Transferencia de Calor - Cant de Mov - Masa

Transport
Properties of Foods
George D. Sanauacos
Rutgers University
New Brunswick, New Jersey
and National Technical University of Athens
Athens, Greece
Zacharias B. Maroulis
National Technical University of Athens
Athens, Greece
MARCEL DEKKER, INC. NEW YORK • BASEL

ISBN: 0-8247-0613-7
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Neither this book nor any part may be reproduced or transmitted in any form or by any
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Current printing (last digit):

10 9 8 7 6 5 4 3 2 1
PRINTED IN THE UNITED STATES OF AMERICA

To our wives
Katie G. Saravacos andRena Z. Maroulis
for their encouragement and support
Contents ix
5. Transport of Water in Food Materials 105
I. INTRODUCTION 105
II. DIFFUSION OF WATER IN SOLIDS 106
A. Diffusion of Water in Polymers 107
III. DETERMINATION OF MASS DIFFUSIVITY IN SOLIDS 109
A. Sorption Kinetics 110
B. Permeability Methods 114
C. Distribution of Diffusant 118
D. Drying Methods 120
E. Simplified Methods 123
F. Simulation Method 124
G. Numerical Methods 124
H. Regular Regime Method 12 5
I. Shrinkage Effect 126
IV. MOISTURE DIFFUSIVITY IN MODEL FOOD MATERIALS 127
A. Effect of Measurement Method 127
B. Effect of Gelatinization and Extrusion 13 0
C. Effect of Sugars 133
D. Effect of Proteins and Lipids 13 5
E. Effect of Inert Particles 137
F. Effect of Pressure 138
G. Effect of Porosity 140
H. Effect of Temperature 141
I. Drying Mechanisms 143
V. WATER TRANSPORT IN FOODS 144
A. Mechanisms of Water Transport 144
B. Effective Moisture Diffusivity 145
C. Water Transport in Cellular Foods 146
D. Water Transport in Osmotic Dehydration 147
E. Effect of Physical Structure 150
F. Effect of Physical/Chemical Treatments 152
G. Characteristic Moisture Diffusivities of Foods 155
6. Moisture Diffusivity Compilation of Literature

Data for Food Materials 163
I. INTRODUCTION 163
II. DATA COMPILATION 164
Preface
The basic transport properties of momentum (flow), heat and mass are an
important part of the engineering properties of foods, which are essential in the
design, operation, and control of food processes and processing equipment. They
are also useful in the quantitative analysis and evaluation of food quality and food
safety during processing, packaging, storage and distribution of foods. The engi-
neering properties are receiving increasing attention recently due to the need for
more efficient processes and equipment for high quality and convenient food
products, under strict environmental and economic constraints.
The fundamentals of transport properties were developed in chemical engi-
neering for simple gases and liquids, based on molecular dynamics and thermody-
namics. However, the complex structure of solid, semi-solid, and fluid foods pre-
vents the direct use of molecular dynamics for the prediction of the transport prop-
erties of foods. Thus, experimental measurements and empirical correlations are
essential for the estimation of these important food properties.
The need for reliable experimental data on physical properties of foods, es-
pecially on transport properties, was realized by the development of national and
international research programs, like the European cooperative projects COST 90
and COST 90 bis, which dealt with such properties as viscosity, thermal conduc-
tivity, and mass diffusivity of foods. One outcome of these projects was the impor-
tance of context (relevancy) of the measurement and sample conditions. This ex-
plains the wide variation of the food transport properties, particularly mass
diffusivity.
Statistical analysis of compiled literature data may yield general conclusions
and certain empirical "constants", which characterize the transport property (ther-
mal conductivity or moisture diffusivity) of a given food or food class.
All transport properties are structure-sensitive at the three levels, i.e. mo-
lecular, microstructural, and macrostructural. Correlation of food macrostructure
to transport properties is relatively easy by means of measurements of density,
porosity, and shrinkage. Correlation to molecular and microstructural (cellular)
structure, although more fundamental, is difficult and requires further theoretical
and applied work before wider application in food systems.
The material of this book is arranged in a logical order: The introduction,
Chapter 1, summarizes the contents of the book, emphasizing the need for a uni-
fied approach to the transport properties based on certain general principles. Chap-
ter 2 introduces the fundamental transport properties as applied to simple gases
and liquids. The three levels of food structure, molecular, micro- and macrostruc-
vi Preface
ture, as related to transport properties are reviewed in Chapter 3. A unified treat-

ment of the rheological properties of fluid foods is presented in Chapter 4. The
theory, measurement and experimental data of moisture diffusivity are discussed
in Chapter 5, while a statistical treatment of the literature data on moisture diffu-
sivity is presented in Chapter 6. The diffusion of solutes in food systems is dis-
cussed in Chapter 7, with special reference to flavor retention and food packaging
films and coatings. Thermal conductivity and thermal diffusivity are discussed in
Chapter 8. Finally, heat and mass transfer coefficients are treated together in
Chapter 9.
We wish to acknowledge the contributions and help of several persons to
our efforts over the years to prepare and utilize the material used in this book: Our
colleagues, associates, and graduate students D. Marinos-Kouris, A. Drouzas, C.
Kiranoudis, M. Krokida, N. Panagiotou, N. Zogzas of the National Technical Uni-
versity, Athens; M. Solberg, M. Karel, J. Kokini, K. Hayakawa, V. Karathanos, S.
Marousis, K. Shah, and N. Papantonis of CAFT and Rutgers University; M.
Bourne and A. Rao of Cornell University, Geneva, NY; A. Kostaropoulos of the
Agricultural University of Athens; and V. Gekas of the Technical University of
Crete. We also appreciate the discussions with the members of the European
groups of cooperative projects COST 90 and COST 90 bis, especially R. Jowitt
and W. Spiess.
Special thanks are due to Dr. Magda Krokida for her substantial contribu-
tions in compilation and statistical analysis of the extensive literature data on
transport properties of foods, and her continued help in preparing the illustrations
and typing the manuscript. Finally, we wish to thank the staff of the publisher
Marcel Dekker, Inc., especially Maria Allegra and Theresa Dominick, for their
help and encouragement.
We hope that this book will help the efforts to develop and establish food
engineering as a basic discipline in the wide area of food science and technology.
We welcome any comments and criticism from the readers. We regret any errors
in the text that may have escaped our attention.
GeorgeD. Saravacos
Zacharias B. Maroulis
Contents
Preface
1. Introduction 1
I. RHEOLOGICAL PROPERTIES 3
II. THERMAL TRANSPORT PROPERTIES 3
III. MASS TRANSPORT PROPERTIES 4
2. Transport Properties of Gases and Liquids 7
I. INTRODUCTION 7
II. ANALOGIES OF TRANSPORT PROCESSES 8
III. MOLECULAR BASIS OF TRANSPORT PROCESSES 9
A. Ideal Gases 9
B. Thermodynamic Quantities 10
C. Real Gases 12
IV. PREDICTION OF TRANSPORT PROPERTIES OF FLUIDS 14
A. Real Gases 15
B. Liquids 16
C. Comparison of Liquid/Gas Transport Properties 18
D. Gas Mixtures 19
V. TABLES AND DATA BANKS OF TRANSPORT PROPERTIES 19
3. Food Structure and Transport Properties 29
I. INTRODUCTION 29
II. MOLECULAR STRUCTURE 29
A. Molecular Dynamics and Molecular Simulations 29
vii
viii Contents
B. Food Materials Science 30

C. Phase Transitions 30
D. Colloid and Surface Chemistry 31
III. FOOD MICROSTRUCTURE AND TRANSPORT PROPERTIES 32
A. Examination of Food Microstructure 32
B. Food Cells and Tissues 32
C. Microstructure and Food Processing 34
D. Microstructure and Mass Transfer 34
IV. FOOD MACROSTRUCTURE AND TRANSPORT PROPERTIES 36
A. Definitions 36
B. Food Macrostructure and Transport Properties 40
C. Determination of Food Macrostructure 45
D. Macrostructure of Model Foods 46
E. Macrostructure of Fruit and Vegetable Materials 50
4. Rheological Properties of Fluid Foods 63

I. INTRODUCTION 63
II. RHEOLOGICAL MODELS OF FLUID FOODS 66
A. Structure and Fluid Viscosity 66
B. Non-Newtonian Fluids 68
C. Effect of Temperature and Concentration 71
D. Dynamic Viscosity 73
III. VISCOMETRIC MEASUREMENTS 74
A. Viscometers 74
B. Measurements on Fluid Foods 78
IV. RHEOLOGICAL DATA OF FLUID FOODS 79
A. Edible Oils 79
B. Aqueous Newtonian Foods 80
C. Plant Biopolymer Solutions and Suspensions 85
D. Cloudy Juices and Pulps 89
E. Emulsions and Complex Suspensions 90
V. REGRESSION OF RHEOLOGICAL DATA OF FOODS 92
A. Edible Oils 92
B. Fruit and Vegetable Products 94
C. Chocolate 100
x Contents
III. MOISTURE DIFFUSIVITY OF FOODS AS A FUNCTION OF

MOISTURE CONTENT AND TEMPERATURE 197
7. Diffusivity and Permeability of Small Solutes

in Food Systems 237
I. INTRODUCTION 237
A. Diffusivity of Small Solutes 237
B. Measurement of Diffusivity 239
II. DIFFUSIVITY IN FLUID FOODS 241
A. Dilute Solutions 241
B. Concentrated Solutions 242
III. DIFFUSION IN POLYMERS 243
A. Diffusivity of Small Solutes in Polymers 244
B. Glass Transition 246
C. Clustering of Solutes in Polymers 247
D. Prediction of Diffusivity 248
IV. DIFFUSION OF SOLUTES IN FOODS 251
A. Diffusivity of Salts 251
B. Diffusivity of Organic Components 252
C. Volatile Flavor Retention 254
D. Flavor Encapsulation 258
V. PERMEABILITY IN FOOD SYSTEMS 259
A. Permeability 259
B. Food Packaging Films 261
C. Food Coatings 262
D. Permeability/Diffusivity Relation 263
8. Thermal Conductivity and Diffusivity of Foods 269

I. INTRODUCTION 269
II. MEASUREMENT OF THERMAL CONDUCTIVITY
AND DIFFUSIVITY 270
A. Thermal Conductivity 270
B. Thermal Diffusivity 273
III. THERMAL CONDUCTIVITY AND DIFFUSIVITY
DATA OF FOODS 275
Contents xi
A. Unfrozen Foods 275

B. Frozen Foods 276
C. Analogy of Heat and Mass Diffusivity 276
D. Empirical Rules 279
IV. MODELING OF THERMAL TRANSPORT PROPERTIES 280
A. Composition Models 280
B. Structural Models 283
V. COMPILATION OF THERMAL CONDUCTIVITY DATA OF FOODS 289
VI. THERMAL CONDUCTIVITY OF FOODS AS A FUNCTION OF
MOISTURE CONTENT AND TEMPERATURE 326
9. Heat and Mass Transfer Coefficients

in Food Systems 359
I. INTRODUCTION 359
II. HEAT TRANSFER COEFFICIENTS 360
A. Definitions 360
B. Determination of Heat Transfer Coefficients 361
C. General Correlations of the Heat Transfer Coefficient 362
D. Simplified Equations for Air and Water 364
III. MASS TRANSFER COEFFICIENTS 364
A. Definitions 364
B. Determination of Mass Transfer Coefficients 365
C. Empirical Correlations 366
D. Theories of Mass Transfer 367
IV. HEAT TRANSFER COEFFICIENTS IN FOOD SYSTEMS 369
A. Heat Transfer in Fluid Foods 369
B. Heat Transfer in Canned Foods 371
C. Evaporation of Fluid Foods 372
D. Improvement of Heat/Mass Transfer 373
V. HEAT TRANSFER COEFFICIENTS IN FOOD PROCESSING:
COMPILATION OF LITERATURE DATA 374
VI. MASS TRANSFER COEFFICIENTS IN FOOD PROCESSING:
COMPILATION OF LITERATURE DATA 391
Appendix: Notation 403
Index 407
1
Introduction
The transport properties of momentum (flow), heat and mass of unit opera-
tions are an important part of the physical and engineering properties of foods,
which are necessary for the quantitative analysis, design, and control of food proc-
esses and food quality.
The transport of momentum (rheological properties) and heat (thermal con-
ductivity) have received more attention in the past (Rao, 1999; Rahman, 1995).
However, mass transport is getting more attention recently, due to its importance
to several traditional and new food processing operations (Saravacos, 1995).
The transport properties of gases and liquids have been studied extensively
and they are a basic element in the design of chemical processes and processing
equipment (Reid et al., 1987). The theoretical analysis and applications of trans-
port phenomena have been advanced by a unified treatment of the three basic
transport processes (Brodkey and Hershey, 1988). The adoption of transport phe-
nomena in food systems is expected to advance the emerging field of food engi-
neering (Gekas, 1992). However, foods are complex heterogeneous and sensitive
materials, mostly solids or semisolids, and application of the principles of trans-
port phenomena requires sustained experimental and theoretical efforts.
Application of modern computer aided design (CAD) to food processing has
been limited by the lack of reliable transport data for the various food processes
and food materials. Mathematical modeling and simulations have made consider-
able progress, but the accuracy of the available scattered data is not adequate for
quantitative applications. Of particular importance is the need for mass transport
properties (Saravacos and Kostaropoulos, 1995; 1996).
While analysis and computation of the transport properties of gases and liq-
uids is based on molecular dynamics, experimental measurements are necessary
for the food materials and food processing systems.
2 Chapter 1
Theoretical analysis and experimental techniques of mass diffusion in poly-

meric materials, developed in polymer science (Vieth, 1991) are finding important
applications in food materials science and in food process engineering. Molecular
dynamics and molecular simulation techniques, developed for the prediction of
mass diffusion in polymer science (Theodorou, 1996), could conceivably be util-
ized in food systems, although the complexity of foods would make such an effort
very difficult.
The transport properties are directly related to the microstructure of food
materials, but limited studies and applications have been reported in the literature
(Aguilera and Stanley, 1999; Aguilera, 2000). Food microstructure plays a particu-
larly important role in mass transfer at the cellular level, for example in fruits and
vegetables during osmotic dehydration.
Food macrostructure has been used widely to analyze and model transport
mechanisms, particularly mass diffusivity and thermal conductivity. Simple meas-
urements of density, porosity and shrinkage can provide quantitative information
on the heat and mass transport properties in important food processing operations,
such as dehydration and frying. A thorough analysis of the transport properties
should involve the momentum, heat and mass transport mechanisms at the mo-
lecular, microstructural, and macrostructural levels. Such a unified analysis might
reveal any analogies among the three transport processes, which would be very
helpful in prediction and empirical correlations of the properties, like the analogies
for gases and liquids.
Reliable data on transport properties of foods are essential because of the
various non-standardized methods used, and the variability of composition and
structure of food materials. An international effort to obtain standardized data of
rheological properties (viscosity), heat conductivity, and mass diffusivity was
made in the European collaborative research projects COST 90 and COST 90bis
(Jowitt et al., 1983; 1987). The viscosity and thermal conductivity of foods were
investigated in a U.S. Department of Agriculture (USDA) cooperative research
project (Okos, 1987). Accurate and useful data were obtained for viscosity and
thermal conductivity, but only limited mass diffusivity data were obtained, dem-
onstrating that mass transport is a much more complicated process. An important
conclusion of these projects is relevancy, i.e. each property refers to a given set of
experimental conditions and sample material.
A comprehensive treatment of the transport properties of foods should be
based on the transport at the molecular, microstructural and macrostructural levels,
and should consider the available literature data in a generalized form of statistical
analysis.
Introduction 3
I. RHEOLOGICAL PROPERTIES
Food rheology has been primarily concerned with food texture and food
quality. However, rheological data of fluid foods are essential in the analysis and
design of important food processing operations, like pumping, heating and cool-
ing, evaporation, and thermal processing (both in cans and aseptic processing).
Most fluid foods are non-Newtonian fluids, and empirical Theological data
are necessary (Rao, 1999). Statistical (regression) analysis of published rheologi-
cal data can provide useful correlations for groups and typical fluid foods (see
Chapter 4).
The effect of temperature on the viscosity of fluid foods appears to be re-
lated to the molecular and microstrure of the material: High energies of activation
for flow (about 50 kJ/mol) are observed in concentrated aqueous sugar solutions
and fruit juices, while very low values (near 10 kJ/mol) characterize the highly
non-Newtonian (and viscous) fruit purees and pulps (Saravacos, 1970).
II. THERMAL TRANSPORT PROPERTIES
Thermal conductivity represents the basic thermal transport property, and it

shows a wider variation than thermal diffusivity, which can be estimated accu-
rately from the thermal conductivity. The thermal conductivity of fluid foods is a
weak function of their composition, and simple empirical models can be used for
its estimation. Structural models are needed to model the thermal conductivity of
solid foods, which varies widely, due to differences in micro- and macrostructure
of the heterogeneous materials. Heat and mass transfer analogies in porous foods
may be related to the known analogies of gas systems.
Application of structural models of thermal conductivity to model foods has
demonstrated the importance of porosity of granular or porous materials (Maroulis
et al., 1990). Regression analysis of published data of thermal conductivity of
various foods, as a function of moisture and temperature, can provide useful em-
pirical parameters characteristic of each material. Such parameters are the thermal
conductivity and the energy of activation of dry and infinitely wet materials (see
Chapter 8).
Chapter 1
III. MASS TRANSPORT PROPERTIES
The diffusion model, developed for mass transport in fluid systems (Cussler,
1997), has been applied widely to mass transfer in food materials, assuming that
the driving force is a concentration gradient. Since mass transfer in heterogeneous
systems may involve other mechanisms than molecular diffusion, the estimated
mass transport property is an effective (or apparent) diffusivity. Most of the pub-
lished data on mass transport in food systems refer to moisture (water) diffusivity
(Marinos-Kouris and Maroulis, 1995), since the transport of water is of fundamen-
tal importance to many food processes, like dehydration, and to food quality
changes during storage.
Mass transport in foods is strongly affected by the molecular, micro- and
macrostructure of food materials. The crucial role of porosity in moisture transfer
has been demonstrated by measurements on model foods of various structures, and
on typical food materials (Marousis et al., 1991; Saravacos, 1995). The effect of
temperature on moisture diffusivity may provide an indication whether mass trans-
fer is controlled by air or liquid/solid phase of the food material. Low energies of
activation for diffusion (about 10 kJ/mol) are obtained in porous materials, while
high values (near 50 kJ/mol) are observed in nonporous products.
The wide range of moisture diffusivities reported in the literature is caused
primarily by the large differences in mass diffusivity among the vapor, liquid, and
solid phases present in heterogeneous food materials. The diffusivity in the solid
phase is also affected strongly by the physical state, i.e. glassy, rubbery or crystal-
line. Application of polymer science to food systems containing biopolymers can
improve the understanding of the underlying transport mechanisms (see Chapters
5 and 7).
Statistical (regression) analysis of published literature data on moisture dif-
fusivity, using an empirical model as a function of moisture content and tempera-
ture, can provide useful parameters, such as diffusivity and activation energy in
the dry and infinitely wet phases (see Chapter 6).
Cellular models for mass transfer can provide an insight into the process of
osmotic dehydration, where water and solutes are transported simultaneously.
However, the diffusion model is often used, because of its simplicity, for the esti-
mation of mass diffusivity of water and solutes during the osmotic process.
Mass transport of important food solutes, such as nutrients and flavor/aroma
components, is usually treated as a diffusion process, and effective mass diffusivi-
ties are used in various food processes and food quality changes, like aroma reten-
tion (see Chapter 7).
Introduction
REFERENCES
Aguilera, J.M. 2000. Microstructure and Food Product Engineering. Food Technol
54(ll):56-65.
Aguilera, J.M., Stanley, D.W. 1999. Microstructural Principles of Food
Processing, Engineering. 2nd ed. Gaithersburg, MD: Aspen Publ.
Brodkey, R.S., Hershey, H.C. 1988. Transport Phenomena. A Unified Approach.
New York: McGraw-Hill.
Cussler, E.L. 1997. Diffusion Mass Transfer in Fluid Systems. Cambridge, UK:
Cambridge University Press.
Gekas, V. 1992. Transport Phenomena of Foods and Biological Materials. New
York: CRC Press.
Jowitt, R., Escher, F., Hallstrom, H., Meffert, H.F.Th., Spiess, W.E.L., Vos, G.,
eds. 1983. Physical Properties of Foods. London: Applied Science Publ.
Jowitt, R., Escher, F., Kent, M., McKenna, B., Roques, M., eds. 1987. Physical
Properties of Foods 2. London: Elsevier Applied Science.
Marinos-Kouris, D., Maroulis, Z.B. 1995. Transport Properties in the Air-Drying
of Solids. In: Handbook of Industrial Drying, 2nd ed. Vol.1, Mujumdar, A.S.
ed. New York: Marcel Dekker.
Maroulis, Z.B., Drouzas, A.E., Saravacos, G.S. 1990. Modeling of Thermal
Conductivity of Granular Starches. J Food Eng 11:255-271.
Marousis, S.N., Karathanos, V.T., Saravacos, G.S. 1991. Effect of Physical Struc-
ture of Starch Materials on Water Diffusivity. J Food Proc Preserv 15:183-
195.
Okos, M.R., ed. 1987. Physical and Chemical Properties of Foods. ASAE Publica-
tion No. Q0986, St. Joseph, MI.
Rahman, S. 1995. Food Properties Handbook. Boca Raton, FL: CRC Press.
Rao, M.A. 1999. Rheology of Fluid and Semisolid Foods. Gaithersburg, MD: As-
pen Publ.
Reid, R.C., Prausnitz, J.M., Poling, B.E. 1987. The Properties of Gases and Liq-
uids. 4th ed. New York: McGraw- Hill.
Saravacos, G.D. 1970. Effect of Temperature on the Viscosity of Fruit Juices and
Purees. J Food Sci 35:122-125.
Saravacos, G.D. 1995. Mass Transfer Properties of Foods. In: Engineering Proper-
ties of Foods. 2nd ed. Rao, M.A., Rizvi, S.S.H. eds. New York: Marcel Dek-
ker, pp. 169-221.
Saravacos, G.D., Kostaropoulos, A.E. 1995. Transport Properties in Processing of
Fruits and Vegetables. Food Technol 49(9):99-105.
Saravacos, G.D., Kostaropoulos, A.E. 1996. Engineering Properties in Food
Processing Simulation. Computers Chem Engng 20:S461-S466.
Theodorou, D.N. 1996. Molecular Simulations of Sorption and Diffusion in
Amorphous Polymers. In: Diffusion in Polymers. Neogi, P. ed. New York:
Marcel Dekker, pp. 67-142.
Chapter 1
Vieth, W.R. 1991. Diffusion In and Through Polymers. Munich, Germany: Hanser
Publ.
Transport Properties of Gases and
Liquids
I. INTRODUCTION
The physical processes and unit operations of process engineering are based
on the transport phenomena of momentum, heat, and mass (Bird et al., 1960;
Geankoplis, 1993). The transport phenomena, originally developed in chemical
engineering, can be applied to the processes and unit operations of food engineer-
ing (Gekas, 1992). The analogy of momentum, heat and mass transport facilitates
a unified mathematical treatment of the three fundamental transport processes
(Brodkey and Hershey, 1988).
The transport properties of simple gases and liquids have been investigated
more extensively than the corresponding properties of solids and semisolids. Mo-
lecular dynamics and thermodynamics have been used to predict, correlate and
evaluate the transport properties of simple gases and liquids (Reid et al., 1987).
Empirical prediction methods, based on theoretical principles, have been used to
predict the transport properties of dense gases and liquids, compiling tables and
data banks, which are utilized in process design and processing operations.
This chapter presents a review of the molecular and empirical prediction of
transport properties of gases and liquids, with examples of simple fluids of impor-
tance to food systems, like air and water. The theoretical treatment of simple fluids
is useful in analyzing and evaluating the transport properties of complex food ma-
terials.
Chapter 2
II. ANALOGIES OF TRANSPORT PROCESSES
The transport processes of momentum (fluid flow), heat and mass can be
expressed mathematically by analogous constitutive equations of the general form
(one-dimensional transport):
<p = -S(dy/8x) (2-1)
where fx is the transport rate, 8 is the transport coefficient or property, and

dy/dx is the transport gradient.
The negative sign of Eq. (2-1) denotes that the transport is in the ^-direction,
i.e. the transport gradient (dy/dx) is negative (Brodkey and Hershey, 1988).
Equation (2-1) is a generalized expression of the empirical laws of Newton,
Fourier and Pick for the transport of momentum, heat and mass, respectively:
r» = -T] (du/dx) (2-2)
(q/A\ = -A (dT/dx) (2-3)
(j/A)x = -D (dC/dx) (2-4)
The basic transport properties, defined by the last equations, are:

77: viscosity, Pa s or kg/m s
X: thermal conductivity, W/m K
D: mass diffusivity, m2/s
In the transport equations, T = F/A is the shear stress in the y-direction for flow
in the ^-direction (Pa), u is the velocity in the ^-direction (m/s), T is the tempera-
ture (K), and C is the concentration (kg/m3). The following transport properties are
also used:
v = Tj/p: momentum diffusivity or kinematic viscosity (m2/s)
a = ^1 p cp : thermal diffusivity (m2/s)
where p (kg/m3) is the density and cp (J/kg K) is the heat capacity at constant pres-
sure of the fluid.
Thus, all three transport properties, v, a, D are expressed in the same units,
m2/s.
Transport Properties of Gases and Liquids 9
It should be noted that, although the three transport processes are expressed
mathematically by the same generalized transport equation (2-1), the mechanisms
of transport of momentum, heat and mass may be quite different.
III. MOLECULAR BASIS OF TRANSPORT PROCESSES
Molecular dynamics, which is concerned with intermolecular forces and

molecular movement, can be utilized in the prediction of transport properties of
simple fluids. The mechanism of the three transport processes are different (Brod-
key and Hershey, 1988). Thus, momentum transport is caused by the relative mo-
tion of fluid layers parallel to the direction of flow; heat conduction is caused by
collision of the molecules, without substantial movement of the species; and mass
diffusion is caused by movement of molecules in mixtures.
A. Ideal Gases
The ideal gases are considered to consist of rigid spherical molecules obey-
ing the laws of mechanics, and their transport properties can be predicted by the
kinetic theory of gases. Although very few gases approach ideality (Ar, Xe, Kr),
the concept of ideal gas is useful in understanding the transport properties.
The mean free path /lm of a gas, defined as the average distance of molecular
movement before collision with another molecule or surface, is given by the equa-
tion (Brodkey and Hershey, 1988):
T
X =5/0= n*> 'l (2-5)
"' '
where u is the mean velocity (m/s), 9 is the collision frequency (1/s), d is the mo-
lecular diameter (m), P is the pressure (Pa), and kB is the Boltzmann constant kB =
1.38xlO' 23 J/moleculeK.
From Eq. (2-5) it follows that,
^mP = constant (2-6)
This means that the mean free path of the molecular motion is inversely propor-
tional to the pressure.
10 Chapter 2
The transport properties of ideal gases, viscosity 77, thermal conductivity /I,
and mass diffusivity D are given by the following equations:
(2-7)
(2-8)
D = - u Am (2-9)
Since v = r/jp and a = A//? cp , Eqs. (2-7) to (2-9) yield the following analogies:
), = cvi] = pcvD (2-10)
v = ay = D (2-11)
where y = cp /cy , and cp, cv are the heat capacities at constant pressure and con-
stant volume, respectively.
B. Thermodynamic Quantities
The transport processes of momentum, heat, and mass take place in systems
that are removed from thermodynamic equilibrium. Thermodynamics cannot pre-
dict transport properties, but some thermodynamic quantities are used in molecular
and empirical predictions (Prausnitz et al., 1999).
Pressure-volume-temperature (PVT) data are needed in calculations and cor-
relations of transport properties of fluids. PVT data are usually obtained from the
cubic equations of state, such as the Redlich-Kwong equation of state (Smith and
van Ness, 1987):
V-b
Equation (2-12) yields the known cubic equation of van der Waals and it reduces
to the ideal gas law (PV=RT), if the empirical constants a and b are taken equal to
zero. The cubic equations of state can be transformed to polynomials of third de-
gree in respect to volume V.
The empirical constants of the Redlich-Kwong equation are related to the
critical properties P0 Tc of the fluid:
(2-13)
^008664^ (2 _ M)
The critical properties of a fluid, Pc, Vc, and Tc, are characteristic for each fluid,
and they are used to calculate the reduced properties:
pr = p/pc, v, = V/Vc, Tr = T/Tc (2-15)
The residual or excess properties of a fluid are the differences between the real and
the ideal properties. Thus, the residual volume VKS is defined as:
(2-16)
RT
therefore V = z—— (2-17)
where z = PV/RTis the compressibility factor, which expresses the non-ideality

of the fluid.
The theorem of corresponding states indicates that all real gases, when com-
pared at some reduced pressure and temperature, have the same compressibility
factor z and all deviate from the ideal gas behavior to almost the same degree.
The molecular structure of real nonspherical gases is characterized by the
acentric factor co, which is related to the molecular shape. For ideal gases ca = 0,
and for real gases, the acentric factor is related to the reduced pressure Pr by the
equation:
a> = 1.0-log(P,)rr.,7 (2-18)
For many fluids the normal boiling point is approximately equal to 0.7TC.
12 Chapter 2
Table 2.1 Critical Constants and Acentric Factors of Selected Fluids

Fluid Vc , crrrVmol r c ,K P c ,bar zc CO
Oxygen 73.4 154.6 50.4 0.288 0.025

Nitrogen 89.8 126.2 33.9 0.290 0.039
Carbon Dioxide 93.9 304.1 73.8 0.274 0.239
Ethylene 130.4 282.4 50.4 0.280 0.089
Ethanol 167.1 531.9 61.4 0.240 0.644
Water 55.1 647.3 221.2 0.235 0.344
ource: Data from Reid et al., 1987.
Table 2.1 shows the critical constants V0 Tc, P0 zc and the acentric factor a>
for selected fluids of interest to food systems.
C. Real Gases
The intermolecular forces of fluids constitute the basis of all transport proc-
esses at the molecular level. Their origin and determination is treated in the spe-
cialized literature (Maitland et al., 1981). In real gases (monoatomic, polyatomic,
nonpolar, and polar) the Chapman-Enskog theory of nonuniform gases is usually
applied. In the prediction of the transport properties, the following empirical pa-
rameters are usually employed (Reid et al., 1987): collision diameter a, potential
energy s, and collision integral Q.
The potential energy u(r) or the Lennard-Jones 12-6 potential of two spheri-
cal nonpolar molecules is given by the equation:
u(r)=4s (2-19)
where cr is the characteristic collision diameter, similar to molecular diameter d of

the kinetic theory, £ is the minimum value of u(r), and r is the intermolecular dis-
tance.
The parameters cr and s are determined from empirical thermodynamic
equations as functions of the critical pressure Pc, the critical temperature Tc and the
acentric factor co of the fluid:
=1CT10(2.3551-0.00876;) (2-20)
Table 2.2 Intermolecular Constants of Selected Components

Gas a, nm £/kB,K
Oxygen 0.35 106.7
Nitrogen 0.38 71.4
Air 0.37 78.6
Carbon Dioxide 0.39 195.2
Ethylene 0.42 224.7
Ethanol 0.45 362.6
Water 0.26 809.1
Source: Data from Reid et al., 1987. Inm = 10A = 1 0 m
s/kBTc =0.17915 + 0.169o> (2-21)
Table 2.2 shows the empirical constants crand e of gases important to food
systems.
The collision integral Q of real fluids is a measure of the active cross section
of collision, depending on temperature, which is related to the intermolecular po-
tential by a complex integral (Assael et al., 1996). The collision cross section for a
molecule is the area, perpendicular to the direction of movement, within which the
center of a second molecule should be located in order to collide.
The collision integral is related to the transport properties of viscosity Qn
and mass diffusivity £2D. The two integrals are different, and the collision integral
for viscosity Qn is usually estimated more accurately than QQ, since viscosity 77 is
determined more accurately than mass diffusivity D. The following empirical
equation is used for estimation of fin (Brodkey and Hershey, 1988):
where T" = TkB/ sis the reduced temperature.

The collision integral for diffusion f2D of nonpolar fluids is estimated as a
complex function of the reduced temperature T*.
For polar fluids, the collision integral for diffusion is estimated from the
equation:
. /r (2-23)
where 5* is the dipole dimensionless number, defined by the equation:
14 Chapter 2
where (DPM) is the dipole moment (given in thermodynamic tables) and V0, Tb
are the molar volume (m3/mol) at the normal boiling point (K). Water, a typical
polar molecule, has a value DPM= 1.8 debye.
IV. PREDICTION OF TRANSPORT PROPERTIES OF FLUIDS
The transport properties of fluids can be considered that they consist of three
contributions, as shown in the following equation (Assael et al., 1996; Millet et al.,
1996):
X(p,T)=X.(T) + AX(p,T) + A* (p,T) (2-25)
where X(p, T) is the transport property (TJ, /I, D), X0(T) is the transport property of
the dilute fluid (gas), AX(p, T) is the excess contribution of the real fluid, and
AXc(p,T) is the critical contribution. The terms X0(T)+ AX(p,T) represent the basic
part of the transport property, while the critical contribution AXc(p, T) becomes of
importance near the critical temperature. The transport properties are affected
mainly by the temperature T and the density or concentration p, while pressure
may have an effect in some special (e.g. critical) conditions.
The excess contributions are important in predictions of viscosity (At] = 77-
rjq) and thermal conductivity (AA = /L-Ag), and they can be estimated when some
data are available in the literature. The critical contribution is more important for A
than for 77.
The accuracy of prediction is higher for viscosity (1-3%) than for thermal
conductivity (about 10%). The mass diffusivity is predicted with lower accuracy
(10-50%), especially at high concentrations of the diffusant (Brodkey and Her-
shey, 1988).
A. Real Gases
The transport properties of real gases, viscosity 77 (Pa s), thermal conductiv-
ity /I (W/m K), and mass diffusivity D (m2/s) can be predicted by the Chapman-
Enskog equations, based on the intermolecular parameters (Brodkey and Hershey,
1988):
(Mr)"
= 2.669x10" (2-26)
= 8.3224x10' (2-27)
D = 1.883x10- (2-28)
where M is the molecular weight, T is the temperature (K), P is the pressure (Pa),
a is the collision diameter (m) and /?7i QD are the collision integrals.
Equations (2-26) to (2-28) show that 77 and /I increase with the square root
of temperature, while D is a function of the cubic power of temperature. Equation
(2-28) indicates that, at constant temperature, PD=constant, i.e. the mass diffusiv-
ity is inversely proportional to the pressure.
Pressure has a negligible effect on /I of gases up to 10 bar, but it is important
at higher pressures, especially near the critical condition.
The viscosity 77 and the thermal conductivity /I of real gases are correlated
by empirical equations, which facilitate the interconversion of the two transport
properties. For monoatomic gases the Eucken factor is used:
AM
= 2.5 (2-29)
where M is the molecular weight (kg/kmol) and cv is the heat capacity at constant
volume (kJ/kmol K).
For polyatomic gases, the Eucken factor is given by the equation:
AM , 2.25 , 2.25
—— = 1 + ——— = 1 + (2-30)
cvIR c IR-\
16 Chapter 2
The heat capacities cv and cp are related by the equation:
cp=cy+R (2-31)
where R = 8.314 kJ/kmol K is the gas constant.
B. Liquids
In liquids, the intermolecular forces are stronger than in gases, due to the
close proximity of the molecules. Prediction of the transport properties by molecu-
lar parameters is difficult, and empirical relationships are normally used. Experi-
mental measurements of the transport properties of liquids are necessary to vali-
date the empirical prediction equations. Measurement techniques are discussed in
the treatment of transport properties of food materials (see Chapters 5 and 7).
/. Viscosity
The Eyring theory of rate processes yields an empirical expression for vis-
cosity, which is similar to the Arrhenius equation:
(2-32)
where A and B are empirical constants for the particular liquid.

The effect of temperature is sharper at higher viscosities, i.e. the sensitivity
of viscosity to temperature variations depends primarily on the value of viscosity.
The viscosity-temperature relationship for liquids is expressed by the empirical
Lewis-Squires equation and diagram (Reid et al, 1987; Syncott, 1996):
-0,66, -0,66,
233
when 77, r/0 are the viscosities (Pa s) at temperatures T, T0, respectively.
2. Thermal Conductivity
The thermal conductivity of liquids can be estimated from empirical equa-
tions as a function of the temperature T, like the following expression:
/i = A + BT + CT2+DT3 (2-34)
where the constants A, B, C, D are given in tables (Reid et al., 1987).

In most liquids, except water and some alcohols, /I is a negative function of
temperature. Pressure has a negligible effect on A up to 50-80 bar, but it becomes
important near the critical point, where the gas behaves like a liquid.
3. Mass Diffusivity
The diffusivity of a species A in a liquid medium B can be estimated from
the Wilke-Chang equation (Brodkey and Hershey, 1988):
(2-35)
where rj is the viscosity of the liquid (Pa s), T is the temperature (K), MB is the
molecular weight of B, VA is the molar volume of A at the boiling point (m3/kmol),
and <f> is an interaction parameter, e.g. 2.26 for water and 1.5 for ethanol.
In general, the mass diffusivity of a particle in a liquid medium is given by
the Stokes - Einstein equation:
If B T
D= (2-36)
where rp is the particle radius (m), TJB is the viscosity of the liquid medium (Pa s),
T is the temperature (K), and &s=1.38xlO"23 J/molecule K is the Boltzmann con-
stant.
From both Eqs. (2-35) and (2-36) it follows that
= constant (2-37)
i.e. the mass diffusivity is inversely proportional to the viscosity of the solution.
18 Chapter 2
The Eyring theory of rate processes predicts for mass diffusivity an Ar-
rhenius-type relationship, analogous to viscosity:
D = Ae\p(-ED/RT) (2-38)
where A is a constant and ED is the energy of activation for diffusion (kJ/kmol).

Experimental measurements of mass diffusivity in liquids are less accurate
than for viscosity, especially at high concentrations of the diffusant. Mass diffusiv-
ity in aqueous systems is important in food and biological materials (Cussler,
1997) and is treated in Chapter 7 of this book.
The mass diffusivity in electrolytes is affected strongly by the ionic species
of the solution. In dilute solutions of a single salt the Nernst-Haskel equation is
used to estimate the diffusivity D°B as a function of the temperature, the valences
of anions and cations, the ionic conductances, and the Faraday constant (Reid et
al., 1987). For concentrated solutions, the empirical Gordon equation is used,
which corrects the D°AB for viscosity, molality and ionic activity of the solute.
The mass diffusivity of a typical electrolyte, sodium chloride, goes through
a minimum at normality 0.2 N (DAB=l .2\\0'9 m2/s at 18.5 °C), and it increases at
lower and higher concentrations.
C. Comparison of Liquid/Gas Transport Properties

Both viscosity 77 and thermal conductivity /I of liquids are much higher than
the corresponding properties of gases. These differences reflect the stronger inter-
molecular forces of the dense liquid state. However, the mass diffusivity in the
liquid state is much lower than in dilute gases, due to the difficulty of mass trans-
port in dense molecular systems. Selected values of transport properties of fluids
of importance to food systems are given in Tables 2.3-2.5. Typical values for air
and water at 25 °C are the following:
• air: 77 = 0.017 mPas, A = 0.025 W/m K

• water: r;=0.90mPas, A = 0.62W/mK
• oxygen/air: DAB= 1.7x1 0"5m2/s
• oxygen/water: DAB- 1.7x1 0"9m2/s
For comparison of transport properties in the liquid (L), and gas (G) state,
the following approximate ratios are useful:
tljjj0 = A t / A G = 10 to 1000, DJDG si/10000 (2-39)

D. Gas Mixtures
The viscosity of steam/air mixtures, which is important in retort processing
of packaged foods, is given by the empirical equation (Kisaalita et al., 1986):
^=vayJ°y*+t?,y,Tby' (2-40)
where rja, rjs are the air and steam viscosities respectively, o=0.039, 6=0.0163,
ya, ys are the mass fractions of air and steam, respectively, and Tis the tempera-
ture in °C.
The calculated values of varied from 0.0144 Pa s (100 °C, yg= 0.1) to
0.0204 (140 °C, y, = 0.5).
V. TABLES AND DATA BANKS OF TRANSPORT PROPERTIES
The transport properties are usually included in tables and data banks of
physical properties of materials. Data on transport properties of common fluids are
found in the well-known Perry's Chemical Engineers' Handbook (1984), in Reid
et al. (1987) and in Cussler (1997). The extensive compilation of thermophysical
properties of matter by Touloukian (1971) includes transport property data. Exten-
sive compilation of physical properties, including transport properties of fluids, are
available in computer databases and data banks, such as the Dechema databank of
the German Chemical Society (Eckermann, 1983), and the PPDS data bank of the
National Engineering Laboratory, U.K. (PPDS, 1996).
The Design Institute for Physical Property Data (DIPPR) of the American
Institute of Chemical Engineers (AIChE) recently published tables of transport
properties for binary mixtures (DIPPR, 1997) and a data bank of the same proper-
ties (DIPMIX, 1997). Compilations of data and plots of physical properties of pure
compounds are available for Windows (DIPPR, 1998).
Packages of extensive data banks of physical properties, requiring main-
frame computers, are used in process equipment design and in processing opera-
tions. Software of selected physical properties for desktop computers and Win-
dows is available (CEP, 1999). Most of the data on transport properties of fluids
published in tables and data banks are related to the chemical, petroleum, and pet-
rochemical industries. Limited information is available on food and biological
products, which are, for the most part, solid or semisolid materials.
20 Chapter 2
Tables 2.3 and 2.4 give some selected values of transport properties of sim-
ple fluids of importance to food processing and food engineering. They are useful
in determining and evaluating the transport properties of food materials, which are
treated in subsequent chapters of this book.
More data for viscosity and thermal conductivity of air and water (liquid and
vapor) as a function of temperature are presented in Figures 2.1 and 2.2.
Table 2.3 Viscosity 77 and Thermal Conductivity A of

Selected Gases and Liquids (25°C)
Material r|, mPa s A., W/m K
Gases
Air 0.017 0.025
Oxygen 0.018 0.020
Nitrogen 0.018 0.026
Carbon dioxide 0.015 0.016
Ethylene 0.012 0.020
Ethanol 0.025 0.015
Water vapor 0.010 0.020
Liquids
Water 0.90 0.62
Ethanol 1.04 0.15
Source: Data from Perry, 1984 and Reid et al., 1987.
Table 2.4 Mass Diffusivity (DAB)

Diffusant (A) in Air (B) in Water (B)
(atm pressure, 25°C) (dilute solutions, 25°C)
DAB, xlO' 5 m 2 /s DAB, xlO' 9 m 2 /s
Oxygen 1.7 1.7
Nitrogen 1.8 1.9
Carbon dioxide 1.9 2.0
Ethanol 1.3 1.3
Ethylene 2.1 1.9
Water 2.0 1.1
Salt (NaCl) - 1.2
Source: Data from Perry, 1984 and Reid et al., 1987.
B
B.
E
0.01
0.001
200 300 400
Temperature (°C)
Figure 2.1 Viscosity of air and water versus temperature. (Adapted from Pa-
kowskietal., 1991.)
22 Chapter 2
•o
e
o
0.01
200 300 400
Temperature (°C)
Figure 2.2 Thermal conductivity of air and water versus temperature. (Adapted from
Pakowski et al., 1991.)
A third degree polynomial was fitted to these data and the results are sum-
marized in Table 2.5. A different equation was used for viscosity data of water,
since the results of the third degree polynomial are not adequate.
In the same table an empirical equation from Pakowski et al. (1991) is pre-
sented for predicting the water vapor diffusivity in air versus temperature and
pressure (see also Figure 2.3).
Table 2.5 Empirical Equations for Calculating the Transport Properties of Water,
Water Vapor and Air
a2 a3 Temperature (°C)
Saturated Vapor 7.95E-03 4.49E-05 -6.13E-08 1.44E-10 0-300
Superheated Vapor 8.07E-03 4.04E-05 1.24E-09 -1.21E-12 100-700
Air 1.69E-02 4.98E-05 -3.19E-08 1.32E-11 0-1000
ao ai a2 a3 Temperature (°C)
Saturated Water -1.07E+01 1.97E-02 -1.47E-05 1.82E+03 0-350
Thermal Conductivity
(W/m K)
Temperature (°C)
Saturated Water 5.70E-01 1.78E-03 -6.94E-06 2.20E-09 0-350
Saturated Vapor 1.76E-02 1.05E-04 -6.7 IE-07 3.07E-09 0-300
Superheated Vapor 1.77E-02 6.01E-05 9.5 IE-08 -3.99E-11 100-700
Air 2.43E-02 7.89E-05 -1.79E-08 -8.57E-12 0-1000
Mass Diffusivitv
(m2/s)
D=ao(T+273)/273)ai P"2
Temperature (°C)
Water Vapor in Air 2.16E-05 1.80E+00 -l.OOEOO 0-1200
Source: Data from Pakowski et al. (1991)

24 Chapter 2
l.E-02
l.E-06
10 100 1000
Temperature (°C)
Figure 2.3 Diffusivity of water vapor in air. (Data from Pakowski et al., 1991.)
Figure 2.4 shows the viscosity of aqueous sucrose solutions as a function of

concentration and temperature. Figure 2.5 shows the thermal conductivity of com-
mon gases of importance to food processes as a function of temperature.
percentage sucrose by weight = 60
50 100
Temperature (°C)
Figure 2.4 Viscosity of aqueous sucrose solutions. (Adapted from Perry et al.,
1984.)
26 Chapter 2
0.070
0.060
0.050
0.040
•a
a
e
(J
0.030
0.020
0.010
-200 200 600
Temperature (°C)
Figure 2.5 Thermal conductivity of gases. (Adapted from Perry et al., 1984.)
REFERENCES
Assael, M.I., Trusler, M.J.P., Tsolakis, T.F. 1996. Thermophysical Properties of

Fluids. An Introduction to Their Prediction. London: Imperial College Press.
Bird, R.B., Stewart, W.E., Lightfoot, E.N. 1960. Transport Phenomena. New
York: John Wiley & Sons.
Brodkey, R.S., Hershey, H.C. 1988. Transport Phenomena. A Unified Approach.
CEP - Chemical Engineering Progress. 1999. Software Directory. New York:
AIChE.
Cussler, E.L. 1997. Diffusion Mass Transfer in Fluid Systems. 2nd ed. Cambridge:
Cambridge University Press.
DIPMIX. 1997. Database of Transport Properties and Related Thermodynamic
Data of Binary Mixtures. College Station, TX: Engineering Research Station,
Texas A&M University.
DIPPR. 1997. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Volumes 1-5. New York: AIChE.
DIPPR. 1998. Data Compilation of Pure Compound Properties. New York: Tech-
nical Data Services Inc.
Eckermann, R. 1983. Information systems for, and prediction of, physical proper-
ties of non-food materials. In: Physical Properties of Foods. Jowitt, R.,
Escher, F., Hallstrom, B., Meffert, H.F. Th., Spiess, W.E.L., Vos, G. eds.
London: Applied Science Publ.
Geankoplis C.J. 1993. Transport Processes and Unit Operations. 3rd ed. New
York: Prentice Hall.
York: CRC Press.
Kisaalita, W.S., Lo, K.V., Staley, L.M. 1986. A Simplified Empirical Expression
for Estimating the Viscosity of Steam/Air Mixtures. JFoodEng 5:123-133.
Maitland, G.C., Rigby, M., Smith, E.B., and Wakeman, W.A. 1981. Intermolecu-
lar Forces. Their Origin and Determination. Oxford: Clarendon Press.
Millet, J., Dymond, J.H., Nieto de Castro, C.A. 1996. Transport Properties of Flu-
ids. Their Correlation, Prediction and Estimation. Cambridge: Cambridge
University Press.
Pakowski, Z., Bartczak, Z., Strumillo, C., Stenstrom, S. 1991. Evaluation of Equa-
tions Approximating Thermodynamic and Transport Properties of Water,
Steam and Air for Use in CAD of Drying Processes. Drying Technol 9:753-
773.
Perry R.J., Green, J.H., Moloney, J.O. 1984. Perry's Chemical Engineers' Hand-
book. 6th ed. New York: McGraw-Hill.
PPDS-Physical Properties Data Service. 1996. Physical Properties Databases.
N.E.L., East Kilbride, U.K.
Prausnitz, J.M., Lichtenthaler, R.N., Azevedo, E.G. 1999. Molecular Thermody-
namics of Fluid Phase Equilibria. 3rd ed. New York: Prentice Hall.
28 Chapter 2
Reid, R.C., Prausnitz, J.M., Poling, B.E. 1987. The Physical Properties of Gases
and Liquids. 4th ed. New York: McGraw-Hill.
Smith, J.M., van Ness, B.C. 1987. Introduction to Chemical Engineering
Thermodynamics. New York: McGraw-Hill.
Syncott, K. 1996. Chemical Engineering Design. In: Coulson and Richardson
Chemical Engineering. Vol. 6. pp 274-280.
Touloukian. Y. S. 1971. Thermophysical Properties of Matter. Volumes 1-13.
New York: IFI/ Plenum.
Food Structure and Transport
Properties
I. INTRODUCTION
Food structure at the molecular, microscopic and macroscopic levels, used

in the study and evaluation of food texture and food quality, can be applied to the
analysis and correlation of the transport properties of foods. Molecular dynamics
and molecular simulations, recently developed in polymer science for the study of
polymer structure, can be extended to more complex food systems, improving the
empirical mechanisms and correlations of transport processes. Food macrostruc-
ture, used in engineering and processing applications, can be related to the recent
advances of food microstructure at the cellular level. Applications of food struc-
tural analysis and experimental data to the transport properties, especially mass
transport, will improve food process and product development, and food product
quality.
I. MOLECULAR STRUCTURE
A. Molecular Dynamics and Molecular Simulations

The transport properties of simple gases and liquids can be predicted by
theoretical and semiempirical models based on molecular dynamics and thermo-
dynamics. Extensive data on the physical and transport properties of gases and
liquids are available in the form of tables and data banks, as outlined in Chapter 2
29
30 Chapter 3
(Reid et al., 1987). These correlations and data are of limited use to food systems,
since food materials are generally heterogeneous solids, which are difficult to ana-
lyze and interpret in terms of pure molecular science.
The mechanical and transport properties of polymers can be predicted by the
new technique of molecular simulation, which is based on molecular dynamics
and uses extensive computer computations. Molecular simulations use statistical
analysis and computer computations of a particular material, from which struc-
tural, thermodynamic and transport properties are estimated (Theodorou, 1996).
Molecular simulations can produce polymer configurations based on equi-
librium statistical mechanics, which show the distribution of sizes and shapes of
open spaces, formed within the polymer structure, where the penetrant molecules
can reside. Application of this technique to polymer science could produce special
polymers for specific application, e.g. separation of various molecules.
B. Food Materials Science

