Journal of Microwave Power and Electromagnetic Energy

ISSN: 0832-7823 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/tpee20

Thermodynamics of Microwave(Polarized) Heating

Systems

B. Adu, L. Otten, E. Afenya & P. Groenevelt

To cite this article: B. Adu, L. Otten, E. Afenya & P. Groenevelt (1995) Thermodynamics of
Microwave(Polarized) Heating Systems, Journal of Microwave Power and Electromagnetic
Energy, 30:2, 90-96, DOI: 10.1080/08327823.1995.11688262

To link to this article: http://dx.doi.org/10.1080/08327823.1995.11688262

Published online: 14 Jun 2016.

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Download by: [Iowa State University] Date: 17 January 2017, At: 05:21
 T H E R M O D Y N A MOICF SM IC R O W A V E
(PO L A R IZ E DH)E A T IN GS Y S T E M S
B. Adu, L. Otten, E. Afenya, and
P. Groenevelt
The equation governing the behavior of microwave (polar-
ized) heating systems is presented. The basic difference be-
tween microwave (polarized) and conventional (non-polar-
ized) heating systems is shown. The influence ofa polarizing
electric field on system properties, parameters, and behavior
is derived. Characteristics predicted by the derived equations
are discussed in relation to published observations. It is re-
vealed that in addition to concentration, temperature, and
pressure gradients, the existence of an electric field intensity
gradient during microwave drying may produces an addi-
tional driving force for mass transport. Thus, at the same
concentration, temperature and pressure, an assisting elec-
tric field intensity gradient may reduce the activation energy
for microwavedrying processes and increase microwave mass
transfer rates for volatile polar or polarizable molecules over
that of conventional heating. A new phenomenological equa-
tion, that accounts for the effect of an electric field gradient
on mass transfer rates during microwave heating is presented.
Key Words:
Thermodynamics, Microwave, Polarized, Heating systems,
Mass transfer.
ABOUT THE AUTHORS:
Benjamin Adu and Lambert Otten are affiliated with the School of
Engineering, University of Guelph, Guelph, Ontario, Canada N1G
2W1. Evans Afenya is affiliated with the Department of Mathemat-
ics, Elmhurst College, Elmhurst, IL 60126. Peiter Groenevelt is af-
filiated with Land Resource Science, University of Guelph, Guelph,
Ontario, Canada N 1G 2W1.
Manuscript received September 19, 1994. Accepted for publication
February 10, 1995.
International Microwave Power Institute
90 Journal of Microwave Power and Electromagnetic Energy
W
he
n
a dielectric material is placed in an electric
or electromagnetic field, the material becomes
polarized, and stores electric energy through po-
larization. The level and mechanism of polarization avail-
able to materials depends on the state and composition of the
material, and the frequency of the applied electric field. The
thermodynamic properties and behavior of a polarized sys-
tem is fundamentally different from that of the same system
not polarized [De Groot and Mazur, 1962]. For example mi-
crowave researchers have observed that material properties
exhibit a dependence O ntheir orientation in a microwave field
[Bengtsson, 1963; Harper and Chichester, 1960; Cole, 1972;
Adelman and Goldman, 19811.Various aspects of microwave
heating are still not well understood [Decareau, 1985]. Con-
sequently, the design of microwave heating processes have
been largely empirical often leading to disappointing results
[Mudgett, 1988]. From available literature [Metaxas and
Meredith, 1983; Decareau, 1985] on microwave heating and/
or mass transfer, for instance, it is clear that the lack of an
adequate understanding of the behavior of microwave heat-
ing and mass transfer systems has persisted mainly because,
apart from volumetric heat generation, microwave heating
systems are generally considered as no different from con-
ventional heating system. Consequently, modification of ex-
isting conventional heating equations to account for internal
heat generated are considered as sufficient in describing the
mechanism and macroscopic behavior of microwave heat and
mass transfer systems. With this approach, peculiar features
important to the understanding of microwave heating and mass
transfer systems are lost within the confines of conventional
