Electrolysis, indirect

In coulometry, one measures the number of coulombs required to convert the analyte specifically and completely by means of direct or indirect electrolysis. 

In electroanalysis, coulometry is an important method in which the analyte is specifically and completely converted via a direct or indirect electrolysis, and the amount of electricity (in coulombs) consumed thereby is measured. According to this definition there are two alternatives (1) the analyte participates in the electrode reaction (primary or direct electrolysis), or (2) the analyte reacts with the reagent, generated (secondary or indirect electrolysis) either internally or externally. 

The special requirements of the indigo dyeing of cotton warp yarns for denim are capable of being met by indirect electrolysis systems [241]. Examples of four suitable redox systems are shown in Table 12.37. Uniform build-up of depth was observed with each successive step, the results being at least equal to those from the conventional dithionite-based process. Apparendy these processes are amenable to scaling up to bulk production levels [241]. 

Table 12.37 Redox recipes used in indirect electrolysis application of indigo to cotton yarn [241]...

Sn—Sn bond formation can be achieved by indirect electrolysis considering the relative ease of SnH-bond activation. Tributylin hydride is a known H atom donor. It is attacked by radicals like Mn(CO)3P(OPh)3]2, electrogenerated from the anion Mn(CO)3P(OPh)3]2p. The kinetics of hydrogen transfer and coupling of Ph3Sn and Mn(CO)3P(OPh)3]2 was studied188. 

The transfer of redox equivalents can be achieved by an electrocatalyst (mediator) or a modified electrode. Indirect electrolysis can lead to a better selectivity due to the specific interaction of the mediator with the substrate. However, low turnovers and the need to separate the mediator from the product are possible disadvantages, as mentioned above. The nickel hydroxide electrode [195,196] is fairly free from these disadvantages. The following mechanism for the oxidation at the nickel hydroxide electrode has been proposed in the literature [195]. 

Electrochemical destruction of organics can be an economically viable alternative to incineration, carbon beds, bioremediation, deep well disposal and other methods as destruction to very low acceptable levels is possible [227a], Electrochemical techniques are in fact superior to incineration or deep well disposal as it is a final solution and not a transfer of a toxic material from one environment to another, e.g. to the groundwater or the atmosphere [285], Common destruction pathways include both direct and indirect electrolysis. Many electrochemical degradation pathways remain unclear and may be a mixture of direct and indirect processes depending on the pollutant and its intermediates [84,285a]. 

Pletcher D (1991) Indirect electrolysis involving phase transfer catalysis, Electroorg Synth (Manuel M Baizer Meml Symp) 1990 (Publ 1991) 255 Chem Abstr 116 (1992) 115434a... 

For the dehydrogenation of CH—XH structures, for example, of alcohols to ketones, of aldehydes to carboxylic acids, or of amines to nitriles, there is a wealth of anodic reactions available, such as the nickel hydroxide electrode [126], indirect electrolysis [127, 128] (Chapter 15) with I , NO, thioanisole [129, 130], or RUO2/CP [131]. Likewise, selective chemical oxidations (Cr(VI), Mn02, MnOJ, DMSO/AC2O, Ag20/Celite , and 02/Pt) [94] are available for that purpose. The advantages of the electrochemical conversion are a lower price, an easier scale-up, and reduced problems of pollution. 

The methanesulfonates (481) of a-hydroxy esters can be converted to the deoxygenated esters (482) in 70 88% yields by indirect electrolysis with PhSeSePh as a recyclable reagent in a divided cell (Scheme 166). The procedure involves the formation of a-phenylselenoester by substitution of the a-methylsulfonyloxyl group with the PhSe followed by displacement of the CK-phenylseleno group with PhSe . The electrolysis is performed in a DMF-NaCl04-(Pt/C) system in the presence of PhSeSePh and ethyl malonate at 50 °C [567]. 

Similar transformations can be carried out via indirect electrolysis using vitamin Bi2 and Bia analogs as mediators [74]. As shown in the accompanying equations, the methodology lends itself nicely to the formation of both spiro and linearly fused materials (Tables 13 and 14) [75]. 

Anodic oxidation of formazane 18 [17], 1-arylmethylenesemicarbazide 19 [55], p-nitrobenzaldehyde phenylhydrazone 20 [56], and 2-benzoylpyridine phenylhydrazone 21 [57] afforded the corresponding heterocycles in a very good yield (Scheme 14). The homogeneous oxidation of compounds 18-20 was carried out by indirect electrolysis by the mediators generated in situ [58]. 

The scheme of reactions proposed to explain the products obtained is shown, after small modifications, in Scheme 8. Primary radicals 12 formed at the anodes produce with added 30 or 36 (equation lOe) the substituted benzyl or allyl radicals 38, which can dimerize to 39 or can couple with the added olefin to form radicals 40 or 41. For allyl radical (38) a 1,1 - or l,3 -coupling is possible yielding 41 and 40, respectively. Further couplings of 40 and 41 with the primary radical 12 produce 39 and head-to-tail dimer 42, respectively. It was evident from the products obtained that the coupling of 38 in the 1-position occurs 5 to 11 times faster than in the 3-position. However, for readily polymerizable olefins, rather polymerization occurs, in particular at graphite electrodes. At Pt electrodes both dimers 39 and 42 are formed, but for Cu electrodes exclusively dimers 39 were obtained with moderate yields. Thus, an indirect electrolysis including the oxidation of copper to Cu+ ions and their further reaction with 5 yielding intermediate RCu was considered, but not proved . ... 

