TERM PAPER

TOPIC: APPLICATIONS OF IN CHEMISTRY Submitted To:
Miss.Vibhuti Walia

MICROWAVES

Submitted By: Mayukh Sarkar B.TechM.B.A (ECE) Section: RK6005 Roll No: A13
Date of Allotment: _____________________ Date of submission: __10/11/2010_____

AKNOWLEDGEMENT

I MAYUKH SARKAR, student of B.Tech – M.B.A. (ECE) (Section – RK6005) express my deep gratitude to my teacher Miss. Priyanka Singh . I am very thankful to her for support that led me to the completion of this term paper.

I am thankful to my parents who encouraged me and provided me all the necessary resources that had made possible for me to be able to accomplish this task. I also thank all my friends who assisted me in completing this work.
CONTENTS
(1) (2) (3) (4) (5) (6)

Microwave heating and their properties. Dipole polarization. Super heating in reactions and their effects. Selectivity of reactions. Some coupling reactions. Microwave heating to polymers.

(7) Application of MW heating in Organometallic compounds. (8) Future prospective of MW in Chemistry. ABSTRACT Although I have to deal with chemistry but actual science of microwaves comes from modern physics. Microwaves are actually some excited particles called Magnetrons which have very high frequency but very low wavelength and thus have very high penetrating power. One of the most interesting properties of microwaves is that they always vibrate in the form of a transverse wave. The microwave oven at our home also uses this technique. It basically releases those magnetron particles which enter into any 1st some basic properties of microwaves (MW) have been discussed. In case of modern chemistry, microwave heating is very important as it completely able to provide heat to any reactions and more food that’s needed to be heated. Now as every material in this world have something liquid inside it (in this case water in food acts as that liquid), it gets heated up due to the frictional and vibration energy which fulfil the heat requirement and thus the food gets warmer. In Chemistry also we generally use microwaves in various aspects and in several organic chemical reaction as a main source of heat energy instead of using conventional burner. than that it can be very helpful in organic synthesis in liquid phase specially in case of coupling reactions. Dipolar polarisation is very important phenomenon in this aspect.MW heating is also important in

polymer reactions and synthesis of ceramic products. It has been seen that MW heating is exponentially increase the rate

of reaction, speed of reaction, better yield and thus decrease the time of reaction.

INTRODUCTION Although reports of the potential of microwaves for chemical syntheses date back to at least 1981 and their application to polymers to 1967 it was only with the publication of several articles in 1986 that their full potential began to be explored. Since then, their chemical applications have been extended to almost all areas of chemistry, and have consequently been the subject of a number of excellent reviews. The aim of this text is to explore the variety of work which has been carried out in microwave induced chemistry. Microwaves lie in the region of the electromagnetic spectrum between millimetre waves and radio waves. Specifically, they are defined as those waves with wavelengths of between 0.01 and 1 metre, corresponding to frequencies of between 30 and 0.3GHz (Figure 1).

USES OF MICROWAVES IN CHEMISTY ARE:(i) Rate enhancement of organic reaction due to the usage of higher temperature. (ii) Increased yield. (iii) (iv) Improved purity. Greater reproducibility.

(v) Selective heating of reactants.

Microwave heating
Chemists are often told that microwave ovens are 'tuned' so that water molecules absorb microwaves into rotational energy levels, and this causes molecular motion, and thus heating. This common misunderstanding comes from a failure to realise that while gaseous water has quantised rotational energy levels in the

microwave region, in the liquid phase, the quantisation of rotational levels is, for all practical purposes, non-existent. The easiest way to visualise the mechanism of microwave heating is to picture a microwave for what it is - ie a high

frequency oscillating electric and magnetic field. Anything that may be electrically or magnetically polarised by this 'oscillating' field will be affected to some extent. Two principal heating methods exist - dipolar polarisation, and conductive heating.