The major components of foods are biopolymers (proteins, carbohydrates
and lipids) and water. Food materials science is essentially polymer science ap-
plied to food materials. Polymer science was developed largely in the synthetic
polymer (plastics) industry, but recently it is applied at a growing rate in food sci-
ence and technology (Slade and Levine, 1991; Levine and Slade, 1992).
The transport properties of foods are closely related to the properties of food
biopolymers, as shown in the analysis of viscometric properties (see Chapter 4),
mass diffusivity (see Chapters 5, 6 and 7) and thermal conductivity/diffusivity (see
Chapter 8). The techniques of polymer science are used widely in the determina-
tion of mass transport (diffusion) of water and other solutes in food materials
(Vieth, 1991).
Food biopolymers of importance to transport properties are structural pro-
teins (collagen, keratin, elastin), storage proteins (albumins, globulins, prolamins
and glutenins), structural polysaccharides (cellulose, hemicelluloses, pectins, sea-
weed, plant gums), storage polysaccharides (starch-amylose and amylopectin), and
lignin (plant cell walls) (Aguilera and Stanley, 1999).
C. Phase Transitions
Phase transitions, shown in the familiar state diagrams of biopolymers and
other food components, have a profound effect on the transport properties of
foods, especially mass transport. Extensive data on the major phase transitions of
foods, including freezing, glass transitions, gelatinization and crystallization, are
presented by Rahman (1995).
Food Structure and Transport Properties 31
Freezing of food materials increases substantially the thermal transport

properties (thermal conductivity and diffusivity), as shown in Chapter 8. Glass
transition, i.e. change from the glassy to the rubbery state, increases sharply the
mass diffusivity of water and other solutes (see Chapters 5, 7). Gelatinization of
starch decreases moisture (solute) diffusivity, but it increases thermal conductivity
(see Chapters 5, 8).
Collapse of the food structures reduces the mass transport properties of
freeze-dried and other porous food materials. Collapse temperature is related to the
glass transition temperature (Karathanos et al., 1996a).
Glass transition of food biopolymers and other components has received
special consideration, because of its importance to the mechanical, transport, tex-
ture and quality properties of several food materials and products (Roos, 1992;
Roos, 1995; Rao and Hartel, 1998).
Due to their heterogeneous structure, solid foods show a diffuse but not
sharp glass temperature change. The phase changes in food materials are deter-
mined usually by differential scanning colorimetry (DSC). The glass transition
temperature Tg increases considerably as the moisture content is reduced. The Tg
of biopolymers is higher than the oligomers.
The effect of temperature on the transport properties (viscosity, diffusivity)
below the glass transition temperature Tg and above (Tg+100K) is described by the
familiar Arrhenius equation, while in the range of Tg to (Tg+100K) the Williams-
Landel-Ferry (WLF) equation (see Chapter 7) gives a better representation.
D. Colloid and Surface Chemistry

Colloid and surface phenomena are important in the structure of most food
materials, especially liquid foods. A detailed analysis of the physicochemical
structure of milk, the most important fluid food, is presented by Aguilera and
Stanley (1999).
Surface phenomena, like emulsions, foams, wetting and adhesion, affect the
transport properties, especially viscosity and mass diffusivity of foods. The
rheological properties of liquid foods are particularly effected by the colloidal
structure of the food components (see Chapter 4). The apparent viscosity of most
complex (non-Newtonian) foods decreases considerably, as the shear rate is in-
creased, due to changes in the flow patterns of the components in the suspension.
Viscoelastic (both viscous and elastic) phenomena in fluid foods are caused
by intramolecular forces during deformation of the material. They are studied by
relaxation/creep experiments or by dynamic rheological tests.
32 Chapter 3
III. FOOD MICROSTRUCTURE AND TRANSPORT PROPERTIES
Food microstructure is concerned with the structure of food materials at the

microscopic level, and its relation to the processing, storage and quality of food
products. Developed initially for the evaluation of food texture and food quality,
food microstructure can be applied to the transport properties of food materials,
i.e. viscosity, thermal conductivity / diffusivity and mass diffusivity.
A. Examination of Food Microstructure

The microstructure of foods can be measured and evaluated by the follow-
ing principal techniques (Aguilera and Stanley, 1999; Blonk, 2000):
1. Light microscopy (magnification x 20-500), which includes the compound,

the polarizing, the fluorescent, the hot-stage, the computer-assisted and the
con focal laser scanning microscopes.
2. Transmission electron microscopy (TEM) with magnification (x200-
500,000), which includes the scanning transmission electron microscope.
3. Scanning electron microscope (SEM) with magnification (x 20-200,000),
which is considered as the best instrument for food microscopical studies and
gives the best pictures of the materials.
In addition, the following techniques may be used for special stud-

ies/examinations: a) scanning probe microscopy; b) X-ray microscopy; c) light
scattering; d) magnetic resonance imaging (MRI); and e) spectroscopy.
Image analysis relies on computer technology to recognize, differentiate and
quantify images. It involves video cameras, scanners and data processing software.
Image analysis is applied to the measurement of particle size and shape (Alien,
1997) and in the control of food processing operations.
Fractal analysis is used to measure the irregularity of particle surfaces,
which are of importance to food properties.
B. Food Cells and Tissues

Both plant and animal tissues consist of microscopic cells, which character-
ize each material. The cells contain several components, which are essential in
living organisms, such as water, starch, sugars, proteins, lipids and salts. A sche-
matic diagram of a plant parenchyma cell is shown in Figure 3.1.
PLD
CW
CM
ML
Figure 3.1 Diagram of a parenchyma plant cell. CW, cell walls; CM, cell membrane
(plasmalemma); V, vacuole; N, nucleus; ML, middle lamella; PLD, plasmodesmata; IS,
intercellular space; TN, tonoplast; P, protein particles; L, lipid particles.
The microscopic plant cell (size of 2-10 um) consists of the cell walls which
contain the cell components in a membrane (plasmalemma) enclosure. The cell
contains protein, starch and lipid particles within the cytoplasm. The vacuole, sur-
rounded by the tonoplast, contains water, soluble sugars and salts (Aguilera and
Stanley, 1999). The vacuole is responsible for the osmotic pressure and the turgor
of the cell.
The cell walls contain the middle lamella and they have small channels
(plasmodesmata), that allow the flow of cytoplasmic material and water/solutes in
and out of the cell. Intercellular spaces may contain water solution or air. The cell
walls contain mainly cellulose, hemicelluloses, pectins and glycoproteins. Plant
tissues consist of storage or parenchyma cells, phloem for transporting organic
materials, xylem for transporting water and protective tissue.
The plant cell walls and membranes are of particular importance to food
processing and food quality. The turgor (hydrostatic pressure) is lost during dehy-
dration, heating or freezing. The cell wall middle lamella complex is related to
food texture.
34 Chapter 3
Animal cells consist of fibrous structures (myofibrils), which have special

mechanical properties, characteristic of each animal material.
C. Microstructure and Food Processing

Food structure is preserved in some processes, while in other it is destroyed
in order to produce useful processed products, as in refining starch, sugars, oil
seeds, grain and milk. Changes in structure occur in freezing, milling (size reduc-
tion), crystallization and emulsification. Restructuring of food materials is used in
extraction, spinning, margarine and ice cream production.
Gels are solidlike structures that contain large amounts of water. They are
produced by different mechanisms using gelling substances, such as starch, pectin,
gelatin, alginates and various plant gums. The Theological and transport properties
of gels are important in the various food processing operations and in food quality.
They are also used for investigations of structure-property relationships.
D. Microstructure and Mass Transfer
/. Solvent Extraction
Solvent/solid extraction or leaching of food components, such as sugars, lip-
ids and flavor compounds is used in various food processing operations. It can be
analyzed and designed by the methods developed in chemical process engineering,
i.e. equilibrium-stage or continuous separations (Perry and Green, 1997).
The mass diffusivity of solutes in solid substrates Ds is smaller than the dif-
fusivity in the liquid solvent DL due to the complex structure of the material, ac-
cording to the empirical equation (Aguilera and Stanley, 1999):
Ds = Fa,DL (3-1)
The correction factor Fm varies in the range (0.1-0.9), with the higher values
obtained when the cell membranes are destroyed, as by heating in the extraction of
sucrose from sugar beets by hot water. Fm becomes very low, approaching zero, in
the extraction of high molecular weight components, like proteins, from plant tis-
sues. Extraction is improved by pretreatment of the solid material, e.g. by size
reduction, or by flaking, which reduces the diffusion path for both solvent and
extracted component. In some applications, extraction can be improved by enzy-
matic treatment of the plant tissues, which break down, e.g. the pectins of the cell
walls.
Values of the diffusivity of food components in various solvents are given

by Schwartzberg (1987). Typical DL for sucrose in water is 5xlO' 10 m2/s and for
caffeine in water is IxlO" 10 rrr/s (see Table 7.5).
2. Food Dehydration
The moisture (water) in heterogeneous solid foods may not be in equilib-
rium at the microstructural level, although macroscopically the system appears to
be in equilibrium. Thus, moisture may be transported between the heterogeneous
components of the food system. Thermodynamic analysis of transport processes at
the cellular level requires transport and equilibrium properties of the cell compo-
nents (Rotstein, 1987).
Microstructural changes during the drying of food materials include loss of
cellular structure, pore formation and shrinkage of the product. These changes
affect strongly the transport properties, especially moisture diffusivity (see Chap-
ter 5).
Heterogeneous structure may affect moisture diffusivity, like the reduction
of the drying rate by the skin of grapes (see Chapter 5). Food microstructure is
related to the retention of volatile aroma components during the drying of food
materials (see Chapter 7).
Microstructure plays an important role in the osmotic dehydration of foods,
especially that of fruits and vegetables: The water is transported from the food
cells to the osmoactive solution (sugar or salt) and the osmoactive agent is infused
into the cellular food (Lewicki and Lenart, 1995). A model of the osmotic dehy-
dration process in cellular foods is presented by Yao and Le Maguer (1996).
Mass transfer in plant tissues during osmotic dehydration was analyzed by
Spiess and Behsinlian (1998); the plant tissue is considered to consist of a solid
matrix, intercellular space, extracellular space and occluded gas. Three pathways
of mass transfer may take place at the microstructural level: a) apoplasmatic trans-
port (outside the cell membrane); b) symplasmatic transport through small chan-
nels (plasmodesmata) between neighboring cells; and c) transmembrane transport
(between the cell and the intercellular space). The function of living plant cells is
examined in plant physiology.
3. Microstructure and Frying

Frying of foods can be considered as a simultaneous heat and mass transfer
process in which water is lost and oil is absorbed by the food product, e.g. potato
pieces. Cells in the interior of the fried product can be intact, while surface cells
are dehydrated and shrunk. Oil uptake during frying is by a complex mechanism,
different from the molecular (Fickian) diffusion, possibly by a capillary or hydro-
dynamic flow (Aguilera and Stanley, 1999; Aguilera, 2000).
36 Chapter 3
IV. FOOD MACROSTRUCTURE AND TRANSPORT PROPERTIES
The transport properties of solid and semisolid food materials are related to
their macroscopic properties, such as density, porosity, particle size and shape.
The design, operation and control of food processing operations is based on these
properties, which can be measured by simple instruments and techniques.
The structure of solid and semisolid foods has been investigated more in re-
lation to food structure and food quality than to transport properties. The structure
of fluid foods is usually related to their rheological and viscometric properties, as
discussed in Chapter 4.
Food macrostructure has received special attention in relation to the dehy-
dration of foods, since significant changes take place during moisture transport in
solid and semisolid food materials.
Model food materials, based on food biopolymers, such as starch, and fruits
and vegetables have been used as experimental materials, since their properties
can be related empirically to their structure at the macroscopic, microscopic and
molecular levels.
Quantitative parameters of physical meaning, i.e. density, porosity and
shrinkage, based on three phases (solids, water and air) can be estimated for the
characterization of structural changes of foods during processing and storage.
Two classes of food materials are examined separately: a) continuous solids,
in which shrinkage and porosity develop when water is removed, and b) particu-
late or granular materials, such as starch granules, in which porosity is a dependent
variable that can be controlled, e.g. by compression.
A. Definitions
Assuming moist material to consist of dry solids, water, and air, the follow-
ing definitions can be considered:
m,= ms+mw (3-2)
where m,, ms, and mw are the total mass and the masses of dry solids and water
respectively (kg), while the mass of air is neglected.
The total volume of the sample is considered as:
V,= Vs+Vw+Va (3-3)
where Vs, Vw and Va, are the volumes of dry solids, water and air pores, respec-
tively (m3). The volume of air is referred to the internal pores only.
The apparent density of the food material pb is defined as:
pb = m,/Vt (3-4)
and the true density pp as:
PP=m,/Vp (3-5)
where Vp = Vs+Vw is the true (particle) volume, which is the total volume of the
sample excluding air pores. Apparent and true density are analogous to the bulk
and particle density of granular materials, respectively. The actual densities of dry
solids PJ and enclosed water pw can also be defined as:
P, = m,/V, (3-6)
pw = mw/Vw (3-7)
The specific volume of the sample u is defined as the total volume per unit mass of
dry solids (m3/kg db):
v=V,/ms (3-8)
The material moisture contention a dry basis (kg water/kg db) is:
X=mw/ms (3-9)
The volume-shrinkage coefficient ft can be defined by the following equation,

which represents the proportion of initial specific volume that shrinks as water is
removed:
(3.10)
A,
where Xi is the initial moisture content of the moist food material, v is the specific
volume at material moisture content X, and o,- is the specific volume at X=Xi. The
shrinkage coefficient ft varies between 0 (no shrinkage) and 1 (full shrinkage).
(See Figure 3. 2.)
Assuming that no volume interaction occurs between the water and the sol-
ids, combining Eqs. (3-5), (3-6), (3-7) and (3-9) results in:
38 Chapter 3
lJrX
Pp= (3-11)
A A..
Equation (3-11) shows the dependence of moisture content on true (particle) den-
sity.
Combining Eqs. (3-4), (3-7), (3-9) and (3-10) results in:
'iW P-12)
A, A,.
where pbi is the apparent density &iX=Xi, the initial moisture content.
When the zero moisture content is considered as initial moisture content
(A)=0), then Eqs. (3-10) and (3-12) are transformed into Eqs. (3-13) and (3-14),
respectively:
o = uo+/3— (3-13)
A
where L>O, and pbo are the specific volume and the apparent density at X = 0, re-
spectively.
Moreover, in fried products, when oil is considered as one more phase, Eqs.
(3-13) and (3-14) are further transformed to Eqs. (3-15) and (3-16), respectively:
( X Y\
o = va+p\ — + — (3-15)
IA PL)
X +—
— Y
A» A PL.
where pL is the oil density and 7 the oil content
Y=mL/ms (3-17)
where mL is the mass of the oil in the sample of ms dry solids.

For fried products Eq. (3-11) is also transformed to Eq. (3-18):
+X +
(3-18)
1
_____
X
j ___
Y
I ___
P, P, Pi
Volume of water which:
disappears (shrinkage)
= p (Xi-X) / pw
remains as water
= X/pw
remains as air (porosity)
= (l-p)(Xi-X)/pw
Initial Final
(Xi) (X)
Figure 3.2 Schematic representation of shrinkage and porosity development, as
part of water is removed.
40 Chapter 3
B. Food Macrostructure and Transport Properties
The food macrostructure, in calculating the effective transport properties of

food materials, is taken into account, using the so-called structural models, some
of which are presented for thermal conductivity in Chapter 8 (Table 8.3). Similar
structural models for moisture diffusivity of starch materials have been proposed
by Vagenas and Karathanos (1991), but their application to food materials remains
to be validated.
These models require the volume fraction of the food phases (solids, water,
air, oil, etc). Thus, the shrinkage and porosity models, described earlier in this
chapter, must be combined with the transport properties models.
Two examples for continuous (Maroulis et al., 2001; Krokida et al., 200la)
and granular foods (Krokida et al., 200Ib) foods follow.
1. Continuous Solids
Table 3.1 summarizes the proposed model that combines the thermal con-
ductivity structural models with the density structural models. The corresponding
information flow diagram is presented in Figure 3.3.
2. Granular Solids
Table 3.2 summarizes the proposed model, which combines the thermal
conductivity structural models with the density structural models. The correspond-
ing informational flow diagram is presented in Figure 3.4.
Table 3.1 Effective Thermal Conductivity Generic Model for Continuous Mate-
rials
Thermal Conductivity Structural Model
(2)
Volume Fraction of the Food Phases
/?,=!-— (4)
* =^ (5)
(6)
Density Structural Model
A, P.
42 Chapter 3
pai, Xi,
O, al, a2, a3 Shrinkage

and
Porosity
Model
Eqs. (7) and (8)
Density
of Pure
Substances ps, pw pa, pt
Volume
Fraction
of Food
Components
Eqs. (4), (5)
and (6)
Thermal es, e\v, ea

Conductivity
of Pure Xs, Xw, Xa
Substances Thermal
Conductivity
Structural
Model
Eqs. (1), (2)
bo, bl, b2, b3 and (3)
JXeff
Figure 3.3 Informational flow diagram for the model of Table 3.1. (Equation numbers
refer to those in Table 3.1.)
Table 3.2 Effective Thermal Conductivity Generic Model for Granular Materials
Thermal Conductivity Structural Model for Granular Material
*«=l-f f <!>
-L J-
(2)
(3)
Thermal Conductivity Structural Model for Granules (Particles)
/
yf
(5)
Volume Fractions
* 0 =1- A (7)
^
Particle Density Structural Model
P
Pp = 1l +X X (9)
^ '
___ I ___
P. P.
44 Chapter 3
f fp
aO, al, a2. a3

Particle Density
Structural Model
Eq. (9)
Density
of Pure
Substances ps, pw PP
pb
Volume
Fractions
Eqs. (7) and (8)
Thermal
Conductivity Xs, Xw
of Pure Thermal Conductivity
Substances Structural Model
for Granules (Particles)
Eqs. (4), (5)
and (6)
bo, bl, b2, b3

1 e
Xp 1
Thermal Conductivity
Xa Structural Model
forGranular Material
Eqs. (1), (2)
and (3)
Xeffl
Figure 3.4 Informational flow diagram for the model of Table 3.2. (Equation numbers
refer to those in Table 3.2.)
C. Determination of Food Macrostructure
The determination of food macrostructure is based on the measurement of

mass and volume and the estimation of the various densities and porosity, as
shown on the informational flow diagram of the Figure 3.5 (Krokida et al., 1997).
The corresponding methods are described by Rahman (1995) and summarized in
Table 3.3.
Mass of Wet Sample

m
(error 1%)
True Density
pp=m,/Vp
(error 2%)
True Volume
Vp
(error 1%)
Apparent Density
pb=mt/Vt
(error 3%)
Total Volume
Vt
(error 2%)
Specific Volume
u = Vt / ms
(error 3%)
Mass of Dried Sample
ms
(error 1%)
Figure 3.5 Experimental data evaluation flow diagram for densities and porosity.
46 Chapter 3
Table 3.3 Volume Measurement Techniques
1. Dimension measurement
2. Buoyant force determination
3. Volume displacement method
a. Liquid displacement method
b. Gas pycnometer method
c. Solid displacement method
D. Macrostructure of Model Foods
Model foods are useful experimental materials for studying the effect of
physical (macro) structure on the transport properties of foods. They consist of a
biopolymer matrix, containing water and typical food components, such as carbo-
hydrates, proteins and lipids assembled in the form of a hydrated solid or a solid-
like gel. Starch materials, particularly linear amylose and branched amylopectin,
have been used in many forms for studies of thermal and mass diffusivity. The
physical phenomena of food dehydration have been investigated using various
starch materials (Saravacos, 1998).
The density of granular starch changes nonlinearly with the moisture con-
tent, according to the empirical equation (Marousis and Saravacos, 1990):
pf = 1442 + 837X-3646X2 + 448 LY 3 -1850^ 4 (3-19)
The granular or particle density pp is expressed in (kg/m3) and the moisture

content A'in (kg/kg db).
Figure 3.6 schematically shows the change of the particle density of granu-
lar starch as a function of moisture content. A maximum ofpp is observed near X
= 0.15, meaning that at this low moisture content, the water is adsorbed strongly
on the biopolymer. At higher moistures, water reduces the particle density by
swelling the starch granules.
The bulk porosity s of hydrated granular starch increases significantly as the
moisture is reduced during air-drying (Figure 3.7). A smaller change of porosity is
observed on the porosity of gelatinized starch during the drying process. These
significant changes in porosity, estimated by measuring the bulk and particle den-
sities of the material, are related to the changes of moisture diffusivity D during
the various drying and rehydration processes (see Chapter 5).
1.60
1.00
0.00 0.20 0.40 0.60 0.80 1 . 0 0
X (kg/kg db)
Figure 3.6 Particle density pp of corn starch as a function of moisture content X.
0.60
0.40
0.20
0.00
0.00 0.20 0.40 0 . 6 0 0 . 8 0 1.00
X (kg/kg db)
Figure 3.7 Bulk porosity s of air-dried granular (GR) and gelatinized (GEL) corn
starch as a function of moisture content^
48 Chapter 3
Gelatinization of starch increases significantly the thermal conductivity of

the starchy materials, evidently due to the changes in the macromolecular and mi-
croscopic structure (see Chapter 8). Changes in porosity of granular starch struc-
tures by the incorporation of sugars, proteins, lipids, and inert particles are re-
flected in significant changes of the moisture diffusivity. Significant reduction of
the porosity of granular starch is obtained by mechanical compression (see Chap-
ter 5).
Figure 3.8 shows schematically the macrostructure of dried granular and ge-
latinized starch materials. The spherical granular starch materials developed radial
channels through which water was transported by hydrodynamic flow during dry-
ing. The gelatinized starch suffered more shrinkage during drying with irregular
cracks in the dried matrix. These changes correspond to changes of moisture diffu-
sivity during the drying processes (Marousis and Saravacos, 1990).
Freeze-drying of model food gels affects strongly their macrostructure and
the transport properties. The development of macrostructure is the combined result
of freezing and drying by sublimation of the ice. Figure 3.9 schematically shows
slabs of two different structures, developed by freeze-drying of model gels. The
CMC gel developed a fibrous structure, parallel to the flow, which significantly
increased the moisture transport rate and thermal conductivity of the material (see
Chapters 5 and 8). The freeze-dried starch gel had a uniform microporous struc-
ture which had lower moisture and thermal diffusivity than the fibrous material.
The pore size distribution in granular, gelatinized and extruded starch mate-
rials, measured by mercury porosimetry, shows that the majority of the pores
(90%) are larger than 1 urn, and only 10% have smaller pores. Bulk porosity,
measured by gas pycnometry, is the most important parameter characterizing the
transport properties (Karathanos and Saravacos, 1993). Structural models, devel-
oped for thermal conductivity, can be adapted to model the effective moisture dif-
fusivity in granular starch materials (Vagenas and Karathanos, 1991). The pore
structure of extruded pasta has significant effect on the moisture sorption and dif-
fusivity of pasta (Xiong et al., 1991).
Stress crack formulation in the air-drying of cylindrical samples of hydrated
starch is affected by the moisture gradient at the transfer interface (Liu et al.,
1997). Crack formation, a problem in pasta drying, is related to the stresses devel-
oped in the glassy state of the biopolymer, and it can be prevented by drying at
temperatures higher than the glass transition temperature (Willis et al., 1999). De-
velopments of cracks in grain kernels can be prevented by intermittent microwave
drying, due to the relaxation of temperature and moisture gradients during the
tempering period (Zhang and Mujumdar, 1992). Tailor-made porous solid foods
can be prepared using a base of freeze-dried alginate gels (Rassis et al., 1997).
a. Granular b. Gelatinized
Figure 3.8 Macrostructure of air-dried spherical samples of corn starch (20 mm diame-
ter).
O - O
O Q O
a. CMC b. Starch
Figure 3.9 Macrostructure of freeze-dried slabs of carboxy methyl cellulose (CMC) and
starch gels (20 mm thickness).
50 Chapter 3
E. Macrostructure of Fruit and Vegetable Materials

The effect of drying method on bulk density, particle density, specific vol-
ume and porosity of banana, apple, carrot and potato at various moisture contents
is presented in Figures 3.6-3.9, using a large set of experimental measurements
(Krokida and Maroulis 1997). Samples were dehydrated with five different drying
methods: conventional, vacuum, microwave, freeze- and osmotic drying. A simple
mathematical model, presented in Table 3.4, was used in order to correlate the
above properties with the material moisture content. Four parameters with physi-
cal meaning were incorporated in the model: the enclosed water density pw, the
dry solids density ps, the dry solids bulk density pbo and the volume shrinkage co-
efficient (3. The effect of drying method on the examined properties was taken into
account through its effect on the corresponding parameters (Table 3.5). Only dry
solid bulk density was dependent on both material and drying method. Freeze-
dried materials developed the highest porosity, whereas the lowest one was ob-
tained using conventional air drying.
The above structural properties for the investigated materials were also ex-
amined during rehydration of dehydrated products, using the drying methods. The
same dehydrated products did not recover their structural properties after rehydra-
tion, due to structural damage that occurred during drying and the hysteresis phe-
nomenon, which took place during rehydration. Porosity of the rehydrated prod-
ucts was higher during rehydration than during dehydration. A structural model of
Table 3.4 was also used to describe the structural properties, and of the four pa-
rameters that were incorporated (also presented in Table 3.5), only the shrinkage
coefficient, which represents volume expansion, changed on rehydration.
Apparent density, true density, specific volume and porosity were investi-
gated during deep fat frying of french fries (Krokida et al., 2000). The effect of
frying conditions (oil temperature, sample thickness and oil type) on the above
properties is presented in Figures 3.10-3.12. Moisture and oil content during deep
fat frying and consequently all the examined properties are affected by frying con-
ditions. The results showed that the porosity of french fries increases with increas-
ing oil temperature and sample thickness, and it is higher for products fried with
hydrogenated oil.
The pore size distribution of fruit and vegetable materials shows three peaks
in the ranges of 20 um, 1 um and 0.2-0.04 urn. The pore size of air-dried food
materials is much smaller than the pore size of freeze-dried products, due to the
collapse of structure during dehydration (Karathanos et al., 1996b).
2.0 - 2.0 T BANANA

Dehydration
convective drying
A vacuum drying
APPLE X microwave drying
freeze drying
osmotic dehydration
calculated
Rehydration
convective drying
vacuum drying
micro\\ave drying
freeze drying
osmotic dehydration
- calculated
0 3 6 0 3 6
Moisture content (kg/kg db) Moisture content (kg/kg db)
2.0 - 2.0 -
CARROT
0 3 6 0 3 6
Figure 3.10 Variation of true density with material moisture content for various drying
methods during dehydration and rehydration.
52 Chapter 3
2.0 -
i
o
Dehyd(ration
convei;tive drying
vacuui•n drying
micro\vave drying
freeze drying
osmoti c dehydration
ited
RehydIration
convet;tive drying
vacuuin drying
microvvave drying
o freeze drying
D osmoti'c dehydration
0.0
0 3 6
CARROT
0.0
0 3 6 0 3 6
Figure 3.11 Variation of apparent density with material moisture content for various
drying methods during dehydration and rehydration.
Dehydration
1.0 T • convective drying
BANANA A vacuumdrying
X microwavedrying
freeze drying
osmotic dehydration
. calculated
Rehydration
convective drying
vacuumdrying
microwave drying
freeze d r y i n g
osmotic dehydration
-calculated
Moisture content (kg/ kg db) Moisture content (kg/ kg db)
1,0 T
CARROT
0 3 6 0 3 6
Moisture content (kg/kg db) Moisture content (kg/ kg db)
Figure 3.12 Variation of porosity with material moisture content for various drying meth-
ods during dehydration and rehydration.
54 Chapter 3
Dehydration
15 • convective drying
A vacuum drying
X microwave drying
• freeze drying
• osmotic dehydration
Rehydration
o convective drying
A vacuum drying
X microwave drying
0 freeze drying
D osmotic dehydration
3 6 0 3 6
15 -
0 3 3 6
Figure 3.13 Variation of specific volume with material moisture content for various drying
methods during dehydration and rehydration.
Table 3.4 Mathematical Model for Structural Properties of Foods
Structural properties
pp True density (kg/L)
pb Apparent density (kg/L)
s Porosity
v Specific volume (L/kg db)
Factors
x Moisture content (kg/kg db)
Properties equations
1+ X
Pp (1)
~ J_ A
Ps P.
i +x
pb =• t (2)
Pbo Pw
(3)
Pp
8 = 1-*-
u = — + B' — (4)
Pbo Pw
Parameters
pw Enclosed water density (kg/L)
ps Dry solid true density (kg/L)
pbo Dry solid apparent density (kg/L)
/?' Shrinkage or expansion coefficient
Factors affecting parameters

Material
Drying method
56 Chapter 3
Table 3.5 Parameter Estimation of the Structural Properties Model

Material/Method
Ps P» P Pbo
Apple
Convective 0.99 0.56
M
e Vacuum 0.96 0.39
'c£• Microwave 1.01
0.34
0.56
0.12
Freeze
Osmotic 0.73
Convective • - '- -g- 0.56
Rehydrat.
Vacuum 1.31 0.39

Microwave 1.30 0.56
Freeze 0.81 0.12
Osmotic 1.22 0.73
Banana
DC
B
Vacuum 0.90 0.63
'E>
Microwave 1.05 1.79
Q Freeze 0.43 0.26
Osmotic 1.04 1.33
L9 L 2
Convective ' ° ° 1.07 1.81
Rehydrat.
Vacuum 1.10 0.63

Microwave 1.07 1.79
Freeze 0.65 0.26
Osmotic 1.07 1.33
Carrot
it
c Vacuum 0.99 0.92
'E>
O Microwave 0.94 0.53
Freeze 0.30 0.14
Convective 1.75 1.02 12Q 1.60
u
•B
>, Vacuum 1.05 0.92
-C
Microwave 1.20 0.53
£ Freeze 0.22 0.14
Potato
BJD
C Vacuum 1.03 1.29
'cE- Microwave 0.81 0.44
Freeze 0.29 0.18
Convective 1.60 1.02 10? 1.50
J>
u
Vacuum 1.05 1.29
i Microwave
Freeze
1.07
0.74
0.44
0.18
1.5 n
0.9
5 10 15 20 5 10 15 20
Time (min) Time (min)
0.6
5 10 15 20 5 10 15 20
Figure 3.14 Effect of oil temperature on structural properties of french fries.
<n
CO
(Q Porosity True density (kg/1)
o o
CO
^
01
H
3
Specific volume (I/kg) Apparent density (kg/1)

s UJ LK> 4^ o o
O <-*» O
I o - ' '
•a
o
<-/!
r•
\ | <
/
d
3
re
1 1 1
r> •
1 I5 " 1 I
3. 5"
x^
•\ 5"
1
<_ft •^ O
Lft 0 (-A 3-
9>
3 3 3 T3
3 3 3 ff
K)
O
1.5 -i
Concentration of
hydrogenated oil (%)
AO
• 50
• 100
5 10 15 20 5 10 15 20
0.
5 10 15 20 0 5 10 15 20
Figure 3.16 Effect of oil type on structural properties of french fries.

60 Chapter 3
REFERENCES
Aguilera, J.M. 2000. Microstructural and Food Product Engineering. Food Tech-
no!54(ll):56-65.
Aguilera, J.M., Stanley, D.W. 1999. Microstructural Principles in Food Processing
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Karathanos, V.T., Anglea, S.A., Karel, M. 1996a. Structure Collapse of Plant Ma-
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Rheological Properties of Fluid Foods
I. INTRODUCTION
The viscosity of fluid foods is an important transport property, which is use-

ful in many applications of food science and technology, such as design of food
processes and processing equipment, quality evaluation and control of food prod-
ucts, and understanding the structure of food materials. Due to the complex
chemical and physical structure of foods, viscosity can not be predicted by theo-
retical methods, such as molecular dynamics and semi-empirical models, applied
to pure fluids, and discussed in Chapter 2 of this book. Therefore, experimental
measurements and empirical models of viscosity are necessary for the characteri-
zation of fluid foods.
Viscosity is part of the wider rheological properties of foods, which cover,
in addition to fluids, the solid and semisolid food materials. Foods, in general, can
be classified as solids, gels, homogeneous liquids, suspensions in liquid, and
emulsions (Rao, 1999). Fluid foods are heterogeneous materials, consisting of
dispersions of fibers, cells, protein particles, oil droplets and air bubbles in a con-
tinuous phase, like an aqueous solution of sugars, or a vegetable oil (Aguilera and
Stanley, 1999).
Recent advances in the design and control of food processes, utilizing com-
puter modeling and simulation, require extensive data on the physical and engi-
neering properties of foods. Limited reliable data are available in the literature,
particularly in the areas of rheological properties (viscosity) and mass diffusivity
of food systems (Saravacos and Kostaropoulos, 1995, 1996; Saravacos, 2000).
Food rheology deals with all the phenomena of deformation and flow of
food materials due to external forces. Viscometry deals with fluids, which are
characterized by mechanical flow, upon the application of an external force.
63
64 Chapter 4
The viscometric properties of fluid foods are discussed here in analogy to

the two other basic transport properties, thermal conductivity and mass diffusivity.
The rheological properties of solid and semisolid foods (elasticity and viscoelastic-
ity) are discussed in specialized books, such as Bourne (1982) and Rao (1999).
Viscosity plays an important role in liquid food texture and in texture-taste
interactions (Kokini, 1987). The tasting reaction is controlled by the diffusion of
the flavor components through the viscous food layer in contact with the tongue.
Fluid viscosity rj is defined by the basic transport Eq. (2-2), which is equiva-
lent to the Newton Eq. (4-1) of shear flow. In most food applications, TJ is syn-
onymous to the shear viscosity in the ^-direction, as shown in Figure 4.1.
T = riy (4-1)
where T = F/A (applied force / surface area) is the shear stress in (Pa) and
y = (du/dy), change of velocity (Aux) in the y-direction, is the shear rate in (1/s).
This book deals mainly with shear viscosity at steady state. However, there
are some other types of viscosity, for example extensional viscosity, which is use-
ful in specialized engineering applications. Extensional flows occur when the flow
geometry changes abruptly, like in orifice flow, spinning of fibers, extrusion, and
impingement (Giesekus, 1983; Padmanabhan, 1995; Rao, 1999). Such flows are
important in polymer processing. In the simple uniaxial extensional flow, a cylin-
drical body is stretched in one direction, while contracting in the other two. In the
biaxial extensional flow, the reverse process takes place, i.e. the material is
stretched in two directions, while contracting in the other. Finally, in the planar
extensional flow, stretching is in one direction, constant in the second, and con-
traction in the third.
Figure 4.1 Shear viscosity in the x-direction.

Rheological Properties of Fluid Foods 65
In dynamic rheometry, applied to viscoelastic materials and gels, the shear

stress-strain relationship is obtained by periodic deformation of the material (Rao
and Steffe, 1992; Urbicain and Lozano, 1997).
In polymer science, the intrinsic viscosity [ r/J expresses the hydrodynamic
volume of the polymer molecule, which is related to the molecular weight and the
dimensions of the molecule. The intrinsic viscosity in dilute polymer solutions is
defined as the zero-concentration limit of the ratio (rjS[/C), where T]sp=[('n-ris)/riJ
is the specific viscosity, r\ and rjs are the viscosity of the solution and the solvent
respectively, and C is the concentration (Rao, 1999).
The intrinsic viscosity [ t] /of dilute food biopolymer solutions (e.g. gums)
has been related to experimental viscosity measurements through empirical mod-
els, like the Huggins equation (Tanglertspaibul and Rao, 1987; Yoo et al, 1994):
(iv'Q-lvJ + krfrifC (4-2)
The Huggins constant kt is related to the polymer-polymer interaction and it

takes values from 0.3 to 1.0. The low kj values characterize the good solvents,
while the high values indicate associations between the macromolecules. Heat
treatment of aqueous gum solutions decreases the intrinsic viscosity, presumably
due to hydrolysis or breakdown of the biopolymer (Rao, 1995).
Real solids are considered as elastic materials, which obey Hooke's law, i.e.
a linear relationship between shear stress rand strain /.
T =EY, or T =GY (4-3

The Young's modulus of elasticity E is used when the applied strain y is the
elongation or compression, y = Al /1. The shear modulus G is used when / is the
shear strain.
Most solid and semisolid foods are not elastic, but they behave as either vis-
coelastic or viscoplastic. The viscoelasticity of the materials is studied by stress
relaxation measurements, i.e. shear stress at constant strain versus time (Rao,
1999). The viscoelastic behavior is characterized by Newton's law (Eq. 4-1),
Hooke's law (Eq. 4-3), and Newton's second law (F = m a, where m is the mass
and a is the acceleration).
Most solid and semisolid foods are considered linear viscoelastic, which al-
lows the adding up of the three elements, i.e. the viscous, elastic, and inertial ef-
fects. Neglecting the inertial component, the viscous (dashpot) and the elastic
(spring) effects are usually combined into two common models, i.e. the Newton
(series model), and the Kelvin-Voigt (parallel model).
66 Chapter 4
II. RHEOLOGICAL MODELS OF FLUID FOODS
The rheological behavior of fluid foods is determined by measurements of

shear stress versus shear rate, and representation of the experimental data by vis-
cometric diagrams and empirical equations, as a function of temperature and/or
concentration. Molecular dynamics can not predict fluid viscosity, but it can be
helpful in understanding the flow mechanism of complex fluid foods. Physical
structure plays a decisive role in determining the fluid viscosity.
A. Structure and Fluid Viscosity

Simple liquid food materials, like aqueous sugar solutions, clarified juices,
and vegetable oils are Newtonian fluids, i.e. the shear stress is linearly propor-
tional to the shear rate, according to Newton's law (Eq. 4-1). Incorporation of
polymer molecules and micelles, solid particles, droplets, and gas bubbles into
Newtonian fluids changes considerably the rheology of fluid foods, evidenced by
the non-linear relationship of shear stress/shear rate.
Model fluid suspensions are useful in understanding the flow behavior of the
complex fluid food systems. The viscosity of fluid suspensions reflects the com-
plex hydrodynamic flow of the particle / solvent and particle / particle interactions.
The particle size, shape and concentration affect strongly the viscometric proper-
ties of fluid foods.
In a simple suspension of spherical particles, the relative viscosity of the
suspension to the viscosity of the continuous phase Tjr is a linear function of the
volume fraction of the particles (/), according to the Einstein equation (Giesekus,
1983):
rjr = 1 + 2.5 <f) (4-4)
The Einstein equation holds for dilute concentrations of spherical particles,

which do not react with the solvent and with each other. Particle-solvent and parti-
cle-particle interactions are reflected by a non-linear relationship of (rjr, (f>). The
shape of the particles affects strongly the behavior of suspensions Figure 4.2.
Thus, the deviation from linearity (Eq. 4-2) increases when the particle shape
changes from spherical to plate and rods. Still, stronger effects are observed with
fibers of increasing aspect (L/D, length / diameter) ratios.
Attracting forces, acting on the particle surfaces, tend to create aggregates,
which significantly increase the viscosity of the suspension. Increasing the shear
rate, the aggregates are broken down, resulting in shear-thinning of the suspension.
The suspended non-spherical particles give higher shear viscosity, due to the diffi-
culty of rotating (flowing) in the suspension. The aspect (L/D) ratio of rodlike par-
tides (e.g. fibers) is related to the build-up of transient network structures. Shear
thinning may be found at low concentrations of rodlike particles (e.g. fibers).
Model suspensions of coarse food particles in aqueous CMC solution ex-
hibit Theological properties similar to inorganic models, i.e. their deviation from
Newtonian behavior increases when the particle shape becomes elongated, and
when the particle concentration is increased (Pordesimo et al., 1994).
The non-linearity of suspensions of spherical particles at high concentrations
can be described by empirical equations, such as the Frankel-Acrivos and Krieger-
Dougherty models, in which the relative viscosity (t|r) is related to the volume
fraction ratio ($/$„), where </>m is a shear-dependent maximum volume fraction
(Rao, 1999).
Food particles are usually non-spherical, and they resemble to rough crys-
tals. The empirical Kitano et al. equation (1981) can be applied:
TJr=[l-(j/A)] (4-5)
where A is a constant, A = 0.68 for spheres, and A = 0.44 for crystals.
Figure 4.2 Relative viscosity r]r of suspensions of glass particles as a function of the
volume fraction </> in water. (1) Einstein's equation, (2) spheres, (3) plates, (4) rods.
(Adapted from Giesekus, 1983.)
68 Chapter 4
Plots of Eq. (4-5) resemble the plots of Figure 4.2. The Kitano et al. model
was applied to reconstituted tomato puree of narrow particle size distribution with
average diameters 0.71 and 0.34 mm, and adjusting parameters A = 0.54 and A =
0.44, respectively (Yoo and Rao, 1994).
Fluid foods are complex suspensions of hydrophilic particles that interact
physically and chemically with the solvent (water), resulting in considerable
deviations from Eq. (4-2). The particle size is affected by the various processing
operations and storage conditions. Thus, the size of starch granules increases
considerably during heating, before gelatinization, resulting in increased relative
viscosity of aqueous suspensions (Rao, 1999). Changes in particle size of tomato
and other fruit and vegetable products, during pulping and screening operations,
will strongly affect the product viscosity. Physicochemical interactions in fluid
foods, such as adsorption, emulsification, polymer conformation, de-poly-
merization, crystallization, and melting have significant effects on viscosity.
B. Non-Newtonian Fluids
Fluid foods, containing dissolved macromolecules and suspended particles,
deviate considerably from Newtonian behavior (Eq. 4-1). Various empirical mod-
els have been used to account for the observed non-linear relationship of shear
stress (T)- shear rate (y) of the non-Newtonian fluids (Holdsworth, 1993; Rao,
1987a, 1987b).
1. Time-Independent Viscosity
The usual non-Newtonian models apply to time-independent fluid foods,
for which the shear stress-shear rate relationship does not change with the time of
shearing.
The Bingham plastic model (Eq. 4-6) applies to Newtonian fluids that will
flow only if a fixed yield stress TO is exceeded:
T = TO + TIY (4-6)
Many non-Newtonian fluid foods are represented by the power-law or
Ostwald-de Waele model (Eq. 4-7):
T = Ky" (4-7)
In the power-law model, two rheological constants (K, n) are required to

characterize the flow behavior, K the flow consistency coefficient or index with
units (Pa sn), and n the flow behavior index (dimensionless). The K value corre-
sponds to the viscosity of Newtonian fluids.
The Herschel-Bulkley model is derived from the power-law model by add-
ing a yield stress term r0:
T = Tn (4-8)
Most non-Newtonian foods are pseudoplastic materials (n<l), while very

few are dilatant (n>Y). The pseudoplastic fluids are also known as shear-thinning
fluids, since their apparent viscosity decreases as the shear rate is increased.
The power law and Herschel-Bulkley models have been used widely, and
extensive rheological data for non-Newtonian fluid foods have been published in
the literature (Prentice and Huber, 1983; Okos, 1986; Kokini, 1992; Urbicain and
Lozano 1997; Rao, 1999). Figure 4.3 shows typical rheological diagrams, r versus
Y, for various non-Newtonian fluids.
The apparent viscosity of non-Newtonian fluids is an important property,
which can be used in several engineering and technological applications in the
place of Newtonian viscosity. The apparent viscosity rja of power-law and
Herschey-Bulkley fluids is defined by the equation
.n-l
(4-9)
In pseudoplastic (shear-thinning fluids), (n-l) < 0, and therefore the apparent

viscosity decreases as the shear rate y is increased.
Shear Rate
Figure 4.3 Shear stress C^-shear rate (y) diagrams for Newtonian (1), Bingham
(2), pseudoplastic (3), and dilatant (4) fluids.
70 Chapter 4
Specialized rheological models have been applied to certain fluid foods,

such as the Casson model for chocolate:
ras = r^+Kcy0'* (4-10)
The Casson plastic viscosity rjCa is calculated as the square of the Casson
coefficient (Rao, 1999):
Ka=(KJ2 (4-11)
The Mizrahi-Berk model (Eq. 4-12) is a modification of the Casson equa-

tion, and it has been applied to concentrated orange juices (Mizrahi and Berk,
1972):
T™ = *„«*+&?" (4-12)
The rheological constants (Kc, n) are characteristic for a fluid at a given

temperature/concentration.
2. Time-Dependent Viscosity
Many non-Newtonian fluid foods of complex structure exhibit time-
dependent rheology, i.e. their apparent viscosity at a given shear rate changes sig-
nificantly with time of shearing. The most common time-dependent materials are
the thixotropic fluids, for which the apparent viscosity decreases with the time of
shearing. The rheopectic fluids exhibit the opposite behavior, i.e. the apparent vis-
cosity increases with the time of shearing. The time-dependent rheological behav-
ior is detected usually by the rheological diagram (T versus y), which forms a
characteristic loop, when ascending and descending values of stress rare plotted
against the corresponding shear rate y. In thixotropic fluids, the descending line
falls below the ascending, while the opposite behavior is observed in the rheopec-
tic fluids (Figure 4.4).
Empirical models have been proposed to descibe the thixotropy of fluid
foods, in which the shear stress is a function of time, with the initial and equilib-
rium stresses as constants.
VI
!_
«
CJ
JS
V)
Shear Rate
Figure 4.4 Shear stress (r)-Shear rate (y) diagrams (loops) for time-dependent fluids:
(1) thixotropic, (2) rheopectic.
C. Effect of Temperature and Concentration
In pure liquids, the effect of temperature on viscosity follows the Arrhenius

equation (2-31), which can be derived from the theory of rate processes. The same
equation has been applied to the viscosity 77 of Newtonian fluid foods, and to the
consistency coefficient K or the apparent viscosity rjaof power-law (non-
Newtonian) food materials (Rao, 1999):
= K0exp(Ea/RT) (4-13)
where K0 is a frequency factor (Pa s"), Ea is the energy of activation for viscous
flow (kJ/mol), T is the temperature (K), and R = 8.314 kJ /kmol K is the gas con-
stant.
72 Chapter 4
In Newtonian fluid foods, the energy of activation has been found to in-
crease from 14.4 kJ/mol (water) to more than 60 kJ/mol (concentrated clear juices
and sugar solutions).
Temperature has a major effect on the consistency coefficient K and the ap-
parent viscosity i]a of the non-Newtonian fluid foods, analogous to the effect on
Newtonian viscosity rj. The flow behavior index n is affected only slightly by
temperature (a small increase at high temperatures). The energy of activation for
flow in non-Newtonian fluids is significantly lower than the corresponding value
for Newtonian fluids of the same solids concentration (Saravacos, 1970). In sus-
pensions of fluid foods of high non-soluble solids concentration, like fruit or vege-
table pulps, Ea may be lower than the activation energy for viscous flow of water
(14.4kJ/mol).
The observed strong effect of temperature on the viscosity of viscous New-
tonian fluid foods (concentrated clear juices, edible oils) is similar to the effect on
the viscosity of nonpolar viscous liquids, such as mineral oils, as is described by
the Lewis-Squires Eq. (2-33).
Concentration of soluble solids (°Brix) and insoluble solids (e.g. pulp) has a
strong non-linear effect on the viscosity of Newtonian fluid foods, the consistency
coefficient K, and the apparent viscosity of non-Newtonian foods. Two similar
exponential models, one for °Brix and a second for % pulp, were proposed by Vi-
tali and Rao (1984a, 1984b) for concentrated orange juice, of the general form:
K = K0exp(BC) (4-14)
where K0 is a frequency factor, C is the concentration and B is a constant.

The combined effect of temperature and solids concentration can be ex-
pressed by combining Eqs. (4-13) and (4-14):
K = K0 exp [ (Ea / RT) +BC] (4-15)
The additive model assumes no temperature-solids concentration interac-

tion. This may not be true when temperature affects the solids structure and parti-
cle size in the suspension, e.g. by hydrolysis of macromolecules, coagulation of
colloids, and breakdown or buildup of agglomerates.
The energy of activation for viscous flow Ea is estimated at a constant shear
rate, usually at 100 (1/s) (Saravacos, 1970; Rao, 1999). However, the structure of
some food suspensions of high particle (pulp) concentration may be changed due
to this relatively high shear rate. For this reason, in such cases, a lower shear rate
may be preferable. Prentice and Huber (1983) used a shear rate of 10 (1/s) in
evaluating the effect of temperature on the rheology of applesauce.
D. Dynamic Viscosity
The rheological characterization of complex semisolid foods requires, in ad-
dition to the shear viscosity 77, the dynamic viscosity 77", which is determined by
oscillating instruments at various frequencies. Three basic (constitutive) equations
are used to simulate the experimental rheological data, i.e. Newton's, Hooke's,
and Maxwell's (Kokini, 1992).
In dynamic rheological tests, the stress or strain is changed periodically (si-
nusoidally) with time at a fixed frequency CD. The complex stresses and strains are
related to the storage and loss moduli of the material, G 'and G "respectively.
The Bird-Carreau constitutive model, derived for polymer solutions, repre-
sents the entire deformation of a material. Thus, the shear and dynamic viscosities
(77 and 77') are estimated from the equations:
77'= Y —— ——2 (4-17)
where 77^ is the shear viscosity of p element, y is the shear rate (1/s), co is the fre-
quency of oscillation (1/s), and A/, /L2 are time constants (s).
When the shear and dynamic viscosities of food suspensions, like mayon-
naise and margarine, are plotted against shear rate or oscillation frequency on log-
log scales, parallel straight lines with negative slopes are obtained (Kokini, 1992).
In rheology, the dimensionless Deborah number (De) is an index of the fluid
or solid behavior of the material. It is defined as the ratio of the time of deforma-
tion tD over the time of observation tm and it can be estimated from the viscosity of
the continuous phase 77,,, the shear rate y, and the plateau storage modulus G0:
De = (tD/t0) = (rlsy/G0) (4-18)
Liquid-like behavior is characterized by small De numbers, while large De

numbers correspond to solidlike materials (Rao, 1999).
74 Chapter 4
III. VISCOMETRIC MEASUREMENTS
A. Viscometers
The shear viscosity of Newtonian fluids and the rheological constants of the
non-Newtonian materials are determined using several instruments, which basi-
cally measure the shear stress versus shear rate at a given temperature. The exter-
nal stress (force/area) is applied at steady state, usually stepwise, either in ascend-
ing or descending order. The stress takes the form of pressure drop in a capillary
tube, or mechanical torque in a rotational system. The resulting rheogram is util-
ized to extract rheological data for the material under the specific measurement
conditions.
Three common types of viscometers are used in most fluid food applica-
tions, i.e. the tube/capillary, the rotational, and the cone-and-plate viscometers
(Figure 4.5). Some other types of instruments are used in special cases, e.g. the
parallel plate, the slit, and the falling ball viscometers. Details on viscometers are
provided by the manufacturers of scientific instruments. Lists and descriptions of
viscometers can be found in the literature of rheology, e.g. van Wazer et al.
(1963), Whorlow (1980), Bourne (1982, 1992), and Rao (1999).
In food process control, special sensors are used to monitor and control the
viscosity of a material, if changes of this property are very important during proc-
essing. A typical example is the hot wire viscometer, which can be used to monitor
milk clotting in cheese tanks, or enzymatic hydrolysis of starch (Sato et al., 1990).
Its operation is based on the change of heat transfer rate on the surface of a hot
wire, caused by a viscosity change.
1. Capillary Tube Viscometer

The tube viscometer (Figure 4.5a) is based on measuring the flow rate (shear
rate) of a fluid in a capillary or small diameter smooth tube at constant pressure
drop (shear stress). For a Newtonian fluid, flowing through a straight tube of circu-
lar cross section with diameter (D, m) and length (L, m) under a pressure drop
(AP, Pa), the Poiseuille equation is applicable:
D(AP) /4L = ri(32Q/ic D3) (4- 1 9)
where Q is the volumetric flow rate (mVs) and rj is the viscosity (Pa s). By com-
paring Eqs. (4-19) and (4-1) it follows that the shear stress rand shear rate yfor
Newtonian fluids are given by the relationships:
T = D (AP) /4Landy=32Q/ (n D3) (4-20)

AP
a. Tube Viscometer
b. Rotating Coaxial Viscometer
<-
^ ->
TO
c. Cone-and-Plate Viscometer
Figure 4.5 Common viscometers a) capillary/tube; b) rotating coaxial; c) cone-and-plate.