heating theories, concepts and parameters. In essence, there
is neither a systematic microwave heat and mass transfer
theory, nor independent microwave heat and mass transfer
concepts and equations outside those established for conven-
tional heating. The lack of a theory, consistent with the fea-
tures of microwave heating and mass transfer systems has
resulted in the lack of explanation for various published ob-
servations unique to microwave processes.
The need for efficient and high quality thermal process-
ing, fast heating, and high mass loss rates in materials with
low thermal conductivity continues to propel the use of mi-
crowave energy in the thermal processing of moist porous
solids. Already, a wide range of applications are actively being
Vol. 30 No. 2, 1995
pursued by industry despite the above stated unresolved
problems. Examples of such industrial microwave thermal
processing ranges from the heating or drying of biomaterials
and pharmaceuticals to the desorption of hazardous chemical
compounds from polymeric medical equipment [Decareau,
1985; Gibson et al., 1988; Smart, 1993]. To limit the high
cost of blind application of microwave energy in industry and
elsewhere, microwave heat and mass transfer, and other mi-
crowave induced phenomena must escape from trappings of
conventional heating. This can only happen if microwave
heating systems are looked at on their own merits. An impor-
tant step in this direction is the development of a theory con-
sistent with the features of microwave heating systems, and
the governing equations for specific processes of interest.
This paper presents a thermodynamic analysis based on
the characterization of microwave heating systems as polar-
ized systems to reveal that the polarization of dielectric ma-
terials by microwaves is central to various published obser-
vations unique to microwave heat and mass transfer systems.
Thermodynamic Equation Polarized Systems
The law of conservation of energy (First law of thermody-
namics) define the total energy of a polarized multi-compo-
nent open system [De Groot and Mazur, 1962] as:
U = TS — PV +(P-E
(1)
i basic difference between microwave (polarized) and conven-
where U is the total internal energy, T is temperature, S is
entropy, P is pressure, V is volume, P is the polarization field
vector, E is electric field strength, H is magnetic field strength,
is magnetic displacement vector, mi is mass of component
i, pi is the chemical potential of component i.
For dielectrics, B =0, and equation (1) simplifies to:
II
U = TS — PV + V(P • E) + (2)
i= 1
Dividing through Equation (2) by the total mass m of the
system gives the specific total internal energy function as:
II= Ts —PV-Fp—i(P•E)±
(3)
1=1
Where u,s, and v are the specific total energy, specific en-
tropy, and specific volume respectively. ci is the concentra-
tion of component i in the system.
International Microwave Power Institute
Basic Difference Between Polarized
and Non-Polarized Systems
From the first law of thermodynamics (Equation (3)), the
extended form of Gibbs equation for a polarized multi-com-
ponent open system may be stated as:
du = Tds — Pdv + E • d(p-1P) + gide; (4)
For a single component system, (dci = 0), Equation (4) be-
comes:
du = Tds - Pdv + E.d(fr 1P) (5)
The equivalent equation for the same multi-component open
system in a non-polarizing field is:
du = Tds = Pdv + Mc; (6)
i
and its single component system equivalent is:
du = Tds - Pdv (7)
From above Equations (5) and (6), it may be seen that the
tional (non-polarized) systems is the existence of electric en-
ergy due to the electrical field E which causes a volumetric
polarization P in the direction of the electric field only. Con-
sequently, any qualitative difference between the behavior of
microwave and conventional systems results from the elec-
tric energy intensity of the system.
E and P obey the causality relations between response
and driving force which may be given as:
E = 2 _p (8)
p =
p - 1P (9)
where lc is the electric susceptibility factor of the system.
Thus, the increase in total internal energy resulting from a
polarization is dictated by the electric field strength and the
electric susceptibility factor of the material.
Physical Effects of the Electric Field Vector
The extensive properties (U,S,V,P) or their linear combina-
tions which are referred to as thermodynamic potentials, are