Dipolar polarisation
If we consider a polar molecule - eg, water, methanol, THF etc - in a liquid, we know that intermolecular forces give rise to some degree of inertia in the liquid's motion. Microwaves heat polar liquids well because their electric field oscillates at such a frequency that the molecules cannot quite keep in phase with it. As molecules vainly attempt to follow the field, they collide with one another, and we observe heating in the sample. Radiation whose frequency is much higher or lower than this will not heat the sample. With higher frequency radiation, the field oscillates too quickly for the molecules to respond, and with lower frequency radiation, the molecules follow the field so well that no random motion is generated. Even though there is a specific frequency at which this heating is most efficient, the range over which heating may take place is very broad (ca 1-100GHz for water, see Fig 1). The frequency of a domestic microwave oven (2.45GHz) is not selected so that it is at the maximum absorbency for water (something like 10GHz). If it were, you would find that most of the microwave energy was absorbed by the outer layers of your food, while the inside stayed unheated and so uncooked.

Conductive heating
If we irradiate an electrical conductor or semiconductor with microwave energy, any mobile charge carriers (electrons, ions etc) move relatively easily through the material under the influence of the electric field. These induced currents heat the sample, owing to electrical resistance. If the sample is a metallic conductor, most of the microwave energy is reflected with relatively little energy penetrating beyond a few microns into the surface. However, colossal surface voltages may still be induced, and these are responsible for the dramatic electrical discharges that are observed when a metal is placed in a microwave oven.

Conductive heating can be demonstrated in a domestic microwave oven by using materials such as copper oxide or carbon. One should be aware, however, that these materials become very hot, very quickly, and that the electrical potentials induced in the materials can sometimes lead to dramatic (but otherwise harmless) electrical discharges. Alternatively, if pure water is heated in a microwave oven, where the polarisation mechanism dominates, the heating rate is significantly lower than that observed when the same

volume of a dilute salt solution is heated. In the latter case, both dipolar polarisation and conductive mechanisms contribute to the heating effect. Microwaves in the laboratory For microwaves to be used as a practical heating method in the laboratory, or in industry, there have to be good reasons for choosing them over existing technology. Studies over the past decade have uncovered several reasons why microwave heating can be advantageous.

Superheating
Consider heating water in a roundbottomed flask by a heating mantle. Heat is slowly transferred from the glass to the core by convection, and boiling occurs when bubbles of vapour form at a nucleation site, a particle or a surface. Because we are heating from the outside in, the core of the water may be as much as 5°C cooler than the edge, even at the boiling point. Microwaves, on the other hand, heat the water directly and almost uniformly. Under these conditions, the core is hotter than the outside because of surface cooling (often incorrectly expressed as heating from the inside-out), so that when the nucleation sites in the glass are hot enough to allow boiling, the core is some 5°C hotter. Thus by using microwaves, we can raise the effective boiling point of water by as much as 5°C, an effect known as superheating. (The reason why people are scalded as they add coffee to a cup of microwave-heated milk is that the grains of coffee provide nucleation sites on which bubbles form explosively.) Solvents such as tetrahydrofuran or acetonitrile (ethanenitrile) exhibit superheating levels of up to 40°C. From a chemical perspective this is important. If we consider that, for an average reaction, a 10°C rise doubles the reaction rate, and then simply using microwaves to heat a reaction can speed it up appreciably.

Selective heating
An important attribute of microwave heating is the ability to put energy directly into the reaction components, or to heat selectively one reaction component.

Consider, for example, the direct synthesis of metal sulphides and selenides. To synthesise these materials, which are used as energy storage devices and as semiconductors, takes several days by conventional methods. The former involves mixing sulphur and the metal, both in powder form, and heating them in a sealed tube. The problem is that sulphur vaporises as it warms up, and if the temperature gets too high or rises too quickly, the pressure of the sulphur vapour will blow the tube apart. To avoid this, the mixture is heated slowly and cautiously,

even though this means it may take a week or more for the ingredients to combine and form the metal sulphide. Microwaves, on the other hand, may be used to heat the mixture rapidly, and without fear of an explosion, because microwaves heat only the metal and not the sulphur. Sulphur vapour re-condenses in the cool parts of the tube before flowing back to the hot metal. Instead of taking days, the reaction is complete in 15 minutes. This is also a visually stunning reaction because the microwaves stimulate a plasma glow in the sulphur vapour.