76 Chapter 4
For non-Newtonian fluids, the shear stress is given by the same relationship,
but the shear rate is a function of the rheological constants K (Pa sn) and n:
Y = [(l+ 3n) / 4n][ 32Q / (nD3)] (4-21)
Therefore, the power-law model for capillary tube flow becomes:
D(AP)/4L =K[(l+3n)/4n]"[32Q/(nD3)]" (4-22)
Equations (4-19) and (4-22) apply to the laminar flow in tubes, i.e. when the
Reynolds number (Re) is lower than 2,000. For flow of Newtonian fluids in circu-
lar tubes of diameter (D, m), Re = (D u p)/r/, where u is the mean velocity (m/s),
p is the density (kg/m3), and 77 is the viscosity (Pa s).
For power-law and Herschel-Bulkley fluids, the (Re) number is calculated
from the equation
Re = [(D"u -'" p)/(8n~1 K)] [ (4n) / (3n + 1)] (4-23)
The velocity profiles of non-Newtonian flows in a tube viscometer can be

measured using nuclear magnetic resonance (McCarthy et al, 1992). The profile
of CMC solutions was as predicted by the laminar flow equations, while the pro-
file of tomato juice showed a significant deviation.
The capillary tube viscometers require no calibration, since the rheological
constants can be determined from fundamental flow equations. They are suitable
for both Newtonian and non-Newtonian fluids, and they can handle suspensions of
relatively large particles. However, they require more time for preparation and
measurement than the rotational viscometers, which are preferred for routine ap-
plications. In tube viscometers, very high shear rates at the wall can be obtained,
when small tube diameters are used. Slip flow near the wall may be a problem
with fluid suspensions of large particles.
2. Rotational Viscometers
The most common rotational viscometer is the Couette or concentric cylin-
der rheometer (Figure 4.5b).
For Newtonian fluids the viscosity rj is given by the empirical equation
(Rao, 1999)
jj = CM/n (4-24)
where M is the applied torque (N m), /2is the rotational velocity (1/s) and C is the
instrument constant (1/m ), which, for the concentric cylinder system, becomes:
C = (l/4xh)[(l/ri)2-(l/rQ)2J (4-25)
The shear rate of non-Newtonian fluids in rotational viscometers is esti-

mated from empirical equations as a function of the rotational velocity Q, the ratio
of the radii (rt/r^, and the flow behavior index n.
In concentric cylinder systems, narrow gaps, e.g. (rt / rj = 0.95 are required
to insure laminar flow. Fluid foods, containing large suspended particles, cannot
be measured in narrow-gap viscometers, and other instruments are more suitable,
e.g. capillary tube.
Simpler rotational viscometers, e.g. rotating plates, bobs or spindles in rela-
tively large fluid volumes, are used in many routine measurements of Newtonian
fluids. Such instruments are not suitable for non-Newtonian fluids, since the ap-
plied shear rate cannot be estimated accurately. However, in some systems, em-
pirical relationships of rotational velocity Q and shear rate y can be used to con-
struct the rheogram (T vrs. f) of the non-Newtonian fluid.
3. Cone-and-Plate Viscometer
The principle of cone-and-plate viscosimeter, or Weissenberger rheogo-
niometer, is shown in Figure 4.5c. This instrument is suitable for non-Newtonian
fluid suspensions, containing small particles. The shear stress rand shear rate y are
calculated from the equations
T =3M/r0A (4-26)
(4-27)
where M (N m) is the torque, r0 (m) is the radius of the plate, and A (m2) is the
area of the cone.
For measurements on non-Newtonian fluids, the cone/plate angle should be
small (0 < 5°), usually 2-3°. Small samples should be used with this instrument.
In both rotational and cone-and-plate viscometers the shear rate is usually
varied stepwise, either in increasing (ascending) or decreasing (descending) order.
78 Chapter 4
B. Measurements on Fluid Foods

In rheological measurements of fluid foods, significant variations are ob-
served on the viscometric data, which may be due to calibration of the instrument
or to changes in the structure of the food material.
Accurate calibration of instruments is essential for non- Newtonian and
time-dependent fluid foods (Sherman, 1984; Bourne, 1992). Standardization of the
instrument and the measuring procedure is necessary. Particular attention should
be paid to fluid dispersions, whose structure may change remarkably (breakdown
or agglomeration) during sample preparation and transfer to the measuring system.
Dispersions of fluid foods develop a complex structure, depending on the
size, shape and concentration of the suspended particles. When subjected to in-
creasing shear or stress, the suspensions may break down gradually, especially at
low shear stresses. These changes are caused by breakdown of particle agglomer-
ates and untangling of non-spherical particles.
Many fluid foods do not obey the empirical non-Newtonian models over the
entire range of shear rate, available in the commercial instruments. Therefore, it is
important to specify the data and model range, which, preferably, should be simi-
lar to the range of application in process engineering or product quality.
Temperature has a strong effect on the viscosity of Newtonian fluid foods,
especially in highly viscous products, such as syrups, honey, and edible oils. Vis-
cous heating during viscometric measurements of thick food fluids may result in
erroneous low viscosities. In general, temperature has little effect on the flow be-
havior index n of non-Newtonian fluid foods. The effect of temperature on the
consistency coefficient K is similar to the effect on the viscosity of Newtonian
fluids, obeying the Arrhenius equation. However, the energy of activation for vis-
cous flow Ea in non-Newtonian fluids is considerably lower than in Newtonian
materials. In several food suspensions and pulps, Ea may be lower than 14.4
kJ/mol, which is the energy of activation for viscous flow of pure water. This is an
indication that the consistency coefficient K is affected more by the structure than
by the temperature of the suspension
The problems of measuring the rheological properties of liquid foods were
investigated in the European cooperative research project, COST 90 (Prentice and
Huber, 1983). Eight laboratories from different countries participated in the study,
using exclusively concentric-cylinder and cone-and-plate viscometers. Some of
the results are analyzed and discussed, in relation to literature data, in Sections IV
and V of this chapter.
IV. RHEOLOGICAL DATA OF FLUID FOODS
Due to the complexity of food composition and structure, rheological data

should be obtained by standardized measurements on each specific material. The
technical literature contains a wide variety of such data, and new results continue
to be reported in recent years. Collections of rheological data of fluid foods have
been published by Steffe et al. (1986), Kokini (1992), Urbicain and Lozano
(1997), and Rao (1999). This critical review includes typical viscometric data
from a wide variety of fluid foods, classified as follows: edible oils, sugar solu-
tions and clarified juices, suspensions of plant materials, and emulsions and com-
plex suspensions.
A. Edible Oils
The edible or cooking oils and fats are generally considered as Newtonian
fluids, if they do not contain particles or emulsions, which may enter the oil phase
during processing and use. Collaborative measurements on a commercial cooking
oil (mixture of soybean and rapeseed) showed a slight deviation from Newton's
law (Prentice and Huber, 1983). Regression analysis of the rheological data, ob-
tained in seven laboratories, using coaxial-cylinder and cone-and-plate viscome-
ters at 25°C, resulted to the following equation:
log (r) = -1.2766 + 0.99673 log (y) (4-28)
where the rheological constants are K = 0.052 Pa s" and n = 0.99673.

According to this equation, the apparent viscosity (r\a = K /"'') of the oil de-
pends slightly on the shear rate, for example r/a = 52 mPa s at 7= 1 (1/s), and r/a =
51mPasat/=1000(l/s).
Temperature has a strong effect on viscosity, especially of viscous oils. The
Arrhenius equation yielded an energy of activation Ea = 28.3 kJ/mol in the tem-
perature range 25-50°C for the oil described by Eq. (4-28). Empirical equations of
viscosity as a function of temperature for specific oils have been proposed in the
literature (Rao, 1999). Typical viscosities of edible oils (Kokini, 1992; Rao, 1999)
are given in Table 4.1.
Table 4.1 Typical Viscosities of Edible Oils

Edible oil Temperature, °C Viscosity, mPa s
Corn oil 23.9 52.3
Soybean oil 23.9 54.3
Olive oil 40.0 36.3
Cocoa butter 25.0 124.1
80 Chapter 4
B. Aqueous Newtonian Foods
]. Sugar Solutions and Clarified Juices

Aqueous food fluids, including sugar solutions, honey, and clarified juices
(containing no paniculate matter) are considered, in general, Newtonian liquids.
However, the COST 90 collaborative measurements on 50°Brix sucrose solution at
25°C (Prentice and Huber, 1983) showed a slight non-Newtonian behavior with an
estimated flow behavior index n = 0.986 and a consistency coefficient K = 7.4
mPa s". This corresponds to an apparent viscosity rja = 6.9 mPa s at a shear rate of
Sugar solutions and clear juices are characterized by sharp decrease of vis-
cosity at higher temperatures, according to the Arrhenius equation. Concentration
has a strong positive effect on viscosity, and the combined tempera-
ture/concentration effect can be expressed in most cases by empirical exponential
equations, similar to the generalized Eq. (4-15).
Figure 4.6 compares the viscosities of clarified apple juice (Saravacos,
1970) and sucrose solutions (Perry et al., 1984) at three different temperatures, 20,
40, and 60°C. It appears that the viscosities of the two fluids are similar, except at
concentrations higher than 60°Brix, where the apple juice becomes more viscous,
probably because of the increased concentration of nonsugar solids.
Figure 4.7 shows that the viscosity of concord grape juice tends to be higher
than the viscosity of the corresponding sucrose solution, particularly at high con-
centrations. This difference may be caused by the precipitation of some com-
pounds of grape juice, which become insoluble at higher concentrations, for ex-
ample tartrates. These compounds are known to precipitate during the storage of
grape juices and wines at low temperatures.
1000
^±ES:^3^di=Ei^:S3^t
• apple juice
, . ,,,,
• sucrose solutions
VI
«
CM
u
w
i>
o.i
Figure 4.6 Comparison of viscosities of depectinized apple juice and sucrose solutions at
20-60°C. (From Saravacos, 1970, and Perry et al., 1984.)
1000
~.( • grape juice

• sucrose solutions
Figure 4.7 Comparison of viscosities of Concord grape juice and sucrose solutions at
40°C. (From Saravacos, 1970, and Perry et al., 1984.)
82 Chapter 4
Figure 4.8 shows the energies of activation for viscous flow of sucrose solu-
tions (Perry et al., 1984), grape juice (Saravacos, 1970), and apple juice (Rao,
1999) as a function of concentration.
The energies of activation Ea of the two juices are close to those of sucrose
solutions, increasing sharply at higher sugar concentrations. The extrapolated en-
ergy of activation at 0°Brix corresponds to the Ea value of water (14.5 kJ/mol),
which was estimated from viscosity-temperature data of the literature (Perry et al.,
1984)
The energy of activation for viscous flow increases as the molecular weight
of the dissolved sugar is increased. The viscosity ij of a sugar solution can be ex-
pressed by an empirical model, analogous to the Arrhenius equation (Chirife and
Buera, 1994):
77 = a exp (EX) (4-29)
where X is the mole fraction of the sugar, a is a constant close to 1, and £ is a

characteristic constant, similar to the Arrhenius activation energy. Calculated val-
ues of constant E are: 27.93 for glucose, 57.19 for sucrose, and 94.46 for corn
syrup of 35.4 DE (dextrose equivalent).
T'\ sucrose solutions

grape juice
™ f-^ • apple juice
Figure 4.8 Activation energies for viscous flow of sucrose solutions (Perry et al., 1984),
grape juice (Saravacos, 1970), and depectinized apple juice (Rao, 1999).
Molasses (thick liquid residues of sugar manufacturing) have high viscosi-

ties, e.g. 6600 to 374 mPa s in the temperature range 21-66°C (Hayes, 1987), from
which an activation energy of 51.3 kJ/mol was estimated.
Clarified cherry juice behaves as a Newtonian fluid in the range 22-74°Brix
and 5-70°C with energies of activation 14.4-61 kJ/mol (Giner et al, 1996). The
combined effect of temperature and concentration on viscosity is described well
with an empirical exponential model similar to Eq. (4-15). Similar activation ener-
gies (26.6-64.4 kJ/mol) were obtained in clarified crab (small) apple juice (Cepeda
et al., 1999). Clarified orange juice behaves as a Newtonian fluid in the range 30-
63.5°Brix with energies of activation Ea in the range 17.7-40 kJ/mol (Ibarz et al.,
1994). The relatively low Ea values may be due to the presence of colloidal parti-
cles in the clarified juice.
Similar rheological behavior is shown by other clarified fruit juices: apple
and pear juices and concentrates (Ibarz et al., 1987), peach juices and concentrates
(Ibarz et al., 1992a), and black currant juices (Ibarz et al., 1992b). Clarified banana
juice (20-79.7°Brix) has viscosities ranging from 1 to 6000 mPa s in the range 30-
70°C, and energies of activation for viscous flow 25-78 kJ/mol (Khalil et al.,
1989).
2. Honey and Sugar Extracts

The viscosity of honeys depends strongly on the concentration of soluble
solids (°Brix), temperature, and plant origin. Most honeys have a concentration
between 75-83°Brix, and their viscosity at 20°C is in the range of 4-20 Pa s. Tem-
perature has a strong effect, with corresponding high energies of activation Ea.
Utilizing the viscosity-temperature data (10-80°C) of five types of honey, pub-
lished by Rao (1999), Ea values of 65-70 kJ/mol were obtained, which are in
agreement with the generalized diagram of Figure 4.8. Chinese honeys (Junzheng
and Changying, 1999) have lower sugar concentrations (71.5-80.2°Brix) and vis-
cosities (0.33-6.30 Pa s at 20°C) with estimated activation energies 60-65 kJ/mol.
Australian honeys have high sugar concentrations (82.4-83.3°Brix) with high vis-
cosities (about 100 Pa s at 10°C), and a strong effect of temperature (Bhandari et
al., 1999).
Licorice extract of soluble solids concentration 3-50°Brix exhibited Newto-
nian behavior in the temperature range of 10-60°C, with energies of activation
14.4-61 kJ/mol (Maskan, 1999).
The viscosity data of honey, presented by Rao (1999), and molasses (Hayes,
1987) are plotted in Figure 4.9, snowing a nearly exponential drop of viscosity
with increasing temperature.
84 Chapter 4
0.1 -L
30 40 50
Temperature (°C)
Figure 4.9 Viscosities of honeys and molasses.
3. Other Clear Solutions

The viscosity of ethanol at 20°C is 1.2 mPa s, and that of glycerol is 1490
mPa s (Lewis, 1987). The viscosity of wines is higher than that of water, ranging
for 1.3-1.67 mPa s for ordinary wines at 25°C, and 1.95-2.45 mPa s for fortified
wines, containing glycerol (Rao, 1999). The energy of activation for viscous flow
of wines is in the range of 18.8-28.2 kJ/mol, i.e. significantly higher than that of
pure water.
The viscosity of fermenting musts is higher than that of wines, due to the
presence of dissolved sugars and suspended particles in the liquid (Lopez et al.,
1989), For white musts, the viscosity varies in the range of 3-4 mPa s at 14-22°C,
with activation energy about that of water (14.4 kJ/mol). The viscosity of beer is
close to that of wine, i.e. 1.3 mPa s at 20°C (Lewis, 1987). The viscosity of salt
(sodium chloride) solutions and brines, depends on the concentration of the ionic
species, for example 2.7 mPa s at 22% salt and 2°C (Hayes, 1987).
C. Plant Biopolymer Solutions and Suspensions

Plant hydrocolloids (gums and starches) are components of many fluid
foods and they are responsible for their non-Newtonian behavior. They are pre-
sent, in relatively low concentrations, as molecular solutions, colloidal dispersions,
and particulate suspensions. Dispersions of plant gums contain macromolecules of
coil configurations, while starch suspensions contain granular particles.
Collaborative measurements, within the COST 90 European project, were
made on solutions of guar gum, carrageenan gum, xanthan gum, and Karaya gum,
using coaxial-cylinder and cone-and-plate viscometers. The results showed high
consistency coefficients (K), some yield stresses (TO), and flow behavior indices
(n) lower than (1), an indication of shear-thinning (pseudoplastic) behavior.
Published shear stress r versus shear rate ^data of 1% gum solutions (Pren-
tice and Huber, 1983) were analyzed statistically, and the resulting regression lines
are shown in the logarithmic plots of Figures 4.10 to 4.13. The Theological con-
stants K and n of the power-law model (Eq. 4-8) are shown in Table 4.2:
The rheological properties of the gums depend strongly on the concentration
and type of macromolecules. Xanthan gums show high consistency and low flow
behavior indices, presumably due to the high molecular weight and the large col-
loidal particles in the solution.
Table 4.2 Rheological Constants of 1% Food Gum Solutions at 25°C

Food gum Consistency coefficient Flow behavior index
_________________K, Pa s"____________n______
Guar 1.24 0.625
Carrageenan 1.40 0.485
Xanthan 9.21 0.183
Karaya_____________1.23____________0.465
86 Chapter 4
1000
0.1
0.01
0.001
0.001 10 1000 100000
Shear Rate (1/s)

Figure 4.10 Rheological data of 1% guar gum solution at 25°C. (Data from Prentice and
Huber,1983.)
1000
Carrageenan gum
solution
0.1
0.001 0.1 10 1000100000
Shear Rate (1/s)
Figure 4.11 Rheological data of 1% carrageenan gum solution at 25°C. (Data from Pren-
tice and Huber, 1983.)
1000
0.001 0.1 10 1000100000

Shear Rate (1/s)
Figure 4.12 Rheological data of 1% xanthan gum solution at 25°C. (Data from Prentice
and Huber, 1983.)
1000
0.1
0.01
0.001 10 1000 100000
Shear Rate (1/s)

Figure 4.13 Rheological data of 1% karaya gum solution at 25°C. (Data from Prentice
and Huber, 1983.)
88 Chapter 4
Tube viscometry of aqueous pectin solutions showed pseudoplastic behavior

(Saravacos et al., 1967). Plots of shear rate rversus sear rate /for 2.5% and 5.0%
pectin solutions at 25°C (Figure 4.14) show the following rheological properties:
K= 3,590 Pa sn and n = 0.767 for the 2.5% solution; K = 57,420 Pa sn
and « = 0.822 for the 5.0% solution.
The power-law model applies to carboxy-methyl-cellulose (CMC) solutions
(0.5-1.5%) in the temperature range 25-125°C, which are of interest to aseptic
processing of foods. The rheological properties (K, n) were obtained using a sealed
pressure rheometer (Vais et al., 1999). The consistency coefficient of the 1.5%
solution decreased from 17 to 3.4 Pa sn, and the flow behavior index n remained
nearly constant at 0.43 at temperatures 25-125°C.
Starch suspensions and solutions exhibit complex rheological properties,
due to the diverse particulate and molecular composition and the physicochemical
changes, induced by temperature (gelatinization) and molecular interactions with
other food components, like proteins. Rheological characterization of starch sys-
tems requires not only shear stress-shear rate data, but also viscoelastic measure-
ments and particle and biopolymer characterization (Rao, 1999).
1000 -,
4 Pectin
— 2.5%
— 5.0%
a
a-
- 100
10
10 100 1000
Shear Rate, 1/s
Figure 4.14 Rheological data of aqueous pectin solutions (From Saravacos et al., 1967.)
D. Cloudy Juices and Pulps

The presence of hydrocolloids (gums) and suspended particles (e.g. gran-
ules or fibers) in fluid plant foods changes the rheological properties into non-
Newtonian, usually pseudoplastic fluids.
Aqueous suspensions of dietary fibers, from orange or peach, exhibit strong
non-Newtonian behavior, particularly at concentrations higher than 5%
(Grigelmo-Miguel et al., 1997). The energy of activation for viscous flow is low,
3-18.4 kJ/mol, and the effect of concentration on the consistency coefficient of the
suspension is higher than that of temperature.
Rheological measurements on applesauce, using a capillary tube viscometer,
yielded the values K = 12.7 Pa sn, and n = 0.28 (Saravacos, 1968). The consistency
coefficient K decreased from 12.7 to 0.49 Pa sn and the flow behavior index n in-
creased slightly from 0.28 to 0.35, when the pulp content was reduced by passing
the applesauce through an 0.04 inch (1 mm) screen. Similar results on the
rheological constants of applesauce were obtained in the COST 90 cooperative
measurements (Section V of this chapter).
Addition of sugar (glucose) to banana pulp reduces the apparent viscosity
and increases the temperature dependence of the juice. The activation energy in-
creased from 8 to 54 kJ/mol when the sugar concentration increased from 21 to
51°Brix (Guerrero and Alzamora, 1997). A similar change of the rheological prop-
erties and activation energy by glucose addition was observed on peach, papaya
and mango purees (Guerrero and Alzamora, 1998). The combined effect of con-
centration and temperature follows the generalized exponential model of Eq. (4-
15).
Cloudy apple juice becomes a non-Newtonian fluid at concentrations higher
than 40°Brix, with flow behavior indices n = 0.65-0.80, and activation energies
lower than the clarified juice, e.g 25.5 kJ/mol versus 35 kJ/mol at 50°Brix (Sara-
vacos, 1970). A similar rheological behavior was observed on raspberry juice,
which changed from Newtonian to non-Newtonian above 25°Brix, with « = 0.90-
0.60 (Ibarz and Pagan, 1987).
Ultrafiltration of orange juice removes part of the particles and hydrocol-
loids (pectin), decreasing the consistency coefficient K, and increasing the flow
behavior index n and the activation energy (Hernandez et al., 1995). This treat-
ment increases significantly the heat transfer coefficient in the evaporation of or-
ange juice. Shear-thinning food fluids have improved heat transfer characteristics
in agitated kettles and heat exchangers, since their apparent viscosity is reduced
considerably by agitation (Saravacos and Moyer, 1967).
The power-law model of non-Newtonian fluids has been applied to various
suspensions of starch and pulp materials: cooked debranned maize flour with flow
behavior indices n = 0.258-0.668 (Bhattacharaya and Bhattacharaya, 1996); rice-
blackgram suspensions (28-44%TS) increased the (n) value from (0.3-0.4) to
(0.45-0.50) by fermentation, evidently due to a breakdown of biopolymers (Bhat-
tacharaya and Bhat, 1997).
90 Chapter 4
Enzymatic breakdown of starches and other biopolymers results in lower

viscosities and higher n values, such as the enzymatic extrusion of rice starch
(Tomas et al., 1997) and the enzyme treatment of mango pulp (Bhattacharaya and
Restogi, 1998). The rheology of tomato juice and tomato concentrates has re-
ceived special attention due to its importance in processing and in product quality.
Typical theological properties are: K = 0.22 to 12.9 Pa sn and n = 0.59 to 0.41 for
5.8 to 25.0% TS (coaxial- cylinder, Harper and El-Sahrigi, 1965); K = 0.22 to 52
Pa s" and n = 0.581 to 0.177 for 5.6 to 32.6°Brix (tube viscometer, Saravacos et al.,
1967).
The processing method has a significant effect on the rheology of tomato
concentrates. The "hot break" product is more viscous than the "cold break" mate-
rial. Thus, in the range 10-25°Brix, the lvalue of the "cold break" tomato concen-
trates decreased from (5-80 Pa sn) to (4-30 sn), and the activation energy from 22.7
to 17.0 kJ/mol, compared to the "hot break" product (Fito et al., 1983).
The particle size and pulp concentration strongly affect the consistency coef-
ficient K of tomato concentrates (Rao, 1999). An empirical rule is to scale the vis-
cosity by a factor of (total solids)2'5.
E. Emulsions and Complex Suspensions
Oil/water (o/w) food emulsions, like mayonnaise and salad dressings, are
non-Newtonian fluids with high consistency coefficients K and flow behavior in-
dices n lower than 1. Mayonnaise contains 70-80% oil particles (droplets) in the
size range 0.01-10 um, dispersed in an aqueous phase. Food emulsions are stabi-
lized by adsorption of biopolymers (gums, proteins, lecithin) on the particle sur-
faces (Rao, 1999). Because of their structure, emulsions may exhibit time-
dependent theological properties, as well as viscoelastic behavior.
Addition of sugar to emulsions changes significantly their theological prop-
erties. Thus, by adding 8% sugar to sunflower oil-water emulsions, the consistency
coefficient K of the power law model decreased from (2.6-3.6) to (0.6-2.2), while
the flow behavior index n remained nearly constant (n = 0.49). The activation en-
ergy Ea decreased from 31 to 10.7 kJ/mol (Maskan and Gogus, 2000).
Milk may be considered as dilute emulsion of fat globules in an aqueous
solution of lactose and other components. Single strength (non concentrated) milk
behaves as a Newtonian fluid with a viscosity higher than that of water (Kokini,
1992). Literature data on homogenized milk show viscosities decreasing from 3.4
to 0.6 mPa s, in the temperature range 0-80°C (Figure 4.15).
Concentration of milk by evaporation above 22.3%TS changes the rheology
to non-Newtonian (n = 0.89 at 42.4%TS), with a sharp increase of the activation
energy from 10 to 49 kJ/mol (Velez-Ruiz and Barbosa, 1998). The combined ef-
fect of temperature and concentration on the consistency coefficient K follows the
generalized model of Eq. (4-15). Freeze-concentrated milk showed a similar
rheological behavior (Chang and Hartel, 1997). The power-law model was found
applicable, with the flow behavior index decreasing from 1.0 to 0.89, and the acti-
vation energy increasing from 20 to 60 kJ/mol in the range of 20-40%TS.
Sodium caseinate suspensions behave as Bingham plastic materials, follow-
ing an empirical model similar to Eq. (4-15). The activation energy of casein sus-
pensions increased from 14.6 to 37.7 kJ/mol in casein concentrations 10-16%TS.
Buttermilk shows a thixotropic (time-dependent) behavior. The Herschel-Bulkley
model can be applied, using a structural correction factor (Butler and McNulty,
1995).
The flow properties of yogurt can be expressed by the power-law or the
Herschel-Bulkley model. However, since yogurt is a complex material, exhibiting
both fluid and semisolid (gel) properties, time-dependency (thixotropy) and vis-
coelasticity should be considered (Afonson and Maia, 1999). A strong degradation
of the yogurt may take place at high shear rate. The activation energy for viscous
flow at temperatures higher than 25°C increases sharply from 24 to 65 kJ/mol,
evidently due to action of thermophilic clotting bacteria (Benezech and Maingon-
nat, 1994).
The rheological properties of salmon surimi can be expressed by either the
Herschel-Bulkley or the Casson models, with the flow behavior index n in the
range of 0.58-0.75 (Bourami et al., 1997).
Table 4.3 shows typical rheological properties of food emulsions.
10 T-
20 40 60 80 100
Temperature (°C)
Figure 4.15 Viscosity of homogenized milk. (Data from Kokini, 1992.)

92 Chapter 4
Table 4.3 Typical Rheological Data of Food Emulsions at 25°C________

Food emulsion Consistency coefficient (K) Flow behavior index (n)
Pas"
Mayonnaise 6.4 0.55
Mustard 18.5 0.39
Margarine 297.6 0.074
Peanut butter 501.1 0.065
Cream, 40% fat 0.0069 (40°C) 1.0
Source: From Kokini, 1992.
V. REGRESSION OF RHEOLOGICAL DATA OF FOODS
Most of the literature data on the viscosity or Theological constants of foods

are available in the form of tables or diagrams at specific temperatures and
concentrations. More information can be gained by analyzing the data statistically,
and extracting a regression line, typical of a food product, or a group of similar
products. However, statistical analysis of the literature data is difficult, because the
measurements were made with different instruments on different products, and the
statistical samples are often small.
Rheological data obtained in the COST 90 cooperative measurements (Pren-
tice and Huber, 1983) are suitable for statistical analysis, and some regression
lines were presented in Section (IV.C) of this chapter. Additional regression lines
are presented in this section for applesauce and chocolate.
Approximate representative lines can be obtained by non-linear regression
of several data on a food material, obtained by different investigators, provided
that the statistical sample is large enough. Details of this regression technique are
given in Chapter 6.
From a review of the literature, rheological data on the following food prod-
ucts were found suitable for regression analysis: edible oils, applesauce, tomato,
orange, pear, and mango juices and concentrates, and chocolate.
A. Edible Oils
Literature data on various edible oils and fats were obtained from Kokini
(1992), Noureddini et al. (1992), and Rao (1999). The oils are assumed to be New-
tonian fluids. The reported viscosities ranged from 1.6 to 451 mPa s at tempera-
tures from 0 to 121°C. The viscosities are plotted versus the temperature in Figure
4.16.
The following form of the Arrhenius equation was applied for the calcula-
tion of the activation energy for viscous flow Ea:
77/ = 77
/ . exp[—-(—
^ ^ -——)]
» (4-30)
where 77 and TJO are the viscosities at temperatures T and T0, respectively, and R is
the gas constant (8.314 J/mol K).
For a reference temperature T0 = 25°C, the estimated viscosity of an "aver-
age" oil is 7j0 = 55 mPa s, and the activation energy Ea = 45 kJ/mol. These values
are comparable to the values (77 = 52 mPa s and Ea = 53.2 kJ/mol) obtained on a
typical edible oil, in the cooperative COST 90 project (Prentice and Huber, 1983).
1000 TZ
a.
s
20 40 60 80 100 120 140

Temperature (°C)
Figure 4.16 Regression line of viscosity data of edible oils.

94 Chapter 4
B. Fruit and Vegetable Products
1. Applesauce
Rheological data (shear stress versus shear rate) were obtained in seven
laboratories on applesauce of 22.5°Brix (screen opening 0.6 mm) at 25°C (Prentice
and Huber, 1983). The regression line of the power-law model yielded the follow-
ing rheological constants: K= 26 A Pa s" and n = 0.286 (Figure 4.17).
1000
I Apple Sauce |
1
0.001 0.01 0.1 1 10 100 1000
Shear Rate (1/s)
Figure 4.17 Rheological data of applesauce at 25°C. (Data from Prentice and Huber,
1983.)
2. Fruit /Vegetable Juices and Concentrates

Rheological data on tomato, orange, pear, and mango juices and concen-
trates, suitable for regression analysis, were obtained from Harper and El-Sahrigi
(1965), Fito (1983), Manohar et al. (1991), and Rao (1999).
The fruit and vegetable juices/concentrates, considered in this section, are
assumed to behave as non-Newtonian fluids, following the power-law or
Herschel-Bulkley models. The consistency coefficient K was estimated from the
following form of the generalized Eq. (4-15), Krokida et al. (2000):
(4-31)
The flow behavior index n is assumed to be a linear function of concentra-

tion and independent of temperature, according to the equation:
n = n0-bC (4-32)
where K = K0 when C = 0 and T = To, n = n0 when C = 0. C is the concentration

and B, b are constants.
The regression lines for the four products are shown in Figures 4.18 to 4.21.
The consistency coefficient K increases exponentially with the concentration,
while the flow behavior index n decreases slightly. Concentration has a stronger
effect on K of tomato than the other three fruits. The higher activation energy for
orange and mango may be due to the higher sugar content.
Table 4.4 Estimated Values of the Parameters of Eqs. (4-31) and (4-32)
Material K0. Pa s" B Em kJ/mol n0 b
Tomato 1.27 0.149 15.8 0.403 0.0028
Orange 9.28 0.077 35.0 0.950 0.0034
Pear 2.15 0.087 16.1 0.348 0.0000
Mango 1.85 0.089 32.1 0.332 0.0017
(Q Flow Behavior Index (-)
C Consistency Coefficient (Pa s")
3 o
o
00
o_
o
OQ
o'
n
o
o
H
o
to
O
J
u
T3
ff
(Q Flow Behavior Index (-) o
C Consistency Coefficient (Pa s")
p o_
3 o o o
o (Q
o'
D>
to
\ TJ
CO
\. a
fl>'
\ in
O
n
o
3
O
o>
3
O
o
C a a.
o
\ u>
8 3
y \
8-
-a
I
c
98 Chapter 4
.-*'^,
^^^
c
M
« 100 -
:
e
r :
^^^' *^»————
=—
.^"^^^^'^
l
J> 10 - _^* ^<^c
cu>
e
£Ift
*^^-^^^ -^^^^^
ix^^^"*^
-^^
I
•
——— Temperature (°C)
uo —————— • 40 —
——————— • 60
n1.
20 40 60
Concentration (% solids)
i.o
•8
_o
R
U
oa
20 40 60
Concentration (% solids)
Figure 4.20 Rheological data of pear juice and concentrates.

(Q Flow Behavior Index (-) Consistency Coefficient (Pas ) <D
C O_
3 P O
o (Q
k) o'
0)
po
n O
•o
<D
to'
to
O
Q o C
a
n OL
-n
o
sa o
Q.
a (0
o
I 8 a
65
to
to
100 Chapter 4
C. Chocolate
The Theological data on chocolate at 40°C, obtained in the COST 90 project,

were analyzed, assuming that the Casson model (Eq. 4-10) is applicable. The re-
gression line, shown in Figure 4.22, gave the following Theological constants: TO =
0.5
27.0 Pa and Kc = 1.68 (Pa s)™.
10000 -p=
I
1000
CO
'I
0.001 0.01 0.1 1 10 100 1000
Shear Rate (1/s)
Figure 4.22 Rheological data of chocolate at 40°C. (Data from Prentice and Huber,
1983.)
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Transport of Water in Food Materials
I. INTRODUCTION
The transport of water in food materials is of fundamental importance to

several food processing operations, as well as to various physical, chemical and
microbiological changes of food products.
Water transport within the food material is the main rate-controlling mecha-
nism in drying operations (Keey, 1972), and various techniques have been devel-
oped to increase the drying rate, resulting in reduction of the cost of drying, and
improvement of food quality. Water transport to and from food products during
storage is important in controlling food preservation and food quality.
Although various mechanisms have been proposed to explain water trans-
port in food materials, the diffusion model yields satisfactory results for engineer-
ing and technological applications. The water chemical potential model appears to
be more appropriate for cellular foods (Gekas, 1992), but the required physical and
chemical properties are difficult to determine and they may change during meas-
urement.
The mechanisms of water transport in solids are reviewed in Section II, with
emphasis on the diffusion in polymers, which constitute the structural backbone of
food materials, and for which basic literature is available (Vieth, 1991). The meth-
ods of measurement and calculation of mass diffusivity are discussed in detail in
Section III.
Food structure plays a decisive role in water transport processes within the
food materials (Saravacos, 1998). Model food materials, based on granular and
gelatinized starch, are convenient experimental materials in studying the mecha-
nism of water transport in various food structures (Section IV). Characteristic
moisture diffusivities in the main classes of foods are given in tabular form in Sec-
tion V. A more detailed and unified regression analysis of the literature data on
moisture diffusivity in foods is presented in Chapter 6.
105
106 Chapters
II. DIFFUSION OF WATER IN SOLIDS
The diffusion of water in simple gases and liquids can be analyzed and pre-
dicted by molecular dynamics and empirical correlations, as discussed in Chapter
2. The transport of water and other small molecules in solids and semisolids is of
particular importance to foods and food processing systems. The mechanism of
water transport in solid materials is less well understood than in fluid systems, and
empirical approaches are often used to estimate the transport properties.
The transport of water is of fundamental importance to the drying of solids
(Keey, 1972). In the drying process, liquid water is removed first by a hydrody-
namic gradient and capillary forces. As drying progresses, water is removed by
vapor diffusion, and finally by desorption from the solids.
The transport of water in solids is usually assumed to be controlled by mo-
lecular diffusion, i.e. the driving force is a concentration gradient (dC/dz) or the
equivalent moisture content gradient (dX/dz). For simplified analysis and calcula-
tions, one-dimensional diffusion is considered, and the Pick diffusion equation is
applied:
(5-1)
dt dz 8z
The diffusion coefficient D of water in solids is usually defined as the effec-

tive moisture diffusivity, which is an overall transport property, incorporating all
transport mechanisms.
In addition to diffusion, water may be transported by other mechanisms,
such as hydrodynamic and capillary flow, depending on the structure of the solid
material.
The effective diffusivity D of a molecular species A in a porous solid is
much lower than the diffusivity of A in a gas medium B, DAB, according to the
equation (Geankoplis, 1993):
D = (s/T)DAB (5-2)
where sis the bulk porosity and ris the tortuosity of the solids (T> 1). The tortu-
osity is a measure of the tortuous (complex) path of the diffusing molecules,
T=Lg/L, where Le is the equivalent length of the diffusion path, and L is the
straight-line thickness of the sample.
Equation (5-2) is applied to catalysts and other solids of fixed structure, and
a reliable tortuosity can be determined experimentally. However, determination of
tortuosity in food materials is difficult because food structure changes substan-
tially during food processing and storage. For this reason, the effective moisture
diffusivity is determined directly by experimental techniques.
Transport of Water in Food Materials 107
Molecular diffusion is the prevalent mass transport mechanism in most food

materials. In molecular diffusion, the mean free path of the diffusing molecules is
much shorter than the pore or capillary diameter, and most collisions are between
the molecules than with the walls.
In Knudsen diffusion, the mean free path of the molecules is near the size of
the pore or capillary diameter, and the molecules collide more with the walls than
with each other (Brodkey and Hershey, 1988).
The Knudsen diffusion coefficient DK is given by the equation
DK = 48.5d0(T/MA)"'2 (5-3)
where d0 is the pore (capillary) diameter, T is the temperature, and MA is the mo-
lecular weight of the diffusing species.
Equation (5-3) indicates that the Knudsen diffusion coefficient DK in gases
is a function of the square root of temperature, in contrast to the molecular diffu-
sivity D, which is proportional to the (3/2) power of the temperature equation (2-
28).
Other diffusion mechanisms, which are of minor importance to food sys-
tems at normal conditions, are:
• Surface diffusion (mass transport by surface concentration gradients)
• Molecular effusion (passage of molecules through a small aperture in a thin
plate into a vacuum)
• Thermal diffusion (mass transport due to a temperature gradient)
The capillaries in Knudsen diffusion are much longer than in molecular ef-
fusion. Knudsen diffusion may be prevalent in capillary systems under vacuum, as
in freeze-drying, where the mean free path of the molecules is very long.
A. Diffusion of Water in Polymers

An indication of the mechanism of water transport in polymers is the sorp-
tion kinetics test on a sample of the material. Gravimetric sorption data (Section
III) in a polymeric sample (usually a film) are compared to the generalized sorp-
tion equation (Peppas and Brannon-Peppas, 1994):
(M/Me)=kf (5-4)
where M and Me are the moisture contents after sorption time t and at equilibrium,
respectively, k is a constant, and n is the diffusion index.
The diffusion index characterizes the type of diffusion in the material:
• n = 0.5 Fickian diffusion

• 0.5 < n < 1 non-Fickian diffusion
• n = 1 type II diffusion
108 Chapters
In the case of Fickian diffusion, the constant k of Eq. (5-4) is related to the
diffusivity D and the sample thickness L by Eq. (5-5), which is derived from Eq.
(5-9):
k = 4(D/nl2) (5-5)
Thus, sorption kinetics data at a constant temperature can be used to deter-

mine D.
The effective moisture diffusivity D depends strongly on the physical struc-
ture of the polymeric material. Thus, values of D of the order of 10'14 are charac-
teristic of the glassy state of foods, while D increases by nearly 1000 times above
the glass transition temperature (rubbery state).
As water enters the polymeric network, mechanical stresses are developed,
resulting in chain rearrangements and significant changes of the polymer structure.
These changes are evidenced by characteristic swelling and relaxation phenomena,
which affect substantially the transport mechanism and transport properties of
water in the polymer. Swelling reduces the density of the polymer material and the
glass transition temperature Tg, resulting in increased moisture diffusivity.
The relative importance of relaxation to diffusion is expressed by the diffu-
sional Deborah number De:
De = A/t = ZD/L2 (5-6)
where /I is the characteristic relaxation time, t = L2/D is the characteristic diffusion

time and L is the film (slab) thickness.
The following diffusion types can be indicated by the Deborah number:
• De » 1, Fickian diffusion: relaxation time is much higher than diffusion time

• De « 1, Fickian diffusion: very fast relaxation
• De = 1, Case II diffusion : diffusion is controlled by molecular relaxation
Equation (5-6) indicates that the Deborah number is inversely proportional

to the square of sample thickness, i.e. the type diffusion mechanism depends
strongly on the dimensions of the material. This dependence is evidenced in the
determination of moisture diffusivity D by various techniques, when different val-
ues of D are obtained for the same material. Thus, smaller D values are obtained
by the sorption kinetics technique, which uses thin firms, than by the drying rate
method, which uses thicker samples. In the drying method, a higher porosity of the
thick sample is obtained, increasing further the moisture diffusivity.
III. DETERMINATION OF MASS DIFFUSIVITY IN SOLIDS
The determination of mass diffusivity in solid and semisolid materials is

essential for the quantitative analysis and control of several mass transfer opera-
tions and applications, such as drying, adsorption, extraction, membrane separa-
tions, ion exchange, and packaging. The methods of measurement and estimation,
discussed in this Section are applicable to the diffusion of all small molecules
(gases, vapors, and liquids) in solid or semisolid substrates. Of particular interest
to food systems is the measurement and estimation of difrusivity of water, or
moisture diffusivity, since water, as a liquid or vapor, is involved in most food
processing operations and packaging/storage applications. There is no standard
method for evaluating the effective diffusivity of water in food materials, due to the
complex physical structure, and the changes that occur to the food samples during
the measurement procedure.
It should be emphasized that most methods estimate the effective diffusivity
D of water in the food material for a well-defined set of conditions. As defined ear-
lier in this chapter, D is an overall transport property, incorporating all transport
mechanisms for the particular process, i.e. liquid and vapor diffusion, Knudsen
diffusion, capillary flow, hydrodynamic flow, etc. It is assumed that the transport of
water is described by the diffusion (Pick) equation (5-1), and the driving force is an
overall concentration gradient, a simplification for the actual transport mecha-
nisms, but nevertheless convenient for obtaining quantitative data for such com-
plex systems. The use of chemical potential of water as a driving force, (Eq. 5-35),
although thermodynamically sound, is difficult to apply in practice, and there is
little literature for food materials (Gekas, 1992).
Table 1 lists the most important methods of measurement and estimation of
the effective moisture diffusivity, which are subsequently discussed and compared
in connection with their applicability to food materials (Zogzas et al., 1994b; Zog-
zas and Maroulis, 1996; Saravacos, 1995). As a general rule, the method of meas-
urement should be related to the actual intended application, for example the drying
method is recommended for applications related to drying, sorption kinetics is ap-
plicable to moisture adsorption in food storage, and moisture distribution is related
to mass transfer between contacted materials.
Some elegant techniques of determination of moisture diffusivity, such as the
nuclear magnetic imaging (NMR) and the pulsed field gradient methods, have been
proposed in the literature (McCarthy et al., 1991, 1994), but have found little prac-
tical application to food materials.
Mass diffusivity in fluid food systems (Cussler, 1997) is discussed in Chapter
7.
110 Chapters
Table 5.1 Methods of Determination of Mass Diffusivity
1. Sorption Kinetics
a. Gravimetric Method
b. Chromatographic Method
2. Permeability
a. Time-Lag Method
b. Unsteady-State Method
3. Distribution of Diffusant
4. Drying Kinetics
a. Constant Diffusivity
b. Variable Diffusivity
1. Simplified Methods
2. Simulation Method
3. Numerical Methods
4. Regular Regime Method
A. Sorption Kinetics
The sorption kinetics and permeability methods were developed and are
applied extensively in polymer science for the determination of mass diffusivity of
gases and vapors in solid materials. Samples in the form of thin slabs (films) are
normally used for transient adsorption or desorption at constant gas or vapor pres-
sure and temperature.
1. Gravimetric Method
The principle of a gravimetric sorption apparatus is shown in Figure 5.1.
The apparatus consists of a constant temperature diffusion chamber, which con-
tains the sample, suspended from a quartz spring or (Cahn) electrobalance. The
chamber is first evacuated to a very low pressure to remove all solute from the
sample, and then the diffusant is introduced at a fixed pressure. The
sorption/diffusion process is followed by recording the sorbed mass (or moisture
content) versus time.
B
V
Figure 5.1 Diagram of a gravimetric diffusion apparatus. B, balance; P, pressure;

RH, constant relative humidity; T, temperature; V, vacuum.
Moisture sorption kinetics can also be measured by enclosing the sample in

a constant humidity chamber at atmospheric pressure, and removing it quickly for
weighing. In adsorption or desorption of water vapor, the diffusion chamber is
maintained at a fixed constant pressure, using either pure water at a specific
temperature, or constant relative humidity solutions, i.e. saturated salt solutions or
sulphuric acid of fixed density (Spiess and Wolf, 1983).
The sorption process is described by the unsteady state diffusion (Pick)
equation, which for one-dimensional diffusion reduces to Eq. (5-1):
(5-7)
dt ~ dz Bz
The initial and boundary conditions require that the initial concentration of
the sample is constant, the surfaces of the sample are kept constant, and the
amount of diffusant (solute) is a negligible fraction of the whole. Under these
conditions, which can be achieved readily in a well-designed sorption experiment,
the diffusion equation for a plane film, assuming a constant diffusivity D yields
the solution (Vieth, 1991)
112 Chapters
i f ~ 2 Z_i /^ . 1\2 ~"~i"| r2 I > /

Me
where A/ and Me are, respectively, the amounts of diffusant sorbed after time t (s)
and infinity (equilibrium), D is the diffusivity (m2/s), and L is the thickness of the
film (m). In gas sorption measurements, the pressure ratio (P/PJ can be used in-
stead of the mass ratio (M/MJ, assuming that the gas law applies.
In determinations of moisture diffusivity, the mass ratio (M/MJ is equal to
the ratio of moisture contents, Y = (X-Xe)/(X0-X<i}, which in high-temperature dry-
ing reduces to (X/X0), since Xe->0.
For small diffusivities and short times, Eq. (5-8) may be approximated by
the simplified equation (Crank, 1975; Vieth, 1991)
(5-9)
M xL'
Thus, a plot of (M/Mg) versus ft1'2) for the first period of sorption yields a
nearly straight line with a slope Qf4(D/7zL2)''2, from which the diffusivity D can be
estimated (Vieth, 1991). Alternatively, the sorption data can be plotted as (MM^
versus ft/L2)1'2, and the diffusivity D be determined from the simplified equation
(Crank, 1975; Saravacos, 1995)
D = 0.049 [ -4 ] (5-10)
where (t/L2)i,2 is the "half-equilibrium time" (HE), corresponding to (M/Mg) = 0.5,

i.e. 50% sorption, andZ is the thickness of the film.
Figure 5.2 shows a typical plot of adsorption of water vapor in a solid food
sample.
1.0
M/Me
0.5
0.0
2U/2
HE (Dt/I/)
Figure 5.2 Adsorption of water vapor in a solid food sample. HE, half-equilibrium
time.
In food materials, exhibiting hysteresis, different D values of water vapor

are obtained in adsorption and desorption measurements, a mean value may be
more representative of the diffusion process (Fish, 1958; Saravacos, 1967). Mois-
ture equilibrium values Xe, at a given temperature, for various food materials can
be obtained from the isotherms, if available, of the specific material, from pub-
lished compilations (Iglesias and Chirife, 1982; Wolf et al., 1985) or from empiri-
cal equations (Saravacos, 1995).
When diffusivity changes with concentration C, which is the usual case with
the diffusivity of water in food materials, the D(C) can be estimated by repeated
measurements of D over various ranges of concentration (Crank, 1975). If the
critical dimension of the sample, e.g. the thickness L, changes during the sorption
measurement, a mean value can be used for the estimation of diffusivity
(Saravacos, 1967).
2. Chromatographic Methods
Gas chromatography methods, widely used in analytical chemistry, have
been proposed for the determination of sorption and diffusion properties of solid
materials (Vieth, 1991). Of particular interest to foods is inverse gas phase chro-
matography (IGPC), which can be used in the study of interaction of polymeric
materials with probes (Gilbert, 1984).
In IGPC, a polymeric material may be the stationary phase in a gas chroma-
tography (GC) column, and a known probe (solute) is introduced as a mobile
phase. A carrier gas transports the probe through the column where it interacts
with the polymeric material, which may be coated on a GC support, e.g. diatoma-
114 Chapters
ceous earth. The chromatogram recording reveals physicochemical properties of

the polymeric material, such as glass transition points, sorption isotherms, and
thermodynamic parameters.
The specific retention volume V°, defined as the net retention volume per
unit weight of polymeric material at 0°C, is given by the equation
V° = (273/T)¥a(\/Ws) (5-11)
where Vn is the net retention volume, Ws is the weight of the polymeric material,
and T is the temperature (K).
The partition coefficient Kp, defined as the ratio between the probe concen-
tration in the polymeric material and in the mobile phase, is given by the equation
Kf=(7°psT)/273 (5-12)
where ps is the density of the polymeric material.