91
functions of state [Katchalsky and Curran, 19651. Because
intensive properties such as temperature, pressure, concen-
tration, or electric field strength may be easily controlled and
measured, researchers find thermodynamic potentials more
useful than the total internal energy U in describing systems.
A typical approach that may be employed to determine the
influence of the electric field on a system would be to keep
the temperature and pressure of the system constant. A useful
thermodynamic potential for such a study is the so called
Gibbs free energy. The specific Gibbs free energy for a polar-
ized open system is defined as:
g = u - Ts + Pv (10)
The total derivative of Equation (10) gives:
dg = du - Tds - sdT + Pdv + vdP (11)
Substituting for du (Equation (4) in Equation (11) gives the
change in specific Gibbs free energy of a polarized multi-
component open system:
dg = — sdT+ vdP + E • d(p) +
(12)
and for a single component system:
dg = - sdT + vdP + E'd(p) (13)
Similarly, substituting Equation (7) in Equation (11) gives:
dgo = - sdT + vdP (14)
where go is the specific Gibbs free energy for a similar sys-
tem at the same temperature, pressure, density, and compo-
nent concentrations, but outside a polarizing electromagnetic
field. Using Equation (8) to substitute for E in Equation (12)
and integrating at constant E gives:
g = go + •,(p• (15)
A similar treatment for a single-constituent system yields the
same result.
Free energy is the energy isothermally available to do
work. Since polarization is volumetric, the use of polarized
energy to effect a phenomenon such as heating or moisture
transfer will result in a volumetric free energy change. The
total volumetric change in free energy of an isothermal, iso-
baric, polarized system at constant electric field strength may
92 Journal of Microwave Power and Electromagnetic Energy
be expressed as:
_rag) + _2 (p•E+ vE 2
L a y T,ciE (16)
where To is the change in Gibbs free energy per unit volume
for the system at the same temperature, pressure and compo-
nent concentration but zero electric field strength. A similar
treatment by De Groot and Mazur [1962] using a Helmholtz's
free energy (f = u - Ts) leads to the same result and conclu-
sion for a polarized system at constant temperature.
From above, it is clear that at the same temperature,
pressure and component concentrations, the free energy con-
tent of a system polarized by a polarizing energy field such
as microwave is higher than the same system with the polar-
ization absent. Higher free energy increases the activity level
of molecules in a system, and reduces the amount of addi-
tional energy (activation energy) that must be supplied to the
system for a process to occur. For example, the supply of
heat to a liquid system increases its total internal energy. This
increases the liquid's temperature and reduces the heat of va-
porization value of the liquid. Essentially, the activation en-
ergy needed to effect a phenomena in a polarized system may
be lower than that in conventional heating situations where
the system is not polarized. Gibson et. al. [1988] observed
this to be true. They found that the activation energy needed
to remove ethylene oxide from polyvinylchloride during mi-
crowave heating was approximately 50% less than that needed
during conventional heating with hot air.
One of the laws of nature is that a system is inclined to
re-organize itself to attain a state of minimum free energy.
The re-organization may take the form of a change in vol-
ume, shape, polarization, concentration, charge intensity
through electrical discharge, or a combination of the above
mentioned phenomenon depending on the state, composition,
and the system's environmental conditions. In essence, a sys-
tem is inclined to change its extensive properties to reduce its
free energy. This physical concept is expressed by the work
term which is given by:
dW = Pdv — fdl — E • d(VP) — ji1dc1+ (17)
i=t
In expending free energy through a change of the extensive
properties or work mode, entropy may be generated result-
ing in further energy dissipation.
The electric or an electromagnetic force field such as
that of microwaves is vectorial in character and the polarized
free energy it provides is similarly vectorial at every instant.
However, in fluid systems, the movement of molecules are