Fig: Preparation of chromium sulphide using microwave radiation

Ajay Bose at the Stevens Institute of Technology in New Jersey uses the preparation of aspirin in a microwave oven to demonstrate this effect. By the conventional method this synthesis takes 30 minutes, but in a microwave oven this Green advantages

is reduced to 90s (see Box 1). This improved reaction time is not a result of any 'non-thermal' effects, but is an example of how reaction times may be reduced by increasing the specificity and rate of heating. Box 1. Preparing aspirin in a microwave
Weigh 5g of salicylic acid (1hydroxybenzoic acid) into a 250ml beaker. Add 5ml of acetic anhydride (ethanoic anhydride) so as to wet the salicylic acid uniformly. Place a beaker containing 200ml of cold water alongside the reaction mixture to absorb excess microwave energy. Cover the beaker with a Petri dish and irradiate at full power for 60s. Carefully remove the beaker and swirl the contents gently to mix. Check the temperature, which should be between 120-130°C. If the temperature is lower than this, continue heating the mixture until the proper temperature has been reached, noting that temperatures above 130°C may generate by-products and reduce the yield of aspirin. Carefully remove the beaker from the microwave oven (it will be hot) and allow the contents to cool to ca 95-100°C before pouring it into cold water (50ml). The mixture will oil out, and should be stirred until solid starts separating out. Keep the mixture stirred to prevent clumping and cool in a bath of ice cold water. Filter the mixture when cold, and wash the product with ice cold water. Air dry using vacuum suction. The melting point of the product should be 134135°C. If necessary, the aspirin may be re-crystallised from a hot mixture of 57ml of 2-propanol and 1-2cm3 of water.

While microwaves are both financially and energetically expensive to produce, the efficiency with which they can be used to make them an attractive 'green' alternative to other forms of heating. Moreover, in recent years there has been a drive within the chemical industry to reduce both the production of waste products and the use of solvents. Waste products equate with wasted resources, and solvents can be toxic, flammable, and expensive to dispose of. Microwave chemistry provides a cleaner alternative, this time by exploiting the ability of microwaves to heat the reactants directly. Using only a minimal amount of solvent, the reactants are absorbed into a sponge-like support material (clays, alumina, zeolites etc). The reactants are then heated directly with microwaves to generate the products, which are then extracted, again with a minimal amount of solvent.

Because microwave heating is essentially uniform throughout the material, there is no time lost waiting for thermal conduction to heat the sample and, consequently, reaction times are often measured in minutes or even seconds. A 'green' approach has been adopted by Chris Strauss, at the Commonwealth Scientific and Industrial Research Organisation (CSIRO) in Australia. Strauss and his team carry out organic reactions in supercritical water - water at high pressures and elevated temperatures instead of organic solvents. Under these conditions, the properties of water change markedly from those that we encounter under ambient conditions, and it acts as an excellent organic solvent. The advantage is that the solvent is non-flammable, and when the reaction is completed, the waste solvent may be disposed of down the laboratory drains. Although this may be indeed has been - performed using conventional heating, the use of microwaves is particularly convenient for generating these conditions because of the efficiency with which water is heated in the microwave oven. That microwave chemistry is more than an academic interest has been demonstrated recently by the Dow Chemical Company in the US. Faced with tighter regulation of emissions from an existing agrochemical plant, Dow Chemical had the option of closing the plant down or cleaning it up. By switching to a 60kW microwave-based process, the plant has reduced its production of waste and unwanted byproducts, while increasing productivity and reducing energy costs.

THEORY OF MICROWAVE HEATING

Dipolar Polarization: • For MW heating to occur the matrix should be dipolar or ionic Polar solvents e.g. water, DMF, CH2Cl2 with a dipole moment, i.e. high dielectric constant are MW-active whereas non-polar solvents like toluene, diethyl ether, benzene are MW-inactive. • In the presence of an electric field - dipole moment tend to align parallel to the applied field by rotation. • If the electric field oscillates, the dipole realigns and rotates in respond to the alternate electric field. • The molecules are extremely agitated, the molecular friction and collisions give rise to dipolar heating, ~100C per second. • Note - gases are not microwave active because the rotating molecules are far apart • MW heating occurs via dipolar polarization or conduction mechanism. Conduction Mechanism: • This applies for ions in solutions.

