Heating Effects of Microwaves

Vishal Gupta

Theoretical Principles
Traditionally Organic synthesis is carried out by conductive heating with an external heat source (Bunsen burner, electric plate heater, oil bath or heating mantle). This is a comparatively slow and inefficient method for transferring energy into the reaction system since it depends on convection currents and on the thermal conductivity of the various materials that must be penetrated, It results in the temperature of the reaction vessel being higher than that of the reaction mixture. In addition, a temperature gradient can develop within the sample and local overheating can lead to product, substrate or reagent decomposition.

Inverted temperature gradient in microwave (left) versus oil bath (right) heating

(the picture from the book C.O. Kappe and A. Stadler Microwaves in Organic and Medicinal Chemisry, Wiley-VCH, Weinheim, 2005)

Microwave heating
Microwave heating Microwave irradiation produces efficient internal heating by direct coupling of microwave energy with the molecules of solvents, reagents or catalysts presented in the reaction mixture. Radiation passes directly into the whole reaction mixture volume and an inverted temperature gradient as compared to conventional thermal heating results.

Inverted temperature gradient in microwave (left) versus oil bath (right) heating

Microwave Oven: Frequencies

In order to avoid interference with other commercial and defence equipment microwave ovens uses ISM band The frequency at which industrial and domestic microwave apparatus may operate is regulated at both national and international levels. 2.450 (+/- 0.050) GHz is the major operating frequency for this purpose, although other frequency allocations exist All domestic ovens operate at 2.45GHz, and their popularity in recent years has resulted in progressively cheaper microwave sources at this frequency.
Frequency (GHz) Tolerance (+/-) Area permitted Austria, Netherlands, Portugal, Germany, Switzerland United Kingdom North and South America Albania, Bulgaria, CIS, Hungary, Romania, Czech /Slovak Republics, World-wide, except where 2.375 is used Netherlands World-wide Netherlands World-wide United Kingdom 0.434 0.896 0.915 2.375 2.450 3.390 5.800 6.780 24.150 40.680 0.2% 10MHz 13MHz 50MHz 50MHz 0.6% 5MHz 0.6% 25MHz 25MHz

Permitted Frequencies for Industrial, Medical and Scientific uses

Microwave heating: Intro

Microwave-heating is based on interactions of molecules with waves Microwaves are electromagnetic waves which consist of an electric and magnetic field component The heating effect of electromagnetic energy arises from the interaction of the electric field component of the wave with charged particles in the material. Two major effects are responsible for the heating which results from this interaction. If the charged particles are free to travel through the material (electrons in a sample of carbon, for example), a current will be induced which will travel in phase with the field. If, on the other hand, the charged particles are bound within regions of the material, the electric field component will cause them to move until opposing forces balance the electric force. The result is a dipolar polarization in the material. Conduction and dipolar polarization may both give rise to heating under microwave irradiation.

Dipolar Polarization
Dipolar polarization is the phenomenon responsible for the majority of microwave heating effects observed in solvent systems. In substances such as water, the different electro-negativites of individual atoms results in the existence of a permanent electric dipole on the molecule. The dipole is sensitive to external electric fields, and will attempt to align with them by rotation, the energy for this rotation being provided by the field. This realignment is rapid for a free molecule, but in liquids instantaneous alignment is prohibited by the presence of other molecules. A limit is therefore placed on the ability of the dipole to respond to a field, which affects the behavior of the molecule with different frequencies of electric field. Under low frequency irradiation, the dipole may react by aligning itself in phase with the electric field. Whilst some energy is gained by the molecule by this behavior, and some is also lost in collisions, the overall heating effect is small. Under the influence of a high frequency electric field, on the other hand, the dipoles do not have sufficient time to respond to the field, and so do not rotate. As no motion is induced in the molecules, no energy transfer takes place, and therefore, no heating. The electric component causes heating by two main mechanisms: dipolar polarization and ionic conduction. The interaction of electric field component with the polar molecules is called the dipolar polarization mechanism

