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The search for alternatives to better our environment is imperative. The voluntary or involuntary contributions to its degradation have grown to the point that the health of many people and of ecosystems is seriously threatened. A bird's eye view of the substances involved in the pollution arena allows one to note that most of them can normally be subject to either an oxidation or a reduction. For example, compounds containing highly oxidized chromium are quite toxic whereas their reduced counterparts are much less dangerous (in fact, chromium compounds in reduced form are essential nutrients). In other words, simple electron transfer can change a compounds toxicity, probably as a result of the concomitant geometry and standard potential changes. Likewise, many organic compounds lose their toxicity upon oxidation (often all the way to carbon dioxide). Such an electron transfer can frequently be achieved on an electrified surface (electrode); this opens a wide door for the electrochemical treatment or destruction of pollutants.
In the same vein, the application of an electric signal and the monitoring of the resulting current or voltage can detect most of these substances. A series of electroanalytical techniques offers the possibility of performing a plethora of qualitative or quantitative determinations of pollutants in a variety of matrices. Some examples include: polarography, voltammetry, chronopotentiometry, chronoamperometry, etc. In addition, many substances are analyzed by other techniques that make use of electrochemical detectors. Electrochemical techniques offer increasing degrees of accuracy and detection limits, often involving dramatically lower costs than other techniques.
In addition, electrochemistry offers a series of advantages that in many cases can be used to make "green" processes. Some include the minimization of waste emissions by improved process design involving the minimization of by-product formation, raw material usage, and energy consumption.
In this way, electrochemistry offers important degrees of:
The literature on these processes is quite abundant, and this article is not intended as a detailed review. Interested readers are encouraged to seek other general or specific sources according to their needs (see the Bibliography). Instead, a summary of the main concepts as applied to these processes is given below. Note that physical states of reactants or products are only given when they are not aqueous.
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| Fig. 1. Electron-transfer schemes for direct (left) and indirect (right) processes. |
To circumvent these impediments one can generate active species (called "mediators") at the electrodes, which are capable of moving into the solution and react there with the target pollutant. Such processes are called "indirect" processes. An advantage here is that the reaction takes place in a homogeneous fashion, and thus the diffusion of the pollutant towards the electrode is not the rate-determining step of the overall process, and thus the effect of low concentrations does not impair the whole reaction pathway. Depending on whether the mediator can be regenerated or not, the process is called "reversible" or "irreversible", respectively. (See Figure 1.)
Organic compounds. Phenols, aromatic amines, halogenated compounds, nitrated derivatives, fecal wastes, dyes, aldehydes, carboxylic acid anions, etc.
Inorganic compounds. Perhaps the inorganic substance that has been most commonly treated by the electrochemical route is cyanide. The main product is the much less toxic cyanate ion.
The electrochemical reduction processes that have reached the highest degree of maturity are undoubtedly those for metal ion recovery from their dissolved ions, as discussed below. Other noxious compounds amenable for direct reduction include:
Organic compounds. The cathodic dehalogenation of chlorinated hydrocarbons (many of which have been classified as toxic and/or carcinogenic) has a triple advantage:
Inorganic compounds. These include chromates, oxychlorinated species (for example, chlorites and chlorates), oxynitrogenated ions (nitrates and nitrites), etc. Metallic ions are treated next.
Metallic ions. Among the most penalized metals in environmental legislation are: cadmium, copper, chromium, mercury, nickel, silver, lead, and aluminum. Fortunately for our environment, their concentrations are typically small. However this introduces an additional complication for their treatment in electrochemical reactors since mass transport becomes severely limited. To counter this, electrochemists have designed reactors that promote more turbulence and higher contact areas. Three-dimensional and moving electrodes offer promising alternatives, many of which have already been implemented in commercial processes.
Among the most popular oxidants are:
Hydrogen peroxide, which can be formed by the reduction of dissolved oxygen at basic pH.
Metallic ions in higher than normal oxidation states. For example, doubly charged silver cation is an excellent oxidizer for organophosphorous, organosulfur, and chlorinated compounds, both aliphatic and aromatic. Triply charged iron cation is also an oxidizer albeit much weaker that can also be used in successful cases of degradation of grease, cellulose derivatives, urea, meat packing wastes, sewage water, carbonaceous fuels, etc. Cerium ions are well known oxidants used in organic synthesis reactions; they are now used in an environmental application to destroy organic pollutants and munitions residues, converting them into innocuous carbon dioxide. When doubly charged manganese cation is electrochemically oxidized to triply charged cation, these ions can also oxidize pollutants on their own. Insoluble metallic oxides such as bismuth oxide and cobalt oxide have also been proposed for this application.
The production of basic hydroxide ions at the cathode can facilitate removal of water hardness-causing species, for example calcium.
