Thousands of electrochemical reactions of organics have been catalogued to date. These comprise direct electron transfer reactions at anodes for oxidation and at cathodes for reduction. Thousands of these also include indirect electron transfer reactions using redox species. Of these, not more than a few hundred pilot and industrial scale organic electrosyntheses have been described (see Tables I-III below for examples). The essential difference between chemical and electrochemical processing is that the reactor is an electrolytic cell powered by a current source. The electrolytic cell contains positively charged anodes and negatively charged cathodes; an electrolyte solution containing ions to carry the current and in which the reactant and product are usually at least partially dissolved; maybe, separators (membranes or porous diaphragms) to separate the processes at the anodes and cathodes; and, some means for stirring or agitating the cell contents. The electrodes may be made of special catalytic material, that is these may be electrocatalytic coatings with special properties for optimizing the yield, increasing product specificity, extending electrode life, and/or lowering cell voltage. The electrodes are preferably spaced as close together as possible without touching to avoid shorting, so as to minimize the cell voltage (See Economics).The dc power supplies or rectifiers electrify the cell, at relatively low cell voltages usually in the range of about 3 to 15 volts. There are many other differences seen in organic electrosynthesis compared to conventional organic synthesis. Useful concentrations of highly reactive cation or anion radicals, not easily or so far impossible to make chemically, can be easily and conveniently produced electrochemically. The resulting electrosynthesis products can be unique (that is not before synthesized by chemical means, or so difficultly made by chemical means that many steps would be required). Many other reactive species can be made conveniently, including superoxide ion, hydroxyl radicals, peroxide, CO2 anion radicals, hydrogen atoms and metal hydrides, and halogens, including fluorine. On the cathode side of the cell, at high negative potentials, solutions of solvated electrons can be readily made and on the anode side, at high positive potentials, powerful oxidants like fluorine, persulfate salts, and ozone. Acid can be made at the anode and alkali at the cathode.
Advantages and disadvantages of electrosynthesisThere are advantages and disadvantages to organic electrochemical processing. Most important among the advantages is the very wide range of oxidation and reduction reactions possible. Other advantages that may be realized are: significantly less energy requirement; less hazardous process; elimination or minimization of polluting byproducts requiring disposal; process simplification so that an otherwise multistep chemical route is simplified to one or two steps; use of cheaper more readily available starting materials; the possibility of reaching very high levels of product purity and selectivity; development of valuable intellectual property; and, in many instances, considerably improved capital and operating costs over conventional methods.Electrosynthesis certainly has disadvantages too. Electrosynthesis usually requires the use of a solvent to solubilize the reactants and products. Water is the ideal solvent but too often organic solvents or co-solvents are required. In addition, supporting electrolytes to carry the current are very often needed. The solvent/supporting electrolyte system can be too expensive or even the source of unacceptable pollutants if not recovered and recycled. Electrolytic cells require stable electrode materials, separators and other components, which may have limited lifetimes and can affect the economics adversely. Electricity is required in all electrochemical processing which may or may not be a critical factor, depending on where the process is located. (Note, however, that the cost of electricity is not at all a deciding factor where higher value added products such as pharmaceuticals are the products). Considering the advantages, critics question why there are so few commercial scale organic electrosyntheses. Indeed, there are many ongoing successful processes (See Tables I-III), but as in conventional processes, some have been discontinued or may never reach commercial scale for various reasons, including:
Chemical industry's attraction to electrosynthesisThe advantages cited above are good reasons for companies to be aware of advances in electrochemical processing. There are also good reasons for chemical companies to have on hand at least the basic laboratory tools and the necessary skills to evaluate potential electrochemical routes alongside conventional methods. But, all too often the primary reason why companies investigate electrochemical processing alternatives is because the company has tried every conceivable chemical method available without success. Then someone in the company, perhaps an electrochemist, an external consultant, or a scientist reading the literature has asked if electrosynthesis might be the long-sought answer. In reality, except for rare instances, there are usually no easy electrosynthesis answers, if no chemical route works.