Dipolar Polarization
When exposed to microwave frequencies, the molecular dipoles align in the applied electric field. As the applied field oscillates, the dipole field attempts to follow these oscillations and the energy is lost in the form of heat through molecular friction and dielectric loss. The amount of heat generated by this process is directly related to the ability of the molecules to align itself with the frequency of the applied field. If the dipole does not have enough time to realign (high-frequency irradiation) or reorientation is too slow (low-frequency irradiation) no heating occurs. The frequency 2.45 GHz usually used in all commercial systems lies between these two extremes and gives the molecule dipole time to align in the field, but not to follow the alternating field precisely. Therefore, as the dipole re-orientates to align itself with the electric field, the field is already changing and generates a phase difference between the orientation of the field and that of the dipole. This phase difference causes energy to be lost from the dipole by molecular friction and collisions, giving rise dielectric heating.

Ionic Conduction
During the ionic conduction, the dissolved charged particles in a sample (usually ions) oscillate back and forth under the influence of the electric component of microwave irradiation. They collide with their neighboring molecules or atoms and these collisions cause agitation or motion, creating heat. The conductivity principle is a much stronger effect than the dipolar rotation mechanism with regard to the heat-generating capacity. Thats why the media containing ions are heated more efficiently by microwaves than just polar solvents. There are three possibilities for rationalizing of rate-enhancements observed in microwave-assisted process: thermal effects (kinetics), specific thermal microwave effects and specific non-thermal microwave effects.

Dielectric Polarization
The inability of partially bound charges to follow the rapid changes in a high frequency electric field gives rise to one mechanism of microwave heating. The total polarization (at) of the material arising from the displacement of charges may be expressed as the sum of a number of components where at = ae + aa + ad + ai ae : Results from the displacement of electron charges in relation to the nuclei in a material, and aa from the displacement of nuclei relative to one another in materials with unequal charge distributions. Polarization of both ae and aa operates on timescales which are very much smaller than that required for microwave frequency field reversals, and therefore follow microwave frequency fields almost exactly. As such they do not contribute to the microwave heating effect

Dielectric Polarization
ad results from the reorientation of polar molecules or other permanent dipoles in the material. As the timescale for its operation is of the order of those associated with microwaves, this is the most important of the polarization phenomena in relation to microwave heating The role of the interfacial polarization (Maxwell Wagner) effect ai, which results from interfacial phenomena in inhomogeneous materials is limited at microwave frequencies, and in general its contribution is limited.

Complex Dielectric Constant

The complex dielectric constant, *, completely describes the dielectric properties of homogeneous materials and is expressed as the sum of real and complex dielectric constants: * = ' + " The real part of * () :represents the ability of a material to be polarized by an external electric field. At very high and very low frequencies, and with static fields, ' will equal the total dielectric constant of the material. Where electromagnetic energy is converted to heat by the material, " is non-zero, and quantifies the efficiency with which the electromagnetic energy is converted to heat. A further quantity, the loss angle d, is also commonly used in the literature, and is more usually given in the form of its tangent. It is related to the complex dielectric constant by Tan = " / ' The angle d is the phase difference between the electric field and the polarization of the material

Effect of Microwave on Water

The asymmetry of the water molecule leads to a dipole moment in the symmetry plane pointed toward the more positive hydrogen atoms. The measured magnitude of this dipole moment is p = 6.2 X 10-30 C. m

Dielectric Loss
For any material, both the real and complex dielectric constants will vary with frequency. The range of frequencies over which the dielectric loss is non-zero, indicating that microwave absorption occurs, is relatively large. There is a clear maximum in the dielectric loss ' for water at a frequency of approximately 20GHz, the same point at which the dielectric constant ' goes through a point of inflexion as it decreases with increasing frequency. The 2.45GHz operating frequency of domestic ovens is selected to be some way from this maximum in order to limit the efficiency of the absorption. Too efficient absorption by the outer layers would inevitably lead to poor heating of the internal volume in large samples. Practically, the amount of energy absorbed by an object, P is defined as: P = 2* pi * f * E2 * E0 * Er * tan where f = frequency of microwave, E = electric field, E0 = dielectric constant of free space, Er = dielectric constant of object and tan = loss tangent.

Variation of ' and " with frequency for water