On the other hand it is now common to find wastewaters containing emulsions, formed with water and a dispersed immiscible liquid (for example, in gasoline stations and oil extraction sites). To counter this type of pollution, an electrical field may be used to break up the emulsion since another electrical field can destabilize dispersions formed by charge stabilization. This phenomenon can be coupled to the electrochemical production of flocculating-coagulating agents (like aluminum and iron hydroxides) and the production of a gas (typically hydrogen). As a result of this flocculation-coagulation, pollutants are removed. The resulting solid is a low-density waste due to the flotation action by the gas, which facilitates its separation from the aqueous phase. This is also applied to the removal of dyes that impair the passage of light to the lower parts of aquifers, thus interfering with natural cycles. (Flotation is a process also used in the separation of metal ores.)
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| Fig. 2. Coupled electrochemical-biological treatments. (From: "Environmental Electrochemistry" K. Rajeshwar and J. G. Ibanez, Academic Press, 1997.) |
Some of the processes involving anion or cation selective membranes are called electrohydrolysis due to the fact that hydrogen ions from water electrolysis hydrolyze the target salt. Some others are called electro-electrodialysis since there is an electrolytic component besides simple electrodialysis. Some examples include:
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| Fig. 3. Membrane cell electrolysis; top: two-compartment cell, bottom: three-compartment cell. (From: "Environmental Electrochemistry" K. Rajeshwar and J. G. Ibanez, Academic Press, 1997.) |
Three-compartment cells. Much like the above process, sodium ions migrate towards the cathode and form sodium hydroxide with the hydroxyl ions produced there, while the sulfate ions migrate towards the anode and produce sulfuric acid. The effluent from the central compartment is a dilute solution of the original feed.
Recent developments in the field include the design and production of bipolar membranes, consisting of two membranes "glued" together (one cationic, one anionic); the result is that water is broken at the interface into its component ions: hydrogen and hydroxyl ions that migrate towards the cathode and anode, respectively. During their migration they react with the target salt to yield its "father" acid and its "mother" base. An advantage in using bipolar membranes is the low energy used (since water "dissociates" rather than being "electrolyzed", and the voltage is used for driving the ion migration rather than for electrolysis). The membranes used in these electrochemical processes are typically organic in nature, with ionizable groups bonded to a highly stable (both mechanically and chemically) organic skeleton.
Membrane-based separation technologies are now an important component in many chemical industries and further applications are on sight. In electrochemical applications alone, membrane sales have soared up to 500% in one year.
A clever spin-off technology involves usage of an ion exchange medium (typically resins) bonded onto an electrode surface. The resin adsorbs the target pollutants from an aqueous solution that are later eluted by a polarity change into a separate chamber. This method is called "electrochemical ion exchange (EIX)".
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| Fig. 4. Electrolytic generation of microorganism deactivators. |
It is necessary to distinguish here between disinfection and sterilization. The first refers to the deactivation of "pathogen" (disease causing) microorganisms, whereas the second refers to the deactivation of all microorganisms present in the target medium. Mechanisms for such a deactivation include modification of, or attack to:
The disinfecting agents most commonly used have properties as oxidants. This makes them useful for the deactivation of most microorganisms, but also brings about undesirable effects such as the discoloration of dyes and the attack of some organic substances. This has an additional drawback in the sense that such effects involve the consumption of extra amounts of the disinfecting agent, thus elevating the corresponding costs. Furthermore, some of these disinfecting agents can produce "disinfection by-products" (DBP) upon their addition or reaction with organic substrates. Such DBP's are frequently toxic, as is the case of most chlorinated hydrocarbons.
The main disinfectants produced by the electrochemical route can be classified according to the oxidizing element as (Figure 4):
Nitrogen dioxide is soluble and can be electrochemically reduced by direct or indirect processes. For example, direct reduction in an acid solution can yield nitrogen gas; an indirect method with thiosulfate (that can then be regenerated) also produces nitrogen.
Nitrous oxide is also much more soluble than nitric oxide and can be captured by solutions of amines; it can also be electrocatalytically reduced to nitrogen in basic or acidic media.
Hydrogen sulfide. Once removed by absorption, this gas can be recovered by the thermal regeneration of the absorbing liquid and sent to the Claus process for the recovery of elemental sulfur (See the Appendix). Unfortunately this process has several limitations, as the hydrogen from hydrogen sulfide is essentially wasted (since it forms water); also, the required conditions are not flexible enough as to withstand sensible variations in hydrogen sulfide composition, and post-treatments are required. Some modern methods involve the use of oxidants such as hydrogen peroxide, and highly oxidized iron species that can often be regenerated in an external cell process and returned to the absorber unit.