A technique of determining D of solutes in polymers, using IGPC, is de-
scribed by Pawlisch and Laurence (1987).
Frontal Analysis (FA) may also be used in studying the transport mecha-
nisms between the mobile and stationary phases in a chromatographic column
(Vieth, 1991). A mixture of carrier gas and probe vapor is forced through the col-
umn at constant flow rate, and the amount adsorbed is obtained from the resulting
breakthrough curve. Solute transfer between mobile and stationary phases can be
estimated by ideal chromatographic models, particularly the non-equilibrium lin-
ear (LNE) model.
B. Permeability Methods
The permeability methods are convenient for estimation of mass diffusivity

and are applied extensively to samples of polymer materials, which can be pre-
pared in the form of thin films of homogeneous microstructure. They are difficult
to apply to solid food materials, which are usually heterogeneous with holes and
cracks. Permeability can be used to protective food coatings, which behave like_
polymer films during the measurement (Krochta et al., 1994). The permeability P
(kg / m s Pa) of a diffusant in a film is given by the equation:
P =——-—— (5-13)
(AP/Az)
where J is the mass flux (kg/m2s), AP is the pressure drop (Pa), and Az is the
thickness (m). _
The mass diffusivity D can be estimated from the permeability P, using the
following equation:
~ (5-14)
where S is the solubility (kg/m3 Pa) of the diffusant (solute) in the substrate.
The solubility S in a gas (vapor)/solid or gas (vapor)/liquid system is defined
by the equation:
S = CIP (5-15)
where C is the concentration of the solute in the liquid or solid substrate and P is
the partial pressure of the solute in the gas (vapor) phase.
Equation (5-15) is a form of the Henry's law, the solubility S being the in-
verse of the Henry's constant (S = 1/H). The constant S is also related to the di-
mensionless partition coefficient, defined as the ratio of concentrations of the sol-
ute in the two contacting phases.
The solubility S of water in food materials can be estimated from the slope
(dX/da) of the moisture sorption isotherm at a given temperature, either analyti-
cally (empirical sorption equation), or graphically. The moisture content X (kg
moisture / kg dry matter) at a given water activity should be converted to moisture
concentration C (kg/m3), using the density of the dry matter, approximately ps -
1500 kg/m3. The water activity a should be converted to partial pressure of water
P (Pa), i.e. P = aPm where P0 (Pa) is the vapor pressure of water at the given tem-
perature. Thus, the slope of the isotherm is converted to (dC/dP), which has the
units of the solubility S (kg/m3Pa).
/. Time-Lag Method
The diffusivity of a gas or vapor D and its solubility S in a polymeric film
can be estimated simultaneously from permeability measurements, using the time-
lag method (Crank and Park, 1968; Crank, 1975; Vieth, 1991).
The unsteady and steady-state permeation of a solute into a polymeric film
is usually measured in a time-lag diffusion cell, shown diagrammatically in Figure
5.3:
116 Chapter 5
I
~m www AP
Figure 5.3 Principle of time-lag permeability/diffusion measurement. F, film; G,

gas flow; S, perforated support; T, constant temperature; AP, pressure drop.
An elaborate experimental set-up is required, in which the polymeric film is

first evacuated to a high vacuum, and a gas stream is passed through, measuring
the accumulation of the solute in the film as function of time. After a transient
period, a steady-state permeation rate is established, which yields the permeability
of the film P , according to Eq. (5-13). The accumulated amount of the solute in
the film Q is plotted as a function of time t, from which the diffusivity can be es-
timated.
Under the specified boundary and initial conditions (initially gas-free film,
equilibrium at the inlet gas/polymer interface, and zero concentration of gas at the
outflow face), and assuming a constant diffusivity D, the Pick equation yields the
following solution:
-exp - (5-16)
6D
where Q is the accumulated amount of penetrant (solute), passing through the film
after time t, Cj is the solute concentration in the gas upstream (high pressure), and
L is the film thickness.
After a short transient period, a steady state is established, and Eq. (5-16) is
reduced to:
(5-17)
6D
Figure 5.4 Estimation of the time lag (TL) from a plot of accumulated diffusant Q
versus time t.
A plot of (Q, t), after a short initial period, yields a straight line with an in-
tercept (TL, time lag) on the t axis, given by Eq. (5-18), from which the diffusivity
D can be estimated.
TL--1L (5-18)
6D
The time required to reach full steady-state diffusion has been found empiri-
cally to be equal to 3(TL).
Figure 5.4 shows a typical permeability plot (Q, t) for estimation of the time
lag.
2. Unsteady-State Method
The solubility 5 and diffusivity D of gases and vapors in polymers can be
determined also by unsteady-state measurements, using specialized sorption appa-
ratus (Crank, 1975; Vieth, 1991).
The polymeric material, usually a thin film of known thickness, is placed
into a closed sorption chamber, which is pressurized quickly to a known initial
pressure. The pressure in the chamber drops gradually, as the gas sorbs and dif-
fuses into the polymer film until equilibrium is established.
The solubility of the gas S in the polymer is estimated from a material bal-
ance in the closed system, resulting in the equation:
118 Chapters
Fv 273(Pi-Pl
S = ——— ———- (5-19)
r, T( P.
where Vv is the void volume, Vp is the volume of the polymer, T is the temperature
(K), and Pk Pe are the initial and equilibrium gas pressures, respectively.
A similar expression for the solubility S can be obtained with desorption
measurements. The polymer sample is first completely degassed, a fixed gas pres-
sure Pt is applied, the chamber is evacuated by rapid pump down to a lower pres-
sure, and the chamber is left to equilibrate to a final pressure Pe.
The desorption of a gas from a polymer film by pump down of a closed
chamber is described by the Pick law. Assuming that the required boundary condi-
tions are met, and that diffusivity D is constant, the solution of the diffusion equa-
tion yields the same equations of sorption kinetics (5-9) and (5-10), from which
the value of D can be calculated.
C. Distribution of Diffusant
This method is based on the unsteady-state diffusion of a component in a

semi-infinite solid, the contact surface of which is maintained at constant concen-
tration of the diffusant. The concentration of the component in the solid is meas-
ured at various distances from the surface as a function of time, obtaining the con-
centration-distance curve, from which the diffusivity can be extracted (Crank,
1975; Zogzas et al., 1994b; Saravacos, 1995; Kostaropoulos et al, 1994).
A common experimental procedure is to use two long cylindrical samples of
different uniform concentration, contacted in series, and let diffusion take place
along the axis, under the influence of a concentration gradient. The cylindrical
sample is maintained at a constant temperature, and after a certain time is removed
from the cylinder and sliced into small sections, which are analyzed quickly for
component concentration. In measurements of moisture diffusivity, the sliced sec-
tions of the sample are analyzed quickly for moisture gravimetrically. The samples
may be contained in plastic cylinders (e.g. 13 mm diameter and 100 mm long),
which are sliced together with the sample during the analysis (Karathanos et al.,
1991). The distance-concentration curve at a specified time is constructed by plot-
ting component concentration versus distance (Figure 5.5).
C,
Figure 5.5 Moisture concentration (C) - distance (z) curves in two contacted cy-
lindrical samples.
The Pick diffusion equation for a semi-infinite solid yields the following
solution, assuming constant diffusivity (Crank, 1975):
-C
C
r = erfc (5-20)
c-c.
where C0 is the initial concentration of the diffusant in the sample, C is the concen-
tration after time t, Ce is the equilibrium concentration, and z is the distance of
penetration. The error functions erf and erfc (= 1-erf) are given in the literature.
The equilibrium concentration at the given temperature is taken from the isotherm
of the product or from empirical equations.
For variable diffusivity, the difrusivity D(Cj) at a specified concentration C/
can be evaluated by the equation:
1
(5-21)
120 Chapters
where z is the distance from the interface of the two cylinders, and t is the time at
which the concentration profile is determined. The integral and the gradient of z at
the specified concentration Cj can be determined by numerical or graphical eva-
luation of the concentration-distance curve. Thus, the diffusivity may be evaluated
as a function of concentration by repeated use of Eq. (5-21).
Both Eqs. (5-20) and (5-21) yield mean diffusivity values for both samples of
the material. An alternative simulation method can be used to determine two sepa-
rate diffusivities D for the two samples (Karathanos et al., 1991). Equation (5-20) is
applied to both cylinders, and the calculated D values are optimized by minimizing
the sum of squares of the differences of predicted and experimental concentrations.
The diffusant concentration method is convenient for estimating the diffusiv-
ity of small molecules in solids, when diffusion is relatively slow, and thus concen-
tration profiles can be determined within reasonable time intervals. It has the advan-
tage of minimum disruption of the material structure during measurement, and it
has been applied to estimate the diffusivities of various components in food materi-
als (see Chapter 7).
Application of this method to measurements of moisture diffusivity in food
systems presents experimental difficulties, mainly due to changes of moisture con-
tent during the analytical procedure (slicing, etc). The method can be used at higher
temperatures and pressures, where the usual methods are difficult to apply (Kara-
thanos etal., 1991).
D. Drying Methods
The drying methods are used widely for the determination of moisture (wa-
ter) diffusivity of food materials, since drying and rehydration are common food
processes, and water transport properties are essential in modeling, calculations and
control of these operations. Most of the literature data were obtained from drying
experiments, and the measurement procedure is relatively simple. Historically, dry-
ing was the first method used for the determination of moisture diffusivity in solid
materials (Sherwood, 1931).
Drying of solids is usually divided into two stages, i.e. the constant rate and
the falling rate periods (Perry and Green, 1997). In the constant rate period, water
evaporates freely from the surface of the solid, and the drying rate is controlled by
the external conditions, i.e. air velocity, temperature, and humidity. In the falling
rate period, the main resistance to mass transfer is within the solid material, and the
transport of water from the interior to the surface of evaporation is controlled by
diffusion and other mechanisms, as discussed earlier in this chapter. Most food
materials have short constant rate periods and they dry entirely in the falling rate
period.
AIR
11
w
I 1
Figure 5.6 Diagram of an experimental apparatus for determining the air-drying
rate. S, sample; W, balance; u, air velocity; T, temperature; RH, relative humidity.
Determination of moisture diffusivity during the falling rate period is based

on the application of the diffusion equation to a suitable sample (slab, cylinder or
sphere) of known basic dimension, assuming that the required initial and boundary
conditions are applicable. The sample is dried at controlled temperature, air velocity
and relative humidity, and the drying curve is constructed by plotting the weight
(moisture content) versus time. Figure 5.6 shows the principal parts of a typical air-
drying apparatus for the determination of the drying rate of a solid or semisolid
sample. In simple experiments, weighing of the samples may be done quickly out-
side the dryer. Elaborate measuring apparatus is available, using electronic sensors
and a PC to record temperature, humidity, and sample weight during the drying
experiment (Marinos-Kouris and Maroulis, 1995).
High air velocities (> Im/s) are used in the drying chamber in order to mini-
mize the external resistance to mass transfer from the sample surface to the air
stream. For vacuum-drying measurements, the air stream is replaced by a vacuum
system with a condenser and a pressure control system. Heat can be supplied by
controlled microwave or infrared devices.
/. Constant Diffusivity
The diffusion equation (5-1) is solved for the three basic shapes of the solids
(slab, infinite cylinder, and sphere), assuming constant diffusivity (D), and appro-
priate initial and boundary conditions (Sherwood, 1931; Crank, 1975). It is also
assumed that the solid is drying entirely in the falling rate period. For a slab or a
film of small thickness (compared to the other two dimensions) the diffusion of
moisture is described by the equation:
122 Chapters
„ „. =JLy2 ——;—— p _ v~» • v2 - ~ • (5.22)

- -
where A' is the mean moisture content after time t, X0 is the initial moisture content,
Xe is the equilibrium moisture content, and L is the sample thickness drying from
both sides. If the sample is drying from one flat side only, the sample thickness L in
the diffusion equation should be substituted by (2L). The moisture content A" is ex-
pressed on dry basis, i.e. kg water/kg dry matter.
For spherical samples, the diffusion equation yields:
(5-23)
where r is the sphere's radius. The diffusivity D is estimated from Eqs. (5-22) or Eq.
(5-23) by an approximate solution or by a numerical method. The units of D are
(m2/s), provided that time is in (s) and sample thickness in (m). Most diffusivities
are determined based on a mean value of the thickness L or the radius r of the sam-
ple during the drying process.
The first reported moisture diffusivities of food materials, obtained from dry-
ing data, assumed constant diffusivity (Saravacos and Charm, 1962a). However, it
was soon realized that diffusivity was a function of concentration (moisture con-
tent), evidently due to the complex structure of the food materials. In some cases,
e.g. drying offish muscle, the falling rate period may consist of two distinct parts.
The bimodal diffusion was evidenced in a plot of log 7 versus t, which yielded two
straight lines with two slopes, Kj > Ki, corresponding to two diffusivities, £>/ > D?
(Jason, 1958; Jason and Peters, 1973).
The slope K (1/s) of the semi-log plot of the drying curve is actually the dry-
ing constant, defined by the equation:
X,) (5-24)
at
If the diffusion equation is applicable, the diffusivity D can be estimated from

the drying constant K, for a slab of thickness L using the equation (Moyne et al,
1987; Marinos-Kouris andMaroulis, 1995):
(5-25)
7t
The drying constant K refers to specific drying conditions (temperature, air humid-
ity and air velocity) and sample thickness.
2. Variable Diffusivity
The moisture diffusivity in drying food materials changes significantly with
the moisture content, due to structural changes of the material during drying, and
the changes of the drying mechanism and the water-substrate interaction. The
changes in difrusivity are evidenced by the non-linearity of the semi-log drying
curve (logY versus f). Although mathematical solution of the diffusion equation
requires a constant difrusivity, various approximate methods are applied to extract
effective moisture diffusivities from experimental drying curves, assuming that
water transport by all mechanisms is caused by a concentration gradient.
E. Simplified Methods
Simplified methods are useful for estimating quickly approximate values of

variable effective diffusivities D, before a mathematically rigorous method can be
applied. They have been used for obtaining D values from irregular drying curves,
as in drying of porous solids at low moistures, where moisture is transported by a
combination of different mechanisms, and mathematical modeling is difficult.
The method of drying constants divides the drying curve (fog7, t) into linear
parts and estimates the drying constant (K = dY/dt) at various moisture ratios, from
which the effective difrusivity is calculated, using Eq. (5-25) for the corresponding
sample thickness.
The method of slopes (Perry and Green, 1997; Karathanos et al., 1990;
Saravacos, 1995; Uzman and Sahbaz, 2000) is essentially similar to the repeated
application of Eq. (5-25). The experimental drying curve (logY, t) is compared to
the theoretical diffusion curve (logY, Fo) where Fo = Dt/L2 (Figure 5.7). The
slopes of the two curves (dY/dt) ^ and (dY/dFo),h are estimated at the same mois-
ture ratio Y and the effective difrusivity is calculated from the equation
(dY/dt)
D = _1———i2L (5.26)
(dY/dFo),, ^ '
124 Chapter 5
logY
th
t o r Fo
Figure 5.7 Comparison of experimental (exp) and theoretical (th) diffusion curves.
F. Simulation Method
The simulation method estimates the effective diffusivity by an optimisation

technique, which fits diffusivity values to the experimental drying curve (Karatha-
nos et al., 1990). The input to the computer program is the drying time, the sample
shape and dimensions, the initial and equilibrium moisture contents, and the initial
guess of the mean diffusivities of the nodes used (e.g. 10).
The simulation technique gave similar diffusivity values with the method of
slopes, using drying data for granular and gelatinized starch samples.
G. Numerical Methods
Numerical methods assume that the effective diffusivity D is a known func-

tion of the moisture content X, and the diffusion equation (5-1) is fitted to the ex-
perimental drying data by regression analysis. In a more general approach, a
mathematical model is proposed that considers both heat and mass transfer, and
the diffusivity is a function of moisture content and temperature (Kiranoudis et al.,
1992, 1995).
An empirical model for moisture diffusivity is the following exponential
expression (Kiranoudis et al., 1994; Marinos-Kouris and Maroulis, 1995):
D = Do exp (5-27)
X
where A' is the moisture content, Tis the temperature, and X0, T0 are adjustable con-
stants.
A large number of drying data is obtained from drying experiments at fixed
drying conditions, and fitted simultaneously to the diffusion equation by a non-
linear regression technique. Two iterative methods of calculation can be used, i.e.
the finite differences of Crank-Nicolson (Crank, 1975) and the control volume (Pa-
tankar, 1980).
A numerical method, based on the exponential function of moisture diffusiv-
ity, (Eq. 5-27), was applied to the air-drying of potato and carrot. Comparison with
the simplified method of drying constants gave acceptable agreement in the low
moisture range, where a complex transport mechanism has been evidenced (Kira-
noudisetal., 1994).
Specialized mathematical models for the effective moisture diffusivity D may
describe irregular changes during the drying process. For example, the bell-shaped
curve of (D, X) curve, observed in drying porous starch materials at low moistures
(X<1) can be represented by the gamma function (Karathanos et al, 1990):
1A-
(5-28)
where /I, j3 are constants, X is the moisture, Xz = X-XRH=O, and F(/3) is the gamma
function.
H. Regular Regime Method
The regular regime method, developed by Schoeber (1976), is based on the

application of mass transfer principles to the experimental drying curve. The
method involves a number of calculations, as outlined briefly below (Schoeber and
Thijessen, 1977; Gekas, 1992).
The drying process involves three periods: the constant rate, the penetration,
and the regular regime. During the regular regime (last) period of drying, the mois-
ture profile is moving toward the center of the product, depending on the diffusivity
of moisture, but not on the initial moisture content of the product.
From the drying curve (X, t) the mass flux per unit external surface of the
sample is calculated (dm/dt, kg/m2s), and then the characteristic flux parameter F =
(dm /dt) ps (L~/2), kg2/m4s, where ps is the dry solids concentration (kg/m3) and L is
the sample thickness (m). The moisture profile in the sample is described by the
relationship FY= constant, where Y is the moisture ratio, Y = (X0-X)/(X0-X^>.
A curve (F, X) is constructed, which constitutes the regular regime curve for
the given material.
126 Chapters
The gradient d(lnF)/d(lnX) is calculated as a function of moisture content X

by numerical differentiation, and correlated to the Sherwood number (Sh = kcL/D,
where kc is the mass transfer coefficient, m/s). A plot of (2F/Sh) versus A'yields the
reduced diffusivity Dr by numerical differentiation. Finally, the mass diffusivity D
is calculated from the reduced diffusivity, using the equation, D = Dr/ps2.
The regular regime method has found limited applications to food materials
(Singh et al, 1984; Tong and Lund, 1990; Sano and Yamamoto, 1990; Inazu and
Iwasaki, 2000). The calculated moisture diffusivities are, in general, very close to
the diffusivities obtained by other methods for the same food material.
I. Shrinkage Effect
Most food materials undergo significant shrinkage during the drying process,
which is reflected in the calculated values of moisture diffusivity, since D is nor-
mally proportional to the square of the sample thickness. Shrinkage models and
experimental data are presented in Chapter 3 (Zogzas et al., 1994a; Krokida and
Maroulis, 1997). In general, shrinkage is a linear function of moisture content, and
it should be determined for each material under the appropriate drying conditions.
Moisture diffusivity values D, calculated for a mean sample thickness, can be con-
verted to values based on the dry solids of the material Ds, using the following
equation (Fish, 1958; Crank, 1975):
Ds = [(p/ps)(l+X)]2/3D (5-29)
where p and ps are the densities of the sample at moisture content X and dry-
ness, respectively. The volumetric shrinkage is assumed to be isotropic. Gekas and
Lamberg (1991) modified the Crank equation (5-29), assuming that shrinkage is not
isotropic, and the moisture diffusivity Df follows a fractal relationship:
Dr[(p/Ps)]2/dD (5-30)
where d is the fractal exponent, e.g. for drying of blanched potato d = 1.42.
IV. MOISTURE DIFFUSIVITY IN MODEL FOOD MATERIALS
Model food systems are useful in understanding and predicting the behavior
of actual food materials in various heat and mass transport processes. Moisture
transport (diffusivity) has been found to vary widely in food materials, due mainly
to different physical structure.
Starch materials have been used in several simulations of food products,
since starch is a basic structural component of various foods of plant origin, e.g.
cereal and potato products. Other food biopolymers can also be used in food
simulations, like pectin, cellulose and various gums. Starch (usually corn or
potato) has the advantage of forming rigid gels when heated, resembling solid
food products. The use of food biopolymers in measurements of moisture
diffusivity can utilize the experience and advances of polymer science in the area
of physical and physicochemical properties.
A. Effect of Measurement Method
The method of measurement may have a profound effect on the value of

moisture diffusivity of solid and semisolid foods, due to the changes in the physi-
cal structure of the sample during the measurement procedure. In liquid foods, as
in pure liquids and gases, the experimental or computed diffusivities are more
likely to be constant for a given set of conditions (see Chapter 2).
Drying causes significant physical changes in the food sample during meas-
urement (formation of cracks, pores, puffing), strongly affecting the estimated
mass transport property (moisture diffusivity). Isothermal adsorption or desorption
of water is a milder transport process, with no major structural changes. As a re-
sult, the moisture diffusivity D calculated from sorption data is usually lower than
the D value obtained from drying data. The method of concentration distribution
does not change the physical structure of the material during measurement, and the
D values obtained are similar to those of sorption.
Although, theoretically, diffusivity should be independent of sample shape
and thickness, different results are obtained in practice when changing sample
dimensions, especially in drying measurements. Thus, thicker samples yield high
D values, evidently due to the formation of larger cracks, pores and channels dur-
ing drying.
Figure 5.8 shows moisture diffusivities D in starch gels at 25°C, obtained by
sorption kinetics. Thin films (1 mm) of potato starch gels were used, and the re-
ported diffusivities were the mean values of adsorption and desorption measure-
ments (Fish, 1958). The D values increased exponentially from 1 x 10"13 to 0.5 x
10"10 m2/s when the moisture content^was increased from 0 to 0.2.
128 Chapters
The increase of moisture diffusivity can be explained by the plasticization of

the polymer (starch), which facilitates the transport of water through the macromo-
lecular network. The thin samples of starch gel behaved like homogeneous poly-
mer materials, and the small moisture diffusivities are of the same order of magni-
tude with the D values of small molecules through polymeric materials (Vieth,
1991).
Temperature has a positive effect on moisture diffusivity, following the Ar-
rhenius equation, in a similar way with the activated diffusion in pure liquids,
which has been explained by the theory of rate processes (Eq. 2-37). The energy of
activation for diffusion ED increases substantially as the moisture content is re-
duced, e.g. ED = 20 to 41 kJ/mol, at moisture contents X= 0.2 to 0.01, respec-
tively.
Higher moisture diffusivities are obtained in starch gels, using drying rate
measurements (Saravacos and Raouzeos, 1983). The D values shown in Figure 5.9
were obtained by drying slabs of starch gels 6 mm thick in an airstream at 2 m/s. A
maximum of D = 5xlO"10m2/s was observed at nearly X= 2. Incorporation of glu-
cose (50% dry basis) in the starch gel reduced significantly the moisture diffusiv-
ity.
The higher D values obtained from drying experiments, compared to the
sorption data, are the result of significant changes in the structure of the gel during
the drying process. Drying experiments require samples much thicker than the thin
films of sorption measurements. Drying increases the porosity and creates cracks
and channels in the sample, through which water can be transported at a faster rate
as a vapor than in the isothermal sorption process (Chapter 3). The presence of
small, water-soluble molecules in the gel, like glucose, reduces moisture diffusiv-
ity, by decreasing the porosity of the sample during drying.
A comparison of moisture diffusivities D obtained from drying and sorption
experiments on the same starch material is shown in Figure 5.10. Granular corn
starch (high-amylose, HYLON) was used to prepare spherical samples 1 cm in
diameter for the drying measurements at 60°C and air velocity 2 m/s. The same
starch material, in the form of a slab (film) 1 mm thick was used in the sorption
measurements (Leslie et al., 1991; Chung, 1991).
In both cases, the diffusivity-moisture content (D versus X) curve goes
through a maximum, which is lower moisture content for the sorption data. Higher
D values (nearly 3 times) were obtained by the drying method, evidently due to
the structural changes in the samples during air-drying.
0.001
0.1 0.2 0.3
X (kg/kg dm)
Figure 5.8 Moisture diffusivity in potato starch gels. Sorption kinetics, 25°C.
(Data from Fish, 1958.)
0 1 2 3 4
X (kg/kg dm)
Figure 5.9 Effective moisture diffusivity in drying slabs of starch gels at 40°C.
S, starch; SG, starch glucose. (Data from Saravacos and Raouzeos, 1983.)
130 Chapter 5
0.4 0.6 0.8

X (kg/kg dm)
Figure 5.10 Comparison of moisture diffusivities in granular starch (AMIOCA),

obtained from drying (DR) and adsorption (ADS) at 60°C. (Data from Leslie et al.,
1991.)
B. Effect of Gelatinization and Extrusion
Gelatinization causes significant physicochemical and structural changes in

starch materials, which considerably affects the heat and mass transport properties
(Chapter 3). The moisture diffiisivity is, in general, reduced by gelatinization, due
to the disruption of the granular structure and the formation of a homogeneous gel.
The effect of gelatinization on diffusivity depends primarily on the chemical and
physical composition of the starch material.
Gelatinization of high-amylose (linear macromolecules) starch (HYLON)
causes a relatively small reduction of moisture diffusiviry, without changing the
characteristic shape of the (D, X) curve of porous materials, as shown in Figure
5.11. The gelatinized spherical sample developed a high porosity with several
cracks, which resulted in relatively high moisture diffusivity. A completely differ-
ent effect of gelatinization on moisture diffusivity was observed in high-
amylopectin (branched macromolecules) starch (AMIOCA), as shown in Figure
5.12(Saravacosetal., 1989).
The moisture diffusivity D in the gelatinized starch was reduced sharply, es-
pecially at low moisture contents. The values of the gelatinized starch increased as
the moisture content X was increased, resembling the (D, X) curve obtained by
sorption kinetics of starch gels. The moisture diffusivity curves of Figure 5.12 can
be explained by the changes of bulk porosity s as a function of moisture content.
In the gelatinized high-amylopectin gel, the porosity increased only slightly during
the drying process, contrary to the sharp increase in the granular (non-gelatinized)
sample (Figure 3.7).
Extrusion cooking of starch material at high temperatures and relatively low
moisture contents, produces highly porous products with high moisture diffusivity.
Figure 5.13 shows typical moisture diffusivities in high-amylopectin extruded
starch, obtained from drying measurements of extruded cylindrical samples.
0.2 0.4 0.6

X (kg/kg dm)
Figure 5.11 Effective moisture diffusivity in drying spherical samples of granular

(GR) and gelatinized (GEL) starch (HYLON) at 60°C. (Data from Saravacos et al.,
1989.)
132 Chapter 5
0.2 0.4 0.6

X (kg/kg dm)
Figure 5.12 Effective moisture diffusivity in drying spherical samples of granular

(GR) and gelatinized (GEL) starch (AMIOCA) at 60°C. (Data from Saravacos et
al., 1989.)
50
40
N 30 EX
o
I 20
a
10
GEL
0.2 0.4 0.6

X (kg/kg dm)
Figure 5.13 Effective moisture diffusivity in drying of extruded (EX) and gelati-
nized (GEL) starch (AMIOCA) at 60°C. (Data from Marousis et al.,1991.)
C. Effect of Sugars
Incorporation of small water-soluble molecules into the starch materials re-

duces, in general, the moisture diffusivity. The effect of sugars is more pro-
nounced in granular (non-gelatinized) than in gelatinized starch materials. Figure
5.14 shows typical effects of sugars on he moisture diffusivity D in high-amylose
(HYLON) starch, obtained from drying experiments using spherical samples 1 cm
in diameter at 60°C. The D values decreased sharply when water-soluble dextrin
was incorporated in the samples. Smaller effects were observed with glucose and
sucrose (Marousis et al., 1989).
The molecular weight of the water-soluble carbohydrate seems to be propor-
tional to the reduction of moisture diffusivity. It is presumed that the water-soluble
molecules precipitate in the starch matrix during drying, reducing significantly the
porosity of the drying sample. This explanation is supported by the observed low
porosities of osmotically (using sugar) dehydrated fruits, compared to the un-
treated materials (Chapter 3).
The effect of sugars on the moisture diffusivity in gelatinized starches is
lower than in granular materials (Figure 5.15). Low molecular weight sugars, like
glucose, appear to have a stronger effect because they are more mobile in the gel
structure, precipitate in pores created during drying, and reduce moisture diffusiv-
ity (see also Figure 5.9). On the other hand, high-molecular weight carbohydrates,
like dextrin, are relatively immobile, and they behave like starch, creating high
porosity during drying, and increasing moisture diffusivity.
Dissolved salts, such as sodium chloride, reduce the moisture diffusivity
strongly in hydrated granular starches, but slightly in the gelatinized materials
(Uzman and Sahbaz, 2000). Sodium chloride, which is mobile in granular starch,
may concentrate and precipitate near the surface of the sample, causing a "case-
hardening" effect, and reducing substantially the effective moisture diffusivity. It
should be noted that the diffusivity of sodium chloride in water is about 12xlO"10
m2/s (Table 2.4).
134 Chapter 5
0.2 0.4 0.6

X (kg/kg dm)
Figure 5.14 Effect of sugars on moisture diffusivity in drying granular starch (HY-
LON) at 60°C. S, starch; SG, starch/glucose; SD, starch/dextrin. (Data from Ma-
rousisetal., 1989.)
0.4 0.6 0.8
X (kg/kg dm)
Figure 5.15 Effect of sugar on moisture diffusivity in drying gelatinized starch

(HYLON) at 60°C. S, starch; SG, starch/glucose; SD starch/dextrose. (Data from
Marousis et al, 1989.)
D. Effect of Proteins and Lipids
Incorporation of proteins in starch materials may substantially reduce the

moisture diffusivity D due to physicochemical interactions. Figure 5.16 shows the
reduction of D in granular amylopectin (branched macromolecule) by the addition
of 25% (by dry weight) gluten (a wheat protein). The D values were estimated
from drying measurements on spherical samples at 60°C. A similar effect was
observed with the addition of 25% lysozyme (Marousis, 1989).
Addition of proteins to amylose (linear macromolecule) reduced the D val-
ues to a lesser degree than amylopectin, presumably due to the weaker pro-
tein/starch interaction, compared to the stronger interaction of proteins with the
branched macromolecules of amylopectin.
Proteins reduce moisture diffusivity in gelatinized starches in a similar man-
ner with the granular materials, suggesting a molecular type of interaction. By
contrast, addition of sugars reduces the D values of granular starches only, due to
significant reduction of porosity (a physical process), but there is little effect in the
gelatinized materials.
Incorporation of lipids in granular starches may reduce the moisture diffu-
sivity D, but there is little effect in the gelatinized materials (Papantonis, 1991).
Figure 5.17 shows a significant reduction in D by the addition of 10% vegetable
oil in granular amylopectin starch during drying of spherical samples at 60°C.
However, there is no significant change in D of gelatinized starches by the addi-
tion of lipids, suggesting a rather physical than chemical interaction.
Measurements of moisture diffusivity in model food systems containing
starch, proteins and lipids, demonstrate the importance of physical and physico-
chemical interactions on the transport of water in actual food materials. Proteins
appear to have a strong physicochemical effect, reducing the mobility of water
molecules. Lipids may reduce moisture diffusivity by physical obstruction of wa-
ter transport, e.g. by forming hydrophobic films in the starch network.
136 Chapter 5
0.2 0.4 0.6

X (kg/kg dm)
Figure 5.16 Effect of gluten (SP) on the moisture diffusivity (D) of granular amy-
lopectin starch (S). Drying of spherical samples at 60°C. (Data from Marousis,
1989.)
0.2 0,4 0.6 0.8
X (kg/kg dm)
Figure 5.17 Effect of vegetable oil (SO) on the moisture diffusivity (D) of granular
amylopectin starch (S). Drying of spherical samples at 60°C. (Data from Papan-
tonis, 1991.)
E. Effect of Inert Particles

Inert particles, i.e. solid particles not interacting with water or biopolymers,
may support the physical and mechanical structure of starch materials during the
drying process. Shrinkage of the samples may be prevented, and the moisture dif-
fusivity may be increased during drying (Leslie et al, 1991).
Figure 5.18 shows that the moisture diffusivity of hydrated granular starch
(HYLON) increases significantly, when silica particles (25% by weight, dry basis)
are incorporated in the spherical samples. A similar effect was observed when
carbon black was incorporated in the starch samples. The bulk porosity s of the
dried starches, containing inert particles, increased significantly, e.g. for hydrated
HYLON starch e increased from 0.45 to 0.52 (silica) and 0.55 (carbon black), and
for AMIOCA starch the increase was from 0.45 to 0.50 (silica) and 0.57 (carbon
black).
0.4 0.6 0.8

X (kg/kg dm)
Figure 5.18 Effect of inert silica particles (SI) on moisture diffusivity of granular
starch S (HYLON). Air drying at 60°C. (Data from Leslie et al., 1991.)
138 Chapters
F. Effect of Pressure
Pressure has a significant effect on the moisture diffusivity of porous mate-

rials, such as granular starches. Pressure can be applied in the form of mechanical
compression or gas (air) pressure in a closed vessel.
As shown in Figure 5.19, the effective moisture diffusivity D in granular
starch at moisture content X = 0.5 decreased from about 10xlO~ 10 to 3x10"'° m2/s,
when the mechanical pressure was increased from 1 to 40 bar (Marousis et al.,
1990). The reduction of D is related directly to the reduction of porosity by the
applied mechanical pressure. The effect of pressure on the gelatinized starch mate-
rials was relatively smaller, corresponding to smaller changes of porosity.
Mechanical pressure reduces the porosity of granular starches, especially at
high moisture contents, when the starch granules can be deformed more easily
than the dry particles. Figure 5.20 shows that the porosity of granular starch at
moisture content X = 0.5 is reduced from about 0.50 to less than 0.10 when the
mechanical pressure is increased from 1 to 40 bar.
Air pressure applied in a closed vessel to granular starch (HYLON) reduced
the moisture diffusivity D in a similar manner with mechanical pressure. Thus, D
decreased from about 10xlO"'°to 2xlO"10 m2/s, when the air pressure was increased
from 1 to 40 bar (Figure 5.21). The values of D were determined by the moisture
distribution method (Karathanos et al., 1991).
The effect of gas (air) pressure on diffusivity in porous materials is related to
the inverse pressure P - diffusivity D relationship in gas systems at constant tem-
perature, according to the simplified equation,
PD = constant (5-31)
Higher moisture diffusivities D are expected in porous materials at pressure below

atmospheric (vacuum), an important characteristic of vacuum and freeze-drying.
Thus, the moisture diffusivity in freeze-dried starch gels increased from about
O.lxlO' 10 m2/s to 10x10"'° m2/s, when the pressure was reduced from 1 bar to be-
low 1 mbar (Saravacos and Stinchfield, 1965). The diffusion data were obtained
by the sorption kinetics method.
Figure 5.19 Effect of mechanical pressure on the moisture diffusivity of granular

starch (HYLON) at moisture X = 0.5. Drying at 60°C. (Data from Marousis et al.,
1990.)
0.6
0.4
0.2
0 10 20 30 40 50
P (bar)
Figure 5.20 Effect of mechanical pressure on the porosity e of granular starch (HY-
LON) at moistureX= 0.5. (Data from Marousis et al., 1990.)
140 Chapter 5
P (bar)
Figure 5.21 Effect of air pressure on the moisture diffusivity of granular starch
(AMIOCA) at moisture X= 0.4. Moisture distribution method at 60°C. (Data from
Karathanos et al, 1991.)
G. Effect of Porosity
The bulk porosity s of solid materials, estimated from measurements of bulk

and solids density (Figure 3.5), is the major parameter affecting mass diffusivity.
Temperature and moisture content are also important, but their effect depends
strongly on the structure of the material. Regression analysis of several experimen-
tal data on granular and gelatinized starch materials has yielded the following
equation (Marousis et al., 1991):
(5-32)
Figure 5.22 shows that the effective moisture diffusivity increases sharply above e
= 0.40. The pore size distribution of dried starch materials is discussed in Chapter
3.
The high porosity, developed in the drying of granular starch, is visualized
by the formation of flow channels, through which water (liquid and vapor) is
transported to the drying surface. Radial channels are formed in drying spherical
samples. Irregular cracks are formed in drying gelatinized starch (Figure 3.8).
The pore shape has a significant effect on the heat and mass transport prop-
erties of solids. Freeze-drying experiments have shown that moisture diffusivity is
higher in samples with long than small pores (Figure 5.23; Saravacos, 1965). The
CMC gel slab, which dried faster, had a fibrous structure with long pores oriented
along the diffusion path, while the starch gel sample had small spherical pores,
distributed evenly (Figure 3.9).
H. Effect of Temperature
The effect of temperature on moisture diffusivity D depends strongly on the

physical structure of the solid material. In porous materials, where vapor diffusion
may be controlling, D is proportional to the (3/2) power of temperature, according
to the fundamental transport equation (2-28). In nonporous gels, where liquid dif-
fusion may predominate, D may be expressed by the Arrhenius equation (2-37):
D = Aexp(-ED/RT) (5-33)
The energy of activation for diffusion ED, estimated from diffusivity data at vari-
ous temperatures, is a good indication of the type of prevailing diffusion mecha-
nism in the material. In general, low ED values indicate a vapor diffusion, while
high values suggest liquid (activated) diffusion (Table 5.2). Higher ED values are
expected at low moisture contents, due to the stronger water-substrate interaction.
Table 5.2 Typical Energies of Activation for Diffusion of Water in Starch Materi-
als__________________________________________
Material____________________Activation energy, kJ / mol____
Granular starch 17.0
Granular starch/sugar 33.5
Gelatinized starch 43.4
Gelatinized starch/sugar 51.4
Granular starch/sodium chloride 61.0
142 Chapter 5
0 0.1 0.2 0.3 0.4 0.5 0.6
Figure 5.22 Effect of porosity on moisture diffusivity of starch materials. (Data

from Marousis et al, 1991.)
0.01
0.001
Figure 5.23 Freeze drying rates of model food gels. S, potato starch; CMC, car-
boxy methyl cellulose. Y = (X-Xe)/(Xo-Xe). (Data from Saravacos, 1965.)
I. Drying Mechanisms
Figure 5.24 shows a typical moisture diffusivity-moisture content (D, X)

curve for a porous food material, e.g. granular, extruded, or freeze-dried food
product. At high moistures (A), e.g. X > 0.5, liquid diffusion and capillary flow
may predominate (relatively low D and low porosity). At intermediate moistures
(B), water may be transported by capillary flow and vapor diffusion, increasing
sharply the D value. In this region, pores, cracks, and channels facilitate the trans-
port of water. At very low moistures (C), strongly bound water is desorbed from
the biopolymer solids, reducing sharply the moisture diffusivity.
The shape of the (D, X) curve of Figure 5.24 is characteristic of mass trans-
port properties of capillary and porous solids at low concentrations (Toei, 1983). A
similar curve is obtained for the change of thermal diffusivity of porous foods in
the low moisture region (Figure 8.7), suggesting a heat and mass transport anal-
ogy.
40
30
20
10
0.2 0.4 O.f 0.8

X (kg/kg dm)
Figure 5.24 Prevailing mechanisms of water transport in porous food materials. A,

liquid diffusion and capillary flow; B, vapor diffusion; C, desorption of sorbed wa-
ter.
144 Chapters
V. WATER TRANSPORT IN FOODS
The transport of water in food materials is an important physical process in

the processing, storage, quality and utilization of food products. Of particular im-
portance is the transport of water within the mass of solid and semisolid foods,
since external transfer to and from the surrounding environment can be understood
and analyzed more readily, based on the principles and applications of interphase
heat and mass transfer (Chapter 9).
Data and conclusions from model food systems are useful in obtaining ap-
proximate values of mass transport properties of broad classes of foods, e.g. po-
rous, gelatinized, and sugar-containing products. However, the structure of real
foods of both plant and animal origin is more complex, containing cells, cellular
materials, membranes, fibers, etc making difficult the exact physical modeling for
analysis of the transport processes. It becomes, therefore, necessary to obtain ex-
perimental data on transport properties of broad classes of foods and individual
food products.
In this section, water transport properties (mainly moisture diffusivity) of
various foods are discussed on the basis of physical and physicochemical struc-
ture, and some characteristic values are given. A more detailed analysis of the
literature data on moisture diffusivity of foods is presented in Chapter 6. Reviews
of moisture diffusivity of foods were presented by Bruin and Luyben (1980),
Chirife (1983), Saravacos (1995, 1998), Zogzas et al. (1996) and Mittal (1999).
Lists of moisture diffusivities are given in some food engineering books
(Gekas, 1992; Okos et al., 1992), and in a food properties database (Singh, 1993).
A more detailed database was developed in the European Union (European Coop-
erative Project FAIR "DOPPOF").
A. Mechanisms of Water Transport
Most of the data on moisture diffusivity have been obtained from drying ex-
periments, since mass transfer within the food material is the rate-controlling resis-
tance. Two drying periods are usually observed, the constant rate and the falling
rate. The constant rate period is controlled by external conditions of heat and mass
transfer, and the interphase transport coefficients are discussed in Chapter 9.
In most foods, drying takes place mainly in the falling rate period, and inter-
nal mass transport becomes very important. Water is transported within the food
materials by a combination of several mechanisms, depending on the physical
structure of the product and the external drying conditions. The prevalent mecha-
nisms are molecular diffusion (liquid and vapor), capillary flow, and hydrody-
namic flow. Other mechanisms may be also involved, such as Knudsen diffusion,
surface diffusion, and thermal diffusion (Soret effect).
B. Effective Moisture Diffusivity
Molecular diffusion, described by the Pick equation (5-1), is used widely for
the estimation of the effective moisture diffusivity D of foods, although water may
be transported by mechanisms other than diffusion. It is assumed that the driving
force for all water transport is the concentration gradient (dC/dz) or the moisture
content gradient (dX/dz). The methods of determination of D are discussed in Sec-
tion III of this chapter.
The drying curve (logY, t), obtained from drying experiments of specified
samples under controlled conditions, provides useful information on the mecha-
nism of moisture transport, and it is utilized for the determination of the effective
moisture diffusivity. The drying ratio is defined as Y = (X-Xg)/(X0-X' J, where X0,
X, and X e, respectively, are the moisture contents (kg/kg dm) at the beginning,
after time (t), and at equilibrium.
Semi-logarithmic plots of logY versus / may result in straight lines, an indi-
cation that the diffusion equation may be applied for the treatment of the drying
data. Low (negative) slopes d(logY)/dt of the drying curve indicate external resis-
tance to mass transfer, while high (negative) slopes characterize internal resistance
(Mulet, 1994).
The applicability of the diffusion equation to the transport of water during
drying of foods can be also tested by the following simple techniques: a) Increas-
ing the air velocity should not have a significant effect on the drying rate; b) the
Biot number Bi = kcL/D (where kc is the mass transfer coefficient, m/s, L is the
sample thickness, m, and D the diffusivity, m2/s) should be very high, e.g. Bi >
1000; and c) the drying time in the falling rate period should be proportional to the
square of the sample thickness (Saravacos and Charm, 1962).
A constant slope of the drying curve indicates a constant moisture diffusiv-
ity D, which can be estimated by analytical or numerical techniques. However, in
most foods, the slope is not constant, suggesting that D is a function of the mois-
ture content. In some cases, there are two straight lines with decreasing slopes,
from which two D values can be estimated (bimodal diffusion). An example of
bimodal diffusion is shown in Figure 5.25, and it refers to the air-drying of codfish
fillet (Jason, 1958). The fish slab had a thickness of 15 mm, and it was dried at
35°C and air velocity of 3.7 m/s. Two effective moisture diffusivities were esti-
mated from the two slopes (drying constants), D, = 3.4xlO'10 and D2 = 0.8x10"'°
m2/s.
The broken drying curve shows that, after some drying period, the moisture
diffusivity decreases significantly, evidently due to shrinkage of the fish muscle,
without pore formation. The increased resistance to moisture transfer at lower
moisture contents is shown from the increase of the energy of activation for diffu-
sion ED from 30 to 37 kJ/mol.
146 Chapter 5
0.01
0.001
Figure 5.25 Drying curve (bimodal diffusion) of codfish fillet at 35°C. Slab thick-
ness 15mm. Y=(X-Xe)/(Xo-Xe). (Data from Jason, 1958.)
C. Water Transport in Cellular Foods
Both plant and animal foods consist basically of cellular tissues of various
components, including water, biopolymers, sugars, salts, membranes, cell walls,
fibers, etc. In food processing, the heat and mass transport processes consider non-
living food materials, i.e. the physiological processes of the living cells are ne-
glected. The physiological processes are normally disrupted by heating, freezing,
and dehydration of the food products.
Mass transport in cellular foods can be analyzed thermodynamically by the
chemical potential approach, instead of the usual concentration gradient of Pick's
equation (Rotstein, 1987; Gekas, 1992; Doulia et al., 2000). The chemical poten-
tial of water ^ (kJ/mol) is related to the water activity aw by the equation:
=RTln(aw) (5-34)
The effective moisture diffusivity D is related to the chemical potential gra-

dient by the equation:
D = [Kfa)/pJ (dn/cK) (5-35)
where K(ju) is the effective mass conductivity based on the chemical potential
gradient, with units kg kmol/s kJ, and ps is the solids density, kg/m3. The chemi-
cal potential can be estimated from the water activity, using Eq. (5-34). Prediction
of water activity is discussed by Rahman (1995).
The effective mass conductivity K(p) is the summation of the mass conduc-
tivities of all cellular components in all phases, including gas diffusivities and
permeabilities. The required values of porosity, tortuosity, and sorption equilibria
are estimated from the physical properties of the food system.
Although the chemical potential approach is thermodynamically sounder
than the concentration gradient (diffusion) method, limited applications have been
reported in the literature, evidently due to the involved calculations and the lack of
reliable data on structural properties of the food material, such as porosity and
tortuosity.
D. Water Transport in Osmotic Dehydration
In osmotic dehydration, water is removed from the food material, due to an

osmotic pressure gradient between the contacting osmotic solution and the prod-
uct. Two transport processes take place simultaneously, i.e. water loss (WL) from
the product and sugar gain (SG) into the product. Osmotic solutions used in prac-
tice are sugar solutions, e.g. 65°Brix glucose or sucrose, and salt (sodium chloride)
solutions.
The transport of water and solute in osmotic dehydration at atmospheric
pressure is usually modeled as a diffusion process, and the Pick equation is applied
to samples of known dimensions at specified boundary conditions (Lazarides et
al., 1997). Typical effective moisture diffusivity in apple tissues in contact with a
sucrose solution at 25°C is D = 5xlO"10m2/s. The diffusivity of sucrose in the same
system is lower as expected: D = Ixl0" 10 m 2 /s. The diffusivity of sodium chloride
in osmotic treatments is close to the diffusivity of salt in water at the same tem-
perature and concentration, e.g. D = lOxlO" 10 m2/s (Table 2.4).
In vacuum osmotic dehydration (VOD), mass transport (water and solute) is
mainly by hydrodynamic flow than by molecular diffusion (Fito, 1994). Hydrody-
namic flow, due to mechanical pressure gradients, is facilitated by the existence of
intercellular pores in the food material, e.g. apple tissues, which can be evacuated
and filled with the osmotic solution by mechanical flow. The osmotic process can
be accelerated by pulsed VOD.
Water loss WL and sugar gain SG during osmotic dehydration can be mod-
eled by the following empirical kinetic models (Panagiotou et al., 1998a; 1998b):
148 Chapters
WL / WLe = 1 - exp(- KWL t) (5-36)
SG /SGe = 1 - exp(- KSG t) (5-37)
where WL, and SGe are the equilibrium water loss and sugar gain, respectively (at
time t -> ac), and KWL, KSG are the corresponding constants. The rate constants KWL
and KSG are related to empirical parameters of sample size, solute concentration
and molecular weight, temperature, and flow conditions (speed of agitation).
The empirical models of Eqs. (5-36) and (5-37) were applied to the osmotic
dehydration of apple, banana, and kiwi. Glucose is a better osmotic agent than
sucrose, because of its lower molecular weight and the higher mobility. The os-
motic dehydration of fruit with sugars has significant effects on the moisture diffu-
sivity in the dried product. Determination of moisture diffusivity D from air-
drying data of osmotically treated apples yielded lower D values, evidently due to
the effect of dissolved sugars (Karathanos et al., 1995). The diffusivity - moisture
content curve (Figure 5.26) is similar to the curves of sugar containing starch ma-
terials (Figure 5.14). The dissolved sugar molecules precipitate in the pores of the
fruit during drying, reducing significantly the porosity of the dried product (Chap-
ter 3). Cylindrical apple samples 10 mm diameter were dried at 55°C and 2 m/s air
velocity.
Sorption kinetics data show a similar effect of sugars on the moisture diffu-
sivity D in osmotically treated apples (Bakalis et al., 1994). Figure 5.27 shows the
changes in D during adsorption of water vapor in dried apple samples 8 mm di-
ameter in humidified air. The D values obtained from sorption experiments were
significantly lower than the data obtained by the drying method, in a similar man-
ner with the data obtained on model food materials (see Section IV).
(S
S
1 2 3 4 5
X (kg/kg dm)
Figure 5.26 Effective moisture diffusivity in air-drying (55°C) of osmo-treated

apples. A, untreated apple; AS, osmo-treated apple. (Data from Karathanos et al.,
1995.)
0.1 0,2 0.3 0.4

