Mercury electrodeposition

Not only compositions containing all the HTSC metal components, but also simpler subsets, may be considered as the precursors. Thus, by a combined technique [189], Ba-Ca-Cu films were obtained by electrodeposition and then thallium was introduced from the vapor phase in the course of simultaneous oxidation. In [190, 191], it was shown that reproducible preparation of Bi-Pb cuprates can be achieved when three-component precursors are deposited and the alkaline earth cations are then introduced before annealing. It is practically impossible to provide reproducible deposition of five-component precursors. Two-stage electrosynthesis of HBCCO [200] included the intermediate annealing of a Ba-Ca-Cu deposit followed by mercury electrodeposition on the resulting oxide substrate. 

The first in situ Raman spectroscopic study on electrochemical systems was reported on thin metal oxide and metal hahde film electrodes by Fleischmann etal. in 1973 [1]. The Raman spectroelectrochemi-cal measurements were made on thin films of Hg2Cl2, Hg2Br2, and HgO formed on droplets of mercury electrodeposited onto platinum electrodes. These mercury compounds have exceptionally high Raman scattering cross sections (very good Raman scatterers) so that the spectra of species as little as a few monolayers could be recorded on these high-surface-area electrodes. These experiments proved the viability of Raman spectroscopic measurements of... 

Fig. 6 Normalized probability density of nearest neighbor distances for 2.2 X 10 drops/cm of mercury, electrodeposited onto vitreous carbon at 220 mV from 0.01 mol dm aqueous solution (A) [58]. Also shown are the probability densities corresponding to uniformly distributed drops (thin line) and excluded nucleation for distances less than rj = [(87rcM//o) D(t — from each drop (heavy line), obtained from digital simulations [59].

Mercury electrodeposition is a model system for experimental studies of electrochemical phase formation. On the one hand, the product obtained is a liquid drop, corresponding very well with the liquid drop model of classical nucleation theory. Besides, electron transfer is fast [61] and therefore the growth of nuclei is controlled by mass transport to the electrode surface [44]. On the other hand, the properties of the mercuryjaqueous solution interface have been the object of study for over a century and hence are fairly well understood. The high overpotential for proton reduction onto both mercury and vitreous carbon favor the study of the process over a wide range of overpotentials. In spite of the complications introduced by the equilibrium between the Hg +, Hg2 " ", and Hg species, this system offers an excellent opportunity to verily the fundamental postulates of the electrochemical nucleation theory. In fact, the dependence of the nucleation rate on the oxidation state of the electrodepositing species is fiiUy consistent with theory critical nuclei appear with similar sizes and onto similar number densities of active sites... 

Fig. 8 Current transients according to Eq. (66), for mercury electrodeposition from 10 mM Hg2 solutions, with D = 10 cm at nucleation rates A and number densities of active sites No, respectively, of (a) 0.02 s and 0.4 x 10 cm (b) 0.04 s and...

Concluding this Qiapter we present a set of experimental N t) relationships obtained by means of the modified pulse potentiostatic technique in the case of mercury electrodeposition on a platinum single crystal microelectrode (Figure 2.20) [2.179]. The data for Al(t) refer to the whole electrode surface S = 1.4xl0 cm and the nucleation rate J t) = dN(t)/dt m dimensions s instead ofcm s. ... 

The authors [35] emphasize that their result regarding the first HgS monolayer, which involves reversible underpotential adsorption, suggests that nucleation cannot be considered as a universal mechanism for the formation of anodic films. Analogous conclusions have been inferred for cathodic HgSe films electrodeposited on mercury electrode by the reduction of selenous acid [37] the first monolayer appeared to be reversibly adsorbed, while formation of the following two layers was preceded by nucleation. 

Studies of the electrodeposition of mercury chalcogenides are scarce, primarily because of the difference in electrochemical potentials needed to deposit mercury and the chalcogens. Mercury is a noble metal the standard redox potential for the... 

The chemical bath deposition of polycrystalline, zinc blende HgSe thin films on TO glass from aqueous alkaline medium has been reported [120]. Examples of electrodeposited ternary mercury compounds will be discussed in the next section. 

Colyer CL, Cocivera M (1992) Thin-film cadmium mercury teUuride prepared by nonaque-ous electrodeposition. J Electrochem Soc 139 406 09... 

In electrogravimetry, also called electrodeposition, an element, e.g., a metal such as copper, is completely precipitated from its ionic solution on an inert cathode, e.g., platinum gauze, via electrolysis and the amount of precipitate is established gravimetrically in the newer and more selective methods one applies slow electrolysis (without stirring) or rapid electrolysis (with stirring), both procedures either with a controlled potential or with a constant current. Often such a method is preceded by an electrolytic separation using a stirred cathodic mercury pool, by means of which elements such as Fe, Ni, Co, Cu, Zn and Cd are quantitatively taken up from an acidic solution whilst other elements remain in solution. 

Kim and Jorne [37] have used a rotating zinc hemisphere to study the kinetics of zinc dissolution and deposition reactions in concentrated zinc chloride solutions. The electrodeposition reaction of cadmium on mercury was used by Mortko and Cover [43] in their investigation of a rotating dropping mercury electrode their data behaved according to Eqs. (74)-(76). 

