Electrolysis Electrogravimetry

Chapter 22 Bulk Electrolysis Electrogravimetry and Coulometry 633 Chapter 23 Voltammetry 665... 

Determination. The most accurate (68) method for the deterrnination of copper in its compounds is by electrogravimetry from a sulfuric and nitric acid solution (45). Pure copper compounds can be readily titrated using ethylene diamine tetracetic acid (EDTA) to a SNAZOXS or Murexide endpoint. lodometric titration using sodium thiosulfate to a starch—iodide endpoint is one of the most common methods used industrially. This latter titration is quicker than electrolysis, almost as accurate, and much more tolerant of impurities than is the titration with EDTA. Gravimetry as the thiocyanate has also been used (68). 

The quantitative execution of chemical reactions is the basis of the traditional or classical methods of chemical analysis gravimetry, titrimetry and volumetry. In gravimetric analysis the substance being determined is converted into an insoluble precipitate which is collected and weighed, or in the special case of electrogravimetry electrolysis is carried out and the material deposited on one of the electrodes is weighed. 

Electrical units 503, 519 Electrification due to wiping 77 Electro-analysis see Electrolysis and Electrogravimetry Electrochemical series 63 Electro-deposition completeness of, 507 Electrode potentials 60 change of during titration, 360 Nernst equation of, 60 reversible, 63 standard 60, (T) 62 Electrode reactions 505 Electrodeless discharge lamps 790 Electrodes antimony, 555 auxiliary, 538, 545 bimetallic, 575... 

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. 

Electrogravimetry is one of the oldest electroanalytical methods and generally consists in the selective cathodic deposition of the analyte metal on an electrode (usually platinum), followed by weighing. Although preferably high, the current efficiency does not need to be 100%, provided that the electrodeposition is complete, i.e., exhaustive electrolysis of the metal of interest this contrasts with coulometry, which in addition to exhaustive electrolysis requires 100% current efficiency. 

Eqn. 3.106 must be considered as an approximate relationship for at least two reasons first, the assumption of a rapid complete coverage of the Pt electrode surface by Ag right from the start of the electrolysis is certainly incorrect (cf., Bard and Faulkner150) second, at the end of the electrolysis the remaining Cu2+ solution is virtually in contact with a silver electrode instead of a copper electrode, for which E u2+, Cu = 0.340 V is valid. Practice has shown that by means of CPE, selective electro-deposition and thus electrogravimetry of silver in addition to copper is possible down to 10 8MAg+, as the above calculation indicates. 

In many instances electrogravimetry must be preceded by a separation between metals suitably this can be an electroseparation by means of constant-current electrolysis as previously described, but more attractively an electroseparation by means of controlled-potential electrolysis at a mercury pool or sometimes at an amalgamated Pt or brass gauze electrode. In this way one can either concentrate the metal of interest on the Hg or remove other metals from the solution alternatively, it can be a rougher separation, i.e., the concentration of a group of metals such as Fe, Ni, Co, Cu, Zn and Cd on the Hg whilst other metals such as alkali and alkaline earth metals, Be, Al, Ti and Zr remain in solution151. In all these procedures specific separation effects can be... 

Electrogravimetry, which is the oldest electroanalytical technique, involves the plating of a metal onto one electrode of an electrolysis cell and weighing the deposit. Conditions are controlled so as to produce a uniformly smooth and adherent deposit in as short a time as possible. In practice, solutions are usually stirred and heated and the metal is often complexed to improve the quality of the deposit. The simplest and most rapid procedures are those in which a fixed applied potential or a constant cell current is employed, but in both cases selectivity is poor and they are generally used when there are... 

A method that completely electrolyzes the substances under study is used in electrogravimetry and coulometry. The method is also useful in electrolytic separations and electrolytic syntheses. Electrolysis is carried out either at a controlled potential or at a controlled current. 

In electrogravimetry [19], the analyte, mostly metal ions, is electrolytically deposited quantitatively onto the working electrode and is determined by the difference in the mass of the electrode before and after the electrolysis. A platinum electrode is usually used as a working electrode. The electrolysis is carried out by the con-trolled-potential or the controlled-current method. The change in the current-potential relation during the process of metal deposition is shown in Fig. 5.33. The curves in Fig. 5.33 differ from those in Fig. 5.31 in that the potentials at i=0 (closed circles) are equal to the equilibrium potential of the M +/M system at each instant. In order that the curves in Fig. 5.33 apply to the case of a platinum working electrode, the electrode surface must be covered with at least a monolayer of metal M. Then, if the potential of the electrode is kept more positive than the equilibrium potential, the metal (M) on the electrode is oxidized and is dissolved into solution. On the other hand, if the potential of the electrode is kept more negative than the equilibrium potential, the metal ion (Mn+) in the solution is reduced and is deposited on the electrode. 

In the electrogravimetry and coulometry described in Section 5.6, the substance under study is completely electrolyzed in obtaining the analytical information. A complete electrolysis is also carried out in electrolytic syntheses and separations. Electrolytic methods are advantageous in that they need no chemical reagent and in that optimum reaction conditions can easily be obtained by controlling electrode potentials. 

Deposition — A process in which a compound or material is deposited on an electrode surface using electrolysis. Deposition processes play an important role in many technologies (e.g., coating of materials with metals or oxides, -> electrodeposition) and in analytical methods (- electrogravimetry, - stripping voltammetry). 

Internal electrolysis — Internal electrolysis, also known as spontaneous electrogravimetric analysis, is the deposition of a metal in an electrochemical cell for the purpose of gravimetric analysis without an external source of electrical energy by proper selection of the anode material. For example Ag can be determined in the presence of Pb, Cu, and Bi by use of a Cu anode. (See also electrogravimetry). 

Bulk electrolysis methods are also classified according to purpose. For example, one form of analysis involves determination of the weight of a deposit on the electrode (electrogravimetry). In this case 100% current efficiency is not required, but the substance of interest must be deposited in a pure, known form. In coulometry, the total quantity of electricity required to carry out an exhaustive electrolysis is determined. The quantity of material or number of electrons involved in the electrode reaction can then be determined by Faraday s laws, if the reaction occurred with 100% current efficiency. For electroseparations, electrolysis is used to remove, selectively, constituents from the solution. 

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