X (kg/kg dm)
Figure 5.27 Effective moisture diffusivity of water vapor in osmo-treated dried

apples, obtained from sorption measurements. A, untreated sample; AS, osmo-
treated sample. (Data from Bakalis et al., 1994.)
150 Chapters
E. Effect of Physical Structure
As shown in model food systems, the physical and physicochemical struc-

ture of foods has a decisive effect on the mechanism of water transport and the
effective moisture diffusivity. Figure 5.28 shows the effect of drying method on
the moisture diffusivity of apple, using the sorption kinetics technique (Saravacos,
1967).
Apple slices were dehydrated by air-drying, explosion-puff drying, and
freeze-drying, resulting in products of entirely different structure. Thin slices of
the dried materials, 1-2 mm thick, were used in adsorption and desorption meas-
urements in a vacuum sorption apparatus at 30°C and increasing water vapor pres-
sures. The obtained low values of moisture diffusivity are characteristic of sorp-
tion measurements on thin samples, resembling the sorption behavior of polymer
(starch) films (Fish, 1958).
It is evident that the moisture diffusivity D in the freeze-dried material is
much higher than in the puff-dried and air-dried samples, over the entire moisture
content range. The (D-X) curve for the puff-dried sample resembles the curves of
granular starches with an intermediate maximum, a characteristic behavior of po-
rous food materials. By contrast, the moisture diffusivity in the air-dried sample
was the lowest, and it increased steadily at higher moisture contents. This behavior
characterizes nonporous food materials and polymers (starches), in which diffu-
sion of water is facilitated by moisture adsorption. Similar effects on moisture
diffusivity are observed with potato samples, dehydrated by the three different
drying methods described previously for the apple (Figure 5.29). A significant
increase of moisture diffusivity in oil containing foods is obtained by solvent
extraction of the oil.
Figure 5.30 shows the moisture diffusivities D of untreated and defatted
soybeans, using the sorption technique. The measurements were made on thin
slices, 1 mm thick, in a vacuum apparatus at 30°C. The D values of untreated sam-
ples increases steadily from O.OlxlO" 10 to 0.03xlO~ 10 m 2 /s as the moisture content is
increased from 0.2 to 0.12 kg/kg dm, a characteristic of sorption in low porosity
biopolymers. By contrast, a higher D value was obtained in the defatted sample
(0.055xlO"10m2/s), which remained constant over the same moisture content range.
The effect of shrinkage and porosity on the moisture diffusivity of fruits and
vegetables is similar to the effect on model foods (Zogzas et al., 1994a; Krokida
andMaroulis, 1997).
o.oi
0.1 0.2 0.3 0.4
X (kg/kg dm)
Figure 5.28 Effect of drying method on the moisture diffusivity in apple. Sorption
kinetics on thin samples, 30°C. AD, air-dried; PD, puff-dried; FD, freeze-dried.
(Data from Saravacos, 1967.)
o.oi
0.00 0.05 0.10 0.15 0.20
X (kg/kg dm)
Figure 5.29 Effect of drying method on the moisture diffusivity in potato. Sorp-
tion kinetics on thin samples, 30°C. AD, air-dried; PD, puff-dried; FD, freeze-
dried. (Data from Saravacos, 1967.)
152 Chapter 5
(S
E
o
0.01
0.00 0.10 0.20
X (kg/kg dm)
Figure 5.30 Moisture diffusivity of full-fat (F) and defatted (DF) soybeans. Sorp-
tion kinetics on thin slices at 30°C. (Data from Saravacos, 1967.)
The decrease of moisture diffusivity in freeze-dried, and in porous foods

generally, at high moisture contents, is directly related to a collapse of the physical
structure (Karel and Flink, 1983).
F. Effect of Physical/Chemical Treatments
Various physical treatments during the processing of foods may change their
physical structure, resulting in changes of moisture diffusivity. As discussed in
Section III, mechanical compression, gelatinization, coating, and mixing with hy-
drophilic food components may reduce substantially the moisture diffusivity, due
primarily to the reduction of porosity. On the other hand, puffing (extrusion, ex-
plosion puffing), vacuum and microwave treatment may increase porosity and,
therefore, moisture diffusivity.
Starch gelatinization reduces considerably moisture diffusivity in cooking
and boiling starch-based foods in water, creating an outside layer of slowly mov-
ing water. The water demand of the inner core may be considered as the driving
force for water transport inwards. The moisture diffusivity in such food systems
can be measured by the NMR technique (Takeuchi et al., 1997; Gomi et al., 1998).
Microwave or dielectric treatment of foods can substantially increase the

moisture diffusivity during drying at atmospheric pressure or in vacuum. Micro-
wave energy is absorbed by the water inside the food product, resulting in fast
evaporation, and creating a porous structure in the dried material. Pretreatment of
fruits and vegetables with microwave energy and subsequent normal air-
dehydration improves the drying rate.
Short-time microwave pretreatment of grapes significantly increases the
drying rate of grapes, due to an increase of the moisture permeability of the grape
skin. The pretreatment can be applied to the sun drying of grapes (raisins), which
is normally very slow, and a long time is required for drying (Kostaropoulos and
Saravacos, 1995). Short-time (0.5-3.0 min) microwave pretreatment of starch gels
and apples considerably increased the drying rate in subsequent air-drying. The
mean effective moisture diffusivity, estimated from the drying curves, increased
from 9xlO' 10 to 18xlO"'°m 2 /s in the starch gels and from 6xlO''°to 12xlO'10m2/s in
the apples (Saravacos et al., 1997).
The skin of some fruits, such as grapes, reduces substantially mass transfer
during drying, due to the presence of waxes and other hydrophobic components,
that have low moisture permeability and diffusivity. Chemical pretreatments can
increase water permeability by dissolving the waxes and breaking down the skin
structure.
Alkali dips in solutions of sodium hydroxide, containing surfactants (surface
active agents), are applied to grapes before sun drying, substantially reducing the
drying time. Ethyl oleate, an edible surfactant, considerably increases the drying
rate by acting on the skin and the grape berry during the drying process. Figure
5.31 shows the effect of addition of 2% ethyl oleate to a solution of 0.5% NaOH,
which was used as pretreatment dip in the air-drying of seedless grapes (Saravacos
and Raouzeos, 1986). A similar effect of alkali dips on the drying of grapes was
reported by Masi and Riva (1988). The mean moisture diffusivity in the alkali-
treated grapes was increased by the addition of ethyl oleate from 0.3x10"10 to
1.0xlO-'°m2/s.
Low concentrations of surfactants sharply reduce the surface tension of wa-
ter. Addition of surfactants can increase the drying rate of porous food materials
by increasing the wetting of the drying surfaces during the early stages of drying.
This effect has been observed in the drying of porous fruits, such as apples
(Saravacos and Charm, 1962b). However, surfactants have little effect on the dry-
ing rate of nonporous food materials, such as blanched potato.
Similar effects of ethyl oleate were observed in the air-drying of granular
(porous) starch (Saravacos et al., 1988). On the other hand, the surfactant treat-
ment had no effect on the drying rate of gelatinized starch, a low-porosity model
food material (see Figure 5-32).
154 Chapter 5
Figure 5.31 Effect of alkali/surfactant dip on the air-drying of grapes at 60°C. CL,
control (0.5% NaOH); TR, treated (0.5% NaOH +2% ethyl oleate).
Y = (X-Xe)/(Xo-Xe). (Data from Saravacos and Raouzeos, 1986.)
Figure 5.32 Effect of ethyl oleate on the drying rate at 60°C of granular starch
(HYLON). CL, control; TR, treated 0.2% ethyl oleate. 7 = (X-Xe)f(Xo-Xe). (Data
from Saravacos et al., 1988.)
G. Characteristic Moisture Diffusivities of Foods
Characteristic values of moisture diffusivity D of various food products are

useful as a first approximation of this important transport property in the design
and evaluation of food processes and food storage/quality changes. The wide
variation of he literature data on D is due to the complex physical and chemical
structure of foods and the different methods of measurement and estimation used.
A unified analysis of the literature data on D is presented in Chapter 6.
Table 5.3 gives some typical D values for important classes of foods, based
on the physical structure and porosity. The effect of structure of foods is similar to
the effect of structure on the D of model food materials, as discussed in Section
IV. Tables 5.4 to 5.8 give typical D values of various food products, selected from
the literature.
Table 5.3 Effect of Physical Structure on the Moisture Diffusivity of Food Prod-
ucts
Food Structure Porosity Activation energy Diffusivity
______________%_______kJ/mol_________xlQ-'V/s
Highly porous 90 10 50
Freeze-dried
Puff-dried
Fibrous
Porous 50 20 20
Granular
Vacuum-dried
Low porosity 20 30 5
Compressed
Gelatinized 10 45 1
Starch/protein foods 10 50 0.1
Starch/lipid foods 10 60 0.01
Glassy-state foods 0 >60 0.0001

156 Chapters
Table 5.4 Typical Moisture Diffusivities of Cereal Grains and Rice at 30°C
(typical activation energy ED = 40 kJ/mol)
Food material Moisture Diffusivity
___________________kg/kg dm______xlQ-'V/s
Corn kernel 0.20 0.40
Corn pericarp 0.20 0.01
Wheat kernel 0.20 0.50
Rice 0.20 0.40
Table 5.5 Typical Moisture Diffusivities of Baked Products and Pasta at 30°C
kg/kg dm xlO'10m2/s
Dough 0.40 5.0
Bread 0.30 2.0
Cookie 0.15 0.5
Pasta 0.15 0.3
Puffed pasta 0.15 1.2
Table 5.6 Typical Moisture Diffusivities of Vegetable Products at 30°C

kg/kg dm xlO-'W/s
Potato 0.30 5.0
Carrot 0.30 2.0
Peas 0.10 3.0
Onion 0.10 0.5
Soybeans 0.20 0.8
Table 5.7 Typical Moisture Diffusivities of Fruit Products at 30°C

_____________________kg/kg dm______xlQ-'°m2/s
Apple 0.50 2.0
Apricots 0.40 1.0
Bananas 0.50 2.0
Raisins 0.40 1.5
Table 5.8 Typical Moisture Diffusivities of Meat and Fish at 30°C

kg/kg dm xlO-'W/s
Minced beef 0.60 1.0
Pork sausage 0.20 0.5
Codfish 0.50 2.0
Herring 0.50 0.8
Mackerel 0.40 0.5
Hulibut 0.40 0.3
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Moisture Diffusivity Compilation of
Literature Data for Food Materials
I. INTRODUCTION
There is a wide variation of the reported experimental data of moisture dif-

fusivity of solid food materials, making difficult their utilization in food process
and food quality applications.
The variation of moisture diffusivity in model and real foods is discussed in
Chapter 5. The physical structure of solid foods plays a decisive role not only on
the absolute value of moisture diffusivity, but also on the effect of moisture con-
tent and temperature on this transport property. Porosity data, obtained from
measurements of bulk and particle densities (Chapter 3) at various moisture con-
tents, provide useful data on the type of water transport (liquid or vapor diffusion)
and the approximate value of moisture diffusivity.
In this chapter, the moisture diffusivity in food materials is approached from
a statistical standpoint. Literature data are treated by regression analysis, using an
empirical mathematical model. Recently published values of moisture diffusivity
in various foods were retrieved from the literature and were classified and ana-
lyzed statistically to reveal the influence of material moisture content and tempera-
ture. Empirical models relating moisture diffusivity to material moisture content
and temperature were fitted to all examined data for each material. The data were
screened carefully, using residual analysis techniques. A promising model was
proposed based on an Arrhenius-type effect of temperature, which uses a parallel
structural model to take into account the effect of material moisture content.
163
164 Chapters
II. DATA COMPILATION
Moisture diffusivity data on foods in the literature are scarce because of the
effect of the following factors: (a) diverse experimental methods, (b) different
methods of analysis used, (c) Variation in composition of the material, and (d)
variation of the structure of the material.
Literature data for moisture diffusivity in foods materials were selected and
presented in the reviews of Bruin and Luyben (1980), Chirife (1983), Gekas
(1992), Marinos-Kouris and Maroulis (1995), Zogzas et al. (1996), Mittal (1999),
and Doulia et al. (2000). In addition to these reviews, an exhaustive literature
search was made in international food engineering and food science journals in
recent years, as follows (Panagiotou et al., 2001):
• Drying Technology, 1983-1999

• Journal of Food Science, 1981-1999
• International Journal for Food Science and Technology, 1988-1999
• Journal of Food Engineering, 1983-1999
• Trans. of the ASAE, 1975-1999
A total of 175 papers were retrieved from the above journals according the
distribution presented in Figure 6.1. The accumulation of the papers versus the
publishing time is presented in Figure 6.2. The search resulted in 1558 data con-
cerning the moisture diffusivity in food materials. The 1558 data retrieved from
the above search, plus 16 data from Bruin and Luyben (1980), 58 data from
Chirife (1983) and 141 data from Gekas (1992) were organized into a database
and analyzed. A total number of 1773 data was obtained. These data are plotted
versus moisture and temperature in Figures 6.3 and 6.4, respectively. These fig-
ures show a good picture concerning the range of variation of diffusivity, moisture
and temperature values. More than 95% of the data are in the ranges:
• Diffusivity IxlO' 1 2 -IxlO" 6 m 2 /s

• Moisture 0.01 - 15.0 kg/kg db
• Temperature 10-200°C
It should be noted that the lowest possible moisture diffusivity is that in

glassy food materials, about IxlO" 14 m2/s, and the highest is the diffusion of water
vapor in air at atmospheric pressure, IxlO" 5 m2/s (Table 2.4). Higher diffusivities
of water vapor can be obtained in vacuum systems. The self diffusivity of water is
near Ixl0" 9 m 2 /s.
Moisture Diffusivity Data Compilation 165
J. Food Drying J. of Food Trans of the Int. J, Food

Engineering Technology Science ASAE Science and
Techn.
Figure 6.1 Number of papers on moisture diffusivity data in food materials pub-
lished in food engineering and food science journals during recent years.
1000 -1—
1975 1985 1995 2005

Year
Figure 6.2 Accumulation of published papers on moisture diffusivity data for food
materials versus time.
166 Chapter 6
l.E-03
l.E-06 - =
•5 l.E-09
l.E-12
l.E-15
0.01 0.1 1 10 100
Moisture (kg/kg db)
Figure 6.3 Moisture diffusivity data for all foods at various moistures.
l.E-03
l.E-15
10 100 1000
Temperature (°C)
Figure 6.4 Moisture diffusiviry data for all foods at various temperatures.
The histogram in Figure 6.5 shows the distribution of the moisture diffusiv-
ity values retrieved from the literature. The results obtained are presented in detail
in Tables 6.1-6.3. More than 100 food materials are incorporated in these tables.
They are classified into 11 food categories. Table 6.1 shows the related publica-
tions for every food material. Table 6.2 summarizes the average literature value
for each material along with the corresponding average values of corresponding
moisture and temperature. Table 6.3 presents the range of variation of moisture
diffusivity for each material along with the corresponding ranges of moisture and
temperature.
1000
1) 100
•c
I a
•M
a
O
B 10
s
Z
l.E-15 l.E-12 l.E-09 l.E-06 l.E-03

Moisture Diffusivity Values (mVs)
Figure 6,5 Histogram of observed values of moisture diffusivity in food materials.

168 Chapter 6
Table 6.1 Literature for Moisture Diffusivity Data in Food Materials:

References and Number of Data Retrieved
Material Reference Data
Baked Products 33
Biscuit 4
Balasubrahmanyam and Datta, 1993 4
Bread 1
Zhouetal., 1994 1
Cookie 2
Gekas, 1992 1
Lomauroetal, 1985 1
Crackers 18
Kirn and Okos, 1999 18
Dough 8
Kamthanos et al., 1995 4
Zanonietal, 1994 4
Cereal Products 499
Barley 16
Fasina et a!., 1998 7
Miketinac et al, 1992 9
Brown rice 36
Engelsetal, 1986 9
Gekas, 1992 7
Hendrickx et al, 1988 3
Lu and Siebenmorgen, 1992
Steffe and Singh, 1980
Table 6.1 Continued

Corn 168
Bakker-Arkema et a!., 1987 6
Galan-Domingo and Martinez-Vera, 1996 3
Gekas, 1992 3
Harosetal, 1995 9
Jumah and Mujumdar, 1996 6
Martinet- Vera eta!., 1 995 5
Mouradetal, 1996 17
Muthukumarappan and Gunasekaran, 1994a, b, c 40
Parti and Dugmanics, 1990 8
Patil, 1988 8
Shivhare et al, 1992 10
Syariefetal., 1987 9
Tolabaetal, 1989 8
Tolabaetal, 1990 4
Verma and Prasad, 1999 7
Waltonetal, 1988 20
Zahedetai, 1995 5
Malt 4
Lopezetal, 1997 4
Milled rice 2
Zhangetal, 1984 2
Paddy rice 3
Base et al, 1987 3
Parboiled brown rice 6
Igathinathane and Chattopadhyay, 1999a, b 6
Parboiled paddy rice 6
Parboiled rice 12
Chandra and Singh, 1984 6
Pasta 51
Litchfield and Okos, 1992 11
Meat et al, 1996 4
Waananen and Okos, 1996 30
Xiongetal, 1991 6
170 Chapter 6
Table 6.1 Continued

Rice 56
Engelsetal, 1986 6
Galan-Domingo and Martinez-Vera, 1996 3
Gekas, 1992 15
Hendrickx et al, 1986 3
Hendrickx and Tobback, 1987 6
Hendrickx etal, 1988 8
Steffe and Singh, 1980 10
Zahedetal, 1995 5
Rough rice 78
Bakker-Arkema et al, 1987 3
Chungu and Jindal, 1993 6
EceandCihan, 1993 6
Gekas, 1992 14
Lague andJenkins, 1991 6
Lu and Siebenmorgen, 1992 8
Sarkeretal, 1994 21
Steffe and Singh, 1980 9
Suarezetal, 1982 1
Tang and Sokhansanj, 1993 4
Wheat 58
Bakker-Arkema et al, 1987 3
Bruin and Luyben, 1980 2
Chirife, 1983 3
Devahastin et al, 1998 3
Gekas, 1992 4
Giner and Calvelo, 1987 4
Gineretal, 1996 4
Gong etal, 1997 4
Igathinathane and Chattopadhyay, 1997 4
Jar os et al, 1992 7
Jayas et al, 1991 9
Lomauro et al, 1985 1
Sapru and Labuza, 1996 1
Suarezetal, 1982 1
Sun and Woods, 1994 5
Zahedetal, 1995 3
Wild rice 3
Gekas, 1992 3
Table 6.1 Continued

Dairy 32
Cheese 9
Change! al, 1998 2
Desobry and Hardy, 1994 5
Luna and Chavez, 1992 2
Dry milk 2
Gekas, 1992 1
Lomauroetal, 1985 1
Milk 6
Straatsmaetal., 1999 6
Skim milk 15
Ferrari et al, 1989 9
Kerkhof, 1994 6
Fish 63
Catfish 1
Chirife, 1983 1
Cod 6
Balaban and Pigott, 1988 4
Chirife, 1983 2
Dogfish 4
Chirife, 1983 3
Fish meal 15
Alvarez and Shene, 1996 8
Blasco and Alvarez, 1999 7
Haddock 2
Chirife, 1983 2
Halibut 2
Chirife, 1983 2
Herring 7
Chirife, 1983 7
Mackerel 1
Chirife, 1983 1
172 Chapter 6
Table 6.1 Continued

Shark 12
Park, 1998 12
Squid 6
Teixeira and Tobinaga, 1995 1
Teixeira and Tobinaga, 1998 5
Swordfish 4
Chirife, 1983 4
Whiting 3
Chirife, 1983 3
Fruits 268
Apple 64
Chirife, 1983 6
Fuscoetai, 1991 2
Gekas, 1992 14
Lazarides et al., 1997 13
Lomauroetal, 1985 1
Nieto et al, 1998 6
Simaletal, 1997 11
Simaletal, 1998a, b 8
Apricot 10
Abdelhaq and Labuza, 1987 2
Vagenas and Marinos-Kouris, 1991 8
Avocado 11
Chirife, 1983 6
Gekas, 1992 5
Banana 55
Garciaetal, 1988 5
Gekas, 1992 6
Johnson et al, 1998 3
Mauro and Menegalli, 1995 9
Rastogietal, 1997 12
Son/cat el al., 1996 11
Waliszewskietal, 1997 9
Blueberries 29
Nsonzi and Ramas\vamy, 1998 11
Ramaswamy and Nsonzi, 1998 18
Coconut 6
Gekas, 1992 6
Table 6.1 Continued

Grapes 52
Alvarez and Legues, 1986 18
Gekas, 1992 4
Mahmutogluetal, 1996 16
Simaletal, 1996 8
Vagenasetal, 1990 6
Mulberry 9
Mas/can andGogus, 1998 9
Peach 1
Gekas, 1992 1
Pineapple 20
Azuaraetal, 1992 6
Beristainetal, 1990 9
Rastogi and Niranjan, 1998 5
Raisins 11
Gekas, 1992 1
Karathanos et al, 1995 8
Lomauro et al, 1985 1
Sapru and Labuza, 1996 1
Legumes 29
Broad bean 7
Ptaszniketal, 1990 7
Fababean 2
Hsu, 1983a, b 2
Lentil 12
Tang and Sokhansanj, 1993 12
Navy beans 8
Radajewski et al, 1992 8
Meat 53
Beef 4
Gekas, 1992 2
Huang and Mittal, 1995 2
174 Chapters
Table 6.1 Continued

Beef carcass 3
Mallikarjunan and Mittal, 1994 3
Broiled 3
McLendon and Gillespie, 1978 3
Bull 3
Gekas, 1992 3
Chicken 6
Ngadi et al, 1997 6
Ground beef 19
Gekas, 1992 1
Hallstrom, 1990 17
Lomauroetai, 1985 1
Heifer 7
Gekas, 1992 7
Pepperoni 5
Chirife, 1983 2
Sausage 1
Dincer and Yildiz, 1996 1
Turkey 2
Chirife, 1983 1
Gekas, 1992 1
Model foods 202
Albumin-flour-bran 27
Strumitto et al, 1996 27
Amioca 59
Karathanos et al., 1990 16
Kostaropoulos and Saravacos, 1997 4
Marousisetal, 1989 20
Seowetal., 1999 10
Vagenas and Karathanos, 1993 9
Cellulose-oil-water 1
Chirife, 1983 1
Corn starch 2
Gekas, 1992 2
Flour 3
Gekas, 1992 1
Lomauroetai., 1985 2
Table 6.1 Continued_________________________________

Glucose-starch 7
Gekas, 1992 1
Gluten-starch 6
Xiong et a!., 1991 6
Hylon-7 59
Karathanosetal, 1990 9
Kostaropoulos and Saravacos, 1997 4
Marousisetal, 1989 18
Seawetal.,1999 11
Tsukadaetal, 1991 9
Vagenas and Karathanos, 1993 8
Polyacrylamide gel 6
Roques et a!., 1994 6
Potato starch 4
Gekas, 1992 4
Rice starch 23
GOBI; e/ a/., 1998 3
Takeuchi et al, 1997 20
Starch 5
Geto, 7P92 5
Nuts_______________________________79
Almond 2
Beviaetai, 1999 2
Hazelnuts 12
Lopezetal, 1998 12
Peanut pods 64
Chinnan and Young, 1977a, b 64
Peanuts 1
SuarezetaL, 1982 1
Other_______________________________45
Canola 24
Thakoretal., 1999 24
Chocolate 4
Biquet and Labuza, 1988 4
176 Chapter 6
Table 6.1 Continued

Coffee 3
Gekas, 1992 3
Egg 6
Kincal, 1987 6
Sunflower seeds 4
Rovedo et al, 1993 4
Toria 4
Raoetal, 1992 4
Vegetables 470
Beet 1
Chirife, 1983 1
Broccoli 22
Sanjuanetal, 1999 10
Simaletal, 1998a, b 12
Carrot 106
Cordova-Quirozet al, 1996 1
Gekas, 1992 4
Kiranoudis et al, 1992 9
Kiranoudis et al., 1993 15
Kompany et al., 1993 10
Mabrouk and Belghith, 1995 8
Markov/ski, 1997 12
Muletetal., 1987 7
Mulet et al, 1989 12
Mulet, 1994 6
Rastogi and Raghavarao, 1997 12
Stapley et al, 1995 10
Cassava 10
Chavez-Mendez et al, 1998 2
Fuscoetal, 1991 8
Garlic 22
Madambaetal, 1996 5
Pezzutti and Crapiste, 1997 6
Pinagaetal, 1984 5
Vazquezetal, 1999 6
Okra 6
Gogus and Maskan, 1999 6
Table 6.1 Continued

Onion 31
Baroni and Hubinger, 1998 9
Kiranoudis et al., 1992 9
Lewicki et al, 1998 9
LopezetaL, 1995 4
Paprika 3
Gekas, 1992 3
Pea 9
Medeiros and Sereno, 1994 9
Pepper 14
Carbonelletal, 1986 5
Pigeon pea 5
Shepherd and Bhardwaj, 1988 5
Potato 165
AfzalandAbe, 1998 12
Bonetal, 1997 6
Chirife, 1983 7
Costa and Oliveira, 1999 4
Fuscoetal, 1991 2
Gekas and Lamberg, 1991 4
Gekas, 1992 12
Lazarides and Mavroudis, 1996 6
Lazaridesetal, 1997 1
Magee and Wilkinson, 1992 8
Maroulis et al., 1995 15
McLaughlin and Magee, 1999 8
McMinn and Magee, 1996 12
Mishkinetai, 1984 9
Mulet, 1994 8
Pinthus et al, 1997 12
Rice and Gamble, 1989 3
Rovedo and Viollaz, 1998 3
Rovedoetal, 1995 3
Rubnov and Saguy, 1997 4
Yusheng and Poulsen, 1988 12
Zhouetal, 1994 1
178 Chapter 6
Table 6.1 Continued

Soya meal 18
Alvarez and Blasco, 1999 12
Alvarez and Shene, 1996 6
Soybean 19
Barrozo et al, 1998 3
Deshpande et al., 1994 1
Gekas, 1992 1
Hsu, 1983a, b 8
Misra and Young, 1980 4
Oliveira and Haghighi, 1998 1
Suarezetal, 1982 1
Sugar beet 7
Chirife, 1983 3
Fuscoetal, 1991 2
Tapioca 4
Chirife, 1983 3
Tomato 16
Dincer and Dost, 1995 3
Hawladeretal., 1991 8
Karatas and Esin, 1994 5
Turnip 10
Lomauro et al., 1985 1
Moreiraetal, 1993 9
Yam 2
Hawladeretal, 1999 2
Table 6.2 Moisture Diffusivity of Foods Versus Moisture and Temperature:

Average Values of Available Data
Material Diffusivity Moisture Temperature No. of
(m2/s) (kg/kg db) (°C) Data
Baked Products 33
Biscuit 4
fondant coated 5.26E-09 0.12 85 4
Bread 1
- 5.00E-08 0.67 80 1
Cookie 2
oatmeal 3.99E-12 0.18 25 2
Crackers 18
- 6.08E-10 0.08 63 18
Dough 8
- 4.89E-10 0.48 122 8
Cereal Products 492

Barley 9
kernel 1.85E-10 0.23 49 9
Brown rice 36
- 2.64E-10 0.19 40 18
bran 2.59E-11 0.22 45 9
endosperm 6.68E-11 0.24 40 3
kernel 4.36E-11 0.24 40 3
testa 4.46E-11 0.24 40 3
Corn 168
- 3.27E-07 0.34 41 31
dent 3.40E-10 0.28 60 15
endosperm 1.08E-10 0.20 40 3
flint 3.20E-11 0.50 55 3
germ 1.31E-10 0.14 35 11
grains 6.04E-10 0.28 48 28
hard endosperm 1.72E-11 0.09 33 4
kernel 4.49E-11 0.35 49 25
pericarp 1.09E-11 0.19 38 13
semident 4.54E-11 0.50 55 3
shelled 1.01E-10 0.19 71 20
soft endosperm 2.96E-11 0.06 33 4
without pericarp 4.06E-13 0.21 33 8
180 Chapter 6
Table 6.2 Continued

Malt 4
- 8.73E-08 0.45 50 4
Milled rice 2
- 1.31E-10 0.32 60 2
Paddy rice 3
grains 1.53E-11 0.11 50 3
Parboiled brown rice 6
bran 3.52E-11 0.33 75 6
Parboiled paddy rice 6
husk 1.01E-IO 0.30 75 6
Parboiled rice 12
endosperm 3.21E-10 0.52 75 6
long grain 6.05E-11 0.50 60 3
short grain 1.37E-10 0.50 60 3
Pasta 51
- 1.94E-11 0.16 63 21
dense 4.76E-11 0.13 81 18
porous 1.21E-10 0.12 68 12
Rice 56
- 4.49E-1 1 0.26 37 13
cooking 4.13E-09 130 2
endosperm 9.94E-11 0.23 39 21
grains 1.05E-10 0.26 61 3
hull 1.20E-11 45 2
kernel 1.21E-10 0.23 40 12
testa 4.43E-11 40 3
Rough rice 78
- 3.71E-09 0.19 49 35
bran 8.68E-12 0.15 43 8
endosperm 1.73E-10 0.15 47 6
grains 1.30E-11 0.15 41 1
hull 1.06E-11 0.23 45 9
husk 2.56E-11 0.15 45 7
kernel 1.62E-08 0.28 60 12
Table 6.2 Continued

Wheat 58
- 1.45E-10 0.23 49 26
bran 1.73E-10 0.35 30 2
endosperm 1.91E-10 0.50 30 2
flakes 8.33E-14 0.50 25 1
grains 3.69E-11 0.15 66 10
hard 2.02E-09 0.17 20 2
kernel 6.54E-11 0.16 63 11
shredded 5.53E-12 0.11 25 1
soft 1.51E-10 0.15 50 3
Wild rice 3
broken 7.00E-13 25 1
unprocessed 4.00E-13 20 1
whole 2.00E-13 20 1
Dairy 32
Cheese 9
- 2.02E-08 0.58 9 9
Dry milk 2
nonfat 2.12E-11 0.12 25 2
Milk 6
powder 6.58E-10 0.30 40 6
Skim milk 15
- 1.36E-10 0.56 46 15
Fish 63
Catfish 1
- 8.00E-1 1 30 1
Cod 6
- 2.78E-10 3.00 42 5
muscle 3.40E-10 30 1
Dogfish 4
- 1.48E-10 30 4
Fish meal 15
- 7.97E-10 0.40 118 15
Haddock 2
- 6.00E-11 30 1
muscle 3.30E-10 30 1
182 Chapter 6
Table 6.2 Continued

Halibut 2
- 5.80E-11 30 1
muscle 2.50E-10 30 1
Herring 7
- 6.53E-11 30 7
Mackerel 1
- 3.50E-11 30 1
Shark 12
muscle 1.80E-10 1.31 30 12
Squid 6
mantle 8.91E-11 1.50 34 6
Swordflsh 4
- 3.45E-10 48 2
salted 2.95E-10 48 2
Whiting 3
- 4.80E-11 30 1
muscle 1.76E-10 28 2
Fruits 268
Apple 64
- 6.64E-10 2.80 47 64
Apricot 10
- 1.39E-07 2.88 53 10
Avocado 11
- 6.35E-10 50 11
Banana 55
- 1.4 IE-09 1.63 53 49
plantain 6.51E-10 0.90 55 3
ripe 1.43E-09 3.00 60 3
Blueberries 29
- 2.12E-10 1.75 45 29
Coconut 6
- 9.77E-10 0.60 83 6
Grapes 52
- 1.37E-10 53 18
red 1.79E-10 60 2
seedless 2.03E-10 1.49 60 32
Mulberry 9
- 1.18E-09 1.50 70 9
Table 6.2 Continued

(mVs) (kg/kg db) (°C) Data
Peach 1
- 8.00E-12 30 1
Pineapple 20
- 1.47E-09 4.50 40 20
Raisins 11
- 1.67E-10 0.37 37 11
Legumes 29
Broad bean 7
seeds 6.53E-07 0.26 30 7
Fababean 2
- 1.78E-07 0.75 30 2
Lentil 12
cotyledons 2.25E-11 0.13 40 3
hilum 7.22E-09 0.15 40 3
seedcoat 1.57E-12 0.18 40 6
Navy beans 8
• 4.56E-08 0.28 50 8
Meat 53
Beef 4
- 5.56E-10 30 1
meatball 3.20E-10 1.40 140 2
raw l.OOE-11 30 1
Beef carcass 3
bone 5.48E-12 1
fat 3.07E-11 1
muscle 5.83E-10 1
Broiled 3
waste 9.81E-06 0.30 21 3
Bull 3
- 7.40E-1 1 0.76 27 3
Ground beef 19
- 3.03E-11 0.16 25 2
heat treated 1.48E-10 0.80 51 8
raw 8.61E-11 1.13 43 9
184 Chapter 6
Table 6.2 Continued

Heifer 7
heat treated 1.69E-10 1.00 51 4
raw 8.33E-11 1.00 43 3
Pepperoni 5
- 5.20E-11 12 2
sausage 5.33E-11 0.19 12 3
Sausage 1
- 1.31E-07 0.32 180 1
Turkey 2
- 8.00E-15 0.04 22 2
Model foods 202

Albumin-flour-bran 27
mixture! 1.45E-09 0.43 92 9
mixture 2 1.0 IE-09 0.49 92 9
mixtures 7.70E-10 0.49 92 9
Amioca 59
- 2.26E-09 0.36 74 49
gel 8.20E-10 0.33 60 5
hydrated 1.90E-09 0.33 60 5
Cellulose-oil-water 1
- 3.10E-09 68 1
Corn starch 2
- 2.25E-10 30 2
Flour 3
- 2.26E-1 1 0.12 25 3
Glucoose-starch 7
- 2.27E-10 0.60 39 7
Gluten-starch 6
gelatinized 3.33E-11 0.14 74 3
ungelatinized 2.67E-11 0.14 74 3
Hylon-7 59
- 2.09E-09 0.30 63 48
gel 2.06E-09 0.44 60 6
hydrated 2.27E-09 0.33 60 5
Polyacrylamide gel 6
- 1.52E-10 0.90 40 6
Potato starch 4
. 6.91E-12 25.28 25 4
Table 6.2 Continued

(m2/s) (kg/kg db) (°C)Data
Rice starch 23
full heated 9.75E-10 1.63 50 13
nonheated 2.1 IE-09 1.50 57 10
Starch 5
- 4.23E-10 0.60 42 5
Nuts 79
Almond 2
- 2.32E-12 0.05 281 2
Hazelnuts 12
shelled 4.03E-09 0.15 55 6
unshelled 6.16E-09 0.15 55 6
Peanut pods 64
hull 4.69E-11 0.60 35 32
kernel 7.28E-11 0.60 35 32
Peanuts 1
- 4.00E-11 0.10 50 1
Other 45
Canola 24
embryo 3.58E-09 0.02 80 12
kernel 5.09E-09 0.02 80 12
Chocolate 4
dark 1.03E-13 2.00 20 4
Coffee 3
extract 1.08E-10 50 3
Egg 6
fresh 1.44E-11 1.00 36 3
incubated 1.61E-11 0.80 36 3
Sunflower seeds 4
hull 4.40E-10 0.07 45 2
kernel 1.20E-10 0.07 45 2
Toria 4
seeds 9.80E-11 0.10 65 4
186 Chapter 6
Table 6.2 Continued

(mVs) (kg/kg db) (°C) Data
Vegetables 467
Beet 1
- 1.50E-09 65 1
Broccoli 22
stems 1.29E-09 8.80 62 22
Carrot 106
- 2.05E-09 4.60 53 106
Cassava 10
roots 6.30E-10 0.63 67 10
Garlic 22
- 1.74E-10 0.80 50 22
Okra 6
- 2.24E-09 2,00 70 6
Onion 31
- 1.0 IE-09 1.65 64 31
Paprika 3
- 2.17E-10 48 3
Pea 9
- 2.74E-10 0.97 48 9
Pepper 14
- 6.22E-09 3.70 70 9
redpo-wder 2.09E-10 0.06 49 5
Pigeon pea 5
kernel 5.07E-11 0.20 70 5
Potato 165
- 1.32E-09 3.17 58 148
restructured product 2.02E-09 105 16
tissue 1.67E-09 1.85 65 1
Soya meal 18
- 1.16E-08 0.10 162 18
Soybean 16
- 9.0 IE-08 0.56 47 13
grains 1.12E-09 0.60 48 2
Sugar beet 7
roots 6.59E-10 2.60 57 7
Tapioca 4
roots 6.00E-10 1.05 78 4
Table 6.2 Continued

Tomato 16
- 7.57E-10 10.00 64 11
concentrate droplets 1.87E-09 0.50 77 5
Turnip 10
- 1.64E-09 6.33 57 10
Yam 2
_ 1.27E-09 0.10 45 2
188 Chapter 6
Table 6.3 Moisture Diffusivity of Foods Versus Moisture and Temperature:

Variation Range of Available Data
Diffusivity Moisture Temperature
(m2/s) (db) (°C)
Material min max min max min max
Baked Products 3.97E-I2 5.00E-08 0.03 0.67 15 203

Biscuit 4.06E-09 6.29E-09 0.03 0.39 77 91
fondant coated 4.06E-09 6.29E-09 0.03 0.39 77 91
Bread 5.00E-08 5.00E-08 0.67 0.67 80 80
- 5.00E-08 5.00E-08 0.67 0.67 80 80
Cookie 3.97E-12 4.00E-12 0.18 0.18 25 25
oatmeal 3.97E-12 4.00E-12 0.18 0.18 25 25
Crackers 1.40E-11 1.81E-09 0.03 0.14 40 90
- 1.40E-11 1.81E-09 0.03 0.14 40 90
Dough 1.30E-10 l.OOE-09 0.20 0.60 15 203
- 1.30E-10 l.OOE-09 0.20 0.60 15 203
Cereal Products 8.33E-14 4.04E-06 0.02 0.56 5 150

Barley 1.31E-11 6.52E-10 0.10 0.27 30 70
kernel 1.31E-11 6.52E-10 0.10 0.27 30 70
Brown Rice 1.81E-12 3.94E-09 0.16 0.25 12 120
- 1.81E-12 3.94E-09 0.16 0.25 12 120
bran 1.48E-11 4.07E-11 0.21 0.24 35 55
endosperm 4.36E-11 9.64E-11 0.24 0.24 30 50
kernel 2.00E-11 7.25E-11 0.24 0.24 30 50
testa 1.25E-11 9.31E-11 0.24 0.24 30 50
Corn 9.72E-14 4.04E-06 0.06 0.56 10 120
- 2.33E-11 4.04E-06 0.10 0.50 10 120
dent 2.39E-11 1.48E-09 0.10 0.50 30 90
endosperm 3.61E-11 2.01E-10 0.10 0.30 40 40
flint 1.90E-11 4.50E-11 0.50 0.50 45 65
germ 5.28E-12 8.42E-10 0.10 0.30 25 40
grains 5.24E-11 6.1 IE-09 0.10 0.40 10 120
hard endosperm 1.29E-11 2.06E-1 1 0.07 0.10 25 40
kernel 1.11E-11 1.14E-10 0.12 0.56 25 90
pericarp 9.72E-14 7.37E-11 0.10 0.30 25 60
semident 2.50E-11 6.80E-11 0.50 0.50 45 65
shelled 2.16E-11 2.23E-10 0.19 0.19 38 104
soft endosperm 2.12E-11 3.72E-11 0.06 0.07 25 40
without pericarp 2.56E-13 5.50E-13 0.19 0.23 25 40
Table 6.3 Continued

(m2/s) (db) (°C)
Malt 1.11E-08 2.14E-07 0.45 0.45 20 80

- 1.1 IE-08 2.14E-07 0.45 0.45 20 80
Milled Rice 8.33E-11 1.78E-10 0.13 0.50 60 60
- 8.33E-11 1.78E-10 0.13 0.50 60 60
Paddy Rice 2.28E-12 3.44E-11 0.11 0.11 40 60
grains 2.28E-12 3.44E-11 0.11 0.11 40 60
Parboiled Brown Rice 1.15E-11 6.26E-11 0.30 0.36 50 100
bran 1.15E-11 6.26E-11 0.30 0.36 50 100
Parboiled Paddy Rice 3.43E-11 1.80E-10 0.28 0.33 50 100
husk 3.43E-11 1.80E-10 0.28 0.33 50 100
Parboiled Rice 2.38E-11 4.84E-10 0.50 0.53 40 100
endosperm 2.12E-10 4.84E-10 0.51 0.53 50 100
long grain 2.62E-11 1.02E-10 0.50 0.50 40 80
short grain 2.38E-11 2.98E-10 0.50 0.50 40 80
Pasta 1.55E-12 3.42E-10 0.02 0.32 40 122
- 1.55E-12 4.84E-1 1 0.02 0.32 40 85
dense 9.40E-12 1.06E-10 0.05 0.23 40 122
porous 2.43E-11 3.42E-10 0.04 0.21 40 105
Rice 3.30E-12 6.33E-09 0.10 0.35 8 150
- 3.30E-12 1.17E-10 0.10 0.35 20 55
cooking 1.92E-09 6.33E-09 110 150
endosperm 4.40E-11 1.98E-10 0.20 0.25 8 55
grains 6.67E-11 1.48E-10 0.22 0.30 61 61
hull 4.00E-12 2.00E-11 35 55
kernel 5.19E-11 2.28E-10 0.23 0.24 30 50
testa 1.20E-11 9.30E-11 30 50
Rough Rice 7.56E-13 1.68E-07 0.05 0.50 12 120
- 7.56E-13 2.64E-08 0.10 0.33 12 120
bran 4.03E-12 2.21E-11 0.15 0.15 25 60
endosperm 9.86E-11 2.20E-10 0.15 0.15 30 60
grains 1.30E-11 1.30E-11 0.15 0.15 41 41
hull 4.08E-12 3.59E-11 0.22 0.24 35 55
husk 1.11E-11 4.41E-11 0.15 0.15 30 60
kernel 4.75E-12 1.68E-07 0.05 0.50 38 82
190 Chapter 6
Table 6.3 Continued

(m2/s) (db) (°C)
Wheat 8.33E-14 3.70E-09 0.10 0.50 5 86

- 6.07E-12 5.30E-10 0.17 0.30 5 85
bran 1.68E-10 1.78E-10 0.35 0.35 30 30
endosperm 1.91E-10 1.92E-10 0.50 0.50 30 30
flakes 8.33E-14 8.33E-14 0.50 0.50 25 25
grains 1.50E-11 7.94E-1 1 0.10 0.20 40 86
hard 3.30E-IO 3.70E-09 0.13 0.20 20 20
kernel 1.15E-11 1.43E-10 0.10 0.30 40 80
shredded 5.53E-12 5.53E-12 0.11 0.11 25 25
soft 2.98E-11 3.19E-10 0.15 0.15 30 70
Wild Rice 2.00E-13 7.00E-13 20 25
broken 7.00E-13 7.00E-13 25 25
unprocessed 4.00E-13 4.00E-13 20 20
whole 2.00E-13 2.00E-13 20 20
Dairy 2.10E-11 9.00E-08 0.12 0.80 0 70

Cheese 5.60E-11 9.00E-08 0.35 0.80 0 13
- 5.60E-11 9.00E-08 0.35 0.80 0 13
Dry Milk 2.10E-11 2.13E-11 0.12 0.12 25 25
nonfat 2.10E-11 2.13E-11 0.12 0.12 25 25
Milk 3.50E-11 1.83E-09 0.20 0.40 10 70
powder 3.50E-11 1.83E-09 0.20 0.40 10 70
Skim Milk 2.51E-11 2.56E-10 0.20 0.80 30 70
2.51E-11 2.56E-10 0.20 0.80 30 70
Fish 1.30E-11 1.89E-09 0.33 3.00 20 170

Catfish 8.00E-11 8.00E-11 30 30
- 8.00E-11 8.00E-11 30 30
Cod 8.10E-11 5.13E-10 3.00 3.00 30 60
- 8.10E-11 5.13E-10 3.00 3.00 30 60
muscle 3.40E-10 3.40E-10 30 30
Table 6.3 Continued

(m2/s) (db) (°C)
Dogfish 8.30E-11 2.20E-10 30 30

- 8.30E-11 2.20E-10 30 30
Fish Meal 1.95E-11 1.89E-09 0.33 0.55 65 170
- 1.95E-11 1.89E-09 0.33 0.55 65 170
Haddock 6.00E-11 3.30E-10 30 30
- 6.00E-1 1 6.00E-11 30 30
muscle 3.30E-10 3.30E-10 30 30
Halibut 5.80E-11 2.50E-10 30 30
- 5.80E-11 5.80E-11 30 30
muscle 2.50E-10 2.50E-10 30 30
Herring 1.30E-11 1.90E-10 30 30
- 1.30E-11 1.90E-10 30 30
Mackerel 3.50E-11 3.50E-11 30 30
- 3.50E-11 3.50E-11 30 30
Shark 8.70E-11 2.85E-10 1.18 1.42 20 40
muscle 8.70E-11 2.85E-10 1.18 1.42 20 40
Squid 8.30E-11 1.09E-10 0.50 2.50 34 34
mantle 8.30E-11 1.09E-10 0.50 2.50 34 34
Swordfish 2.60E-10 3.90E-10 40 55
- 3.00E-10 3.90E-10 40 55
salted 2.60E-10 3.30E-10 40 55
Whiting 4.80E-11 2.70E-10 25 30
- 4.80E-11 4.80E-11 30 30
muscle 8.20E-11 2.70E-10 25 30
Fruits 4.00E-13 6.10E-07 0.00 8.70 15 110

Apple 4.00E-12 6.40E-09 0.00 8.70 20 90
- 4.00E-12 6.40E-09 0.00 8.70 20 90
Apricot l.OOE-11 6.10E-07 0.50 3.48 40 80
- l.OOE-11 6.10E-07 0.50 3.48 40 80
Avocado 1.10E-10 1.80E-09 31 60
- 1.10E-10 1.80E-09 31 60
Banana 1.60E-10 3.40E-09 0.25 3.00 25 110
- 1.60E-10 3.40E-09 0.25 3.00 25 110
plantain 3.16E-10 1.15E-09 0.90 0.90 40 70
ripe 5.50E-10 2.66E-09 3.00 3.00 60 60
192 Chapter 6
Table 6.3 Continued

(mVs) (db) (°C)
Blueberries 3.80E-11 5.10E-10 0.50 4.00 37 60

- 3.80E-11 5.10E-10 0.50 4.00 37 60
Coconut 4.60E-10 1.28E-09 0.60 0.60 45 110
- 4.60E-10 1.28E-09 0.60 0.60 45 110
Grapes 4.83E-11 9.28E-10 0.39 2.35 30 75
- 4.85E-11 4.20E-10 50 70
red 5.80E-11 3.00E-10 50 70
seedless 4.83E-11 9.28E-10 0.39 2.35 30 75
Mulberry 2.32E-10 2.76E-09 0.50 3.00 60 80
- 2.32E-10 2.76E-09 0.50 3.00 60 80
Peach 8.00E-12 8.00E-12 30 30
- 8.00E-12 8.00E-12 30 30
Pineapple 5.38E-10 2.64E-09 3.80 5.00 30 50
- 5.38E-10 2.64E-09 3.80 5.00 30 50
Raisins 4.00E-13 4.80E-10 0.15 0.60 15 70
~ 4.00E-13 4.80E-10 0.15 0.60 15 70
Legumes 2.06E-14 1.07E-06 0.12 1.00 20 65

Broad Bean 3.66E-07 1.07E-06 0.17 0.37 20 40
seeds 3.66E-07 1.07E-06 0.17 0.37 20 40
Fababean 1.28E-07 2.27E-07 0.50 1.00 30 30
- 1.28E-07 2.27E-07 0.50 1.00 30 30
Lentil 2.06E-14 1.02E-08 0.12 0.24 30 50
cotyledons 1.43E-11 3.17E-11 0.13 0.13 30 50
hilutn 4.58E-09 1.02E-08 0.15 0.15 30 50
seedcoat 2.06E-14 4.03E-12 0.12 0.24 30 50
Navy Beans 3.33E-08 5.56E-08 0.15 0.40 35 65
3.33E-08 5.56E-08 0.15 0.40 35 65
"
Meat 5.48E-12 1.17E-05 0.04 2.45 10 180

Beef l.OOE-11 5.56E-10 1.40 1.40 30 140
- 5.56E-10 5.56E-10 30 30
meatball 2.50E-10 3.90E-10 1.40 1.40 140 140
raw l.OOE-11 l.OOE-11 30 30
Table 6.3 Continued

(mVs) (db) (°C)
Beef Carcass 5.48E-12 5.83E-10

bone 5.48E-12 5.48E-12
fat 3.07E-11 3.07E-11
muscle 5.83E-10 5.83E-10
Broiled 8.06E-06 1.17E-05 0.30 0.30 10 32
waste 8.06E-06 1.17E-05 0.30 0.30 10 32
Bull 6.30E-11 8.20E-11 0.76 0.76 20 30
- 6.30E-11 8.20E-11 0.76 0.76 20 30
Ground Beef 3.00E-11 2.30E-10 0.16 1.60 25 75
- 3.00E-11 3.07E-11 0.16 0.16 25 25
heat treated 7.50E-11 2.30E-10 0.60 1.00 30 75
raw 4.00E-11 1.70E-10 0.60 1.60 30 60
Heifer 5.40E-11 2.14E-10 1.00 1.00 30 75
heat treated 1.30E-10 2.14E-10 1.00 1.00 30 75
raw 5.40E-11 1.20E-10 1.00 1.00 30 60
Pepperoni 4.70E-11 5.70E-11 0.19 0.19 12 12
- 4.70E-11 5.70E-11 12 12
sausage 4.70E-1 1 5.70E-11 0.19 0.19 12 12
Sausage 1.3 IE-07 1.3 IE-07 0.32 0.32 180 180
- 1.3 IE-07 1.3 IE-07 0.32 0.32 180 180
Turkey 8.00E-15 8.00E-15 0.04 0.04 22 22
8.00E-15 8.00E-15 0.04 0.04 22 22
Model Foods l.OOE-14 2.25E-08 0.02 80.00 20 105

Albumin-Flour-Bran 5.80E-10 1.85E-09 0.08 0.83 75 105
mixture! 1.15E-09 1.85E-09 0.08 0.82 75 105
mixlure2 8.00E-10 1.26E-09 0.13 0.83 75 105
mixtures 5.80E-10 1.05E-09 0.10 0.80 75 105
Amioca 6.13E-11 7.30E-09 0.02 0.93 20 100
- 6.13E-11 7.30E-09 0.02 0.93 20 100
gel 5.50E-10 1.20E-09 0.07 0.75 60 60
hydrated 1.40E-09 2.40E-09 0.05 0.75 60 60
Cellulose-oil-water 3.10E-09 3.10E-09 68 68
- 3.10E-09 3.10E-09 68 68
Corn Starch 1.89E-10 2.60E-10 30 30
. 1.89E-10 2.60E-10 30 30
194 Chapter 6
Table 6.3 Continued

