ELECTROCHEMICAL SYNTHESIS

Electrochemistry is widely used in industry, for example in effluent treatment, corrosion prevention and electroplating as well as in electrochemical synthesis. Electrochemical synthesis is a well-established technology for major processes such as aluminium and chlorine production; there is, however, increased interest in the use of electrochemistry for clean synthesis of fine chemicals. The possible green benefits of using electrochemical synthesis include: often water-based processes usually mild operating conditions relatively energy efficient! atom efficient - replacement of reagents by electrons novel chemistry possible The basis of electrochemical synthesis is the electrochemical cell of which there are many types, both batch and continuous flow, with a multitude of electrode variations. " common type of cell used in synthesis is shown in #igure $.%, exemplified by the membrane cell for the production of chlorine. Examples of Electrochemical Synthesis : The membrane cell for production of chlorine is the most recent of three competing processes for chlorine production

i!"re Schematic of an electrochemical membrane cell for production of C12

Catalysts
A material which changes usually increases! the rate of attainment of chemical equilibrium without itsew being changed or consumed in the process.

#hase transfer catalysts: these have been around for about &' years and were developed as a means of
increasing the rates and yields of reactions in which the reactants are in two separate phases. (n these cases poor mass transport often limits the reaction. )hase transfer catalysts act by transporting the reactants from one phase into another, thus overcoming mass-transport limitations.

$iocatalysts: these are essential for life and play a vital role in most processes occurring within the
body as well as in plants. (n the laboratory biocatalysts are usually natural en*ymes or en*ymes produced in situ from whole cells. They offer the possibility of carrying out many difficult transformations under mild conditions and are especially valuable for producing enantiomerically pure materials. Their huge potential is currently largely untapped, partially due to the time and expense of isolating and screening en*ymes.

#hotocatalysts: these harness energy from the sun to carry out chemical transformations. These energyefficient catalysts are proving especially beneficial in destroying harmful waste and for water clean-up.

OR%ANIC SOL&ENTS

+rganic solvents have played a ,ey role in the development of many useful products. (n chemical manufacture, organic solvents are widely used in a variety of unit operations including extraction, recrystalli*ation and the dissolution of solids

SOL&ENT' REE SYSTEMS

(t is a misconception that most chemicals are manufactured in organic solvents. -ost high-volume bul, chemicals are actually produced in solvent-free processes, or at least ones in which one of the reactants also acts as a solvent. Typical examples of such large-scale processes include the manufacture of ben*ene, methanol, -T.E, phenol and polypropylene. (n addition, some heterogeneous gas-phase catalytic reactions, a class of solvent-free processes, Solvent-free Reactions /uch reactions are especially suitable for microwave heating since energy conduction is not re0uired as it is when using more conventional heat sources!. (n the absence of solvent, the radiation is directly absorbed by the reactants, giving enhanced energy efficiency. (n addition many noncrystalline solid supports absorb microwave energy efficiently but are rather poor (e.g. some metal oxides! at conducting heat. e.g 1iels-"lder reactions by 2ewis acids using solid catalysts such as 3 4' montmorillonite

S(#ERCRITICAL L(I)S
A supercritical fluid /5#! can be defined as a compound which is above its critical pressure (P ! and above its critical temperature (TJ. "bove and Pc the material is in a single condensed state with properties between those of a gas and a li0uid. /imply it is the process of densities of the li0uid and gaseous phases coming together as the co-existence line shown in #igure

i!"re Phase diagram showing supercritical fluid region

As the temperature of a li0uid rises it becomes less dense and as the pressure of a gas rises it becomes more dense; at the critical point the densities become e0uivalent. (n general /5#s have densities nearer to li0uids and viscosities similar to gases, leading to high diffusion rates. The properties of the fluid can be adjusted by altering the temperature and pressure, as long as they remain above their critical points. /upercritical fluids have been ,nown for well over a hundred years but it is only since about 467' that their huge potential has been recogni*ed. That said, a small number of high temperature and pressure processes have been operated in the supercritical region for many years. Two of the most widely ,nown ones are: 8igh-temperature and -pressure free radical polymeri*ation of ethene, to produce low-density polyethene 21)E!.

The 8aber process for ammonia manufacture, which operates above the critical point of ammonia. The ,ey advantages of carrying out a process under supercritical conditions include: (mproved heat and mass transfer due to high diffusion rates and low viscosities. The possibility of fine-tuning solvent properties by varying temperature and pressure. A potentially large operating window in supercritical region. Easy solvent removal and recycle. Eg. S"percritical Car*on )ioxi+e ,scC-./ The two main uses for sc5'9 are as an extraction solvent and as an inprocess solvent. "nother, as yet small-scale but environmentally significant, use is as a solvent:dispersion medium for spray coating.

IONIC LI0(I)S
The major advantage of using ionic li0uids as solvents is their very low vapour pressure, which, coupled with the fact that they can often act as both catalyst and solvent. The main issues still to be resolved centre on their toxicity most ionic li0uids have not been assessed! and, despite the potential for recycling, the fate and protocol for their ultimate disposal has not been established. (onic li0uids or more correctly non-a0ueous ionic li0uids! have been ,nown for many years. (n broad terms they can be viewed li,e common ionic materials such as sodium chloride, the difference being that they are li0uid at low temperatures, this being due to poor pac,ing of the respective ions. (n order to achieve this poor pac,ing re0uirement, room-temperature ionic li0uids are generally made from relatively large, non-coordinating, asymmetric ions. (nvariably at least one of these ions is organic in nature. (onic li0uids are not currently available in significant 0uantities for most commercial operations but their preparation is relatively straightforward although synthesis of very pure materials is more difficult!. #or example, ;<.upy="454& can simply be prepared by mixing the imida*olium chloride with aluminium chloride, the resulting exothermic reaction producing the li0uid product.