Vol. 30 No. 2, 1995
characterized by brownian motion. In such motion, individual
molecules move freely and randomly, and collide with each
other, thus transferring and redistributing their momentum.
Inter-molecular momentum transfer resulting from brownian
motion transforms the stress tensor of polarized molecules in
an electric field to a scalar internal stress which manifests
itself as hydrostatic pressure. In essence, polarized free en-
ergy in a closed or confined fluid system manifests itself as
additional fluid pressure. Thus, the hydrostatic pressure mea-
sured in a polarized dielectric fluid by a pressure sensor is
greater than the pressure of the same dielectric fluid under
the same condition but outside an electromagnetic field [De
Groot and Mazur, 1962]. Consequently, for confined or closed
fluid systems Equation (4) may be presented as:
du = Tds — P * dv + gide; (18)
i
For a single component system, (dci = 0), Equation (18)
becomes:
du = Tds - P*dv (19)
P*=P+Pf (20)
where P is the pressure outside a polarizing field and Pf is
the induced additional pressure due to the electric field.
Diffusible constituents in porous media may be classi-
fied as a confined fluid systems. For such systems, the impli-
cation of Equations (18) and (19) is profound. For example,
Equations (18) and (19) indicate that conventional heating
process equations, property value, and system parameters,
that are influenced by fluid pressure will need to be modified
appropriately to reflect the effect of the electric field inten-
sity if they are to predict the behavior of polarized fluid or
microwave heating systems. For example, the Clausius-
Clapeyron equation used in determining the latent heat of
desorption in porous media, and existing conventional heat-
ing equilibrium moisture content (EMC) equations that de-
pend on vapor pressure measurement will need to consider
the induced pressure by the electromagnetic field when the
equations are used in predicting EMC values for microwave
heating processes.
When fluid molecules are not confined, i.e. in an open
system, a mode by which a polarized fluid system may re-
duce its free energy and move towards an equilibrium state is
by reducing the concentration of volatile constituents. For
example, in moist porous media such as grain, moisture may
be lost to reduce the free energy of the system. Contribution
of the electric field to moisture loss will depend on the field
International Microwave Power Institute
strength. Experimental results by researchers in microwave
drying have shown that equilibrium moisture content (EMC)
of grain heated by microwaves are significantly lower than
that of the same grain conventionally heated at the same tem-
perature and ambient pressure [St. John, 1988; Shivare, 1991;
Adu, 1992]. The level of decrease depended on the absorbed
power level used with powers over 0.4 W/g dry basis result-
ing in near zero EMC values. Similarly, microwave drying
rates indicate a strong dependence on absorbed power level
and hence field intensity.
In solids, molecular movement is restricted and stress
distribution is not allowed to occur equally in all directions.
The vectorial character of a polarizing electric field and con-
sequently the work force resulting from it may express itself
as an internal stress mainly in the direction of the field. The
intensity of electric field effects will increase with increasing
electric field intensity.
Thermodynamic Properties of
Polarized Material
Equations that govern thermodynamic properties of materi-
als are derived from the internal energy equation, or the ther-
modynamic potentials of the system. A change in an internal
parameter (temperature, pressure, moisture content, etc.) of a
system changes its total internal, or free energy. While polar-
ization due to a microwave field increases the total internal,
or free energy of a system, its effect on a system's thermody-
namic properties value are ignored.
The thermodynamic property that affects the rate of tem-
perature rise during microwave heating is the heat capacity.
The heat capacity at constant pressure, C. of a system is
defined as:
=(aHh
C
P aT)P (21)
But
Hh = u + Pv (22)
dHh = du + Pdv + vdP (23)
Substituting Equation (4) in Equation (23) yields:
dHh = Tds + vdP + Ed (p-1P) (24)
at constant pressure
93