(m2/s) (db) (°C)
Flour 3.86E-12 3.20E-11 0.07 0.17 25 25

- 3.86E-12 3.20E-11 0.07 0.17 25 25
Glucoose-Starch 6.60E-11 5.90E-10 0.60 0.60 30 50
- 6.60E-11 5.90E-10 0.60 0.60 30 50
Gluten-Starch 1.90E-11 4.00E-11 0.09 0.20 74 74
gelatinized 2.20E-1 1 4.00E-1 1 0.09 0.20 74 74
ungelatinized 1.90E-11 3.20E-11 0.09 0.20 74 74
Hylon-7 2.48E-10 2.25E-08 0.03 1.00 20 100
- 2.48E-10 2.25E-08 0.03 0.90 20 100
gel 8.00E-10 3.70E-09 0.05 1.00 60 60
hydrated 1.70E-09 2.70E-09 0.05 0.75 60 60
Polyacrylamide Gel 8.77E-12 3.00E-10 0.10 2.00 40 40
- 8.77E-12 3.00E-10 0.10 2.00 40 40
Potato Starch l.OOE-14 2.40E-11 0.80 80.00 25 25
- l.OOE-14 2.40E-1 1 0.80 80.00 25 25
Rice Starch 8.48E-11 4.62E-09 0.67 4.00 25 80
full heated 8.48E-11 2.84E-09 0.67 4.00 25 80
non-heated 3.92E-10 4.62E-09 0.67 2.33 25 80
Starch 1.50E-10 6.90E-10 0.60 0.60 30 50
~ 1.50E-10 6.90E-10 0.60 0.60 30 50
Nuts 4.36E-13 1.24E-08 0.05 0.60 27 281

Almond 2.24E-12 2.39E-12 0.05 0.05 281 281
- 2.24E-12 2.39E-12 0.05 0.05 281 281
Hazelnuts 1.48E-09 1.24E-08 0.15 0.15 30 80
shelled 1.48E-09 8.39E-09 0.15 0.15 30 80
unshelled 3.65E-09 1.24E-08 0.15 0.15 30 80
Peanut Pods 4.36E-13 2.36E-10 0.60 0.60 27 43
hull 4.36E-13 1.17E-10 0.60 0.60 27 43
kernel 8.52E-12 2.36E-10 0.60 0.60 27 43
Peanuts 4.00E-11 4.00E-11 0.10 0.10 50 50
. 4.00E-11 4.00E-11 0.10 0.10 50 50
Table 6.3 Continued

(mVs) (db) (°C)
Other 8.20E-14 6.60E-09 0.00 2.00 20 80

Canola 2.10E-09 6.60E-09 0.00 0.05 80 80
embryo 2.10E-09 5.20E-09 0.00 0.05 80 80
kernel 3.70E-09 6.60E-09 0.00 0.05 80 80
Chocolate 8.20E-14 1.33E-13 2.00 2.00 20 20
dark 8.20E-14 1.33E-13 2.00 2.00 20 20
Coffee 5.00E-11 1.65E-10 30 70
extract 5.00E-11 1.65E-10 30 70
Egg 1.03E-11 2.03E-11 0.80 1.00 33 40
fresh 1.03E-11 2.03E-11 1.00 1.00 33 40
incubated 1.39E-11 1.90E-11 0.80 0.80 33 40
Sunflower Seeds 7.00E-11 7.10E-10 0.07 0.07 40 50
hull 1.70E-10 7.10E-10 0.07 0.07 40 50
kernel 7.00E-1 1 1.70E-10 0.07 0.07 40 50
Toria 2.85E-11 2.08E-10 0.08 0.12 50 80
seeds 2.85E-11 2.08E-10 0.08 0.12 50 80
Vegetables 2.20E-12 3.05E-07 0.03 15.00 20 300

Beet 1.50E-09 1.50E-09 65 65
- 1.50E-09 1.50E-09 65 65
Broccoli 1.78E-10 3.41E-09 2.00 13.93 25 90
stems 1.78E-10 3.41E-09 2.00 13.93 25 90
Carrot 2.20E-12 7.46E-09 0.10 15.00 20 100
- 2.20E-12 7.46E-09 0.10 15.00 20 100
Cassava 1.07E-10 2.15E-09 0.60 0.64 55 90
roots 1.07E-10 2.15E-09 0.60 0.64 55 90
Garlic 1.14E-11 4.18E-10 0.10 1.50 22 90
- 1.14E-11 4.18E-10 0.10 1.50 22 90
Okra 4.28E-10 6.80E-09 2.00 2.00 60 80
- 4.28E-10 6.80E-09 2.00 2.00 60 80
Onion 1.38E-11 6.60E-09 0.10 10.00 40 80
- 1.38E-11 6.60E-09 0.10 10.00 40 80
Paprika 5.80E-11 4.08E-10 25 70
- 5.80E-11 4.08E-10 25 70
Pea 1.10E-10 4.40E-10 0.50 1.50 30 65
. 1.10E-10 4.40E-10 0.50 1.50 30 65
196 Chapter 6
Table 6.3 Continued

(m2/s) (db) CO
Pepper 5.86E-11 1.16E-08 0.06 10.00 25 80

- 1.85E-09 1.16E-08 0.10 10.00 60 80
redpowder 5.86E-11 4.08E-10 0.06 0.06 25 70
Pigeon Pea 2.88E-11 7.70E-11 0.20 0.20 50 90
kernel 2.88E-11 7.70E-11 0.20 0.20 50 90
Potato 8.00E-12 1.25E-08 0.10 10.00 24 185
- 8.00E-12 1.25E-08 0.10 10.00 24 185
restructured product 7.30E-10 4.52E-09 105 105
tissue 1.67E-09 1.67E-09 1.85 1.85 65 65
Soya Meal 1.47E-10 4.01E-08 0.03 0.22 65 300
- 1.47E-10 4.01E-08 0.03 0.22 65 300
Soybean 9.30E-11 1.17E-05 0.19 1.00 20 95
- 9.30E-11 3.05E-07 0.19 1.00 20 95
grains 9.30E-11 2.15E-09 0.20 1.00 25 72
Sugar Beet 1.96E-10 1.30E-09 2.21 3.00 40 81
roots 1.96E-10 1.30E-09 2.21 3.00 40 81
Tapioca 3.50E-10 9.00E-10 1.05 1.05 55 97
roots 3.50E-10 9.00E-10 1.05 1.05 55 97
Tomato 1.52E-10 6.46E-09 0.50 10.00 40 100
- 1.52E-10 2.36E-09 10.00 10.00 40 80
concentrate droplets 1.69E-10 6.46E-09 0.50 0.50 60 100
Turnip 7.61E-12 3.62E-09 0.31 7.00 20 100
- 7.61E-12 3.62E-09 0.31 7.00 20 100
Yam 7.30E-10 1.81E-09 0.06 0.14 40 50
. 7.30E-10 1.81E-09 0.06 0.14 40 50
III. MOISTURE DIFFUSIVITY OF FOODS AS A FUNCTION OF

MOISTURE CONTENT AND TEMPERATURE
Moisture diffusivity of foods depends strongly on moisture, temperature and

structure of the material. In porous materials, the porosity and the pore structure
distribution significantly affect diffusivity. Limited information concerning the
effect of structure on diffusivity is available in the literature (Chapter 5). On the
other hand, the effect of moisture and temperature on diffusivity has been studied
more extensively. Nevertheless, general models describing the effect of moisture
content and temperature on diffusivity of foods do not exist.
A large number of empirical equations are summarized and analyzed in de-
tail by Marinos-Kouris and Maroulis (1995), Zogzas et al. (1996), and Mittal
(1999). According to the most popular consideration, the effect of temperature and
moisture content is introduced into the Arrhenius model.
A concept proposed by Maroulis et al. (2001) is adopted here and applied to
obtain an integrated and uniform analysis of the available moisture diffusivity
data. The concept was applied simultaneously to all the data of each material, re-
gardless of data sources. Thus, the results are not based on the data of only one
author, and consequently they are of elevated accuracy.
Assume that a material of intermediate moisture content consists of a uni-
form mixture of two different materials: (a) a dried material and (b) a wet material
with infinite moisture. Moisture diffusivity is, generally, different for each mate-
rial. The diffusivity of the mixture could be estimated using a two-phase structural
model:
^ (6-1)
l +X " l +X
where D (m2/s) the effective moisture diffusivity, DXo (m2/s) the moisture diffusiv-
ity of the dried material (phase a), DXj (m2/s) the moisture diffusivity of the wet
material (phase b), X (kg/kg db) the material moisture content, and T (°C) the ma-
terial temperature.
Assume that the diffusivities of both phases depend on temperature by an
Arrhenius-type model:
= u exp - — (6-2)
R(T T
198 Chapters
x, , -r R , T T
(6-3)
where Tr= 60°C a reference temperature, R = 0.0083143 kJ/mol K, the ideal gas
constant, and D0,DI,E0,EI are adjustable parameters of the proposed model. The
reference temperature of 60°C was chosen as a typical temperature of air-drying of
foods.
Thus, the moisture diffusivity for every material is characterized and de-
scribed by four parameters with physical meaning:
• D0 (m2/s) diffusivity at moisture X = 0 and temperature T = Tr

• Dj (m2/s) diffusivity at moisture X = oo and temperature T - Tr
• E0 (kJ/mol) activation energy for diffusion in dry material at X = 0
• Ei (kJ/mol) activation energy for diffusion in wet material at X = oo
The resulting model is summarized in Table 6.4 and can be fitted to data us-
ing a nonlinear regression analysis method. The model is fitted to all literature data
for each material and the estimates of the model parameters are obtained. Then the
residuals are examined and the data with large residuals are rejected. The proce-
dure is repeated until an acceptable standard deviation between experimental and
calculated values is obtained (Draper and Smith, 1981).
Among the available data only 19 materials have more than 10 data, which
come from more than 3 publications. The procedure is applied to these data and
the results of parameter estimation are presented in Table 6.5 and in Figure 6.6. It
is clear that moisture diffusivity is larger in wet materials.
Figures 6.7-6.29 present retrieved moisture diffusivities from the literature

and model-calculated values for selected food materials as a function of moisture
content and temperature. Moisture diffusivity D tends to increase with the mois-
ture content X and the temperature T. The maxima of the curves observed at low
moisture contents in the model foods (see Chapter 5) are smoothed out by the sta-
tistical treatment of the data.
It must be noted that the regression procedure was applied simultaneously to
all the data of each material, regardless of the data sources. Thus, the results are
not based on the data of only one author and consequently they are of higher accu-
racy and general applicability.
The diffusivity parameters D0 and Z)/ of the proposed model, shown in Fig-
ure 6.6, vary in the range of 10~10 to 10~8 m2/s. It should be noted that the self-
diffusivity of water is approximately 10"9 m2/s, and the moisture diffusivity in
bone-dry food material should be lower (in our analysis, by a factor of 100).
Low moisture diffusivities are found in nonporous and sugar-containing
foods, while higher values of moisture diffusivity characterize porous food materi-
als. Diffusivities higher than the self-diffusivity of water are indicative of vapor
diffusion in porous solids.
The moisture diffusivity increases, in general, with increasing moisture con-
tent. Temperature has a positive effect, which depends strongly on the food mate-
rial. The energy of activation for diffusion E of water is, in general, higher in the
dry food materials. Some observed exceptions may be explained by the prevailing
type of diffusion. Thus, lower values of activation energy for diffusion are ex-
pected for porous foods, where vapor diffusion is important. In general, tempera-
ture has a stronger effect on diffusivity in the liquids and solids than in the gas
state (see Chapter 2).
200 Chapter 6
Table 6.4 Mathematical Model for Calculating Moisture Diffusivity in Foods as a

Function of Moisture Content and Temperature
Proposed Mathematical Model
X
£> = • Do exp exp
l +X RT T \+x t
RT T
where D (m2/s) the moisture diffusivity,

X (kg/kg db) the material moisture content,
r(°C) the material temperature,
Tr = 60°C a reference temperature, and
R = 0.0083143 kJ/mol K the ideal gas constant.
Adjustable Model Parameters
• D0 (m2/s) diffusivity at moisture X = 0 and temperature T = Tr

• D, (m2/s) diffusivity at moisture X = oo and temperature T = T.
• E0 (kJ/mol) activation energy for diffusion in dry material at X = 0
• EI (kJ/mol) activation energy for diffusion in wet material at X = oo
Table 6.5 Parameter Estimates of the Proposed Mathematical Model
Material No. of No. of Di Do Ei Eo sd

Papers Data (m2/s) (mVs) (kJ/mol) (kJ/mol) (m2/s)
Cereal products
Corn
- 4 26 4.40E-09 O.OOE+00 0.0 10.4 1.48E-10
dent 3 15 1.19E-08 O.OOE+00 49.4 73.1 3.30E-10
grains 3 28 1.15E-09 6.66E-11 10.2 57.8 3.17E-10
kernel 4 25 5.87E-10 5.32E-10 0.0 33,8 1.88E-11
pericarp 3 13 1.13E-09 O.OOE+00 10.0 5.0 2.34E-11
Pasta
- 3 21 1.39E-09 O.OOE+00 16.2 2.0 7.71E-12
Rice
kernel 3 12 9.75E-09 O.OOE+00 12.5 2.0 5.52E-11
Rough rice
- 7 35 2.27E-09 O.OOE+00 12.7 0.7 3.66E-11
Wheat
- 6 22 1.94E-09 1.30E-09 0.0 46.3 9.53E-11
Fruits
Apple
- 8 39 7.97E-10 1.16E-10 16.7 56.6 1.92E-10
Banana
- 4 34 2.03E-09 4.66E-10 9.9 4.6 1.77E-10
Grapes
seedless 3 32 5.35E-09 O.OOE+00 34.0 10.4 1.45E-10
Raisins
- 3 10 8.11E-10 1.05E-10 21.4 50.1 6.88E-11
Model foods
Amioca
- 4 49 1.52E-08 1.52E-08 0.0 33.3 1.02E-09
Hvlon-7
- 5 48 1.96E-08 1.96E-08 0.0 24.2 3.87E-09
Vegetables
Carrot
- 9 90 2.47E-09 1.54E-09 13.9 11.3 1.69E-09
Garlic
- 4 22 5.33E-10 1.68E-11 15.4 7.1 7.43E-11
Onion
- 4 31 1.45E-08 O.OOE+00 70.2 10.4 1.58E-09
Potato
- 16 106 1.57E-09 4.31E-10 44.7 76.9 4.02E-10
202 Chapter 6
l.E-06
• Moisture - infinite
l.E-07 Q Moisture - zero
S" l.E-08
S,
•I" l.E-09
IS l.E-10
l.E-11
l.E-12
T S .a a a
8 1 11 = t •= •! a
i a o o ,2
£ o- JJ
3 | «
100
• Moisture = infinite
o 13 Moisture = zero
E
i-:
^
>.
£*
I
. * I 1
o o S.
Figure 6.6 Parameter estimates of the proposed mathematical model.

l.E-06
l.E-07
Moisture (kg/kg db)
Figure 6.7 Predicted values of moisture diffusivity of model foods at 25°C.

204 Chapter 6
.E-06
H Model foods |——
:ratui•e (°C) = 60
-f
.E-07 —
l.E-08
Hylon-7
.|" l.E-09 — Amioca —

i 1
l.E-10
.E-ll
l.E-12
0.1 1 10
Moisture (kg/kg db)
Figure 6.8 Predicted values of moisture diffusivity of model foods at 60°C.

l.E-06
l.E-07
l.E-08
f l.E-09 4
l.E-10
l.E-1
l.E-12
Moisture (kg/kg db)
Figure 6.9 Predicted values of moisture diffusivity of fruits at 25°C.

206 Chapter 6
l.E-06
Temperature (°C) = 60 -4
l.E-07
Moisture (kg/kg db)
Figure 6.10 Predicted values of moisture diffusivity of fruits at 60°C.

l.E-06
1
H Vegetables
Tempera ture i °C) = 25
l.E-07
l.E-08
l.E-12
0.1 10
Moisture (kg/kg db)
Figure 6.11 Predicted values of moisture diffusivity of vegetables at 25°C.

208 Chapter 6
l.E-06
l.E-07
l.E-12
0.1 1 10
Moisture (kg/kg db)
Figure 6.12 Predicted values of moisture diffusivity of vegetables at 60°C.

l.E-06
l.E-07
l.E-12
0.1 10
Moisture (kg/kg db)
Figure 6.13 Predicted values of moisture diffusivity of corn at 25°C.

210 Chapter 6
l.E-06
- r
——|Cere al products (corn)
Jtr
h- Temperature (°C) = 60
f
.E-07
l.E-12
0.1
Moisture (kg/kg db)
Figure 6.14 Predicted values of moisture diffusivity of corn at 60°C.

Garlfc.E-06
real products
——————— | C( t~r
Temperature (°C) = 25
i i
.E-07 -
-
.E-08 - ——
.E-09 -
— Rice kernel
Corn i
.E-10 -j ^^ •"
r^j i Vheat
•"^^
j !
Lx^' Rough rice '
x
X ^|x-
.E-ll -——^^^r —————— F asta
^^^ Pact n
F.n a
0.1 1 10
Moisture (kg/kg db)
Figure 6.15 Predicted values of moisture diffusivity of cereal products at 25°C.

212 Chapter 6
l.E-06
1^«™-™-™M™«»™I»™
Cereal products
Temperature (°C) = 60
.E-07
l.E-08
£
£ l.E-09
' Rice kernel
wheat
l.E-10 -I
Rough rice
Pasta
l.E-11
l.E-12
0.1 1 10
Moisture (kg/kg db)
Figure 6.16 Predicted values of moisture diffusivity of cereal products at 60°C.

Fruits Apple
Total Number of Papers 8
Total Experimental Points 64
Points Used in Regression Analysis 36 (56%)
Standard Deviation (sd, rti'/s) 1.92E-10
Relative Standard Deviation (rsd, %) 457
Parameter Estimates
Di (m2/s) 7.97E-10
Do (mj/s) 1.16E-10
Ei (kJ/mol) 16.7
Eo (kJ/mol) 56.6
.E-06
Temperature (°C)
— 140
— «60
l.E-07 A 80
l.E-08
•I" l.E-09
l.E-10
l.E-11
l.E-12
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.17 Moisture diffusivity of apple at various temperatures and moisture

contents.
214 Chapter 6
Fruits Grapes seedless

Standard Deviation (sd, rrrVs) 1.45E-10
Relative Standard Deviation (rsd, %) 1 31
Parameter Estimates
Di(m 2 /s) 5.35E-10
Do (m2/s) O.OOE+00
Ei (kJ/mol) 34.0
Eo(kJAnol) 10.4
1 F-Ofi ————————————————— ;—————— —
— Tem perat ure (°C) _L
• 40 —
• 60
l.E-07 - A 80
—————
————————
————————
l.E-08 - 1
——————————
h-
•f l.E-09 - —————————— —————— -1
1 ^>•
^^ ^
^^
=^
1 ~~~~
^ !• •• *
•*
i 1
l.E-10 -
1
=1IE I
J r^ i
01
-_
~*—» ———
'-
l.E-11 -
l.E-12 ————————————————————————————————————
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.18 Moisture diffusivity of grapes at various temperatures and moisture

contents.
Fruits Banana
Standard Deviation (sd, rrvVs) 1.77E-10
Parameter Estimates
Di (m'Vs) 2.03E-09
Do(m'Vs) 4.66E-10
Ei (kJ/mol) 9.9
Eo (kJ/mol) 4.6
l.F-06 ———————————
—— Tern perature (°C) —
'
• 60
l.E-07 - -4- A 80 ———
——— ———
l.E-08 -
(i
Diffusivity (m2/s)
Sm.
^
h=Hs_^M ^s.
BH Si
• |—
o
MD
m
-1——————f ———
I "
*
^-
hn
0
—— ———
l.E-11 -
l.E-12 -
01 1.0 10.0
Moisture (kg/kg db)
Figure 6.19 Moisture diffusivity of banana at various temperatures and moisture

contents.
216 Chapter 6
Vegetables Potato
Standard Deviation (sd, m2/s) 4.02E-10
Relative Standard Deviation (rsd, %)______122
Parameter Estimates
Di (m2/s) 1.57E-09
Do (m2/s) 4.31E-10
Ei (kJ/mol) 44.7
Eo (kJ/mol) 76.9
l.E-06
Temperature ( C)
• 40
• 60
l.E-07 A SO
l.E-12
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.20 Moisture difrusivity of potato at various temperatures and moisture

contents.
Vegetables Carrot
Relative Standard Deviation (rsd, %)_____18699
Parameter Estimates
Di (m"/s) 2.47E-09
Do(rrrVs) 1.54E-09
Ei (kJ/mol) 13.9
Eo(kJ/mol) 11.3
I.F-Ofi
l.E-07
l.E-08
• l.E-09
l.E-10
l.E-11
l.E-12
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.21 Moisture diffusivity of carrot at various temperatures and moisture

contents.
218 Chapter 6
Vegetables Onion
Standard Deviation (sd, m'Vs) 1.58E-09
Parameter Estimates
Di (m"/s) 1.45E-09
Do (mVs) O.OOE+00
Ei (kJ/mol) 70.2
Eo (kJ/mol) 10.4
1.E-06
l.E-
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.22 Moisture diffusivity of onion at various temperatures and moisture

contents.
Vegetables Garlic
Standard Deviation (sd, m'Vs) 7.43E-1 1
Parameter Estimates
Di (m"/s) 5.33E-10
Do(nWs) 1.68E-11
Ei(kJ/moI) 15.4
Eo(kJ/mol) 7.1
l.E-06 - —j —
— Tern perat ure(°C) =

re
=P
• 40
• 60
l.E-07 - A 80
l.E-08 -
W5
"E,
•f l.E-09 -
la r-
1
3 i~~*
r*~m
5 «• ~
*•?
*—• ^ -}
l.E-10 , ^ •if* •*
«• -
1
*~\fff* ^*^ ——
———— •—————
l.E-11 - 1
l.E-12 - —— — — - - - - - -
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.23 Moisture diffusivity of garlic at various temperatures and moisture

contents.
220 Chapter 6
Cereal Products Wheat

Standard Deviation (sd, m2/s) 9.53E-1 1
Parameter Estimates
Di(m"/s) 1.94E-10
Do(mVs) 1.30E-10
Ei (kJ/mol) 0.0
Eo (kJ/mol) 46.3
1 ,F,-06 i————— i—————
!
)
———— B40 ———
• 60
l.E-07 - A 80 ———
i i
l.E-08 -
tfi
1
-
\
i
•1" l.E-09 -
V)
———4,
S ———*-• k A I\
\
»
l.E-10 - ^fc
J —f—
1
— •-
1 1
l.E-11 - 1
1
———— I EE^ 1——
l.E-12 -
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.24 Moisture diffusivity of wheat at various temperatures and moisture

contents.
Cereal Products Corn dent

Standard Deviation (sd, rrrVs) 3.30E-10
Parameter Estimates
Di(rrrVs) 1.19E-09
Do (m"/s) O.OOE+00
Ei (kJ/mol) 49.4
Eo(kJ/mol) 73.1
l.E-06 -
peral ure CC)
• 40
• 60
l.E-07 - A80
l.E-08 -
5"
= \
^^
+*
•f l.E-09 -- _>1
M - .^T —*
**?—-———— < k—
^*
a
i
\±*
L****T
•^M
;\^^j^^
J
l.E-10
i
1 —« t-
1 11
l.E-11 -
0.1 1.0 10.0

Moisture (kg/kg db)
Figure 6.25 Moisture diffusivity of corn (dent) at various temperatures and mois-
ture contents.
222 Chapter 6
Cereal Products Corn grains

Standard Deviation (sd, m'Vs) 3 . 1 7E- 1 0
Relative Standard Deviation (rsd, %) 1 53
Parameter Estimates
Di(m<Vs) 1.15E-09
Do (m'Vs) 6.66E-11
Ei (kJ/mol) 10.2
Eo(kJ/mol) 57.8
l.F-06 —————————————————————————————————— ,—
u
T A m n o r n + i i f o ("f~
) ^
-i
———— «40 ——— - -
• 60
l.E-07 - ————— A 80 —p-
l.E-08 -
k—
•—
"E I
Jj
1
li
•f l.E-09 -
1 ^•^ r^
1 \
l.E-10 -
• "* | => 1 3
l.E-11 T
0.1 1.0 10.0

Moisture (kg/kg db)
Figure 6.26 Moisture diffiisivity of corn (grains) at various temperatures and

moisture contents.
Cereal Products Corn kernel

Standard Deviation (sd, nWs) 1.88E-1 1
Parameter Estimates
Di(m'Vs) 5.87E-11
Do(m'Vs) 5.32E-11
Ei (kJ/mol) 0.0
Eo (kJ/mol) 33.8
I P-flfi ————————————————— r-i————————————————————————
tE
CO =E ~ q
———— B40 —
• 60
l.E-07 - ———— A 80 —
l.E-08 -
•f l.E-09 -
ia
4
l.E-10 - -f-
=^1
• J ^Ît 4=^
l.E-11 - _•
l.E-12 -
0.1 1.0 10.0
Moisture (kg/kg db)
Figure 6.27 Moisture diffusivity of corn (kernel) at various temperatures and

moisture contents.
224 Chapter 6
Cereal Products Corn pericarp

Standard Deviation (sd, nTVs) 2.34E-1 1
Parameter Estimates
Di(m 2 /s) 1.13E-10
Do (nrVs) O.OOE+00
Ei (kJ/mol) 10.0
Eo (kJ/mol) 5.0
l.E-06 - r = i ^
—— Temperat ure(°C) =g= q
- ———— «40
• 60
l.E-07 - -p——— A 80 — i
l.E-08 -
ff> :
(S
•f l.E-09 -
•a
1
'
Q
l.E-10 -
i—————
•
——i
l.E-11 '| ^
*
l.E-12 -
01 1.0 10.0
Moisture (kg/kg db)
Figure 6.28 Moisture diffusivity of corn (pericarp) at various temperatures and

moisture contents.
Cereal Products Pasta

Parameter Estimates
Di(m 2 /s) 1.39E-10
Do(m 2 /s) -1.6 IE-21
Ei(kJ/mol) 16.2
Eo (kJ/mol) 2.0
i F-Ofi ———————
~ 1_ f
—— Tern perat ure(°C) =t4=

• 40 _ . ^rj^
• 60
l.E-07 - A 80
l.E-08 -
Sfl
ts
•f l.E-09 -
'&
3
l.E-10 -
-jfr-
^**^&k *—
=^TJ
l.E-ll ^^
' •————
l.E-12 -
01 1.0 10.0
Moisture (kg/kg db)
Figure 6.29 Moisture diffusivity of pasta at various temperatures and moisture

contents.
226 Chapter 6
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Diffusivity and Permeability of Small
Solutes in Food Systems
I. INTRODUCTION
The diffusion of small molecules in food and food packaging materials is

important in food processing operations, food product development, and food
process control. It involves the transport of small molecules, such as sugars, or-
ganic acids, flavor components, salts, preservatives, and gases (e.g. oxygen, car-
bon dioxide). In addition, the transport of larger molecules, such as lipids, is of
interest to food processing, such as oil extraction. The transport of solutes is of
fundamental importance to the physical separation processes, such as solvent ex-
traction (e.g. sugar/water), ion exchange (e.g. de-acidification and de-bittering of
juices), reverse osmosis, and ultrafiltration. Mass diffusivity is the basic compo-
nent of permeability of packaging films and food coatings, which are used as bar-
riers to water, oxygen, and carbon dioxide transport in food materials.
Theoretical prediction of solute diffusivity in solid and semisolid food mate-
rials is not feasible, and experimental measurements and data are necessary. The
experimental methods and theoretical analysis of water transport in food materials
(Chapter 5) are utilized in the diffusion of small solutes in food systems.
A. Diffusivity of Small Solutes

Mass transfer of small molecules can be analyzed by either the diffusion
(Pick) model or the mass transfer coefficient concept (Cussler, 1997). The diffu-
sion model, in general, is used in modeling mass transport of water and small sol-
utes within foods, since solid and semisolid food materials have complex struc-
tures that strongly effect mass diffusivity. Mass transfer coefficients are used in
237
238 Chapter 7
designing processing equipment where mass is transported between phases, as in

drying and separation processes, such as extraction and membrane processing.
The transport of small solutes in simple gases and liquids can be predicted
by molecular dynamics (see Chapter 2), and reliable data on mass diffusivity is
available in the literature. Prediction of diffusivity is difficult in complex fluid
foods and in solid/semisolid foods, where experimental measurements and empiri-
cal correlations are essential.
Although small solutes can be transported in food systems by different
mechanisms, molecular diffusion is generally accepted as the basic transport proc-
ess, in a similar manner with the transport of water (see Chapter 5). Thus, the ef-
fective diffusivity, an overall transport coefficient, can be defined, assuming that
the driving force is a concentration gradient (dC/dz), and applying the diffusion
(Pick) equation:
(8C/&) = (d/dz) [D(cC/&)} (7-1)
Table 7.1 shows some typical values of diffusivity in gases, liquids, and sol-
ids (see also Table 2-4).
The diffusivity of solutes in fluid foods is of the order of 1x10"9 m2/s, while
in solid and semisolid foods the diffusivity varies widely in the range 10'14 to 10~8
m2/s, due to heterogeneous structure, which involves diffusion in gas and liquid
phases. Diffusion in polymers varies from 10"18 to 10'10 m2/s, due to different
structures (rubbery and glassy states).
Table 7.1. Typical Diffusivities of Small Solutes
Diffusivity in D, m / s
Gases IxlO' 5
Liquids IxlO' 9
Polymers (rubbery) IxlO' 14 - IxlO' 10
Polymers (glassy) IxlO' 18 - IxlO' 12
Diffusivity and Permeability of Small Solutes in Food Systems 239
B. Measurement of Diffusivity
The measurement of diffusivities of small molecules in solid food materials
is discussed in Chapter 5, in connection with the transport of water (moisture).
Some of these methods are also used for the determination of the diffusivities of
small solutes in polymers and food solids, especially the sorption kinetics, the
permeability and the concentration-distribution techniques. Additionally, two
more experimental methods, used for the measurement of diffusivities of solutes in
gases, liquids, and membranes, are important for mass transfer in food systems,
i.e. the diaphragm cell and the Taylor dispersion method.
1. The Diaphragm Cell

The Stokes diaphragm cell is used for the measurement of the diffusion co-
efficients in gases, liquids, and across membranes, with an accuracy of up to 0.2%
(Cussler, 1997). The method is based on the diffusion of the solute between two
compartments separated by either a fritted glass surface or by a porous membrane,
as shown diagrammatically in Figure 7.1.
The two compartments are kept at different but constant solute concentra-
tions, using magnetic stirring. The fritted glass diaphragm may be replaced by a
piece of filter paper for faster measurement.
A magnetic
stirrer
glass
"frit
stirring
B bars
Figure 7.1 Stokes diaphragm cell.

240 Chapter 7
After a certain time t of diffusion, the contents of the two compartments are
analyzed for the concentration of the solute, and the diffusivity D is estimated
from the equation:
D = (I/ft) [(C, o - C2 o)/(Cj - C2)] (7-2)
where C/o, C?ft C/ C2 are, respectively, the initial and final solute concentrations in
compartments 1 and 2, and jBis the calibration constant, related to the dimensions
of the cell:
P=(Alt)(\IV,+ \/V2) (7-3)
where A is the area available for diffusion, / is effective thickness of the dia-
phragm, and F; and V2 are the volumes of the two cell compartments.
The two compartments are placed vertically, so that the diaphragm surface
for diffusion is horizontal. Usually, 1 and 2 indicate the bottom and top cell com-
partments, respectively. The horizontal position of the diaphragm is necessary to
assure uniform concentration gradient and prevent free convection, which might
develop in a vertical or inclined position. The accuracy of the method depends on
the accuracy of determination of the concentration differences between the com-
partments, and not on the concentrations themselves.
2. The Taylor Dispersion Method

The Taylor dispersion method, used for both gases and liquids, is based on
the dispersion by diffusion of a solute injected in a stream of a carrying fluid (Cus-
sler, 1997). A sharp pulse on the solute is injected into a fluid moving in laminar
flow in a long tube. The flow exiting the tube is analyzed for the solute (by differ-
ential refractometry) over a period of time and the concentration profile is deter-
mined. The diffusivity D is estimated from the concentration profile C at time t,
representing the decay of a pulse, using the equation:
C = (Ml nr ') exp[-(z - u t)2 / 4 E t] I (4 nEi )1/2 (7-4)
where Mis the total solute injected, r is the tube radius, z is the diffusion distance,
and £ is a dispersion coefficient given by the equation:
E = (u r)21 (48 D) (7-5)
where u is the average velocity of the flowing solvent. Since the refractive index is
a linear function of concentration, the refractive index profile can be used for the
determination of the diffusivity.
Very high accuracies in the determination of diffusivity of solutes in fluids

can be obtained by interferometers, such as the Gouy, the Mach-Zehnder, and the
Rayleigh instruments. The interferometers are based on measuring an unsteady-
state profile of the refractive index of two solutions in a transparent system, diffus-
ing into each other.
II. DIFFUSIVITY IN FLUID FOODS
The diffusivity of solutes in dilute aqueous solutions is of importance to

food systems, since most food components are present in foods at low concentra-
tions (infinitely dilute solutions).
A. Dilute Solutions
Table 7.2 shows some typical diffusivities of solute gases in dilute aqueous
solutions (Cussler, 1997) (see also Table 2-4). The diffusivity of water and oxygen
in dilute ethanol solutions at 25°C is 1.24 x 1Q"9 and 2.64 x 10~9m2/s, respectively.
Table 7.3 shows some typical diffusivities of solutes in dilute water solu-
tions, which are of interest to food systems (Cussler, 1997; Schwartzberg and
Chao, 1982).
The diffusivity of low-molecular weight solutes is in the same range with
the self-diffusivity of water (1 x 1Q"9 m2/s). The diffusivity, in general, decreases
as the molecular size of the solute is increased. High-molecular weight food com-
ponents, such as proteins and polysaccharides, have diffusivities close to that of
water in a solid starch/sugar gel (see Chapter 5).
Table 7.2 Diffusivities of Gases in Dilute Water

Solutions at 25°C
Solute________________Ax 10'9m2/s
Air 2.00
Oxygen 2.10
Nitrogen 1.90
Chlorine 1.25
Carbon dioxide 1.90
Ethylene 1.87
Hydrogen 4.50
Methane 1.49
Ammonia 1.64
242 Chapter 7
Table 7.3 Diffusivities of Solutes in Dilute

Water Solutions at 25°C
Solute D, x 10-'°m2/s
Ethanol 8.40
Acetic acid 12.1
Butyric acid 9.20
Glycine 10.6
Sucrose 5.40
Glucose/fructose 6.90
Maltose 4.80
Glycerol 9.20
Hemoglobin 0.69
Fibrinogen 0.20
Lactoglobulin 0.70
Ovalbumin 0.78
The diffusivity of solutes in dilute water solutions can be predicted by em-

pirical equations based on molecular dynamics and hydrodynamics, like the
Wilke-Chang equation (2-34) and the Stokes-Einstein equation (7-6):
D = (kBr>/(6xtiBr) (7-6)
where r is the particle radius, rjB is the viscosity of the solvent (water), T is the
absolute temperature, and kB = 1.38xlO"22 J/molecule K is the Boltzmann constant.
The Stokes-Einstein equation is based on hydrodynamic and not molecular
forces, and it is applicable to solutes of molecular size five times larger than the
solvent. For smaller molecules, the Wilke-Chang equation gives better prediction
(Cussler, 1997). In both equations, the diffusivity is inversely proportional to the
viscosity of the solution. In very viscous solutions, the diffusivity becomes inde-
pendent of viscosity, e.g. the D of sugar in a gel is nearly equal to the D in water.
B. Concentrated Solutions
The diffusivity of solutes in liquids D varies considerably with the concen-
tration, sometimes with maximum or minimum values at certain concentrations.
The D can be estimated from the diffusivity at infinite dilution Dm using a correc-
tion factor to account for the effect of chemical activity on the transport rate (Reid
etal., 1987; Cussler, 1997):
D = D0(l+dlna/dlnC) (7-7)
where a is the activity and C is the concentration of the solute in the solution.
The diffiisivity of the mixture at infinite dilution D0 can be estimated from
the diffusivities at infinite dilution of the solute and the solvent, and the corre-
sponding mole fractions (x/ and *?):
A, = [A,(x,= i)]MZ) 0 fe=im (7-8

The correction factor (d lnor/9 InQ represents the molecular and hydrodynamic
interactions in the concentrated solution, and it is negative in nonideal solutions
(Cussler, 1997). Thus, D of the solute in a mixture becomes lower than D0 at both
extreme concentrations (xlt x 2 = 1), with a minimum at an intermediate concentra-
tion.
III. DIFFUSION IN POLYMERS
The sorption and transport of small molecules (solutes) in polymeric materi-

als are the basic physical phenomena of several important applications, such as
separation processes, barrier films, and controlled release. Most of the research
and theory in this area concerns synthetic polymers of known composition and
structure, but the available knowledge can be applied to natural polymers, which
are the basic structural components of most food materials.
Molecular (Fickian) diffusion is assumed as the main mass transport mecha-
nism, although in some cases other mechanisms may be involved. Solution of the
diffusion equation (7-1) forms the basis of mathematical analysis of the experi-
mental data. Most of the diffusivity data of solutes in polymers have been obtained
using the sorption and/or the permeability methods (Chapter 5).
The physical and transport properties of polymers are affected strongly by
the size and shape (linear, branched, cross-linked) of the molecules (van Krevelen,
1990; Bicerano, 1996). Polymer materials can change their size (molecular
weight) and microstructure during processing, changing their thermodynamic and
transport properties, such as phase equilibria and diffusion coefficients. These
changes should be considered in modeling and simulations of industrial processing
and applications of polymers (Bokis et al., 1999).
The polymer structure is defined by the chemical constitution, set by synthe-
sis (or biosynthesis) and the morphology (microstructure), set by processing
(Theodorou, 1996). Quantitative relations can be established between polymer
structure and transport properties (diffusivity, permeability), based mainly on ex-
perimental measurements and phenomenological correlations from various sys-
tems (Petropoulos, 1994). Theoretical predictions and computer simulations, based
on molecular science, are still at the development stage, and they could find useful
applications in the future.
244 Chapter 7
A. Diffusivity of Small Solutes in Polymers

The transport of small solutes (penetrants) normally obeys the Pick diffusion
equation, and an effective diffusivity D can be estimated, assuming that the driv-
ing force is the concentration gradient. The Fickian diffusion is applicable to low
concentrations (infinite dilution) of the solute, which is the case of most applica-
tions in polymer and food systems.
In some biological systems, the thermodynamic diffusivity DT is used, based
on the chemical potential gradient, which is related to the normal diffusivity D by
the equation.
D = DT(d\na/d\nQ (7-9)
where a is the chemical activity of the species at concentration C (Frisch and

Stern, 1983).
In most food-related applications, the concentration of the solutes in the
polymer matrix is low, and the two coefficients become equal (D = D-f). Sorption
kinetics and permeability measurements (see Chapter 5) can be used for the de-
termination of diffusivity D of solutes in polymeric materials (Vieth, 1991)
Solid polymers are amorphous materials, which exist in two nonequilibrium
states, i.e. glassy and rubbery, with transition between the states at the glass transi-
tion temperature (Tg). The glassy state is characterized by a dense, tough, and low
porosity (2-8%) structure. The diffusivity of small solutes in the glassy state is
very low, e.g. IxlO" 18 to IxlO" 10 m2/s, depending on the polymer structure and the
molecular size and concentration of the penetrant. The solute diffusivity increases
substantially at higher solute concentrations, by plasticization of the polymer ma-
trix. The activation energy for diffusion is much higher than in the rubbery state,
and it increases near the glass transition temperature.
In the rubbery state, polymers are flexible, elastic materials, with relatively
large free volume, which facilitates molecular diffusion. Crystallization or stretch-
ing (induced orientation) of the polymers can reduce solute diffusivity. Liquids
and vapors may cause swelling of the glass polymeric matrix, facilitating the dif-
fusion process.
Normal diffusion in the glassy and rubbery state is Fickian, i.e. the diffusion
rate is proportional to the square root of time, according to Eq. (5-4) (Peppas and
Brannon-Peppas, 1994). In glassy polymers (T < Tg), non-Fickian or anomalous
diffusion of solutes may take place, since diffusion and polymer relaxation are
comparable. Case II diffusion is also possible, when the diffusion rate is much
faster than the relaxation of polymer molecules.
l.E-09 T
l.E-14
30 35 40
Temperature (°C)
Figure 7.2 Arrhenius plots of diffusivity of solutes (water and carbon dioxide) in a poly-
meric material showing breaks at the glass transition temperature (Tg).
Most of the research and development in polymer science and engineering is

directed to the design of specific polymer structures of known barrier properties
(membranes), which can be used in separation processes of various molecular
species. Separations based on molecular or particle size include reverse osmosis,
gas separation, and ultrafiltration.
246 Chapter 7
B. Glass Transition
Mass transport (diffusion) of solutes in polymers is affected strongly by the
thermodynamic state of the material. The molten polymer is a viscous fluid of
non-Newtonian characteristics, which upon cooling forms two amorphous solid
states, the rubbery, and, at lower temperature, the glassy state. The glass transition
temperature Tg, a second-order transformation, is an important characteristic of the
polymeric materials (Roos, 1992).
The nonequilibrium rubbery and glassy states are affected strongly by the
presence of solutes, such as gases, water and organic solvents, which reduce, in
general, the glass transition temperature.
The mechanical and transport properties of polymers at temperatures below
and much above Tg, are affected by the temperature, following the familiar Ar-
rhenius equation. However, in the temperature range Tg to (rg+100°C) the Wil-
liams-Landel-Ferry (WLF) equation is more appropriate (Levine and Slade, 1992):
log (ar) = [-C, (T - T,)} I [ C , + (T- Tg)] (7-10)
where aT is a scaling parameter, or the property ratio at T and Tgi e.g. relaxation
time, viscosity, or diffusivity, and C/ and C2 are characteristic parameters of the
WLF equation, determined experimentally. In normal systems the values C\ =
17.44 and C2 = 51.6 are used.
The WLF equation predicts a sharp change of the scaling factor as the tem-
perature is increased immediately above Tg, e.g. the viscosity decreases 3 to 5 or-
ders of magnitude at temperatures 20-3 0°C above Tg. The WLF equation can be
used to nonpolymer systems, which exhibit a glass transition temperature, such as
sugar solutions, which are of interest to foods (Roos, 1992)
The effect of water on the glass transition temperature of polymers and other
food components, exhibiting glass transition, is of particular importance to food
processing and food quality. The Tg of dry food components is relatively high but
it decreases continuously even below 0°C as the moisture content is increased.
Figure 7.3 schematically shows the change of Tg of a food biopolymer as a func-
tion of moisture content (Roos, 1992).
—————-
!
V
C
>w
!
\.
\
cmpcraturc (°C)
o
\
X
0
n
X.
x^
x^
3
-
^\^^
%v
0 -
î ——
r -
0 5 10 15 2
Moisture (%)
Figure 7.3 Change of glass transition temperature Tg of maltodextrin with water content.
C. Clustering of Solutes in Polymers

Clustering of solute molecules in polymeric materials is of importance to the
sorption and diffusion properties of the system. The clustering of water is of par-
ticular interest to food systems. The clustering theory of Zimm and Lundberg is
based on the statistical mechanics of fluctuations, and a simplified version of clus-
tering of water in polymers is presented by Vieth (1991). The theory interprets the
sorption isotherm over the entire range of penetrant activities.
The clustering function CF is a characteristic quantity that enables the calcu-
lation of the tendency of the (water) molecules to cluster in the given polymer
matrix. The clustering function is defined as the ratio CF = Gu/V,, where G// is
the cluster integral, calculated from the molecular pair distribution, and V\ is the
partial molecular volume of the solute (e.g. water).
The cluster function varies normally from -1 to above 2. Positive CF means
that the solute increases the free volume of the polymer matrix, increasing the
sorption capacity, diffusivity, and permeability (high relative humidity RH). Nega-
tive CF means that the solute molecules are attached to specific sites dispersed
throughout the polymer matrix, reducing the sorption and transport properties (low
RH). Clustering of water can occur even at low RH by cross-linking of the poly-
mer, or by the addition of plasticizers, like polyols.
248 Chapter 7
D. Prediction of Diffusivity
The experimental data of diffusivity of small solutes in polymers are often
correlated by empirical equations as a function of concentration and temperature,
in a similar manner with the data on moisture diffusivity (see Chapters 5 and 6).
Although satisfactory prediction is presently not feasible, some theoretical ap-
proaches have been used for this purpose, i.e. the dual-sorption model, the free-
volume model, and the molecular simulation method.
1. Dual-Sorption Model
This model has been applied to the sorption and diffusion of small mole-
cules (mainly gases) in glassy polymers. The glassy matrix is assumed to contain
some microcavities or "holes", created when the polymer melt or rubber is
quenched (cooled rapidly). The solute is dissolved in the glassy polymer by two
parallel mechanisms, i.e. dissolution in the polymer mass according to the Henry
law, and filling of the "holes" according to the Langmuir model (Frisch and Stern,
1983; Vieth, 1991).
The Henry law for dissolution is written in the form:
CD = SDp (7-11)
where CD is the concentration of the solute in the polymer, p is the partial pressure
of the solute (gas), and SD is the solubility, which is equal to \/H, where H is the
Henry constant.
The Lagmuir equation for filling the holes takes the form:
CH = (C'bp)l(\+bp) (7-12)
where C'is a "hole saturation" constant, and b is a "hole affinity constant", repre-
senting the ratio of rate constants of gas adsorption and desorption in microcavi-
ties.
The two populations are assumed to be in local equilibrium, and the overall
solubility Sp, derived from the last equation, is given by:
S p = C / P = SD + ( C ' b ) / ( l + bp) (7-13)
The effective diffusivity D and the solubility S of the solute in the polymer
are determined experimentally from sorption and permeability measurements (see
Chapter 5). The effective diffusivity D is related to the diffusivities in the dis-
solved state DD and in the holes DH by the overall flux equation:
J= - D (dCI dz) = - DD(dCDl dz) - DH (dCHl dz) (7-14)

The dissolved solute can diffuse readily, while only part of the solute in the
"holes" is available for diffusion, i.e. DD > DH (partial-immobilization model).
2. Free- Volume Model

Free-volume models have been proposed for the prediction of transport
properties in liquids and solids, based on the availability of elements of free vol-
ume within the material, through which the solute molecules can be transported
(Frisch and Stern, 1983: Petropoulos, 1994). For polymeric materials, the Vrentas
and Duda model, which can be used for both the glassy and the rubbery state, is
discussed briefly here (Duda and Zielinski, 1 996).
The self-diffusion coefficient of a molecule (1) in a binary mixture is an ex-
ponential function of the ratio of the volume required for diffusion of one mole V \
to the total free ("hole") volume per diffusing mole VFH. The diffusion coefficient
DI of a solute (1) in a binary polymer (2) mixture, in the rubbery state, is given by
the equation:
D, = Do exp(- E I RT) exp { - [ y(a>, V* , + w^ V\}\ I VFH } (7- 1 5)
where D0 is a constant, E is the activation energy, R is the gas constant, T is the

absolute temperature, coj and ca2 are the mass fractions of 1 and 2, f=F*; MjV^M^
and MI and A/? are the molecular weights of 1 and 2. The accommodation factor
y is taken between 0.5 and 1 .0.
The specific free- volume VFH is calculated from the equation:
VFH= (o,K,, (K2, + T- Tgl) + co2KI2 (K22 + T- Tg2) (7-16)
where Tgt, Tg2 are the glass transition temperatures of 1 and 2, and Klh K2i, KI2
and K22 are free-volume parameters of 1 and 2, determined experimentally.
The diffusivity (D = £>;) of trace amounts of a solute (1) in a glassy polymer
(2) is given by the simplified equations:
D, = Do exp(-E/RT) exp [ -(yco2 £ V'2) I VFm ] (7-17)
and
Tg2)} (7-18)
where /L= 1 - (a2-a2g), and a2wd a2g are the thermal expansion coefficients of
the rubbery and glassy states of the polymer.
The free-volume theory predicts the following changes of diffusion coeffi-
cient (Duda and Zielinski, 1996): Strong effect of temperature and concentration
250 Chapter 7
near the glass transition temperature; increase with the size of solute molecule;
plasticizers increase the available free volume, decrease the Tg, and increase the
diffusivity; addition of impermeable fillers reduces D by increasing the tortuosity
of the diffusing solute.
Yildiz and Kokini (1999) modified the free-volume theory to account for
the effect of temperature and water activity on the retention and release of flavor
compounds in food polymers. The diffusivity of hexanol, hexanal, and octanoic
acid in uncooked soy flour was predicted to decrease sharply as the temperature is
reduced in the rubbery state until the Tg, leveling-off at lower temperatures (glassy
state). The diffusivity of flavor compounds in gliadin was predicted to increase
sharply from about 1 x 10~18 m2/s to 1 x 10~10 m2/s, as the water activity was in-
creased from 0.2 to 0.8 (at 25°C). Cross-linking of food polymers, e.g. by cooking
of soy flour, predicts significant increase of diffusivity (i.e. reduced retention) of
flavor compounds (e.g. hexanal).
3. Molecular Simulation
Molecular simulations can describe sorption and diffusion phenomena in
polymer systems, based on chemical constitution of the components. Most of the
simulation work is related to simple amorphous rubbery and glassy systems, in
which solute transport is assumed to follow the solution-Fickian diffusion mecha-
nism of mass transport (Theodorou, 1996).
Molecular simulations are essentially solutions of the statistical mechanics
of a model of given molecular geometry and interaction parameters. They involve
the generation of configurations of the system, from which structural, thermody-
namic and transport properties can be extracted. Molecular dynamics (MD) as-
sumes that the penetrant (solute) moves into channels of the sorption sites, created
by small fluctuations in the polymer configuration.
Transition state theory (TST) provides a more approximate treatment of the
penetrant diffusion process, assuming a jumplike transport mechanism. The com-
puter time required for the extensive computations can be reduced by certain ap-
proximations, which are less severe than the ones used in the dual-sorption and
free-volume models. Computer calculations involve the estimation of the Henry
constant, the geometric characteristics of the accessible volume in the polymer
matrix, and its distribution and rearrangement with thermal action, using Monte
Carlo algorithms.
Molecular dynamics simulations have successfully predicted the self-
diffusion coefficient in glassy and rubbery polymers, interacting with penetrant
solutes. The objective of molecular simulations is to develop the field of applied
"molecular engineering of materials" for producing materials with tailored separa-
tion and barrier properties.
IV. DIFFUSION OF SOLUTES IN FOODS
The diffusivity of solutes and other molecules in food materials depends

primarily on the size of the diffusing molecule and the food structure. The needed
experimental measurements of diffusivity in solid and semisolid foods are usually
based on the concentration-distribution method, described in Chapter 5 (Naessens
et al., 1981, 1982; Giannakopoulos and Guilbert, 1986). Diffusivity data on salts,
organic and flavor components are of particular interest to food processing and
food quality.
A. Diffusivity of Salts
Table 7.4 shows typical diffusivities of sodium chloride in model food gels
and food materials. The diffusivity depends strongly on the physical structure of
the food material.
The diffusivity D of salt in dilute gels (Gros and Ruegg, 1987) is very close
to the D of salt in aqueous solutions, i.e. 12.5 * 10"10 m2 / s (see Table 2.4). Similar
high diffusivities are observed in high-moisture foods of gel structure, like pickles
(Pflug et al., 1975). Evidently, the salt ions can migrate in such gels at rates similar
to the diffusion in liquid water.
The salt diffusivity in Swiss cheese (Gros and Ruegg, 1987) is considerably
lower than in gels (1.9x 10"10 m2/s), evidently due to the higher solids concentra-
tion and the presence of fat globules in the material. Higher salt diffusivity values
D were reported by Pajonk et al. (2000) in brining Swiss cheese. The D value de-
creased from about 7 x 10"10 to 2 x 10"10m2/s when the brine concentration was
increased from 0 to 20% NaCl. The diffusivity of salt in white feta cheese was
determined as 2.3 x 10"10 m2/s (Yanniotis et al., 1994).
Table 7.4 Diffusivities D of Sodium Chloride in