• The ions will move through the solution under the influence of an electric field, the increased collision rate generates heat. • Heat generated is stronger than the dipolar mechanism, e.g. tap water will have higher temperature than distilled water at the same MW radiation power. • One problem is non polar solvents are MW-inactive. Superheating effect: • The combination of temperature and frequency of the MW causes the loss tangent to increase. This causes the heating rate to increase during MW heating by limiting the formation of "Boiling nuclei". Superheating may result in a raised of boiling point by up to 260C • This phenomenon is believed to be responsible for the rate increases in solution phase MW reaction.

• MW produces efficient internal energy transfer (in situ heating) Compared to the wall heat transfer in the conventional Thermal heating. As a result the tendency for seed formation (The initiation of boiling) is reduced and superheating is possible. • Temperature profiles of MW flash-heated palladium catalyzed alkylation in acetonitrile (bp, 81- 820C). The reaction was performed in Septum-sealed Pyrex vessels. Is there a Specific MW effect? • Since the introduction of MW in organic chemistry in 1986, the main debate still remains, what alter the outcome of the synthesis.

Is it merely a thermal or a specific MW effect? Arrhenius Equation: • Does not decrease reaction (Ea) but Increases pre-exponential factor (A) The pre-exponential factor, A, describes the molecular mobility and depends on the frequency of vibrations of the molecules. Since, MW induces an increase in molecular vibrations, it's been proposed that this factor, A, can also be affected. MICROWAVE EFFECT ON SWLECTIVITY OF THE REACTION MW effect on selectivity of reactions: • Since MW can interact with a polar TS. The product formed via more polar TS will be favoured. • Regioselectivity in Cycloaditions of C70 fullerene under MW can be altered.

Classical heating: MW:

ODCB, 8% 0%

TIME 120 min 30 min

Yield 46% 50%

• Theoretical studies suggest that under kinetic control, 1a and 1b have more polar TS. N.B: ODCB is (o-dichlorobenzene). MICROWVE ACCELERATED HOMOGENOUS CATALYSIS 1. Heck-Coupling

2. Sonogashira Coupling

3. Suzuki Cross Coupling

4. Stille Coupling:

Microwave Heating Applied to Polymers
Alongside ceramic processing, polymer chemistry forms probably the largest single discipline in microwave chemistry, and the methods used are certainly among the most developed. Polar starting materials and very often products, allow rapid and controllable syntheses, the dielectric properties themselves being an excellent indicator of reaction progress. The ability to control syntheses with high accuracy and with direct heating of the reactants has the advantage of large potential savings in energy. Economic analyses suggest that the costs of curing polymers may be reduced from 4-11MJKg1 to 0.3-0.5 MJKg-1 by switching to the use of microwaves.53 Epoxy resins have been most widely investigated primarily because of their industrial importance, and because their dielectric properties predispose them to effective microwave induced curing.54 Surprisingly, investigations have indicated that the rate of curing depends less upon the total power which is applied to the sample than it does on the way in which microwave pulses are applied. Investigations into the curing of the diglycidyl ester of bisphenol A (DGEBA) with a number of cross-linking agents 4,4' diaminophenolsulphone (DDS), Dicyandiamide (DDA), 4,4' diaminodiphenylether (DDE), diaminodiphenylethane (DDM),55, 56 - have been carried out and indicate that the curing rate is not directly related to the sample temperature either. With DDS, short high power pulses with a low timeaveraged power (2x10 -3sec, average power 700Watts) were found to give comparable results to those of longer pulses, with high time-averaged power (2x10-2 sec, 1500Watts). Moreover, the pulse induces

