strontium behaved as a nonvolatile element in the process of the formation of the hot particles investigated. The activity ratio 147Pm:144Ce was 0.078 which is half of the theoretical result. Although 147Pm is considered to be a refractory nuclide, it seems that significant part of 147Pm went to the homogeneous fraction of the general fallout. The surface density of hot particles (of higher than about 50 Bq activity) was about 1,600 m(-2) and that of the activities of the nuclides 90Sr, 106Ru, 134Cs, 137Cs, 144Ce and 147Pm as components of hot particles was 12.2, 54.3, 5.9, 9.7, 234 and 18.3 kBq m(-2) (activity values counted for 26 April 1986), respectively, in downtown Kiev city in 1987.
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