Food Materials (20°C)
Material D, x 10"'° m2/s
Agar gel, 3 % solids 12.0
Pickles 11.0
Swiss cheese 1.90
Meat muscle, fresh 2.20
Meat muscle, thawed 4.00
Herring 2.30
Green olives, fresh 0.38
Green olives, treated 1.95
252 Chapter 7
The salt diffusivity in fresh meat muscle is 2.2 x 10"'° m2/s, while it is con-
siderably higher (4.0x 10~10 m2/s) in meat flesh that has been frozen and then
thawed (Dussap and Gros, 1980; Fox, 1980). The relatively low D of salt in the
meat is caused by the resistance of the cellular structure to mass transfer. The salt
diffusivity in fish is, in general, similar to the D in meat, e.g. 2.3 x 10"10 m2/s in
herring (Rodger et al, 1984).
The diffusivity of salt in fresh green olives is quite low (0.38 x 10"'° m2/s),
evidently due to the presence of skin and to high oil concentration. Treatment of
the olives with 1.8% caustic soda increases the D value to 1.95 x 10"10m2/s (Dru-
sasetal., 1988).
The diffusivity of sodium hydroxide in tomato skin, measured with a modi-
fied diffusion cell (Figure 7.1), was found to be 0.02 x 10"10m2/s (Floras et al.,
1989). A higher value was found for the diffusivity of the same alkali in the skin
of pimiento pepper (0.055 x 10~10m2/s).
Diffusivities of other salts of interest to foods (chlorides, nitrites, nitrates,
etc.) are similar to the D values of sodium chloride. A bibliography on the diffu-
sivity of salt in foods was prepard by Ruegg and Schar (1985).
B. Diffusivity of Organic Components

The diffusivity of organic solutes in food materials is important in food
processing operations, like extraction (sugars, lipids, flavors), and in food quality
(e.g. sugar taste, volatile flavor retention).
The diffusivity D of organics in liquid foods is related closely to the viscos-
ity 77 of the solution, through the relation r/D/T= constant Eq. (2-36). Organoleptic
flavor perception is related to the diffusivity of the flavor component (e.g. sugar)
and the viscosity of the liquid food (Kokini et al., 1982; Kokini, 1987). The flavor
of highly viscous pseudoplastic foods is enhanced by shearing, which reduces
considerably the apparent viscosity, increasing at the same time the diffusivity of
the flavor component(s).
For large molecules in food liquids, like peroxydase, the Stokes-Einstein
equation (7-6) can be applied, while for smaller solutes in sugar solutions (e.g.
nicotidamine) the Wilke-Chang equation (2-34) has been found applicable (Lon-
cin, 1980; Stahl and Loncin, 1979).
The diffusivity of nicotinamide in fructose solutions decreases from about
8 x 10~10 to 0.5 x 10~10 m2/s, when the sugar concentration is increased from 0 to
60%. In the same range of fructose concentration, the diffusivity of peroxidase
decreases from 1.0 x 10"10 to 0.1 x IQ"10 m2/s. The activation energy for diffusion
of both species increases sharply from 20 to 45 kJ/mol in the same sugar concen-
tration range.
The prediction models for the diffusivity of solutes in polymers, discussed
earlier in this chapter, are difficult to apply in solid and semisolid foods, due
mainly to the heterogeneous physical structure of the food materials. The presence
of significant open space in food solids, such as pores, cracks, and channels, com-
plicates the diffusion process, since a portion of the solutes can diffuse quickly in
the gas phase, while the rest diffuses very slowly from the sorbed or trapped state.
The diffusivity in the gas phase is about five orders of magnitude (x 105) higher
than in the solid phase.
The free-volume model, suggested for the prediction of diffusivities in
polymers, was applied by Yildiz and Kokini (1999) for the prediction of diffusiv-
ity of flavor components in solid foods. Application of this model assumes that the
food material behaves as a homogeneous polymer material of low porosity, such
as uniform protein, carbohydrate or lipid films.
The molecular simulation model (Theodorou, 1996), requiring extensive
computer calculations, when developed and applied further in the polymer field,
could be adapted to food materials in the future.
Table 7.5 shows some typical diffusivities of organic solutes in food materi-
als, which are useful in calculations involving solvent extraction (leaching) and
liquid infusion operations (Schwartzberg and Chao, 1982). The diffusivity of sug-
ars in gels (e.g. agar) is similar to the diffusivity in water solutions, Table 7.3
(Warin et al., 1997).
The diffusivity of solutes in solid foods D is considerably lower than in di-
lute water solutions, shown in Tables 7.2 and 7.3, due to blockage of diffusion
paths, occlusion (trapping), and sorption by the food biopolymers. The D in solids
is related to the diffusivity of the solutes in water Dw by an empirical relation
analogous to Eq. (5-2):
D = (ew/r)Dw (7-19)
where ew is the volume fraction of free water in the solid (analogous to porosity),
and T is the tortuosity of the diffusion path.
Table 7.5 Diffusivities of Solutes in Solid Foods

Solid Solute Solvent r,°c 7,
D, x 10'10 m /s
Sugar beets Sucrose Water 65 6.80
Sugar cane Sucrose Water 75 2.00
Apple slices Sugars Water 75 11.5
Coffee beans Coffee solubles Water 98 1.00
Soybean flakes Soybean oil Hexane 69 1.00
Cottonseed oil Cottonseed oil Hexane 69 0.27
Peanuts Peanut oil Hexane 25 0.006
254 Chapter 7
The free water fraction in the solid can be estimated from the moisture con-
tent and the sorption isotherm, but the tortuosity factor must be estimated indi-
rectly from the measured D. Both parameters are not constant during food process-
ing and storage, due to the significant changes of the food structure.
The effect of solids content on the diffusivity of organic compounds in
foods, is illustrated by the diffusivity of cyclohexanol in potato, which decreases
from 6 x 10'10 to 2 x 10~10 m2/s in high solids potato (Loncin, 1980). The activation
energy for diffusion is analogous to that of water in potato, 35.7 kJ/mol.
The diffusivity of a solute may be reduced significantly by the presence of
another solute, diffusing simultaneously in a solid food material (multicomponent
diffusion). Thus, the individual diffusivity of citric acid (1) in prepeeled potato is
reduced from /)/ = 4.3 x 10~10 to D12 = 6.6 x 10"" m2/s in the presence of ascorbic
acid (2), diffusing simultaneously. At the same time, the diffusivity of ascorbic
acid is reduced from D2 = 5.4 x IQ' 10 to D2, = 8.3 x IQ"11 m2/s (Lombardi et al,
1996). The diffusivities of the two solutes in dilute water solutions (w) are D!w =
6.6 x 10'10andZ)2w= 8.4 x I(r10m2/s.
C. Volatile Flavor Retention

The diffusion of volatile flavor (aroma) components in foods is important in
food processing operations, such as evaporation and drying, and in storage and
quality of food products. Most aroma components are very volatile in aqueous
solutions, since they form highly nonideal mixtures with water. The volatility of
these components at thermodynamic equilibrium is characterized by the activity
coefficient and the relative volatility, which are the basic elements of the vapor-
liquid equilibria (VLB). Calculation of (VLB) is required for the analysis of any
vapor-liquid separation or interaction (Prausnitz et al., 1986; Reid et al., 1987; Le
Maguer, 1992).
The relative volatility of an aroma compound A in dilute water solution aAw
is defined by the equation (Saravacos, 1995)
aAw=yApAo/Pwo (7-20)
where yA is the activity coefficient of A, and pAO, pHO are the vapor pressures of A
and water, respectively, at the given temperature.
The activity coefficient of a component YA is related to the concentration Q
and the chemical activity aA by the equation:
aA = /ACA (7-21)
The activity coefficients of aroma components in water and aqueous foods

are very high, especially for partially soluble organic flavor components, like es-
ters and higher alcohols. They are estimated by computer-aided techniques using
empirical models, like the UNIQUAC and the UNIFAC (Reid et al., 1987). The
presence of sugars in aqueous solutions, like in food materials, increases consid-
erably the activity coefficient (Saravacos et al., 1990; Sancho and Rao, 1997).
Table 7.6 shows some typical relative volatilities of volatile flavor com-
pounds in dilute water solutions (Saravacos, 1995; Chandraskaren and King,
1972).
The relative volatility of these compounds in aqueous solutions of 60% su-
crose is 20 to 10 times higher than in water, due to the strong interactions of the 3-
component system (Saravacos et al., 1990).
The volatile flavors (aromas) are normally recovered during the evaporation
of fruit juices and other aqueous systems by stripping and distillation processes
(Saravacos, 1995; Karlsson and Tragardh, 1997). Maximum removal of a volatile
from the liquid phase is obtained when vapor-liquid equilibrium (VLB) is estab-
lished. However, establishment of true equilibrium requires infinite time, so
evaporation and distillation are actually nonequilibrium processes with partial
removal of volatiles. Diffusion of the flavor components from the interior to the
surface of food particles is reduced sharply in the presence of sugars and other
solids. Evaporation from falling liquid films (Lazarides et al., 1990) or from me-
chanically agitated films (Marinos-Kouris and Saravacos, 1974) can increase the
stripping efficiency of volatiles.
Table 7.6 Typical Relative Volatilities

of Aroma Compounds in Aqueous
Solutions aAw at Infinite Dilution (25°C)
Volatile compound aAw
Methyl anthranilate 3.90
Methanol 8.30
Ethanol 8.60
1 -Propanol 9.50
1-Butanol 14.1
n-Amyl alcohol 23.0
Hexanol 31.0
2-Butanone 76.0
Diethyl ketone 77.0
Ethyl acetate 205
Ethyl butyrate 643
256 Chapter 7
The retention of volatile flavors during food dehydration depends primarily

on the presence of sugars and other solids, which reduce the aroma diffusivity in
the food material. Contrary to aroma recovery processes, aroma retention is a
highly nonequilibrium process, utilizing conditions that will prevent the flavor
compounds from reaching the evaporation surface, such as fast surface drying
(Rulkens and Thijssen, 1972).
The loss of volatile flavors depends on the evaporation or drying rate of wa-
ter. The mass transport of volatiles should be considered as a ternary diffusion
process, with three binary diffusivities, i.e. water/solids, volatile/water and vola-
tile/solids (Coumans et al., 1994a).
Figure 7.4 shows the loss of a very volatile flavor compound, ethyl butyrate
(relative volatility in water aAw = 643), as function of % water evaporated in
aqueous solutions and during vacuum- or freeze-drying (Saravacos and Moyer,
1968a, b). The loss of the volatile ester from the water solution is very rapid, e.g.
90% loss by evaporation of 30% water. The presence of pectin in the water solu-
tion reduces the volatile loss and increases its retention. A higher retention is ob-
tained by freeze-drying.
Volatile retention during spray drying depends not only on the relative vola-
tility but also on the interaction of the compound with the nonvolatile components
of the food liquid. Thus, in spray drying of food emulsions containing flavors,
ethyl butyrate is retained only by 20%, while limonene may be retained almost
quantitatively (Furuta et al., 2000).
The retention of volatile flavors during food dehydration is a very important
consideration in the selection of drying processes and equipment for optimum
product quality. Flavor retention is related to the reduction of diffusivity of flavor
compounds by sugars and other food solids. Figure 7.5 shows that the diffusivity
of diacetyl in water solutions is reduced by almost 100 times, when the sugar con-
centration is increased from 0 to 70% (Voilley and Simatos, 1980; Voilley and
Roques, 1987).
50 100
Evaporation (%)
Figure 7.4 Retention of ethyl butyrate: W, evaporation of water; VD, vacuum-drying of

pectin solution; FD, freeze-drying of pectin solution.
Thermodynamic and transport phenomena analysis indicate that flavor retention is

a diffusion-controlled process (Kerkhof, 1975; Bruin and Luyben, 1980). Fast
drying processes, like spray drying, improve volatile retention by trapping the
solute in the solid matrix. A selective diffusion mechanism may explain the vola-
tile retention in spray- and freeze-drying (Coumans et al., 1994b). Atomization
and evaporation of water/volatiles from drops control flavor retention in spray-
dried particles (King, 1994; Hecht and King, 2000).
Retention of charactertistic aroma during storage of dried fruits can be im-
proved by using low relative humidities (Rff) and low temperatures. Moisture
sorption of stored fruits increases sharply at RH > 60%, resulting in a strong rise of
flavor diffusivity and subsequent loss of aroma (Saravacos et al., 1988).
258 Chapter 7
l.E-09
l.E-10
l.E-11
l.E-12
20 40 80
Sugar(%)
Figure 7.5 Diffusivity of diacetyl in sucrose solutions.
D. Flavor Encapsulation
Encapsulation and controlled release of solutes is used widely in pharma-
ceuticals, medicinal products, flavors, and pesticides. Controlled release is based
on relaxation-controlled dissolution of the coating material, which consists usually
of a glassy polymer (Cussler, 1997).
Encapsulation of flavors, acidulants (citric and ascorbic acid), salts, and en-
zymes is used to prevent or control the diffusion of the solutes in various food
processing and food utilization operations (Karel, 1990). Encapsulation can be
achieved by entrapment in glassy polymers or in sugar crystals, in fat-based matri-
ces, or by incorporation in liposomes (e.g. lecithin).
Release of encapsulated solutes is achieved by temperture and moisture con-
trol, enzymatic release, grinding etc. The role of glass transition temperature Tg to
solute release is important, since diffusivity rises sharply above Tg. The WLF
equation (7-10) relates the diffusivitiy to the temperature and the Ts. The "collapse
temperature" is related to T& and both temperatures decrease as the moisture con-
tent is increased.
Spray- and freeze-drying are used to encapsulate flavor solutes in polymer
matrices, using high initial drying rates to form a dried polymer layer, which re-
duces diffusivity.
V. PERMEABILITY IN FOOD SYSTEMS
The transport of small solutes, such as water, oxygen, and carbon dioxide
through polymer films and protective coatings is of fundamental importance to
food packaging and food processing. The permeability of these materials is based
on the principles of diffusion of solutes in polymer systems. The permeability of
synthetic membranes is important to separation processes used in food processing,
such as reverse osmosis, gas separation, and ultrafiltration.
The structural and physicochemical factors, which affect the diffusivity of
solutes in polymers, are also important in characterizing the performance of pack-
aging films and food coatings. Control of such factors as glassy/rubbery state,
cross-linking, and polymer orientation, can determine the permeability of these
materials.
A. Permeability
The permeability P of a film or thin layer of thickness z is related to the dif-
fusivity D and the solubility S of the penetrant (solute) in the material, according
to the equation:
J = P (Aplz) = DS (Aplz) (7-22)
where J is the mass transfer rate (kg/m2s), Aplz is the pressure gradient (Pa/m), and
5 is the gas/liquid equilibrium constant, S = C/p where C is the concentration
(kg/m3) and p the pressure (Pa). The solubility S is equal to the inverse of the
Henry constant (S=1/H), and it has units (kg/m3Pa); it can be determined as the
slope of the sorption isotherm (C versus p).
From equations (7-22) it follows that:
P = DS (7-23)
The permeability has SI units (kg/m s Pa) or (g/m s Pa), but various other
units are used in packaging, reflecting the measuring technique or the particular
food/package application (Hernandez, 1997; Donhowe and Fennema, 1994).
260 Chapter 7
The permeability P is related to the permeance PM or transmission rate 77?

(=PM) and the water vapor transfer rate WVTR by the equation (McHugh and
Krochta, 1994):
P = PMz = WVTR I Ap (7-24)
The units of permeance (kg/m2 s Pa) are identical to the units of the mass transfer
coefficient kp. The units of WVTR are (kg/m s) (Saravacos, 1997).
The SI units are useful in relating and comparing the literature data on P and
WVTR to the fundamental mass transport property of diffusivity D (m2/s).
The permeability of polymer films and coatings can be determined by
measurements of sorption kinetics and diffusion, discussed in Chapter 5, in rela-
tion to water transport. Conversion of solubility S and diffusivity D data to perme-
ability P though Eq. (7-23) is possible, when the material behaves like a homoge-
neous medium and Fickian diffusion can be assumed.
Simplified permeability measurement methods are used for packaging and
coating films (barriers), and most of the literature data are reported in units related
to the special methods used (ASTM, 1990, 1994). The measured permeabilities
represent an overall transport property of the material, based on the applied pres-
sure gradient. Since the polymer film may have structural inhomogeneities, such
as pores, channels, cracks, and pinholes, mass transport may involve, in addition
to molecular diffusion, Knudsen diffusion and hydrodynamic or capillary flow
(Hernardez, 1997). In such cases, the simplified relationship between diffusivity
and permeability Eq. (7-23) is not applicable.
Permeability is affected significantly by environmental condition, such as air
relative humidity (RH), which may increase sharply the permeability of most
packaging and coating films.
The total permeability PT of a multilayer laminate is related to the perme-
abilities and the thicknesses of the individual films (P, z/) by the equation (Cook-
seyetal., 1999)
/V=[(Sr,)]/[W/)] (7-25)
The total permeance PMT or transmission rate TRT can be calculated from the
equation:
PMT=l/I,(z,/Pd (7-26)
Temperature increases permeability P according to the Arrhenius equation

in a similar manner with the effect of temperature on diffusivity D and solubility
S:
= P0 exp(-£//?7), D = D0 exp(-ED/RT), S = S0 exp(-Es /RT) (7-27)

Table 7.7 Conversion Factors to SI Permeability Units (g/m s Pa)

Conversion from / to (g / m s Pa) Multiplying factor
3 2
cm (STP) mil /100 in day atm 6.42 x 10'17
3 2
cm (STP) mil / m day atm 4.14* 10"18
cm3(STP) urn / m2 day kPa 1.65 x 1Q'17
g)im/m 2 daykPa 1.16X10' 1 4
2
gmm/m daykPa 1.16x10""
2
g mil/m day atm 2.90 x 10"15
g mil/m2 day (mm Hg) 2.20 x 10'12
2
g mil/m day (90 % RH, 100 °F) 4.50 x 10'14
g mil/100 in2 day (90 % RH, 100 °F) 7.00 x 10'13
perm (ASTM, 1990)____________________1.45 x 1Q-9
STP = standard temperature and pressure. 1 mil = 0.001 inch = 2.54xl0 0 m.
Pressure drop of water vapor across the film at 90/0% RH and 100°F,
AP = 6560 Pa. 1 mm Hg = 133.3 Pa.
The energy of activation for permeability Ep may vary, depending on the

type of polymer and the temperature, in the wide range of 10 to 80 kJ/mol (Her-
nandez, 1997).
Table 7.7 shows the conversion factors from the various literature units of
permeability to SI units (g/m s Pa).
B. Food Packaging Films

Synthetic polymer firms are used as barriers to the transport of water vapor,
oxygen, carbon dioxide, and food components, like aroma/flavor compounds and
lipids, from or to the packaged food product. Food packaging films are made of
special polymeric materials, like polyethylene, both low density (LDPE) and high
density (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS),
polyethylene terephthalate (PET) and polyamides (nylon) (Hernandez, 1997;
Miltz, 1992). Permeability, mechanical properties, food compatibility (non-
toxicity), and cost are the main characteristics in selecting the proper material
(Brody and Marsh, 1997; Hanlon et al., 1998). Permeability, like diffusivity, is
affected significantly by polymer microstructure, solute-polymer interactions, sol-
ute concentration (especially moisture content or RH), and temperature.
Some typical permeabilities of common packaging films to water vapor and
oxygen are shown in Table 7.8 at 25°C (Miltz, 1992; Hernandez, 1997).
262 Chapter 7
Table 7.8 Permeabilities of Packaging Films to Water

Vapor and Oxygen (25°C)
Permeability, x 1 0 - 1 2 g / m s P a
Packaging film Water vapor Oxygen
LDPE 1.40 0.031
HDPE 0.20 0.007
PP 1.00 0.010
PVC 3.00 0.005
PS 12.0 0.018
PET 1.40 0.0006
Nylon 0.002 0.0004
LDPE = low density polyethylene, HOPE = high density polyethylene,
PP = polypropylene, PVC = polyvinyl chloride, PS = polystyrene,
PET = polyethylene terephthalate, Nylon = polyamide.
The permeability of nylon to oxygen at various moisture contents has been

analyzed by the dual-sorption model (Hernandez, 1994). Although the water diffu-
sivity increases at higher moistures, the solubility and the permeability decrease
sharply at the beginning, leveling-off at water activities above 0.2.
The permeability of polymer firms and food coatings to carbon dioxide is
important in food packaging and storage. Typical values of permeability of carbon
dioxide at 25°C are: LDPE, 1.6 x 10'13; HDPE, 5.3 x 10'15 g/m s Pa.
C. Food Coatings
The permeability of edible food coatings to water is of particular interest to
food quality, since their primary function is to act as barriers to moisture transport
during storage. Food coatings can also control the transport of gases (mostly oxy-
gen), flavor components and lipids in food systems. Edible coatings, used as barri-
ers in foods, include proteins (wheat gluten, caseinates, whey protein, corn zein),
polysaccharides (starch, dextrins), pectins, lipids, and chocolate. Composite coat-
ings, containing a food biopolymer (e.g. protein) and a hydrophobic material, like
lipid, fatty acid, chocolate, and beeswax, usually have very low water permeabil-
ities.
The food coatings are prepared as solutions or dispersions/emulsions of the
primary biopolymer in solvents (ethanol, alkalis, or acids). They contain various
plasticizers, such as glycerine and sorbitol, which improve the physical and me-
chanical properties of the coating. They are applied to the various fresh and proc-
essed foods, like fruits and vegetables by dipping in an emulsion, spraying or
foaming and brushing.
Table 7.9 shows typical water permeabilities of food coatings (McHugh and
Krochta, 1994):
Table 7.9 Water Vapor Permeabilities P

of Food Coatings (25°C)
Food coating P, xlO- 1 0 g/msPa
Gluten-glycerine 6.10
Whey protein-sorbitol 7.20
Zein-glycerine 1.00
Sodium casemate 4.20
Chocolate 0.12
Beeswax 0.006
D. Permeability/Diffusivity Relation
The simple permeability/diffusivity/solubility relation of Eq. (7-23) is useful
for estimating the permeability P from diffusivity D and solubility S data of poly-
mer films, and for comparison of P and D data. This relation applies to systems
behaving as homogeneous materials, in which solute transport is by Fickian mo-
lecular diffusion. It does not hold for heterogeneous materials, consisting of pores,
channels and capillaries, in which a significant portion of mass transfer takes place
by mechanisms other than molecular diffusion. Table 7.10 shows some typical
diffusivity and permeability data for packaging films and food coatings. The com-
parison is facilitated by using consistent (SI) units (Saravacos, 2000).
A typical application of the permeability-diffusivity relation is given for
chocolate film, using published data of Biquet and Labuza (1988): Typical perme-
ability P and diffusivity D values for a chocolate coating about 0.6 mm thick at
20 0 C:P = 0.11 x 10-'°g/msPaandZ)=l x 10-13m2/s. The solubility S of water in
the chocolate material can be estimated from the sorption isotherm at 20°C. It is
defined by the Henry equation, C = S p, where C is the concentration (kg/m3) in
the material andp is the partial pressure of water (Pa). Thus, the solubility is equal
to the slope of the isotherm (S = C/p). Considering the initial sorption stage, water
activity a,v 0 to 0.1, S = (1.7 kg water/100 kg solids)/Ap where Ap = a,vp0 or Ap =
0.1 PO, and PO is the vapor pressure of water at 20°C (p0 = 2340 Pa), and Ap =
234Pa. The concentration of water in the chocolate material is converted to consis-
tent (SI) units, as follows: Assume density of dry chocolate 1600 kg/m3; therefore,
the volume of 100 kg dry material will be 100/1600 = 0.0625 m3. The water con-
centration in the chocolate becomes C = (1.7/0.0625) = 27.2 kg/m3, and the solu-
bility S = 27.2/232= 0.116 kg/m3 Pa.
Using the measured diffusivity of the system (D = 1 x 10~13 m2/s), the per-
meability of the chocolate film according to Eq. (7-23) will be P = D S = 0.116 x
10"13kg/ms Pa, or P = 0.116 x 10"'°g/ms Pa, which is very close to the measured
permeability.
264 Chapter 7
Table 7.10 Typical Water Vapor Permeabilities and Diffusivities

Film or coating P, x 10-'°g/msPa A xio-'°m 2 /s
HDPE 0.002 0.005
LDPE 0.014 0.010
PP 0.010 0.010
PVC 0.041 0.050
Cellophane 3.70 1.00
Protein films 0.10-10.0 0.100
Polysaccharide films 0.10-1.00 0.100
Lipid films 0.003-0.100 0.010
Chocolate 0.11 0.001
Gluten 5.00 1.00
Com pericarp 1.60 0.10
LPDE = low density polyethylene, HDPE = high density polyethylene,
PP = polypropylene, PVC = polyvinyl chloride
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8
Thermal Conductivity and Diffusivity
of Foods
I. INTRODUCTION
The thermal transport properties, thermal conductivity and thermal diffusiv-

ity of simple gases and liquids can be predicted by molecular dynamics and semi-
empirical correlations, and numerous tables and data banks are available in the
literature (Chapter 2). Experimental measurements are necessary for the thermal
transport properties of foods, due to their complex physical structure. Empirical
models have been proposed for the correlation of experimental data and the possi-
ble explanation of the heat transport mechanisms.
The thermal conductivity (X) of a material is a measure of its ability to con-
duct heat and is defined by the basic transport equation (2-3), which is integrated
to give:
q/A=A(TrT2)/x (8-1)
where qlA is the heat flux (W/m), x is the thickness of the material (m), T, and T2
are the two surface temperatures of the material, and A is the surface of the mate-
rial normal to the direction of heat flow (m2). The S.I. units of A are W/mK. Equa-
tion (8-1) is the basis for the direct measurement of A (guarded hot-plate method).
The thermal diffusivity a of a material can be estimated from the thermal
conductivity A using the equation:
a = JJpCp (8-2)
where p is the density (kg/m3) and Cp is the specific heat (J/kgK) of the material.
The S.I. units of a are m2/s.
269
270 Chapter 8
The thermal conductivity of foods depends of the chemical composition, the

physical structure, the moisture content, and the temperature of the material. The A
of unfrozen foods varies between the A, of air (0.020 W/mK) and water (0.62
W/mK). Higher A values characterize the frozen foods (about 1.5 W/mK).
The thermal diffusivity of foods does not change substantially, because any
changes of A are compensated by changes of the density of the material Eq. (8-2).
Typical values of a for unfrozen food are 1.3xlO"7 m2/s and for frozen food 4xlO"7
m2/s.
The thermal conductivity of solid foods is a strong function of the porosity
of the material. This variation is about one order of magnitude, compared to the
very wide variation of mass diffusivity in porous foods. The changes in heat and
mass transport properties of porous foods reflect the differences in /I and D of
gases and liquids, according to the approximate relations:
A(gas)//l(liquid)=l/10 (8-3)
£>(gas)/£>(liquid) = 10000/1 (8-4)
Empirical models of thermal conductivity, analogous to the models of elec-

trical conductivity, can be used to correlate the experimental data. The literature
data on X can be analyzed statistically, using correlations analogous to the models
of moisture diffusivity (see Chapter 6).
II. MEASUREMENT OF THERMAL CONDUCTIVITY AND DIFFUSIVITY
The measurement of the thermal transport properties of foods is described

by several authors in the literature, notably by Mohsenin (1980), Nesvadba (1982),
Sweat (1995), Rahman (1995), and Urbicain and Lozano (1997). A comprehen-
sive study of the subject was undertaken within the collaborative research project
COST 90 in the European Union (Meffert, 1983; Kent et al., 1984).
A. Thermal Conductivity
Two experimental methods are normally used for the measurement of the
thermal conductivity (X), i.e. the guarded hotplate and the heated probe. Other
methods, suggested for food materials, are the Fitch method and its modifications,
the thermal comparator method, and the temperature history method (Rahman,
1995).
Thermal Conductivity and Diffusivity of Foods 271
1. Guarded Hot Plate

The guarded hot-plate method is based on the Fourier equation for steady-
state heat flux (8-1). The experimental apparatus is diagrammatically shown in
Figure 8.1. Details of the apparatus are given by Drouzas and Saravacos (1985).
The apparatus consists of two circular brass plates, between which the sam-
ple material is placed. The upper plate is heated electrically and the lower cold
plate is maintained at a constant temperature. Unidirectional flow of heat is as-
sured by two guard rings around the plates. After establishment of steady state, the
heat flow is measured with an electrical meter and the thermal conductivity (X) is
determined from equation (8-1).
Although the guarded hot plate is an accurate method, it requires special
precautions, like uniform sample thickness, good contact with the plates, and rela-
tively long time to reach steady state, which may change the moisture content of
the material.
2. Heated Probe
The heated probe method is faster and it requires less sample material. For
these reasons it is used more widely than the guarded hot-plate method. The hot
probe is a transient method, based on the measurement of the sample temperature
as a function of time, while the sample is heated by a known line heat source. As-
suming that the line heat source is an infinite medium, and that the heat flow is
radial, the temperature T at a point very close to the line source, after a time t will
be (Rahman, 1995):
hot plate
/ , sample
quard rings ••f'H.4.-^ *-:; -a.-^:-; "'. s-y "£• ' %-'•-"-'"- •<<.':£ ":- iffigam /
Jjpyjij*
cold plate
81_ AAAAAA^
Figure 8.1 Diagram of a guarded hot plate apparatus.

272 Chapter 8
(8-5)
where ft is a constant, and q is the heat flow per unit length of the line source
(W/m).
The temperature difference (ArP=T2-T1) after times t} and tt of heating will
be:
Thus the thermal conductivity A can be obtained from the slope (qttnX) of a se-
milog plot of T versus t.
The heated probe method requires short measurement times (less than a
minute), and relatively small samples.
heated wire
thermocouple
seal
stainless
steel
needle
filling
material
seal
Figure 8.2 Principle of heated probe.

Figure 8.2 shows schematically a heated probe used for thermal conductivity
(Drouzas and Saravacos, 1988; Sweat, 1995). A stainless steel needle (or syringe)
is used to house the line source (a heated constantan wire) and the thermocouple
(chromel-constantan). Time-temperature data of the probe, inserted in the sample,
are used to calculate /I from Eq. (8-7), which is derived directly from (8-6):
A = [23I2R logfo/?;)]/[4^)7] (8-7)
where / is the electrical current (A) and R' is the specific electrical resistance of
the heating wire (H/m). The heated probe is calibrated with glycerin solutions or
with known insulating materials.
B. Thermal Diffusivity
The thermal diffusivity a is usually estimated indirectly from the thermal
conductivity A, the density p and the specific heat Cp of the material, according to
Eq. (8-2).
Direct measurement of a can be made using various methods, discussed by
Rahman (1995). All methods are based to some simplified solutions of the un-
steady-state heat conduction equation (Fourier):
(8-8)
/. Dickerson Method
The simplest experimental method is the transient method of Dickerson
(1965), modified by Poulsen (1982), and used by Drouzas and Saravacos (1985).
The principle of the method is to obtain time-temperature data in a cylindrical
sample of material, as shown in the diagram of Figure 8.3.
The transient heating time t in the cylindrical container is given by the semi-
empirical equation (Ball and Olson, 1957):
t=f\Qg\j(Ts-T0)l(Ts-T)} (8-9)
where T0 is the initial temperature, Ts is the outside surface temperature, and T is

the temperature after time t. The linear semilog relationship is defined by the lag
factory and the reciprocal of the slope/ Equation (8-9) is used in thermal process
(sterilization) calculations of the formula method.
274 Chapter 8
thermocouples
constant
temperature"
sample
Figure 8.3 Transient method for thermal diffusivity.
For a long cylindrical container with high surface heat transfer coefficients
h, i.e. for Biot numbers Bi > 40 (Bi = MX), the parameter/of the heating source is
given by the equation:
/= 0.398(r2/a) (8-10)
where r is the radius of the container.

Thus, the thermal diffUsivity (a) can be obtained from Eq. (8-10).
2, Modified Heated Probe

The thermal diffusivity (a) can be obtained experimentally, using a modified
heated probe (Mohsenin, 1980; Drouzas et al., 1991). The second thermocouple is
inserted in the basic probe (Figure 8.2) at a fixed short distance r from the initial
thermocouple. The temperature rise AT at the distance r at the heating time t is
given by the following solution of the unsteady-state heat conduction in a cylindri-
cal solid:
AT= (q/4aX) [-0.58/2 - ! - (34/4x2! (8-11)
where j3 = r/2(af)1'2
Thus, a can be calculated from Eq. (8-11), using the corresponding A value
from a parallel measurement with the normal probe.
The exact distance r of the two thermocouples is critical in the modified
probe method and a calibration of the system may be required. A comparison of
the direct probe method with the indirect calculation of a indicated a better accu-
racy of the indirect method (Drouzas et al., 1991).
III. THERMAL CONDUCTIVITY AND DIFFUSIVITY DATA OF FOODS
The literature contains several data on the thermal transport properties of

foods in the form of tables, empirical models, regression equations, and data
banks.
A. Unfrozen Foods
Table 8.1 shows typical values of thermal conductivity of foods: Kostaro-
poulos (1971), Mohsenin (1980), Rahman (1995), Sweat (1995), and Singh
(1995). Sections IV and V of this chapter contain some mathematical models and
statistical compilations of thermal conductivity and diffusivity.
Table 8.1 Thermal Conductivity K of Unfrozen Foods (25°C)

Food material % Moisture A, W/mK
Water 100 0.620
Sucrose solution 85 0.567
Granular starch 15 0.110
Gelatinized starch 85 0.547
Potato 82 0.533
Apple 85 0.513
Tomato paste 65 0.550
Beef 74 0.452
Fish 80 0.460
Milk 85 0.530
Vegetable oil 0.180
Dried fruit 18 0.237
Freeze-dried gel 4 0.041
276 Chapter 8
The thermal conductivity A of foods decreases, in general, as the moisture

content of the material is reduced. The A of dried food materials decreases sharply
as the porosity is increased, e.g. by freeze-drying or puffing.
The /I of fibrous dry foods is higher parallel than across the fiber (Chapter
3). Thus, the /I of freeze-dried cellulose gum (fibrous structure) was 0.0627 W/mK
compared to 0.0410 W/mK of porous freeze-dried starch gel (Saravacos and Pils-
worth, 1965). An analogous effect was noticed in the drying rates of the two mate-
rials (see Chapter 5).
Figure 8.4 shows the effect of air pressure on the thermal conductivity of a
freeze-dried gel (Saravacos and Pilsworth, 1965). The A decreases sharply from
0.041 to about 0.010 W/mK as the air pressure is reduced from atmospheric to
below 1 mbar. Similar effects of pressure was observed in freeze-dried fruits
(Harper, 1962) and milk and orange pulp (Fito et al., 1984).
The thermal diffusivity (a) of unfrozen foods does not change appreciably
with the moisture and temperature, ranging from about l.OxlO' 7 to 1.5xlO"7 m2/s.
Detailed tables of (a) for various food materials are presented by Rahman (1995).
B. Frozen Foods
The thermal conductivity of frozen foods is significantly higher than the A. of
unfrozen materials, due to the higher /I of ice. The /I of a frozen food of 85% mois-
ture content decreases gradually from about 1.5 W/mK at -40°C to 0.5 W/mK at
0°C, as shown in the diagram of Figure 8.5. A sharp drop of A is observed near
0°C, due to the melting of ice.
An analogous variation of the thermal diffusivity a of the frozen foods is ob-
served below the freezing point (Figure 8.6). The a of a typical frozen food de-
creases from about 1x10'6 m2/s at -40°C to 1x10'7 m2/s above 0°C. The sharp drop
near the freezing point is due to the sharp increase of cp, which incorporates the
heat of melting, near 0°C (Singh, 1995).
C. Analogy of Heat and Mass Diffusivity

The heat and mass transport analogy in gases (Chapter 2) has been observed
in porous foods at low moisture content (Kostaropoulos and Saravacos, 1997). The
analogy is based on the transport mechanisms in the gas phase, which becomes
important in highly porous materials, like granular, freeze-dried, and extrusion-
cooked foods. As in the case of moisture diffusivity (Figure 5.24), the thermal
diffusivity of granular starch shows a maximum near 15% moisture, and it in-
creases gradually at moistures higher than 35% (Figure 8.7).
0.050
0.000
0.1 10 100 1000
Pressure (mbar)
Figure 8.4 Effect of air pressure on thermal conductivity of porous food material.
-40 -30 -20 -10 0 10 20 30 40

Temperature (°C)
Figure 8.5 Thermal conductivity of frozen food material.

278 Chapter 8
l.OE-06
-40 -30 -20 -10 0 10 20 30 40

Temperature (°C)
Figure 8.6 Thermal diffusivity of frozen food material.
10 20 30 40 50 60
Moisture Content (%)
Figure 8.7 Thermal diffusivity versus moisture content of porous food material.
D. Empirical Rules
A preliminary checking of thermal transport property data can be made, us-
ing the empirical rules, suggested by Kostaropoulos (1981):
I. Thermal Conductivity
i. Food with moisture content (Xw) > 30-40%

Xi~ 0.40- 0.58 W/mK
ii. Frozen foods, Xw > 30-40%

XK ~ 2.5 A, j
iii. Dry food
iv. Fats and oils

X i v ~ 0.25- 0.50
2. Thermal Diffusivity
i Foods, X w >30%
ctj^ 1.4xlO" 7 r
ii. Frozen food
iii. Dry food
iv Fats and oils

280 Chapter 8
IV. MODELING OF THERMAL TRANSPORT PROPERTIES
A. Composition Models
Several composition models have been proposed in the literature, most of
which are summarized by Miles et al. (1983), Sweat (1995), and Rahman, (1995).
The most promising seems to be the model proposed of Sweat (1995):
A = Q.5SXv + Q.l55Xp+Q.25Xc+Q.l6Xf+Q.135Xa (8-12)
where Xm Xp, Xf and Xa are the mass fractions of water, protein, fat, and ash, re-
spectively.
The above model was fitted to more than 430 liquids and solid foods with
satisfactory results. It is not accurate for porous foods containing air, for which
structural models are needed.
The thermal conductivity of water in the above equation was fitted to about
0.58W/mK which is less than the thermal conductivity of pure water, 0.605W/mK.
Either the selected data are biased, or they indicate that the effective thermal con-
ductivity of water in foods is less than the thermal conductivity of pure water
(Sweat, 1995).
The key to the accuracy of the above equation is having accurate values for
the thermal conductivity of "pure" components. This is easy for the water and oil
fractions but very difficult for the other fractions. In fact, the thermal conductivity
of proteins and carbohydrates probably varies according to their chemical and
physical form.
However, it is not needed to find more accurate additive composition mod-
els, because of the inherent inaccuracy in the composition models, which they
don't take into account the geometry of the component mixing. As in the case of
air-containing foods, structural models must be used. The temperature effect is not
included in the above equation. Thus, it is valid at the fitting region approximately
at 25°C. The temperature effects of the major food components are summarized by
Rahman (1995) in Table 8.2 and in Figure 8.8.
Table 8.2 Effect of Temperature on the Major Food Components
X=bo+biT+b2T2+b3T:1 bo b, b2 b,
Air 2.43E-02 7.89E-05 -1.79E-08 -8.57E-12
Protein 1.79E-01 1.20E-03 -2.72E-06
Gelatin 3.03E-01 1.20E-03 -2.72E-06
Ovalbumin 2.68E-01 2.50E-03
Carbohydrate 2.01E-01 1.39E-03 -4.33E-06
Starch 8.7 IE-02 9.36E-04
Gelatinized Starch 3.22E-01 4.10E-04
Sucrose 3.04E-01 9.93E-04
Fat 1.81E-01 2.76E-03 -1.77E-07
Fiber 1.83E-01 1.25E-03 -3.17E-06
Ash 3.30E-01 1.40E-03 -2.91E-06
Water 5.70E-01 1.78E-03 -6.94E-06 2.20E-09
Ice 2.22E+00 -6.25E-03 1.02E-04

282 Chapter 8
0.75
u
3
•U
B
O
U
"5
E
0.25
50 100
Temperature (°C)
Figure 8.8 Effect of temperature on the major food components.

B. Structural Models
For heterogeneous foods, the effect of geometry must be considered using
structural models. Utilizing Maxwell's and Eucken's work in the field of electric-
ity, Luikov et al. (1968) initially used the idea of an elementary cell, as represen-
tative of the model structure of materials, in order to calculate the effective thermal
conductivity of powdered systems and solid porous materials. In the same paper, a
method is proposed for the estimation of the effective thermal conductivity of mix-
tures of powdered and solid porous materials.
Since then, a number of structural models have been proposed, some of
which are given in Table 8.3. The series model assumes that heat conduction is
perpendicular to alternate layers of the two phases, while the parallel model as-
sumes that the two phases are parallel to heat conduction. In the random model,
the two phases are assumed to be randomly mixed. The Maxwell model assumes
that one phase is continuous, while the other phase is dispersed as uniform
spheres. Several other models have been reviewed by Rahman (1995), among
others.
In the mixed model (also called and Krischer model) heat conduction is as-
sumed to take place by a combination of parallel and perpendicular heat flow. This
model recognizes that there are two extremes in thermal conductivity values, one
being derived from the parallel model and the other from the series model, whilst
the real value of thermal conductivity should be somewhat in between these two
extremes. A conceptual diagram is shown in Figure 8.9. The distribution factor/is
a weighting factor between these extremes. It characterizes the structure of the
material and it should be independent of material moisture content and tempera-
ture,
I-/ Parallel Structure
/ Series Structure
Figure 8.9 The mixed model of thermal conductivity.

284 Chapter 8
Granular (particulate) materials consist of granules (particles) and air, ran-

domly packed (Figure 8.10). The induvidual particles consist of solids and water
(Figure 8.10). The use of some of these structural models to calculate the thermal
conductivity of a hypothetical porous material is presented in Figure 8.11. The
parallel model gives the largest value for the effective thermal conductivity, while
the series model gives the lowest. All other models predict values in between. Fig-
ure 8.12 represents the mixed model for various values of the distribution factor/
as a function of the void fraction (porosity).
A systematic general procedure for selecting suitable structural models, even
in multiphase systems, has been proposed by Maroulis et al. (1990). The method
is based on a model discrimination procedure. If a component has unknown ther-
mal conductivity, the method estimates the dependence of the temperature on the
unknown thermal conductivity, and the suitable structural models simultaneously.
An excellent example of applicability of the above is in the case of starch,
an important component of plant foods. The granular starch consists of two
phases, the wet granules and the air/vapor mixture in the intergranular space. The
starch granule also consists of two phases, the dry starch and the water. Conse-
quently, the thermal conductivity of the granular starch depends on the thermal
conductivities of pure materials (that is, dry pure starch, water, air, and vapor, all
functions of temperature) and the structures of granular starch and the starch gran-
ule. It has been shown that the parallel model is the best model for both the granu-
lar starch and the starch granule (Maroulis et al., 1990). These results led to simul-
taneous experimental determination of the thermal conductivity of dry pure starch
versus temperature. Dry pure starch is a material that cannot be isolated for direct
measurement.
GRANULAR MATERIAL
Particles
GRANULE (PARTICLE)
Figure 8.10 Schematic model of granular materials.

286 Chapter 8
Table 8.3 Structural Models for Thermal Conductivity
Series
1 \-e) g
Random
Mixed (Krischer )
=
0.125
Parallel
Maxwell (Continuous phase 1)
Random
Maxwell (Continuous phase 2)
Series
0.025
0.00 0.25 0.50 0.75
Void Fraction
Figure 8.11 Structural models for porous materials.