Attaining successful industrial organic electrochemical processesThe importance of adopting a strategic approach cannot be overemphasized, especially where a company does not have the necessary in-house expertise. Reaching an informed decision on whether or not to pursue a proposed electrochemical route requires consideration of all of the following:
Engineering considerationsAfter successful R&D/preliminary economics, the optimization of the commercial process requires attention to:
The rate of mass transfer of reactants and products across the boundary layer at the electrode can be improved by:
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Table I. Commercial processes | ||
Product | Starting material | Company |
Acetoin | Butanone | BASF |
Acetylenedicarboxylic Acid | 1,4-Butynediol | BASF |
Adipoin Dimethyl Acetal | Cyclohexanone | BASF |
Adiponitrile | Acrylonitrile | Monsanto (Solutia), BASF, Asahi Chemical ![]() |
4-Aminomethylpyridine | 4-Cyanopyridine | Reilly Tar |
Anthraquinone | Anthracene | L. B. Holliday, ECRC |
Azobenzene | Nitrobenzene | ? |
Bleached Montan Wax | Raw Montan Wax | Hoechst |
Calcium Gluconate | Glucose | Sandoz, India |
Calcium lactobionate | Lactose | Sandoz, India |
S-Carbomethoxymethylcysteine | Cysteine + Chloroacetic Acid | Spain |
L-Cysteine | L-Cystine | Several |
Diacetone-2-ketogulonic Acid | Diacetone-L-sorbose | Hoffman-LaRoche |
Dialdehyde Starch | Starch | India, Others |
1,4-Dihydronaphthalene | Naphthalene | Hoechst |
2,5-Dimethoxy-2,5-dihydrofuran | Furan | BASF |
2,5-Dimethoxy-2,5-dihydrofuryl-1-ethanol ![]() | Furfuryl-1-ethanol | Otsuka |
Dimethylsebacate | Monomethyladipate | Asahi Chemical |
Gluconic Acid | Glucose | Sandoz, India |
Hexafluoropropyleneoxide | Hexafluoropropylene | Hoechst |
m-Hydroxybenzyl Alcohol | m-Hydroxybenzoic Acid | Otsuka |
Mucic Acid | Galacturonic Acid | EDF |
Perfluorinated hydrocarbons | Alkyl substrates | 3M, Bayer, Hoechst |
Phthalide + t-Butylbenzaldehyde Acetal | Dimethyl Phthalate + t-Butyltoluene ![]() | BASF |
p-Methoxybenzaldehyde | p-Methoxytoluene | BASF |
Polysilanes | Chlorosilanes | Osaka Gas |
p-t-Butylbenzaldehyde | p-t-Butyltoluene | BASF, Givaudan |
Salicylic Aldeyde | o-Hydroxybenzoic Acid | India |
Succinic Acid | Maleic Acid | CERCI, India |
3,4,5-Trimethoxybenzaldehyde | 3,4,5-Trimethoxytoluene | Otsuka Chemical |
3,4,5-Trimethoxytolyl Alcohol | 3,4,5-Trimethoxytoluene | Otsuka Chemical |
Table II. Piloted processes/not yet commercialized | ||
Product | Starting material | Company |
1-Acetoxynaphthalene | Naphthalene | BASF |
Acetylenedicarboxylic Acid | 2-Butyne-1,4-diol | BASF |
2-Aminobenzyl Alcohol | Anthranilic Acid | BASF |
Anthraquinone | Naphthalene, Butadiene | Hydro Quebec |
Arabinose | Gluconate | Electrosynthesis Co. |
1,2,3,4-Butanetetracarboxylic Acid ![]() | Dimethyl Maleate | Monsanto |
Ceftibuten | Cephalosporin C | Electrosynthesis Co., Schering Plough ![]() |
3,6-Dichloropicolinic Acid | 3,4,5,6-tetrachloro-picolinic Acid ![]() | Dow |
Ditolyliodonium Salts | p-Iodotoluene, Toluene | Eastman Chemical, Electrosynthesis Co. |
Ethylene Glycol | Formaldehyde | Electrosynthesis Co. |
Glyoxylic Acid | Oxalic Acid | Rhone Poulenc, Steetley |
Hydroxymethylbenzoic Acid | Dimethyl Terephthalate | Hoechst |