causes selectivity in bond formation - the reaction with the amines being favoured by longer pulses, whilst selfpolymerisation is preferred under short pulse irradiation. The optimum pulse frequency for cross linking is dependent upon the cross linking agent, and for example with DDM57-59 optimum repetition frequencies of 23.8, 200, and 1000Hz have been identified. Although no specific relationship is proposed, it has been suggested that these frequencies may correspond to particular polar components (hydroxy-, amine-, epoxy- groups, etc) in the molecules. The synthesis of polyamides60 and polyurethane films61 studied in a similar manner showed a similar relationship to the pulse period, suggesting that energy transfer is more efficient with the use of pulsed microwaves (optimum pulse frequency 13.3-14.3Hz) than by continuous power. Once again, it is concluded that this behaviour is characteristic of a relaxation mechanism which is derived from the movement of chain segments in the macromolecular network.61 Moreover, the hardness of the polyurethane films (Persoz method, given as the damping time for a pendulum oscillation) is generally harder (370-380s) when formed under these conditions than when formed thermally (340-360s). Under optimum microwave curing, the hardness may be as high as 400s.

The intrinsic dielectric properties of a substance may be enhanced or reduced by the incorporation of a secondary material.62 The effect of secondary materials upon dielectric or related properties in polymers have been extensively studied using copper,63 aluminium,64 carbon black or fibres,65 or other conducting materials.66 Carbon fibres have been studied as coabsorbent materials in the microwave curing of epoxy resins to form composite materials.67 Heating arises steadily at the carbon fibre particles, leading to temperatures some 75&#176C higher than that of the bulk sample, and leads to increased and stress free interface adhesion between fibre and matrix.68 The specimens cured in this way showed increased interfacial shear strength (14.15 Ksi) than are available by thermal curing techniques (8.3Ksi). Inherently conducting polymers such as polyaniline p-toluene sulphonate ([sigma]=9.0+/-1.0 S cm-1) or polypyrrole p-toluene sulphonate ([sigma]=22.0+/-2.0 S cm-1) are excellent microwave absorbers, and make ideal materials with which to effect welding of plastics.69 Their inherently organic nature helps to form good bonds between the welded thermoplastics as diffusion occurs into their surfaces, and enables joins with high lap shear strengths (19.0+/-2 Nmm-1) to be produced in as little as 2-120 seconds.

Microwave Heating Applied to Organometallic Chemistry
Organometallic and co-ordination compounds have received surprisingly little attention by microwave chemists in relation to other areas of study, despite indications that here, too, improved syntheses may result. The synthesis of a number of B-metal compounds have been accomplished in pressure vessels similar to those used in high pressure organic syntheses.50 Reactions were run using 100cm3 teflon pressure vessels containing relatively small quantities of solvent (~12cm3). Large reaction rate increases of up to 40 times were observed relative to the conventionally heated samples, and for comparable yields (Table 1). In the

particular case of a reaction of Al(OPri)3 with 1,2-propandiol, a mixture of products resulted, and despite 60x rate increase the microwave synthesis was not especially advantageous. This simply underlines the

fact that often, microwave heating may simply increase the rate of reaction, but not necessarily improve product selectivity despite cases where the latter occurs.

REACTION

SOL VEN T

Micro wave t(min)/ Yield (%)

Thermal t(hrs)/Yield (%)

EtOH

30 / 33

22 /40

EtOH

47 / 29

24 / 36

PrOH EtOH

6 / 46 6/1

3-4 / 30-68

n/a with up to 60 times rate increases, and comparable yields to those seen by published thermal routes. Similar reactions to these run using DMF, methanol or ethanol as a solvent in 23cm3 Teflon digestion vessels, showed even greater rate increases (see Table 2). Product Microw ave yiel d/% (t /sec) 91(50) 68(35) 72(45) 62(30) 89(35) 70(45) 71(40) Thermal yield/ % (t/hr) 94 (18) 72 (24) 95 (4) 85-90 (12) 65 (24)

The synthesis of a range of transition metal co-ordination compounds at atmospheric pressure under reflux conditions has also been carried out with some success.51 Stirring was not employed in these reactions since it proved possible to maintain a steady reflux in its absence. Again, large time savings were recorded,
Reactants

RhCl3.xH2O,C8H12,EtOH/H2O(5:1) RhCl3.xH2O, NBD,EtOH/H2O(5:1) IrCl3.xH2O, C8H12, EtOH/H2O(5:1) RhCl3.xH2O, C6H5, MeOHa RhCl3.xH2O,1,3cyclohexadiene,EtOH IrCl3.xH2O, PPh3, DMF CrCl3.6H2O,Urea,aq.EtOH,Dipivaloylmeth ane