As schematically demonstrated in Fig. 1, the indirect electrolysis combines a heterogeneous step, that is the formation and regeneration of the redox-catalyst (Med = mediator) in its active form, with the homogeneous redox reaction of the substrate involving the active mediator. 

A third way of indirect electrolysis is given, if the redox agent which is activated electrochemically, is fixed at the electrode surface and is regenerated there continuously after reaction with the substrate. In this case a separation step is unnecessary (see Fig. 4). 

Synthetically especially valuable is the oxidation of carbonyl compounds and nitroalkanes by manganese(III) salts to form carboxymethyl and nitromethyl radicals, respectively. These radicals can be trapped by olefins like 1,3-butadiene or aromatic compounds to yield synthetically interesting products. In this case it is very advantageous to generate and regenerate the oxidizing species in situ by indirect electrolysis. This was the basis for the development of a process for the synthesis of sorbic acid viay-vinyl-y-butyrolactone Equations (31)—(35) summarize the im-... 

The direct electrochemical oxidation of aliphatic alcohols occurs at potentials which are much more positive than 2.0 V w. SCE. Therefore, the indirect electrolysis plays a very important role in this case. Using KI or NaBr as redox catalysts those oxidations can be performed already at 0.6 V vs. SCE. Primary alcohols are transformed to esters while secondary alcohols yield ketones In the case of KI, the iodo cation is supposed to be the active species. Using the polymer bound mediator poly-4-vinyl-pyridine hydrobromide, it is possible to oxidize secondary hydroxyl groups selectively in the presence of primary ones (Table 4, No. 40) The double mediator system RuOJCU, already mentioned above (Eq. (29)), can also be used effectively Another double mediator system... 

This is the mechanism of an indirect electrolysis, where the nickel oxide hydroxide acts as an electrocatalyst that is continuously renewed. Some observations, however, are not consistent with this mechanism. The addition of an oxidizable alcohol should lead to an increase of the current for the nickel hydroxide oxidation and a decrease for its reduction This is not the case. The currents for nickel hydroxide and nickel oxide hydroxide remain unchanged, whilst at more anodic potential a new peak for the alcohol oxidation appears. This problem has also been addressed by Vertes... 

Dehalogenation. Barton et at. (1, 148) effected dehalogenation of steroidal /i-hydroxy halides with chromium(II) acetate and butancthiol as the proton donor in DMSO. The method is only useful with tertiary halides. A recent improvement that permits reduction of halides of all types uses the ethylenediamine complex of CrtCIOzh and the tetrahydropyranyl ethers of the /J-hydroxy halide. Catalytic amounts of the reducing agent can be used in "indirect electrolysis." The reaction is convenient for preparation of deoxynucleosides.1... 

In a direct electrolysis, the electron is exchanged between the electrode and the substrate, and the rate of the reaction depends on the electrode potential and the rate constant of the heterogeneous electron-transfer reaction. In an indirect electrolysis, the electron is primarily exchanged with a substance (a mediator) that exchanges the electron with the substrate in a chemical reaction, and the rate does not depend on the ability of the substrate to exchange an electron with the electrode. 

Electrochemical regeneration of expensive but highly selective chemical redox agents (indirect electrolysis). This is very attractive, if the application of such reagents in stoichiometric amounts is excluded because of economical and ecological reasons. 

Quinones can be synthesized by anodic nuclear aromatic substitution, if high-valent chromium(VI) acts as an electrochemically generated and regenerated chemical oxidant in acidic solution (indirect electrolysis) [6] ... 

Typical examples for type 1 are the anodic cleavages of two carbon-sulfur bonds in 1,3-dithianes [46] or dithiolanes [47]. This reaction is especially effective if performed under the conditions of indirect electrolysis using triarylamine cation radicals as regenerable oxidative mediators [47] ... 

Another important classification of electroorganic reactions is obtained by dividing them into those in which the substrate undergoes direct electron transfer with the electrode (direct electrolysis) and those in which an additional compound (redox catalyst, mediator) transfers the redox equivalents between the substrate and the electrode (indirect electrolysis). 

In an indirect electrolysis silver beads are used as anode in a flow cell to achieve coupling of sodium nitrite and nitroaliphatic in excellent yield (Eq. (169) ) 88 ... 

Figure 1 Schemes for different electrochemical treatments of organic pollutants, (a) Direct electrolysis by anodic oxidation in which the pollutant reacts at the electrode surface with adsorbed OH" produced from water oxidation at a high 02-overpotential anode, (b) Indirect electrolysis where the pollutant reacts in the solution with an irreversibly electrogenerated reagent B+ produced from the oxidation of inactive B at the anode.

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