E.g. chloroaluminate materials also display useful 2ewis acid properties they are highly air and moisture sensitive Characteristics for reaction solvents include: Tunability - by varying the catiodanion ratio, type and al,yl chain length properties such as acidityhasicity, melting temperature and viscosity can be varied to meet particular demands. -any ionic li0uids are stable at temperatures over %'' >5, providing the opportunity to carry out high-temperature reactions at low pressure. (onic li0uids that are not miscible with organic solvents or water may be used to aid product separation or used in li0uid-li0uid extraction processes. #or a given cation the density and viscosity of an ionic li0uid are dependent on the anion; in general density increases in the order .# & < )#? < 5#%/'9!9< and viscosity increases in the order 5#%/'9!9< < .#, < )#?- < <+% Ionic Li1"i+s as Sol2ents (f ionic li0uids become widely used it is li,ely to be the less water and air sensitive ones which prove to be more commercially attractive, and the main emphasis will lie with their use as solvents rather than as catalysts. Ionic Li1"i+s as Catalysts
-. -

5hloroaluminate ionic li0uids are also highly active #riedel-5rafts catalysts, in fact with active al,yl halides mono-al,ylation is often difficult to achieve owing to the very high activity of the catalyst. -ore success has been achieved using al,enes as the al,ylating agents, since they have lower activity than al,yl halides. The acidic and catalytic properties of chloroaluminate ((4! ionic li0uids are fre0uently said to arise from the species "4954$ E.g. /eddon@s synthesis use as 2ewis acid catalyst,which 0uench water to isolate the product. (n 1iels-"lder reaction ionic li0uids greatly enhances their ease of recovery and recycle.
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Alternati2e Ener!y So"rces

Micro3a2e Heatin! -icrowaves have wavelengths between 4 mm and 4 m and hence have similar fre0uencies to radar and telecommunication devices. -echanism of heat generation Ahen a substance possessing a dipole moment water is the obvious example! is subject to electromagnetic radiation it will attempt to align itself to the electromagnetic field by rotation. (n li0uids this rotation causes friction between adjacent molecules, which in turn causes a temperature rise. #or substances containing ions the most effective heating mechanism is conduction. The ions will move through the solution under the influence of the electric field, undergoing fre0uent collisions, this ,inetic energy being converted into heat. "icrowave-assisted Reactions in #ater (t was noted earlier that, despite microwave energy being targeted at polar molecules, a reaction mixture usually rapidly reaches temperature e0uilibrium through molecular collisions, etc. "n exception to this rule has led to a high-yielding synthesis of a thermally unstable 8ofmann elimination product. (n this example a poorly mixed two-phase water: chloroform system was used. .eing polar the starting 0uaternary ammonium compound was water-soluble. -icrowave irradiation 0uic,ly heated the water phase to over 4'' >5, 4 min!.

Scheme "icrowave assisted $ofmann elimination

Aater-based microwave reactions have been relatively well studied for hydrolysis and hydrogen peroxide oxidation reactions, where the natural solvent of choice would be water (n the hydrolysis of ben*amide with sulfuric acid, 0uantitative conversion was achieved in $ rnin under microwave irradiation at 4&' >5, compared to a 6'B conversion after a 4-h reflux using a conventional heating source

Scheme #ater-bused microwave assisted reactions

SONOCHEMISTRY
Cltrasound refers to sound waves with fre0uencies higher than those detectable by the human ear, i.e. around 47 ,8*. Ahen a sound wave, propagated by a series of compression and rarefaction cycles, passes through a li0uid medium it causes the molecules to oscillate around their mean position. 1uring the compression cycle the average distance between molecules is reduced and, conversely, it is increased during rarefaction. Cnder appropriate conditions in the rarefaction cycle the attractive forces of the molecules of the li0uid may be overcome, causing bubbles to form. (f the internal forces are great enough to cause collapse of these bubbles very high local temperatures around D''' >5! and pressures over 4''' bar! may be created. (t is these very high temperatures and pressures that initiate chemical reaction. The sound waves are generated by converting electrical energy using a transducer. There are several different types available; only the most common, pie*oelectric transducers. Sonochemistry an+ %reen Chemistry The term sonochemistry is used to denote reactions initiated by ultrasound. As with microwaves many studies have tried to discover Especial effectsF, but in most cases the reaction follows the predicted pathway. 8owever, rates are often higher, whilst bul, reaction temperatures remain low indicating good energy efficiency. There are cases in which different pathways are followed; for example radicals are sometimes formed in ultrasonic reactions owing to the high local temperatures. "n interesting example of Esonochemical switching pathwaysF is the reaction between ben*yl bromide and potassium cyanide using an alumina catalyst in toluene. (n the absence of ultrasound al,ylation is the preferred pathway but when ultrasound is applied ben*yl cyanide is produced in $?B yield.

Scheme %&ample of sonochemical switching

The range of reactions carried out under sonochemical conditions is large and growing rapidly; in many cases some green benefits are obvious. Typical reaction types assessed include: o&idation! which can often be carried out more rapidly at lower temperatures, radical reactions! with the radicals being generated under mild conditions, and s'nthesis of nanopartides. 8ere the high temperatures generated, followed by rapid cooling are favourable to the formation of these particles.