Monochloroacetic Acid | Tri- and dichloroacetic Acid | Hoechst |
Nitrobenzene | p-Aminophenol | India, Monsanto |
5-Nitronaphthoquinone | 1-Nitronaphthalene | Hydro Quebec |
Partially Fluorinated Hydrocarbons | Alkanes and Alkenes | Phillips Petroleum |
Pinacol | Acetone | BASF, Diamond Shamrock |
Propiolic Acid | Propargyl Alcohol | BASF |
Propylene Oxide | Propylene | Kellog, Shell |
Substituted Benzaldehydes | Substituted Toluenes | Hydro Quebec, W.R. Grace |
Table III. Discontinued commercial processes | ||
Product | Starting material | Company |
1,2-Dihydrophthalic Acid ![]() | o-Phthalic Acid | BASF |
2-Methyldihydroindole | 2-Methylindole | L. B. Holliday, BASF ![]() |
Hexahydrocarbazole | Tetrahydrocarbazole | L. B. Holliday, BASF |
Piperidine | Pyridine | Robinson Bros. |
Sorbitol | Glucose | Hercules |
Tetraalkyl Lead | Alkyl Halide, Pb (anode) ![]() | Nalco |
There are at this writing no academic institutions where courses in applied electrochemistry are taught. In the USA, the closest disciplines taught are electroanalytical chemistry and electrochemical engineering. Fortunately, there is a large literature of resource materials, including excellent books (see Bibliography). Electrochemical Society meetings (http://www.electrochem.org) and other international symposia, such as the Annual International Forum on Applied Electrochemistry (http://www.electrosynthesis.com) are excellent meetings to explore ideas and find assistance from experts in the field.
What is available also to help those interested in applied organic electrosynthesis are many commercial cells of flexible design; stable cell components, including catalytic electrodes, highly selective membranes and a number of novel electrode/membrane composites; a sound theoretical and practical knowledge base in electrochemistry and electrochemical engineering; and, experienced groups that can advise on R&D, engineering, plant design, construction, and start-up.
K = ( 100 Ko n F V ) / ( Mp Ec )
A = ( 1.12 × 103 n P ) / ( Mp i Ec )
where:
K | = | ![]() |
Ko | = | ![]() |
n | = | ![]() |
F | = | ![]() |
V | = | ![]() |
Mp | = | ![]() |
Ec | = | ![]() |
A | = | ![]() |
P | = | ![]() |
i | = | ![]() |
To calculate an approximate cell cost, using the above determined electrode area requirement, use $10,000/m2 for larger installations (say, >10 m2) and $15,000/m2 for smaller installations (<10 m2). Theses figures include electrodes (anodes and cathodes), membranes, frames, spacers, gaskets or o-rings, end-plates and cell fittings for electrolyte, and electrode connections. Contact the cell manufacturer to determine an exact cell cost. For the best economics, it can be seen that low cell voltage, high current density, high current efficiency, and high product selectivity are needed.
2 CH2 = CHCN + 2 H + + 2 e - ==> NC-CH2CH2CH2CH2-CN
Aluminum production
Brine electrolysis
Current density distribution in electrochemical cells
Extracting metals from sulfide ores
Listings of electrochemistry books, review chapters, proceedings volumes, and full text of some historical publications are also available in the Electrochemistry Science and Technology Information Resource (ESTIR). (http://knowledge.electrochem.org/estir/)
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