Sulfur dioxide. "Flue Gas Desulfurization" processes (FGD) remove sulfur dioxide by its irreversible reactive absorption with lime or limestone, or by its reversible absorption in sodium citrate solutions. There are many electrochemical methods that have been studied for this purpose. Most of these involve the direct or indirect oxidation of sulfur dioxide to sulfate ion, although some involve its reduction to elemental sulfur.
Sulfur trioxide. A technically and economically viable process for the selective removal of sulfur trioxide from thermoelectrical plants uses high temperature, 500oC (932oF), for its selective removal by a molten electrolyte.
Chlorine. Waste and impure chlorine can be treated by its dissolution in a metal ion solution, whereby chlorine oxidizes metallic ions and becomes reduced to chloride ions. These are then sent to the anodic compartment of a divided cell to be re-oxidized and produce pure gaseous chlorine.
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| Fig. 5. Electrokinetic remediation of soil. (From: "Environmental Electrochemistry" K. Rajeshwar and J. G. Ibanez, Academic Press, 1997.) |
Electrophoresis involves the movement of charged particles (typically colloids) under the influence of an electric field.
Electroosmosis involves the movement of the solvent (typically water) within the soil pores, due to the formation of an electric double layer between charged surface particles and dissolved ions or solvent dipoles. The external field then attracts the solvent, which in turn drags dissolved species. This phenomenon is known since the middle of the past century by civil engineers, who use it for the removal of humidity from soils, walls, and roofs. Waste wet solids or sludge can also be dewatered in this way.
Electromigration consists of the movement of ionic species in the liquid phase towards the oppositely charged electrode.
Electrokinetic remediation (also called electroreclamation, electrorestoration, electroremediation, electrokinetic processing, or electropotential ion transport) has been used for a variety of applications. Among the species in soils that have been treated with this technique are organic substances (benzene, toluene, ethyl benzene, xylenes, gasoline, warfare agents, acetates, phenols, trichloroethylene, etc.), inorganic species (metallic ions of zinc, mercury, cadmium, nickel, lead, chromium, copper, iron, and silver, in addition to anionic forms of arsenic, chloride, nitrate, sulfate, and cyanide anions, complexes, etc.) as well as radioactive substances. This technique is also in use for the clean up of sludge and groundwater.
Electrokinetic remediation is also used in combination with biological remediation in cases where the organic pollutant is very insoluble or else has a large mass/charge ratio. The problem with soil bioremediation alone is the difficulty for the transportation of oxygen and nutrients to microorganisms, and the requirement of temperatures somewhat higher than ambient. Fortunately, electrokinetic remediation is capable of transporting the necessary oxygen and nutrients in the remediation fluid; also, the passage of electrical current generates some heat that helps to reach the necessary temperature for bioremediation, and facilitates the movement of microorganisms in a directed way (after all, they have a certain surface charge). Thus, the combination of both techniques is a promising route. Numerical simulations of electrokinetic phenomena are an important aid in the calculation of the required parameters for an efficient use of the current.
Interestingly, oxidized electronic components that cannot be soldered due to the presence of oxide layers on their surfaces can be chemically reduced to restore their solderability, and the spent reducer can be electrochemically regenerated.
| [1] | 2H2O(l) ==> O2(g) + 4H+ + 4e- | (water oxidation) |
| [2] | 2H2O(l) + 2e- ==> H2(g) + 2OH- | (water reduction) |
| [3] | RCl + 2H+ + 2e- ==> RH + HCl | (dehalogenation of hydrocarbons) |
| [4] | HCO3- + OH- ==> CO32- + H2O(l) | (hardness removal 1) |
| [5] | Ca2+ + CO32- ==> CaCO3(s) | (hardness removal 2) |
| [6] | H2S(g) + 3/2O2(g) ==> SO2(g) + H2O(g) | (Claus process 1) |
| [7] | H2S(g) + SO2(g) ==> 2S(g,l) + H2O(g,l) + 1/2 O2(g) | (Claus process 2) |
CO2 + (ne- + nH+) ==> (HCOO)2, HCOOH, CO, C, HCHO, CH3OH, CH4
H2 ==> S, S2, SO42-, H2S(conc) + (ne- + H2)
SO2 ==> SO3, H2SO4 + (ne-)
SO2 + (ne-) ==> S
NO + (ne- + nH+) ==> N2, N2O, NH2OH, NH3
NO2 + (ne- + nH+) ==> NH3
N2O + (ne-) ==> N2
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://electrochem.cwru.edu/estir/)
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The Encyclopedia is hosted by the
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and the
Chemical Engineering Department,
Case Western Reserve University, Cleveland, Ohio.
Copyright Notice.
Edited by
Zoltan Nagy ( nagyz@email.unc.edu ),
Department of Chemistry,
The University of North Carolina at Chapel
Hill.