[Rh(cod)Cl]2 [Rh(C7H8)Cl]2 [Ir(C8H12)Cl]2 [Rh(C5H5)2]+ [Rh(C6H6)Cl]2 Ir(CO)Cl(PPh3)2 Cr(DPM)3

Dry media reactions & MW
Dry media reaction under microwaves is an effort toward “green chemistry”. Effects of microwaves in dry media organic reactions have shown synthetic utility for the preparation of biodynamic heterocycles. Nowadays, the microwave dielectric heating effect uses the ability of some liquids and solids to transform electromagnetic energy into heat and thereby drive chemical reactions. This in situ mode of energy conversion has many attractions for chemists [1–2], because its magnitude depends on the properties of the molecules. This allows some control of the material’s properties and may lead to reaction selectivity. There are a variety of methods for carrying out microwave-assisted organic reactions using domestic or commercial ovens; this is basically known as microwave-induced organic reaction enhancement (MORE) chemistry [3]. Microwave heating has not been restricted to organic chemistry as various aspects of inorganic chemistry and polymer chemistry have also been investigated. However, usually the same chemistry (conventional heating) has been observed when the organic reactions involved were carried out. The difference lies in the choice of reaction conditions: The reactions were carried out in high boiling solvents (dimethylformamide, DMF). Heating is fast, but maximum temperatures were chosen below the boiling point of the solvent in order to avoid solvent evaporation. One could work this in open reaction vessels and could choose a small amount of solvent when targeting for solubility at the reaction temperature. Overall, Bose [3] claims that the method is more cost effective (only simple glassware needed) and environment friendly (less solvent needed). To demonstrate the versatility of MORE chemistry, a variety of organic reactions have been done using domestic microwave oven or commercial ovens. Reaction of 7-ACA with carboxylic acids by adsorption on basic alumina under MWI for 90–120 s (Scheme 2) afforded the 7-substituted cephalosporanic acid derivatives with amidic

bond 5-Substituted-2-amino-1,3,4-thiadiazoles were synthesized within 40–80 s with improved yield using acidic alumina, which undergo insertion reaction with 5-alkyl-2-mercapto-1,3,4oxadiazoles yielding the thiadiazolyl-substituted triazoles within 40–80 s (Scheme 3). A drastic reduction in reaction time and improved yield was observed due to the rapid heating capability of solid support under microwaves.

A series of novel bioactive organotin compounds have been synthesized on basic alumina in an open vessel under MWI (Scheme 4). The reaction time has been brought down from hours to seconds as compared to the conventional heating

ADVANTAGES OF MW STUDY IN CHEMISTRYAND ITS FUTURE PROSPECTIVES
Research on ceramic sintering has suggested that sintering conditions usually affect sintering behaviour not throughout the whole process, but primarily through the early stage52. The mechanism is that the initial nucleation directs the sintering process. If a larger population of nuclei has formed in the early stage, the ensuing densification will assume a higher rate and a finer microstructure will result. The microwave-assisted wet chemical synthesis, at least in the case of ceramic powder synthesis, may behave in a similar fashion to ceramic sintering, since it is also a process of nucleation and growth. The microwave effects, if they exist in both the initial and the later stages, may differently affect synthesis kinetics as well as the synthesized structures. Comparison of the microwave effects at initial stage with that at later stages is important for the development of the synthesis systems. If the effects at the initial stage do dominate the whole process, we can focus the microwave radiation on that stage, leaving the later stages to conventional heating approaches. In the situation where the investment cost of a microwave heating facility is much higher than that of a conventional facility, such an allocation of the two kinds of energy could be an optimal strategy.

For the initial stage, it is also necessary to discern the microwave a thermal effects from the effects induced by microwaveinduced rapid heating. While conventional heating normally takes over an hour to heat the contents up to 200°C, microwave heating needs only several minutes or even less. Some researchers on ceramic sintering have attributed the enhanced densification kinetics and the refined microstructures to the microwave-induced high heating rate53, 54. Meanwhile, research on ceramic powder preparation also accounted for the responsibility of rapid heating for the development of monodispersed fine particles55. If the athermal effect is overwhelming, our further efforts should be devoted to the optimal microwave intensity and frequency. Otherwise, we should consider that the fast-heating function could be performed by other approaches, such as low frequency microwave or radio frequency heating, for which large capacity equipment is commercially available and the equipment cost is cheaper.