A method has been developed for differentiating hexavalent from trivalent chromium [33]. The metal is electrodeposited with mercury on pyrolytic graphite-coated tubular furnaces in the temperature range 1000-3000 °C, using a flow-through assembly. Both the hexa- and trivalent forms are deposited as the metal at pH 4.7 and a potential at -1.8 V against the standard calomel electrode, while at pH 4.7, but at -0.3 V, the hexavalent form is selectively reduced to the trivalent form and accumulated by adsorption. This method was applied to the analysis of chromium species in samples of different salinity, in conjunction with atomic absorption spectrophotometry. The limit of detection was 0.05 xg/l chromium and relative standard deviation from replicate measurements of 0.4 xg chromium (VI) was 13%. Matrix interference was largely overcome in this procedure. 

A hanging mercury drop electrodeposition technique has been used [297] for a carbon filament flameless atomic absorption spectrometric method for the determination of copper in seawater. In this method, copper is transferred to the mercury drop in a simple three-electrode cell (including a counterelectrode) by electrolysis for 30 min at -0.35 V versus the SCE. After electrolysis, the drop is rinsed and transferred directly to a prepositioned water-cooled carbon-filament atomiser, and the mercury is volatilised by heating the filament to 425 °C. Copper is then atomised and determined by atomic absorption. The detection limit is 0.2 pg copper per litre simulated seawater. 

In contrast, the coupling of electrochemical and spectroscopic techniques, e.g., electrodeposition of a metal followed by detection by atomic absorption spectrometry, has received limited attention. Wire filaments, graphite rods, pyrolytic graphite tubes, and hanging drop mercury electrodes have been tested [383-394] for electrochemical preconcentration of the analyte to be determined by atomic absorption spectroscopy. However, these ex situ preconcentration methods are often characterised by unavoidable irreproducibility, contaminations arising from handling of the support, and detection limits unsuitable for lead detection at sub-ppb levels. 

Batley [780] examined the techniques available for the in situ electrodeposition of lead and cadmium in seawater. These included anodic scanning voltammetry at a glass carbon thin film electrode and the hanging drop mercury electrode in the presence of oxygen, and in situ electrodeposition on mercury-coated graphite tubes. 

Batley [780] found that in situ deposition of lead and cadmium on a mercury-coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal AAS. 

Batley [28] examined the techniques available for the in situ electrodeposition of lead and cadmium in estuary water. These included anodic stripping voltammetry at a glass carbon thin film electrode and the hanging drop mercury electrode in the presence of oxygen and in situ electrodeposition on mercury coated graphite tubes. Batley [28] found that in situ deposition of lead and cadmium on a mercury coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal atomic absorption spectrometry, Hasle and Abdullah [29] used differential pulse anodic stripping voltammetry in speciation studies on dissolved copper, lead, and cadmium in coastal sea water. 

Substrates DME = dropping mercury electrode FTO = fluorine-doped tin oxide G = graphite GC = glassy carbon GrC = graphic carbon ITO = indium tin oxide-coated glass SC = single crystals SS = stainless steel TCO = transparent conducting oxide VC = vitrious carbon. Miscellaneous ECALE = electrochemical atomic layer epitaxy ED = electrodeposition ML = monolayer RT = room temperature SMD = sequential monolayer deposition V = vacuum. 

Temperature effect on the electrodeposition of zinc on the static mercury drop electrode (SMDE) and glassy carbon (GG) electrode was studied in acetate solutions [44]. From the obtained kinetic parameters, the activation energies of Zn(II)/Zn(Hg) process were determined. 

The literature data on the kinetics of Cd(II), Zn(II), and Pb(II) electrodeposition on mercury electrode in different organic solvents were also analyzed [69]. 

Fig. 2 Comparison of the experimental dimensionless current-time transients for electrodeposition of mercury onto boron-doped diamond electrode with the theoretical transients for instantaneous (upper curve) and progressive (lower curve) nucleation overpotentials (x) 0.862 V and ( ) 0.903 V (from Ref 33).

Camarero et al. [41] have prepared graded cadmium-mercury-telluride thin films (CdxFlgi cTe) applying cathodic electrodeposition at variable deposition voltage. Atomic proportions of mercury in the range 0.05-0.15 were considered. 

U(III) species and a second three-electron reduction to give U(0) metal. The first reduction, U(IV)/U(III) couple, is elec-trochemically and chemically irreversible except in hexamethylphosphoramide at 298 K where the authors report full chemical reversibility on the voltammetric timescale. The second reduction process is electrochemically irreversible in all solvents and only in dimethylsulfone at 400 K was an anodic return wave associated with uranium metal stripping noted. Electrodeposition of uranium metal as small dendrites from CS2UCI6 starting material was achieved from molten dimethylsulfone at 400 K with 0.1 M LiCl as supporting electrolyte at a platinum cathode. The deposits of uranium and the absence of U CI3, UCI4, UO2, and UO3 were determined by X-ray diffraction. Faradaic yield was low at 17.8%, but the yield can be increased (55.7%) through use of a mercury pool cathode. 

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