(PIP)
(25)
aT aT aT
=
TA±
E
P
For non-polarized system a similar treatment gives the famil-
iar expression:
C =
aT ) =T
A
a T = (a()a T (26)
P
Thus, the specific heat capacity of a material in an elec-
tromagnetic field is not necessarily the same as that in a non-
electromagnetic field. Equation (25) states that the heat ca-
pacity of a polarized material consists of the energy required
to change the non-polarized mass and the polarization inten-
sity per unit change in temperature.
Changes in polarization intensity due to temperature
changes require heat to be added or taken from a system. This
affects the value of the heat capacity of polarized systems.
The polarized and non-polarized heat capacity(s) of a system
may be equal only when the polarization intensity is inde-
pendent of temperature. Data from Bengtsson and Risman
[1971] indicate that between 40 and 60°C the loss factor for
foods such as mashed potato, cooked carrots, raw beef and
distilled water is practically independent of temperature.
A similar treatment (above) for the heat capacity at con-
stant volume, and other thermodynamic properties affected
by the electrical state of the material reveals a similar effect
when the material is in a polarizing electric field. Conse-
quently, in microwave heating situations where the dielectric
constant or effective loss factor exhibits a significant change
with temperature or other thermodynamic parameters, cau-
tion must be exercised in assuming that the thermal proper-
ties of the material are constant, or equal to their conven-
tional heating values, as is often assumed to be the case in
modeling microwave heating behavior.
The Chemical Potential of Constituents
A thermodynamic potential, or free energy, of the Legendre
form is useful in defining the chemical potential of constitu-
ents in a multi-component system. A Legendre form thermo-
dynamic potential for a polarized system may be given as:
G* = U — TS + PV — V(P • E) mitt; (27)
i= 1
94 Journal of Microwave Power and Electromagnetic Energy
Differentiating G* and substituting for dU gives:
dG* = SdT + VdP — VP • dE + Ilidm; (28)
From Equation (28), the chemical potential of any constitu-
ent in a polarizing electromagnetic field is defined as:
ac*
=(-- (29)
-m i T,P,E,mi
Moisture Transport During Microwave Heating
During the drying of a moist porous medium, we are inter-
ested in moisture transport from the medium. The transport
of moisture depends on the gradients or thermodynamic forces
present in the system. The relationship between thermody-
namic forces in a system are given by Gibbs-Duhem equa-
tion. By differentiating Equation (3), and substituting Equa-
tion (4) as done in all Gibbs-Duhem equation derivations,
one obtains the important results:
sdT — vdP p • dE + cidtti =0 (30)
i
Equation (30) is the extended form of the classical Gibbs-
Duhem equation.
Porous media such as seeds and other moist granular
particles consist of three main phases; solid, liquid, and gas.
Each phase may consist of several constituents. Thus, we may
write the multi-component term of Equation (30) for a moist
granular material as
= cadtta+ cdl1 + cadtta (31)
Since it is the transport of water that is of major interest dur-
ing drying, we assume that the liquid phase consists of a single
constituent which is water. Applying Equation (30) to the
liquid phase and assuming no change in the chemical poten-
tial of air, the gradient in the chemical potential of water may
be given as:
dl1 (32)
ac,
Vol. 30 No. 2, 1995
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thlye e n e rg py re s e nint th es y s te m
T d t( eq
a n dn e e dtos b ea c c o u n tefodrin a n a ly z inmgic ro w ahveea te d
T h elin e apr h e n o m e n o lo glaicwca ol rre s p o n dtoinEgq u a tio nsy ste m s. In e sse n c em, ic ro w a vh e a te dsy ste m asrep o -
( 3 3 )a fte rs u b s titu tin
fogrE e qis : la riz e dsy ste m asn dsh o u ldb e a n a ly z eads s u c hi.e .,th e

International Microwave Power Institute 95

electric energy present in the system should be accounted
for. The thermodynamics of polarized systems indicates that
material properties are influenced by the material's electrical
state, and the behavior of a polarized system is not necessar-
ily the same as that of the system not polarized. For example,
in microwave polarized porous system, an additional driving
force for mass transport is created when electric field gradi-
ents exist (within, or at the surface of the material). This ad-
ditional driving force, when accounted for, results in a new
mass transport equation that predicts that at the same tem-
perature and pressure conditions, mass transport rates in mi-
crowave drying process may be higher than that in conven-
tional drying. This is supported by the literature on micro-
wave drying.
List of Symbols
= concentration of i constituent
= mass of i constituent
= total mass of system
= volume
= pressure
= entropy
= temperature
= total internal energy
= magnetic displacement vector
=. electric field intensity
= magnetic field intensity
= polarization field vector
= density
= electric susceptibility factor
= dissipation function
= chemical potential of component i
= entropy source strength
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Vol. 30 No. 2, 1995