One answer to the question, “How Do Microwaves Influence Chemistry at Interfaces?” is that microwaves can change the relative energies of reaction intermediates in a given sequence. This is based on experimental studies as we have demonstrated that microwave exposure can change the “effective temperatures” and, thus the relative energies for individual sorbing and sorbed species. The reaction rate for a sequence of meta-stable intermediates in a reaction mechanism can be increased significantly even if the activation energy maxima do not decrease, easily by over an order in magnitude. In a similar manner, microwaves and their variation could influence other processes comprising a sequence of meta-stable energy states as an example, interface transport such as “configurational” diffusion in porous media, etc.

A dual-function reactor could satisfy the study on the microwave effects at separate stages. The reactor could comprise a microwave autoclave and a conventional autoclave. The two autoclaves will be connected to each other and have a method for materials to flow in each direction. For studies on the microwave effects at initial stage, reaction contents can be first charged into the microwave autoclave and heated up by microwaves to the reaction temperature. The reaction contents would be then transferred into the conventional autoclave and the temperature would be kept constant by conventional heating. On the other hand, for studies on the microwave effects at the later stage, reaction contents can be first charged into the conventional autoclave and heated by conventional method to the reaction temperature. The reaction contents would then be transferred into the microwave autoclave and the temperature kept constant by microwave heating. Again a heat-removing device should be present in the microwave autoclave for dissipating various levels of microwave intensity without disturbing the temperature profile. Interfaces are particularly susceptible to this influence. The kinetic consequences for a series reaction due to changes in the effective temperature of a single reactionintermediate species were simulated. The following conclusions can be drawn from these simulations. 1- Increases in the relative effective temperature of reaction intermediates due to exposure to microwaves can increase reaction rates by orders of magnitude at a fraction of the energy required to break specific bonds. 2- Periodic variation of reaction intermediate energies will (most often) be dominated by the most favourable energy pathways. 3- Variation of reaction intermediate energies can give rise to greater overall reaction rates than either reaction path at moderate conversions. 4- Product/reactant ratios can exceed those normally attainable during the periodic manipulations of the reaction

intermediates. The effect depends on the frequency of variation. It is not necessary to absorb sufficient energy to break chemical bonds in order to have a significant influence on reaction kinetics. Stuerga and Guillard(5,6) have correctly pointed out that microwave energies are not large enough to break chemical bonds. Changes in the intermediate energy states in a reaction sequence are found to significantly change the reaction kinetics at energies far below those required to break specific chemical bonds. Indeed, the ability of microwaves to manipulate intermediate energies within the context of a given surface reaction sequence could lead to significant rate enhancement. This explanation of how microwaves can enhance reaction rates does not exclude the other explanations for microwave

enhancement: rapid heating etc.. Overall reaction rates can often be increased by several different methods (new catalysts, pressures, temperatures, and reactor configurations, transient behaviour, etc.). One advantage of microwave enhancement might then be that microwaves provide sufficient energy to enhance reaction rates by manipulating the relative energies in a reaction sequence but less energy than would result in a change in mechanism. Our ability fully to employ microwave energy to enhance catalytic reactions has heretofore suffered from an understanding of the reason(s) for the enhancement. This paper demonstrates the consequences of our experimental results for adsorption measurements in the presence of microwaves on the influence of microwaves on catalytic and other interfacial reactions.

REFERENCES CITED
(i) (ii)

http://sciencedirect.com http://tandelta-microwaves.com

(iii) http://e-books.com

(iv)Microwaves in Chemistry by Wutsu Chang & Zo-ho Chang
(v)

Chemistry word and microwaves by Robert Jones.S. Komarneni, V.C. Menon and Q.H. Li; “Synthesis of ceramic powders by novel microwave-hydrothermal processing”; Ceramic Transactions, 62 1042-1122 (1996).

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