288 Chapter 8
0.125
Mixed Model (Krischer)

Distribution Factor =
0.00 (Parallel)
0.25
0.50
0.75
1.00 (Series)
0.025
0.00 0.25 0 . 5 0 0.75 1.00
Void Fraction
Figure 8.12 The mixed (Krischer) model for various values of distribution factor.
V. COMPILATION OF THERMAL CONDUCTIVITY DATA OF FOODS
There is a wide variation of the reported experimental data of thermal con-

ductivity of solid food materials, making difficult their utilization in food process
and food quality applications. The variation of thermal conductivity in model and
real foods is discussed in Section III of this chapter. The physical structure of solid
foods plays a decisive role not only on the absolute value of thermal conductivity,
but also on the effect of moisture content and temperature on this transport prop-
erty.
In this section, the thermal conductivity in food materials is approached
from a statistical standpoint. Literature data are treated by regression analysis,
using the parallel structural model.
Recently published values of thermal conductivity in various foods were re-
trieved from the literature, and they were classified and analyzed statistically to
reveal the influence of material moisture content and temperature. Structural mod-
els, relating thermal conductivity to material moisture content and temperature
were fitted to all examined data for each material. The data were screened care-
fully, using residual analysis techniques. The most promising model was pro-
posed, which is based on an Arrhenius-type effect of temperature and it uses a
parallel structural model to take into account the effect of material moisture con-
tent.
Thermal conductivity data in the literature show a wide variation due to the
effect of the following factors: (a) diverse experimental methods, (b) variation in
composition of the material, (c) variation of the structure of the material. Thermal
conductivity depends strongly on moisture, temperature and structure of the mate-
rial.
An exhaustive literature search was made in international food engineering
and food science journals in recent years, as follows (Krokida et al., 2001):

• Transactions of the ASAE, 1975-1999
• International Journal of Food Properties, 1998-2000
A total number of 146 papers were retrieved from the above journals ac-
cording to the distribution presented in Figure 8.13. The accumulation of the pa-
pers versus the publishing time is presented in Figure 8.14. The search resulted in
1210 data concerning the thermal conductivity in food materials.
290 Chapter 8
J. Food J, of Food Drying Trans of the Int. J. Food International

Engineering Science Technology ASAE Science & Journal of
Techn. Food
Properties
Figure 8.13 Number of papers on thermal conductivity data in food materials pub-
lished in food engineering and food science journals during recent years.
160
120
o
L.
1
sa
Z
o
1970 1980 1990 2000

year
Figure 8.14 Accumulation of published papers on thermal conductivity data for

food materials versus time.
0.001 0.01 0.1 1 10 100

Moisture (kg/kg db)
Figure 8.15 Thermal conductivity data for all foods at various moistures.
0.01
0.1 1 10 100 1000
Temperature (oQ
Figure 8.16 Thermal conductivity data for all foods at various temperatures.
292 Chapter 8
These data are plotted versus moisture and temperature in Figures 8.15 and
8.16, respectively. These figures show a good picture concerning the range of
variation of thermal conductivity, moisture and temperature values. More than
95% of the data are in the ranges:
• Thermal Conductivity 0.03 - 2.0 W/mK

• Moisture 0.01-65 kg/kg db
• Temperature -43 -160 °C
The histogram in Figure 8.17 shows the distribution of the thermal conduc-
tivity values retrieved from the literature. Most of the K values are between 0.1 and
1.0 W/mK. Thermal conductivities higher than that of water (0.62 W/mK at 25°C)
are characteristic of frozen foods of high moisture content, since the thermal con-
ductivity of ice is about 2 W/mK.
The results obtained are presented in detail in Tables 8.4-8.6. More than 100
food materials are incorporated in the tables. They are classified into 11 food cate-
gories. Table 8.4 shows the related publications for every food material. Table 8.5
summarizes the average literature value for each material along with the corre-
sponding average values of corresponding moisture and temperature. Table 8.6
presents the range of variation of thermal conductivity for each material along
with the corresponding ranges of moisture and temperature.
1000
•a
I
'= 100
o
L.
10
£
0.01 0.03 0.10 0.30

3.00 1.00
Thermal Conductivity Values (W/mK)
Figure 8.17 Histogram of observed values of thermal conductivity in food materi-

als.
Table 8.4 Literature for Thermal Conductivity Data in Food Materials:

References and Number of Data Retrieved
Baked products 60
Bread 14
Zanonietal, 1995 5
Zanonietal., 1994 3
Goedeken et a!., 1998 6
Dough 20
Bouvier et al, 1987 3
Zanonietal, 1995 8
Griffith etal., 1985 9
Soy flour 11
Maroulisetal.,1990 7
Wallapapan et al., 1982 4
Cake 2
Zanonietal., 1995 2
Yellow batter 1
Baiketal, 1999 1
Cup batter 12
Baiketal., 1999 12
Cereal products 76
Barley 9
Alagusundaram et al., 1991 9
Corn 21
Bekeetal, 1994 9
Changetal, 1980 3
Okos etal, 1986 9
Rice 13
Okos etal, 1986 4
Ramesh, 2000 9
Wheat 10
Changetal., 1980 3
Okos etal., 1986 7
Corn meal 7
Laietal, 1992 4
Kumaretal, 1989 3
294 Chapter 8
Table 8.4 Continued

Iclli batter 4
Murthyetal, 1997 4
Maize 11
Halltdayetal, 1995 9
Tolabaetal.,1988 2
Oat 1
Okosetal.,1986 1
Dairy 136
Cheese 23
Lunaetal., 1985 1
Tavmanetal., 1999 22
Milk 84
Duaneetal., 1992 1
Duaneetal, 1993 1
Duaneetal, 1994 1
Me Proud eta!., 1983 1
Hori, 1983 6
Zieglereta!., 1985 3
Ready etal, 1993 9
Tavmanetal, 1999 9
Okosetal.,1986 53
Cream 1
Duaneetal, 1998 1
Butter 5
Tavmanetal, 1999 2
Okosetal.,1986 3
Yogurt 19
Kirn etal, 1997 9
Tavmanetal., 1999 10
Whey 4
Okosetal.,1986 4
Table 8.4 Continued

Fish 83
Cod 5
Sam et a!., 1987 5
Mackerel 5
Sametal., 1987 5
Squid 16
Rahman et al, 1991 12
Rahman, 1991 4
Carp 2
Hung el al., 1983 2
Surimi 30
Wangetal., 1990 21
AbuDaggaetal, 1997 9
Cake 1
Borquezetal, 1999 1
Shrimp 13
Karunakar et al, 1998 13
Calamari 2
Rahman, 1991 2
Salmon 9
Sametal., 1987 9
Fruits 143
Apple 82
Ramaswamy elal, 1981 11
Mattea et al., 1989 3
Telis-Romero et al, 1998 3
Rahman, 1991 2
Constenlaetal, 1989 9
Bhumblaetal, 1989 25
Ziegleretal, 1985 3
Mattea etal, 1986 3
Madambaetal, 1995 2
Sheen etal, 1993 1
Buhrietal, 1993 1
Okos etal, 1986 10
Chenetal, 1998 9
Banana 1
Njieetal, 1998 1
296 Chapter 8
Table 8.4 Continued

Peach 1
Okosetal.,1986 1
Strawberry 5
Delgado et al, 1997 3
Bhumbla et al., 1989 1
Okosetal.,1986 1
Raspberry 2
Bhumbla etal, 1989 1
Okosetal.,1986 1
Grape 8
Bhumbla et al, 1989 1
Okosetal.,1986 7
Plantain 6
Njieetal, 1998 6
Raisin 4
Vagenas et al., 1990 4
Pear 15
Matteaetal, 1989 3
Rahman, 1991 2
Dincer, 1997 1
Mattea et al., 1986 3
Okosetal.,1986 6
Orange 15
Telis-Romeroetal, 1998 9
Ziegler et al, 1985 4
Okosetal.,1986 1
Bilberry 2
Bhumbla et al, 1989 1
Okosetal.,1986 1
Cherry 2
Okosetal.,1986 1
Legumes 9
Lentils 9
Alagusundaram et al, 1991 9
Table 8.4 Continued

Meat 134
Beef 75
Hung etai, 1983 4
Marinos-Kouris et al, 1995 2
Me Proud et al., 1983 2
Perezetal, 1984 9
Rahman, 1991 2
Baghe-Khandan et al, 1982 30
Sanzetal, 1987 25
Califano et al, 1997 1
Chicken 9
Rahman, 1991 2
Sanzetal, 1987 7
Sausage 13
Sheen etal, 1990 2
Ziegleretal, 1987 10
Akterian, 1997 1
Turkey 12
Sanzetal, 1987 12
Mutton 10
Sanzetal, 1987 10
Pork 11
Sanzetal, 1987 11
Pork/soy 4
Muzillaetal, 1990 4
Model foods 281

Amioca 51
Maroulis etal, 1990 7
Laietal, 1992 18
Drouzasetal, 1991 8
Maroulis et al, 1991 9
Drouzasetal, 1988 9
Hylon-7 43
Maroulis etal, 1990 9
Laietal, 1992 19
Drouzasetal, 1988 6
298 Chapter 8
Table 8.4 Continued

Potato starch 2
Okosetal.,1986 2
Starch 61
Renaudetal, 1991 24
Njieetal, 1998 1
Morley et al, 1997 6
Wangetal.,1993 18
Lanetal, 2000 6
Sucrose 33
Renaudetal., 1991 30
Ziegleretai., 1985 3
Gelatin 26
Renaudetal, 1991 24
Okosetal.,1986 2
Ovalbumin 36
Renaudetal, 1991 24
Cornillon et al, 1995 12
Tylose 6
Phametal, 1990 6
Agar-water 2
Barringer et al, 1995 1
Bentonite-water 1
Sheen et al, 1993 1
Gelatin-water 1
HalUdayetal.,1995 1
Amylose 4
Voudouris et al, 1995 4
Cellulose gum 2
Saravacos et al,1965 2
Pectin 5% 2
Saravacos et al.,1965 2
Pectin 10% 2
Saravacos el al.,1965 2
Pectin 5%-glucose 5% 2
Saravacos et al.,1965 2
Gelatin-sucrose-water 2
Hallidayetal, 1995 2
Glycerin 3
Ryniecki et al, 1993 3
Table 8.4 Continued

Nuts 1
Macadamia 1
Rahman, 1991 1
Other 134
Coconut 10
Duane et a!., 1995 1
Chenetal, 1998 9
Coffee 10
Sagaraetal., 1994 10
Soybean 12
Okos et al, 1986 12
Palm kernel 1
Duane etal, 1996 1
Lard 1
Duane et al., 1997
Agar-water
Wang etal, 1992
Water-NaCI
Lucas etal, 1999
Water-sucrose
Lucas etal, 1999 1
Rapeseed 52
Bilanskietal, 1976 18
Moyseyetal, 1977 10
Okos eta!., 1986 24
Tobacco 3
Casadaetal, 1989 3
Sorghum 7
Changetal, 1980 3
Okos etal. ,1986 4
Sugar 15
Okos etal, 1986 15
Albumen 2
Okos etal, 1986 2
NaCl 3
Okos etal, 1986 3
300 Chapter 8
Table 8.4 Continued

Honey 12
Okos et al.,1986 12
Albumine 3
Okos eta!., 1986 3
Vegetables 154
Carrot 5
Niesteruk, 1998 1
Njie et al, 1998 1
Rahman, 1991 2
Buhri et al, 1993 1
Cassava 6
Njieetal, 1998 6
Garlic 3
Madamba et al, 1995 3
Onion 7
Rapusasetal, 1994 7
Pea 12
Sastry et al, 1983 3
Alagusundarametal, 1991 9
Potato 45
Niesteruk, 1996 1
Niesteruk, 1997 1
Niesteruk, 1998 1
Hungetal.,1983 2
Luelal, 1999 1
Njieetal, 1998 2
WangetaL, 1992 16
Rahman, 1991 2
Matteaetal, 1986 3
Hallidayetal, 1995 9
Madamba eta!., 1995 2
Buhri eta!., 1993 1
Cratzeketal.,1993 4
Sugar beet 7
Niesteruk, 1998 4
Okos etal, 1986 3
Turnip 1
Buhri et al, 1993 1
Table 8.4 Continued

Yam 6
Njieetal., 1998 6
Beetroot 2
Niesteruk, 1998 2
Parsley 1
Niesteruk, 1998 1
Celery 1
Niesteruk, 1998 1
Tomato 31
Dincer, 1997 1
Choietd.,1983 9
Filkovaetal, 1987 3
Okos eta!., 1986 9
Drouzasetal., 1985 9
Cucumber 1
Dincer, 1997 1
Spinach 10
Mushrooms 9
Shrivastavaetal, 1999 9
Rutabagas 1
Buhri et al, 1993 1
Radish 1
Buhrietal, 1993 1
Parsnip 1
Buhri etai, 1993 1
Kidney bean 4
Zuritz et al, 1989 4
302 Chapter 8
Table 8.5 Thermal Conductivity of Foods Versus Moisture and Temperature:

Average Values of Available Data
Conductivity Moisture Temperature
Material (W/mK) (kg/kg db) (°C) Data
Baked products 0.34 0.57 46 60

Bread 0.23 0.39 44 14
- 0.27 0.35 47 9
Crust 0.06 0.00 68 2
Crumb 0.26 0.76 17 3
Dough 0.34 0.89 60 20
Wheat bread 0.41 0.78 23 3
Rye bread 0.47 1.06 20 3
Biscuit 0.40 0.07 20 2
Soy 0.35 0.33 150 3
Soy flour 0.22 0.21 27 11
Defatted 0.44 0.36 25 4
Dry defatted 0.12 0.00 40 3
Cup cake batter 0.17 0.63 15 2
- 0.17 0.63 15 2
Yellow cake batter 0.22 0.71 20 1
- 0.22 0.71 20 1
Cake 0.25 0.56 51 12
0.25 0.56 51 12
"
Cereal products 0.29 0.67 40 76

Barley 0.20 0.18 0 9
Seeds 0.20 0.18 0 9
Corn 0.39 1.55 36 21
Dent 0.16 0.20 36 3
Shelled 0.55 0.73 30 9
Dust 0.09 0.15 22 3
Syrup 0.43 4.16 52 6
Table 8.5 Continued

Rice 0.15 0.22 48 13

Paddy 0.15 0.22 48 13
Wheat 0.26 0.13 26 10
Dust 0.07 0.15 22 3
Hard red spring 0.16 0.17 -3 2
Soft white 0.13 0.13 16 2
Flour 0.59 0.10 56 3
Corn meal 0.36 0.27 88 7
- 0.36 0.27 88 7
Idli batter 0.45 1.71 16 4
- 0.45 1.71 16 4
Maize 0.27 0.32 62 11
Kernel 0.17 0.16 50 2
Grits 0.29 0.36 65 9
Oat 0.13 0.14 27 1
White 0.13 0.14 27 1
Dairy 0.45 3.78 38 136

Cheese 0.42 1.20 22 23
Cheddar 0.35 0.56 23 2
Mozzarella 0.38 0.80 23 2
Cuartirolo Argentina 0.37 1.20 15 1
Hamburger 0.39 0.69 23 2
Old Kashkaval 0.38 0.69 23 2
Tulum 0.38 0.69 23 2
Fresh Kashkaval 0.40 0.78 23 2
Buffet Kashkaval 0.41 0.99 23 2
Fresh cream 0.43 1.29 23 2
Spreadable cheese 0.49 1.54 23 2
Labne 0.47 2.24 23 2
Low fat labne 0.55 2.94 23 2
304 Chapter 8
Table 8.5 Continued

Milk 0.46 4.02 46 84

- 0.46 4.00 20 3
Fresh 0.57 9.00 23 1
Powder 0.11 25.33 25 3
Whole 0.46 3.04 53 18
Skim 0.57 6.33 36 15
Concentrated 0.41 0.92 50 9
Condensed 0.49 4.01 54 9
Half-half 0.54 5.11 40 9
Baby food 0.55 0.03 50 6
Powdered 0.30 0.05 54 11
Butter 0.22 0.20 21 5
- 0.23 0.18 23 2
Fat 0.21 0.21 20 3
Yogurt 0.45 3.60 31 19
- 0.56 6.25 21 2
Plain 0.33 2.05 40 9
Strained 0.54 2.88 23 2
Pasterized 0.58 4.71 23 2
Light 0.58 4.54 23 2
Extra light 0.59 6.58 23 2
Whey 0.59 9.00 40 4
- 0.59 9.00 40 4
Cream 0.13 44.00 25 1
Powder 0.13 44.00 25 1
Fish 0.79 3.29 8 83

Cod 1.23 4.88 -10 5
Perpendicular 1.23 4.88 -10 5
Mackerel 0.80 3.42 0 5
Perpendicular 0.80 3.42 0 5
Table 8.5 Continued

Squid 0.35 2.36 26 16

Fresh 0.50 5.04 30 3
Mantle 0.50 3.83 15 2
Dried 0.24 0.87 30 9
Tentacle, arrow 0.48 3.56 15 1
Tentacle 0.50 3.56 15 1
Carp 1.21 0.83 0 2
- 1.21 0.83 0 2
Surimi 0.78 4.02 14 30
- 0.85 4.08 -2 7
6% cryoprotectant cone 0.87 4.08 -2 7
12% cryoprotectant cone 0.86 4.08 -2 7
Pacific whiting 0.59 3.88 53 9
Cake 0.10 0.00 15 1
Pressed 0.10 0.00 15 1
Shrimp 1.03 3.24 -8 13
peeled and head removed 1.03 3.24 -8 13
Calamari 0.51 4.04 15 2
mantle 0.51 4.04 15 2
Salmon 1.06 2.40 -12 9
Perpendicular 1.06 2.40 -12 9
Fruits 0.45 3.73 30 143

Apple 0.45 3.44 30 82
- 0.32 2.44 20 25
Red 0.51 5.60 15 1
Green 0.41 0.14 45 1
Golden delicious 0.41 4.89 18 4
Granny Smith 0.19 2.17 25 3
Juice 0.53 3.81 37 47
Sauce 0.59 10.11 1
306 Chapter 8
Table 8.5 Continued

Banana 0.48 3.12 20 1

Dessert 0.48 3.12 20 1
Peach 0.04 35 1
Freeze-dried 0.04 35 1
Plantain 0.37 0.98 30 6
Fruits 0.37 0.98 30 6
Pear 0.49 3.22 34 15
- 0.47 2.85 24 4
Green 0.52 7.41 15 2
Juice 0.51 2.60 50 6
Williams 0.45 2.17 25 3
Orange 0.41 4.28 27 15
Juice 0.41 4.28 27 15
Bilberry 0.55 8.52 18 2
Juice 0.55 8.52 18 2
Cherry 0.55 6.52 18 2
Juice 0.55 6.52 18 2
Grape 0.52 4.08 42 8
- 0.52 3.60 50 6
Juice 0.55 5.54 18 2
Raspberry 0.55 7.70 18 2
Juice 0.55 7.70 18 2
Strawberry 0.63 8.44 14 5
Juice 0.57 11.05 18 2
Tioga 0.67 6.70 11 3
Raisin 0.23 1.35 45 4
- 0.23 1.35 45 4
Legumes 0.22 0.18 2 9

Lentils 0.22 0.18 2 9
Seeds 0.22 0.18 2 9
Table 8.5 Continued

Meat 0.71 2.40 16 134

Beef 0.63 2.22 28 75
- 0.54 2.43 1 2
Fat 0.28 0.14 7 3
Lean 1.03 0.63 0 2
Ground 1.01 0.75 0 2
Minced 0.56 1.96 11 5
Muscle semitendinosus 0.31 0.99 20 5
Dryfiber 0.21 1.03 25 4
Boneless 1.03 3.31 -4 20
Ground round 0.51 2.53 60 3
Whole round 0.49 2.32 60 3
Ground shank 0.51 2.45 60 3
Ground brisket 0.44 2.38 60 3
Whole rib steak 0.50 1.84 60 3
Ground sirloin tip 0.49 2.35 60 3
Whole sirloin tip 0.48 2.27 60 3
Ground rib 0.41 1.11 60 3
Ground s\viss steak 0.51 2.90 60 3
Whole swiss steak 0.49 2.82 60 3
Loaf, uncooked 0.40 2.58 15 1
Loaf heated 0.47 1.96 60 1
Chicken 1.05 3.46 -9 9
Boneless 0.97 3.00 -4 7
White 1.33 5.10 -25 2
308 Chapter 8
Table 8.5 Continued

Sausage 0.42 1.02 18 13

- 0.33 1.24 22 4
Italian 0.93 0.64 0 2
Salami cooked 0.37 1.70 22 1
Lebanon bologna 0.36 1.63 22 1
Salami cotto 0.37 1.33 22 1
Thuringer 0.35 0.96 22 1
Salami Genoa 0.30 0.56 22 1
Salami hard 0.32 0.52 22 1
Pepperoni 0.28 0.37 22 1
Turkey 1.18 2.85 -12 12
Boneless 1.18 2.85 -12 12
Mutton 0.86 2.66 -3 10
Boneless 0.86 2.66 -3 10
Pork 0.93 3.25 -4 11
Boneless 0.93 3.25 -4 11
Pork/soy 0.05 3.41 25 4
Unprocessed 0.05 3.17 25 2
Processed 0.05 3.64 25 2
Model foods 0.63 5.26 30 281

Amioca 0.32 3.35 52 51
- 0.25 2.86 58 20
Gelatinized 0.51 1.23 52 16
Powder 0.13 10.37 48 9
Granular 0.34 0.12 40 6
Table 8.5 Continued

Hylon-7 0.33 5.08 60 43

- 0.22 5.99 85 16
Powder 0.13 15.55 48 6
Granular 0.34 0.12 40 6
Potato starch 0.04 0.08 41 2
Gel 0.04 0.08 41 2
Starch 0.68 4.71 42 61
- 0.10 0.00 25 1
Gel 1.02 8.80 4 29
Hydrated 0.38 0.28 47 3
Granular 0.09 0.20 45 7
Gels 0.50 1.65 100 18
Sucrose 0.85 3.57 -1 33
- 0.48 3.72 20 3
Gel 0.89 3.56 -4 30
Gelatin 0.96 7.92 0 26
Gel 0.96 7.92 0 26
Ovalbumin 0.99 7.59 -5 36
- 0.88 4.23 -7 12
Gel 1.05 9.28 -4 24
Xylose 0.99 3.35 5 6
Gel 0.99 3.35 5 6
Agar-water 0.61 36.95 25 2
Gel 0.61 36,95 25 2
Gelatin-water 0.59 65.67 25 1
- 0.59 65.67 25 1
Amylose 0.53 3.50 30 4
Gel 0.53 3.50 30 4
310 Chapter 8
Table 8.5 Continued

Cellulose gum 0.06 0.08 41 2

Freeze-dried gel 0.06 0.08 41 2
Pectin 5% 0.04 0.08 41 2
Pectin 10% 0.05 0.08 41 2
Pectin 5%-glucose 5% 0.05 0.08 41 2
Glycerin 0.47 3.79 20 3
- 0.47 3.79 20 3
Gelatin-sucrose-water 0.44 1.44 15 2
0.44 1.44 15 2
"
Nuts 0.22 0.02 15 1

Macadamia 0.22 0.02 15 1
Integrifolia 0.22 0.02 15 1
Vegetables 0.43 3.81 39 154

Carrot 0.48 5.85 22 5
- 0.45 3.82 27 3
Large 0.52 8.91 15 2
Cassava 0.47 1.22 30 6
Roots 0.47 1.22 30 6
Garlic 0.36 0.80 15 3
- 0.36 0.80 15 3
Onion 0.42 2.05 32 7
. 0.42 2.05 32 7
Table 8.5 Continued

Pea 0.22 0.18 2 9

Seeds 0.22 0.18 2 9
Potato 0.45 2.35 49 45
- 0.42 2.74 57 25
Mashed 1.22 0.72 0 2
Flesh 0.54 4.54 20 1
Granule 0.35 0.64 62 10
White 0.53 4.55 18 4
Spunta 0.46 2.17 25 3
Sugar beet 0.53 3.38 22 7
- 0.56 4.22 25 3
Roots 0.52 2.75 20 4
Turnip 0.48 0.08 45 1
- 0.48 0.08 45 1
Yam 0.47 1.45 30 6
Tubers 0.47 1.45 30 6
Beetroot 0.56 9.10 20 2
- 0.56 9.10 20 2
Parsley 0.17 2.30 20 1
- 0.17 2.30 20 1
Celery 0.15 2.30 20 1
- 0.15 2.30 20 1
Tomato 0.51 6.23 68 31
- 0.61 15.60 21 1
Juice 0.48 7.71 83 21
Paste 0.55 1.73 40 9
Cucumber 0.62 24.00 22 1
- 0.62 24.00 22 1
Spinach 0.38 11.01 -2 10
Fresh 0.37 13.66 -2 5
Blanched 0.39 8.35 -2 5
312 Chapter 8
Table 8.5 Continued

Mushrooms 0.37 3.27 55 9

Pleurotusflorida 0.37 3.27 55 9
Rutabagas 0.45 0.08 45 1
- 0.45 0.08 45 1
Radish 0.50 0.06 45 1
- 0.50 0.06 45 1
Parsnip 0.39 0.21 45 1
- 0.39 0.21 45 1
Kidney bean 0.15 0.24 20 4

- 0.15 0.24 20 4
Other 0.23 2.06 25 134

Coconut 0.15 3.08 37 10
Milkpowder 0.15 3.08 37 10
Coffee 0.21 1.62 6 10
Solutions 0.21 1.62 6 10
Soybean 0.09 0.14 34 12
Powder 0.08 0.10 36 3
Whole 0.11 0.13 36 3
Crushed 0.10 0.11 36 3
Flour 0.05 0.22 26 3
Palm kernel 0.10 26.00 25 1
Milkpowder 0.10 26.00 25 1
Lard 0.12 32.00 25 1
Milkpowder 0.12 32.00 25 1
Water-Nad 0.46 4.00 10 1
Solution 0.46 4.00 10 1
Water-sucrose 0.32 0.67 10 1
Solution 0.32 0.67 10 1
Table 8.5 Continued

Rapeseed 0.11 0.10 14 52

mole 0.13 0.11 17 21
Ground 0.07 0.11 16 9
Torch 0.10 0.10 -4 9
Midas 0.09 0.01 19 1
Crushed 0.13 0.11 18 12
Agar-water 0.62 19.90 30 1
Gel 0.62 19.90 30 1
Tobacco 0.06 0.26 15 3
- 0.06 0.26 15 3
Sugar 0.52 4.32 42 15
Glucose 0.54 4.80 44 6
Cane sugar 0.51 4.00 40 9
Albumen 0.04 0.08 41 2
Sorghum 0.24 0.17 21 7
Rs610 0.14 0.22 5 2
NC+RS66 0.56 0.16 36 2
Grain dust 0.09 0.15 22 3
NaCl 0.61 4.00 43 3
Solution 0.61 4.00 43 3
Honey 0.53 4.83 36 12
- 0.53 4.83 36 12
Albumine 0.41 0.67 60 3
Solution 0.41 0.67 60 3
314 Chapter 8
Table 8.6. Thermal Conductivity of Foods Versus Moisture and Temperature:

Variation Range of Available Data
Material Conductivity (W/mK) Moisture (Kg/Kg db) Temperature (°C)
Min Max Min Max Min Max
Baked products 0.048 0.650 0.00 1.17 15 150

Bread 0.055 0.530 0.00 0.82 15 120
- 0.080 0.530 0.05 0.79 25 100
Crust 0.055 0.066 0.00 0.00 15 120
Crumb 0.232 0.298 0.72 0.82 15 18
Dough 0.230 0.600 0.04 1.17 20 150
Wheat bread 0.327 0.500 0.72 0.82 20 28
Rye bread 0.396 0.600 0.85 1.17 20 20
Biscuit 0.390 0.405 0.04 0.09 20 20
Soy 0.230 0.488 0.10 0.60 150 150
Soy flour 0.106 0.650 0.00 0.64 20 60
defatted 0.180 0.650 0.10 0.64 25 25
dry defatted 0.106 0.143 0.00 0.00 20 60
Cup cake barter 0.121 0.223 0.55 0.71 15 15
- 0.121 0.223 0.55 0.71 15 15
Yellow cake batter 0.223 0.223 0.71 0.71 20 20
- 0.223 0.223 0.71 0.71 20 20
Cake 0.048 0.356 0.11 1.22 20 103
- 0.048 0.356 0.11 1.22 20 103
Cereal products 0.067 0.740 0.01 8.09 -28 160

Barley 0.167 0.225 0.11 0.26 -28 29
Seeds 0.167 0.225 0.11 0.26 -28 29
Corn 0.085 0.740 0.01 8.09 10 77
Dent 0.142 0.175 0.01 0.42 36 36
Shelled 0.371 0.740 0.40 1.00 10 50
Dust 0.085 0.101 0.10 0.20 22 22
Syrup 0.347 0.513 0.23 8.09 27 77
Table 8.6. Continued

Rice 0.082 0.366 0.11 0.43 20 70

Paddy 0.082 0.366 0.11 0.43 20 70
Wheat 0.067 0.689 0.01 0.29 -3 66
Dust 0.067 0.073 0.10 0.20 22 22
Hard red spring 0.144 0.166 0.05 0.29 -3 -3
Soft white 0.118 0.140 0.01 0.25 15 16
Flour 0.450 0.689 0.10 0.10 43 66
Corn meal 0.270 0.464 0.18 0.43 20 160
- 0.270 0.464 0.18 0.43 20 160
Idli batter 0.395 0.493 1.00 2.33 15 20
- 0.395 0.493 1.00 2.33 15 20
Maize 0.067 0.525 0.11 0.59 35 95
Kernel 0.156 0.174 0.11 0.20 50 50
Grits 0.067 0.525 0.16 0.59 35 95
Oat 0.130 0.130 0.14 0.14 27 27
White 0.130 0.130 0.14 0.14 27 27
Dairy 0.039 0.686 0.02 44.00 1 90

Cheese 0.345 0.548 0.56 2.94 15 30
Cheddar 0.345 0.351 0.56 0.56 15 30
Mozzaretta 0.380 0.383 0.80 0.80 15 30
Cuartirolo Argen-
Tino 0.372 0.372 1.20 1.20 15 15
Hamburger 0.381 0.398 0.69 0.69 15 30
Old Kashkaval 0.368 0.384 0.69 0.69 15 30
Tulum 0.377 0.379 0.69 0.69 15 30
Fresh Kashkaval 0.403 0.403 0.78 0.78 15 30
Buffet Kashkaval 0.406 0.409 0.99 0.99 15 30
Fresh cream 0.433 0.434 1.29 1.29 15 30
Spreadable cheese 0.476 0.494 1.54 1.54 15 30
Labne 0.463 0.486 2.24 2.24 15 30
Low fat labne 0,542 0.548 2.94 2.94 15 30
316 Chapter 8

Milk 0.112 0.686 0.02 30.00 5 90

- 0.325 0.576 1.00 9.00 20 20
Fresh 0.570 0.570 9.00 9.00 23 23
Powder 0.112 0.115 22.00 30.00 25 25
mole 0.280 0.629 0.39 9.00 5 90
Skim 0.481 0.646 1.50 19.00 5 75
Concentrated 0.325 0.498 0.43 1.50 35 65
Condensed 0.325 0.634 1.00 9.00 23 79
Half-half 0.471 0.634 2.33 9.00 5 75
Baby food 0.405 0.686 0.03 0.04 35 65
Powdered 0.182 0.538 0.02 0.14 54 54
Butter 0.093 0.345 0.02 0.42 15 30
- 0.227 0.233 0.18 0.18 15 30
Fat 0.093 0.345 0.02 0.42 20 20
Yogurt 0.039 0.639 0.06 6.58 1 55
- 0.525 0.603 6.25 6.25 1 40
Plain 0.039 0.639 0.06 5.66 25 55
Strained 0.539 0.540 2.88 2.88 15 30
Pasterized 0.571 0.593 4.71 4.71 15 30
Light 0.571 0.583 4.54 4.54 15 30
Extra light 0.584 0.596 6.58 6.58 15 30
Whey 0.547 0.642 9.00 9.00 7 87
- 0.547 0.642 9.00 9.00 7 87
Cream 0.127 0.127 44.00 44.00 25 25
Powder 0.127 0.127 44.00 44.00 25 25
Fish 0.040 1.720 0.00 5.25 -40 80

Cod 0.549 1.543 4.88 4.88 -22 3
Perpendicular 0.549 1.543 4.88 4.88 -22 3
Mackerel 0.409 1.428 3.42 3.42 -20 20
Perpendicular 0,409 1.428 3.42 3.42 -20 20

Squid 0.040 0.507 0.10 5.20 15 30

Fresh 0.490 0.500 4.75 5.20 30 30
Mantle 0.483 0.507 3.83 3.83 15 15
Dried 0.040 0.440 0.10 2.86 30 30
Tentacle, arrow 0.475 0.475 3.56 3.56 15 15
Tentacle 0.501 0.501 3.56 3.56 15 15
Carp 0.700 1.720 0.83 0.83 -15 15
- 0.700 1.720 0.83 0.83 -15 15
Surimi 0.477 1.508 2.85 5.25 -40 80
- 0.487 1.473 4.08 4.08 -40 30
6% cryoprotectant 0.477 1.508 4.08 4.08 -40 30
12% cryoprotectant 0.489 1.465 4.08 4.08 -40 30
Pacific whiting 0.524 0.708 2.85 5.25 30 80
Cake 0.100 0.100 0.00 0.00 15 15
Pressed 0.100 0.100 0.00 0.00 15 15
Shrimp 0.490 1.600 1.00 4.20 -30 30
Peeled and head
removed 0.490 1.600 1.00 4.20 -30 30
Calamari 0.508 0.517 4.04 4.04 15 15
Mantle 0.508 0.517 4.04 4.04 15 15
Salmon 0.497 1.245 2.03 2.70 -24 5
Perpendicular 0.497 1.245 2.03 2.70 -24 5
Fruits 0.043 2.270 0.14 19.00 -40 90

Apple 0.070 2.270 0.14 19.00 -40 90
- 0.070 1.510 0.25 5.99 -40 45
Red 0.513 0.513 5.60 5.60 15 15
Green 0.405 0.405 0.14 0.14 45 45
Golden delicious 0.401 0.412 4.88 4.89 15 20
Granny Smith 0.090 0.296 0.50 4.00 25 25
Juice 0.230 2.270 0.25 19.00 -7 90
Sauce 0.591 0.591 10.11 10.11
318 Chapters

Banana 0.481 0.481 3.12 3.12 20 20

Dessert 0.481 0.481 3.12 3.12 20 20
Peach 0.043 0.043 35 35
Freeze-dried 0.043 0.043 35 35
Plantain 0.130 0.520 0.16 2.00 30 30
Fruits 0.130 0.520 0.16 2.00 30 30
Pear 0.340 0.629 0.50 7.41 15 80
- 0.340 0.557 0.50 4.90 23 25
Green 0.514 0.533 7.41 7.41 15 15
Juice 0.402 0.629 0.64 5.67 20 80
Williams 0.359 0.505 0.50 4.00 25 25
Orange 0.290 0.560 0.64 19.00 1 62
Juice 0.290 0.560 0.64 19.00 1 62
Bilberry 0.553 0.554 8.52 8.52 16 20
Juice 0.553 0.554 8.52 8.52 16 20
Cherry 0.553 0.554 6.52 6.52 16 20
Juice 0.553 0.554 6.52 6.52 16 20
Grape 0.396 0.639 0.59 8.09 16 80
- 0.396 0.639 0.59 8.09 20 80
Juice 0.537 0.556 5.54 5.54 16 20
Raspberry 0.544 0.553 7.70 7.70 16 20
Juice 0.544 0.553 7.70 7.70 16 20
Strawberry 0.520 0.935 6.70 11.05 -15 28
Juice 0.571 0.571 11.05 11.05 16 20
Tioga 0.520 0.935 6.70 6.70 -15 28
Raisin 0.126 0.392 0.16 4.00 45 45
- 0.126 0.392 0.16 4.00 45 45
Legumes 0.187 0.253 0.11 0.26 -21 28

Lentils 0.187 0.253 0.11 0.26 -21 28
Seeds 0.187 0.253 0.11 0.26 -21 28

Meat 0.049 1.660 0.01 5.10 -40 90

Beef 0.095 1.650 0.01 3.69 -30 90
- 0.454 0.622 2.28 2.57 -18 20
Fat 0.264 0.311 0.10 0.16 -10 15
Lean 0.510 1.550 0.63 0.63 -15 15
Ground 0.400 1.620 0.75 0.75 -15 15
Minced 0.360 0.844 1.11 3.44 -5 30
Muscle semitendi-
nosus 0,095 0.490 0.01 2.84 20 20
Dry fiber 0,140 0.243 0.38 2.30 25 25
Boneless 0.429 1.650 2.92 3.69 -30 30
Ground round 0.452 0.590 1.99 2.94 30 90
Whole round 0.475 0.504 1.50 2.94 30 90
Ground shank 0.442 0,598 1.58 2.92 30 90
Ground brisket 0.436 0.458 1.36 3.05 30 90
Whole rib steak 0.459 0.552 1.07 2.32 30 90
Ground sirloin tip 0.460 0.518 1.61 2.92 30 90
Whole sirloin tip 0.467 0.494 1.30 2.92 30 90
Ground rib 0.368 0.450 0.78 1.37 30 90
Ground Swiss steak 0.467 0.575 2.16 3.44 30 90
Whole swiss steak 0.467 0.508 1.84 3.44 30 90
Loaf, uncooked 0.400 0.400 2.58 2.58 15 15
Loaf, heated 0.470 0.470 1.96 1.96 60 60
Chicken 0.490 1.452 2.91 5.10 -25 20
Boneless 0.490 1.452 2.91 3.22 -20 20
White 1.268 1.387 5.10 5.10 -25 -25
320 Chapter 8

Sausage 0.275 1.380 0.37 1.86 -10 22

- 0.283 0.367 0.40 1.86 20 22
Italian 0.470 1.380 0.64 0.64 -10 10
Salami cooked 0.370 0.370 1.70 1.70 22 22
Lebanon bologna 0.355 0.355 1.63 1.63 22 22
Salami cotto 0.365 0.365 1.33 1.33 22 22
Thuringer 0.345 0.345 0.96 0.96 22 22
Salami genoa 0.295 0.295 0.56 0.56 22 22
Salami hard 0.315 0.315 0.52 0.52 22 22
Pepperoni 0.275 0.275 0.37 0.37 22 22
Turkey 0.490 1.660 2.85 2.85 -24 4
Boneless 0.490 1.660 2.85 2.85 -24 4
Mutton 0.391 1.510 2.45 2.80 -40 24
Boneless 0.391 1.510 2.45 2.80 -40 24
Pork 0.480 1.450 3.15 3.31 -30 30
Boneless 0.480 1.450 3.15 3.31 -30 30
Pork/soy 0.049 0.055 3.08 3.75 25 25
Unprocessed 0.049 0.051 3.08 3.25 25 25
Processed 0.053 0.055 3.54 3.75 25 25
Model Foods 0.038 2.330 0.00 65.67 -43 150

Amioca 0.080 0.661 0.00 20.00 20 150
Gelatinized 0.432 0.661 0.01 3.00 20 135
Powder 0.080 0.195 0.00 20.00 25 70
Granular 0.227 0.454 0.01 0.23 20 60

Hylon-7 0.100 0.661 0.00 20.00 20 150

Gelatinized 0.442 0.661 0.01 4.00 20 70
Powder 0.100 0.160 11.10 20.00 25 70
Granular 0.227 0.454 0.01 0.23 20 60
Potato starch 0.039 0.041 0.02 0.14 41 41
Gel 0.039 0.041 0.02 0.14 41 41
Starch 0.061 2.100 0.00 24.00 -42 120
- 0.100 0.100 0.00 0.00 25 25
Gel 0.480 2.100 1.78 24.00 -42 50
Gelatinized 0.330 0.355 0.10 0.10 20 80
Hydrated 0.364 0.388 0.28 0.28 10 80
Granular 0.061 0.125 0.05 0.30 15 75
Gels 0.436 0.567 0.66 3.00 80 120
Sucrose 0.350 1.770 0.67 9.00 -41 32
- 0.405 0.566 0.67 9.00 20 20
Gel 0.350 1.770 1.00 9.00 -41 32
Gelatin 0.039 2.070 0.02 19.00 -41 41
Gel 0.039 2.070 0.02 19.00 -41 41
Ovalbumin 0.450 2.330 2.30 19.00 -43 26
- 0.470 1.750 2.30 6.40 -43 20
Gel 0.450 2.330 3.20 19.00 -42 26
Tylose 0.483 1.530 3.35 3.35 -30 50
Gel 0.483 1.530 3.35 3.35 -30 50
Agar-water 0.600 0.622 24.90 49.00 20 30
Gel 0.600 0.622 24.90 49.00 20 30
Gelatin-water 0.594 0.594 65.67 65.67 25 25
- 0.594 0.594 65.67 65.67 25 25
Amylose 0.515 0.551 3.00 4.00 30 30
Gel 0,515 0.551 3.00 4.00 30 30
322 Chapter 8

Cellulose gum 0.056 0.063 0.02 0.14 41 41

Freeze-dried gel 0.056 0.063 0.02 0.14 41 41
Pectin 5% 0.038 0.039 0.02 0.14 41 41
Freeze-dried gel 0.038 0.039 0.02 0.14 41 41
Pectin 10% 0.044 0.047 0.02 0.14 41 41
Freeze-dried gel 0.044 0.047 0.02 0.14 41 41
Pectin 5%-glucose
5% 0.04S 0.050 0.02 0.14 41 41
Freeze-dried gel 0.048 0.050 0.02 0.14 41 41
Glycerin 0.450 0.490 3.35 4.26 20 20
0.450 0.490 3.35 4.26 20 20
Gelatin-sucrose-
water 0.396 0.487 0.65 2.22 15 15
- 0.396 0.487 0.65 2.22 15 15
Nuts 0.224 0.224 0.02 0.02 15 15

Macadamia 0.224 0.224 0.02 0.02 15 15
Integrifolia 0.224 0.224 0.02 0.02 15 15
Vegetables 0.103 0.670 0.06 24.00 -29 150

Carrot 0.182 0.605 0.15 9.00 15 45
- 0.182 0.605 0.15 9.00 15 45
Large 0.509 0.532 8.91 8.91 15 15
Cassava 0.160 0.570 0.22 2.33 30 30
Roots 0.160 0.570 0.22 2.33 30 30
Garlic 0.230 0.448 0.08 1.65 15 15
- 0.230 0.448 0.08 1.65 15 15
Onion 0.290 0.520 0.32 4.15 31 33
_ 0.290 0.520 0.32 4.15 31 33

Pea 0.181 0.256 0.11 4.50 -29 28

Seeds 0.181 0.256 0.11 0.26 -21 28
Potato 0.120 0.643 0.11 7.33 -15 130
- 0.209 0.643 0.34 7.33 24 130
Flesh 0.536 0.536 4.54 4.54 20 20
Granule 0.120 0.579 0.11 1.44 30 95
White 0.519 0.536 4.54 4.55 15 20
Spunta 0.331 0.550 0.50 4.00 25 25
Sugar beet 0.448 0.589 1.50 5.67 20 25
- 0.535 0.585 3.00 5.67 25 25
Roots 0.448 0.589 1.50 4.00 20 20
Turnip 0.480 0.480 0.08 0.08 45 45
- 0.480 0.480 0.08 0.08 45 45
Yam 0.160 0.600 0.19 3.76 30 30
Tubers 0.160 0.600 0.19 3.76 30 30
Beetroot 0.549 0.572 6.90 11.30 20 20
- 0.549 0.572 6.90 11.30 20 20
Parsley 0.170 0.170 2.30 2.30 20 20
- 0.170 0.170 2.30 2.30 20 20
Celery 0.147 0.147 2.30 2.30 20 20
- 0.147 0.147 2.30 2.30 20 20
Tomato 0.230 0.670 0.25 19.83 20 150
- 0.611 0.611 15.60 15.60 21 21
Juice 0.230 0.670 0.25 19.83 20 150
Paste 0.460 0.660 1.16 2.40 30 50
Cucumber 0.621 0.621 24.00 24.00 22 22
- 0.621 0.621 24.00 24.00 22 22
Spinach 0.347 0.434 8.35 13.66 -20 21
Fresh 0.347 0.400 13.66 13.66 -20 21
Blanched 0.356 0.434 8.35 8.35 -20 16
324 Chapter 8

Mushrooms 0.218 0.520 0.11 8.69 40 70

Pleurotusflorida 0.218 0.520 0.11 8.69 40 70
Rutabagas 0.447 0.447 0.08 0.08 45 45
- 0.447 0.447 0.08 0.08 45 45
Radish 0.499 0.499 0.06 0.06 45 45
- 0.499 0.499 0.06 0.06 45 45
Parsnip 0.392 0.392 0.21 0.21 45 45
- 0.392 0.392 0.21 0.21 45 45
Kidney bean 0.103 0.201 0.12 0.41 20 20
0.103 0.201 0.12 0.41 20 20
Other 0.039 0.656 0.01 32.00 -26 90

Coconut 0.115 0.217 0.19 26.00 25 50
Milkpowder 0.115 0.217 0.19 26.00 25 50
Coffee 0.153 0.277 1.22 2.51 -14 26
Solutions 0.153 0.277 1.22 2.51 -14 26
Soybean 0.040 0.133 0.05 0.40 10 66
Powder 0.066 0.104 0.10 0,10 10 66
Whole 0.095 0.133 0.13 0.13 10 66
Crushed 0.085 0.126 0.11 0.11 10 66
Flour 0.040 0.061 0.05 0.40 26 26
Palm kernel 0.102 0.102 26.00 26.00 25 25
Milkpowder 0.102 0.102 26.00 26.00 25 25
Lard 0.120 0.120 32.00 32.00 25 25
Milkpowder 0.120 0.120 32.00 32.00 25 25
Water-NaCl 0.460 0.460 4.00 4.00 10 10
Solution 0.460 0.460 4.00 4.00 10 10
Water-sucrose 0.320 0.320 0.67 0.67 10 10
Solution 0.320 0.320 0.67 0.67 10 10

Rapeseed 0.060 0.155 0.01 0.24 -26 32

Whole 0.108 0.155 0.06 0.15 4 32
Ground 0.062 0.088 0.07 0.15 4 32
Torch 0.086 0.120 0.01 0.24 -26 19
Midas 0.092 0.092 0.01 0.01 19 19
Crushed 0.060 0.080 0.07 0.15 4 32
Agar-water 0.617 0.617 19.90 19.90 30 30
Gel 0.617 0.617 19.90 19.90 30 30
Tobacco 0.055 0.070 0.20 0.32 15 15
- 0.055 0.070 0.20 0.32 15 15
Sugar 0.382 0.637 0.67 9.00 0 80
Glucose 0.450 0.637 1.50 8.09 2 80
Cane sugar 0.382 0.637 0.67 9.00 0 80
Albumen 0.039 0.042 0.02 0.14 41 41
Freeze-dried gel 0.039 0.042 0.02 0.14 41 41
Sorghum 0.084 0.150 0.01 0.30 5 36
Rs6lO 0.130 0.150 0.15 0.28 5 5
Grain dust 0.084 0.094 0.10 0.20 22 22
NaCI 0.568 0.656 4.00 4.00 10 80
Solution 0.568 0.656 4.00 4.00 10 80
Honey 0.440 0.618 1.50 9.00 2 71
- 0.440 0.618 1.50 9.00 2 71
Albumine 0.382 0.425 0.67 0.67 27 90
Solution 0.382 0.425 0.67 0.67 27 90
Note: Thermal conductivities higher than that of water (0.62 W/mK at 25°C) are characteristic of frozen
foods of high moisture content, since the thermal conductivity of ice is about 2 W/mK
326 Chapter 8
VI. THERMAL CONDUCTIVITY OF FOODS AS A FUNCTION OF

MOISTURE CONTENT AND TEMPERATURE
A concept proposed by Maroulis et al. (2001) is adopted here and applied to

obtain an integrated and uniform analysis of the available data. The concept was
applied simultaneously to all the data of each material, regardless the data sources.
Thus, the results are not based on the data of only one author and consequently
they are of elevated accuracy. A simplified analysis is presented in Chapter 6 for
the moisture diffusivity.
Assume that a material of intermediate moisture content consists of a uni-
form mixture of two different materials: (a) a dried material and (b) a wet material
with infinite moisture. The thermal conductivity is, generally, different for each
material. The thermal conductivity of the mixture could be estimated using a two
phase structural model:
1 X
A, Y { 1 / ~r
x :(T) (8-13)
"
where /I (W/mK) the effective thermal conductivity, Ax (W/mK) the thermal

conductivity of the dried material (phase a), Axi (W/mK) the thermal conductivity
of the wet material (phase b), X (kg/kg db) the material moisture content, and T
(°C) the material temperature.
Assume that the thermal conductivities of both phases depend on tempera-
ture by an Arrhenius-type model:
= A0 exp (8-14)
R(T T
exp (8-15)
where Tr =60°C a reference temperature, R = 0.0083\43kJImolKthe

ideal gas constant, and A0, /l(., E0, Et are adjustable parameters of the proposed
model.
The reference temperature of 60°C was chosen as a typical temperature of
air-drying of foods. Thus, the thermal conductivity for every material is character-
ized and described by four parameters with physical meaning:
/l0(W/mK) thermal conductivity at moisture X = 0 and temperature T = Tr

At (WlmK} thermal conductivity at moisture X = oo and temperature T = Tr
Ea (kJ I moT) Activation Energy for heat conduction in dry material at X = 0
Et (kJ I mol) Activation Energy for heat conduction in wet material at X — co
The resulting model is summarized in Table 8.7 and can be fitted to data using a
nonlinear regression analysis method.
The model is fitted to all literature data for each material and the estimates
of the model parameters are obtained. Then the residuals are examined and the
data with large residuals are rejected. The procedure is repeated until an accepted
standard deviation between experimental and calculated values is obtained (Draper
and Smith, 1981).
Among the available data only 13 materials have more than 10 data, which
come from more than 3 publications. The procedure is applied to these data and
the results of parameter estimation are presented in Table 8.8 and in Figure 8.18. It
is clear that thermal conductivity is larger in wet materials.
Figures 8.19-8.36 present retrieved thermal conductivities from the literature
and model-calculated values for selected food materials as a function of moisture
content and temperature. Thermal conductivity A, tends to increase with the mois-
ture content X and the temperature T.
The thermal conductivity parameters /10 and A/, shown in Figure 8.18, vary
in the range of 0.05 to 1.0 W/mK. It should be noted that the thermal conductivity
of air is about 0.026 W/mK, while that of water is 0.60 W/mK. Values of thermal
conductivity of foods higher than 0.60 W/mK are normally found in frozen food
materials (Aice=2 W/mK).
The thermal conductivity increases, in general, with increasing moisture
content. Temperature has a positive effect, which depends strongly on the food
material. The energy of activation for heat conduction E is, in general, higher in
the dry food materials.
328 Chapter 8
Table 8.7 Mathematical Model for Calculating Thermal Conductivity in Foods as

a Function of Moisture Content and Temperature
Proposed Mathematical Model
X .
X0exp +——X.exp
RT T, l +X RT T
where /i (W/mK) the thermal conductivity,

X (kg/kg db) the material moisture content,
T(°C) the material temperature,
Tr = 60°C a reference temperature, and
R = 0.0083143 kJ/mol K the ideal gas constant.
Adjustable Model Parameters
• Ka(W /mK) thermal conductivity at moisture X = 0 and temperature T = Tr

• "k.(W/ mK) thermal conductivity at moisture X = °o and temperature T = Tr
• E/U / mol) activation energy for heat conduction in dry material at X = 0
• E,(kJ/ mol) activation energy for heat conduction in wet material at X = oo
Table 8.8. Parameter Estimates of the Proposed Mathematical Model
No. of No. of 4 4, E; E0 sd
Material Papers Data (W/mK) (W/mK) (kJ/mol) (kJ/mol) (W/mK)
Cereal products
Corn 3 15 1.580 0.070 7.2 5.0 0.047
Fruits
Apple 12 68 0.589 0.287 2.4 11.7 0.114
Orange 4 13 0.642 0.106 1.3 0.0 0.007
Pear 5 15 0.658 0.270 2.4 1.9 0.016
Model foods
Amioca 5 29 0.718 0.120 3.2 14.4 0.037
Starch 4 24 0.623 0.243 0.3 0.4 0.006
Hylon 3 21 0.800 0.180 9.9 0.072
Vegetables
Potato 12 37 0.611 0.049 0.0 47.0 0.059
Tomato 5 28 0.680 0.220 0.2 5.0 0.047
Dairy
Milk 5 33 0.665 0.212 1.7 1.9 0.005
Meat
Beef 6 37 0.568 0.280 2.2 3.2 0.017
Other
Rapeseed 3 35 0.239 0.088 3.6 0.6 0.023
Baked products
Dough 3 15 0.800 0.273 2.7 0.0 0.183
330 Chapter 8
I Moisture=infinite
Moist ure=zero
.t! 0,1
•I
u
•a
a
o
U
0.01
100
• Moisture=infinite
O 0 Moisture=zero
S
e 10
&
<u
a
.2 i
13
•^
u
o.i
o
Figure 8.18 Parameter estimates of the proposed mathematical model.

Moisture (kg/kg db)
Figure 8.19 Predicted values of thermal conductivity of fruits at 25°C.

332 Chapter 8
Moisture (kg/kg db)
Figure 8.20 Predicted values of thermal conductivity of fruits at 60°C.

Moisture (kg/kg db)
Figure 8.21 Predicted values of thermal conductivity of vegetables at 25°C.

334 Chapter 8
Moisture (kg/kg db)
Figure 8.22 Predicted values of thermal conductivity of vegetables at 60°C.

1.0 10.0
Moisture (kg/kg db)
Figure 8.23 Predicted values of thermal conductivity of miscellaneous foods at

25°C.
336 Chapter 8
Moisture (kg/kg db)
Figure 8.24 Predicted values of thermal conductivity of miscellaneous foods at

60°C.
Fruits APPLE
Standard Deviation (sd, W/mK) 0.11
Parameter Estimates
Xi (W/mK) 0.59
Xo (W/mK) 0,29
Ei (kJ/mol) 2.45
_____Eo (kJ/mol) 11.7
1.0 10.0
Moisture (kg.kg db)
Figure 8.25 Thermal conductivity of apple at various temperatures and moisture

contents.
338 Chapter 8
Fruits ORANGE
Parameter Estimates
Xi (W/mK) 0.64
/u>(W/mK.) 0.11
Ei(kJ/mol) 1.26
_____Eo (kJ/mol)______0.0
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.26 Thermal conductivity of orange at various temperatures and moisture

contents.
Fruits PEAR
Parameter Estimates
Xi (W/mK) 0.66
Xo (W/mK) 0.27
Ei (kJ/mol) 2.45
Eo(kJ/mol) 1.9
1 —————————————————————
——— Temperature °C -
• 40
i
^ »60 ,——L i
A80
u-E
<:&?
^
••
& ->
A ••
A **
V s^ +*
^
s+
0
E i
I i ££
"5
a
•a
o
i
\
0.1 - ————— ———— —— — —— — - - -r —— — - - - - -
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.27 Thermal conductivity of pear at various temperatures and moisture

contents.
340 Chapter 8
Vegetables POTATO
Relative Standard Deviation (rsd, %)_____2209
Parameter Estimates
W(W/mK) 0.61
Xo (W/mK) 0.05
Ei (kJ/mol) 0.00
Eo (kJ/mol) 47.0
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.28 Thermal conductivity of potato at various temperatures and moisture

contents.
Vegetables TOMATO
Parameter Estimates
Xi (W/mK) 0.68
Xo (W/mK) 0.22
Ei(kJ/mol) 0.17
____Eo (kJ/mol)______5.0
1.0 10.0
Moisture (kg.kg db)
Figure 8.29 Thermal conductivity of tomato at various temperatures and moisture

contents.
342 Chapter 8
Model Foods AMIOCA

Parameter Estimates
Xi (W/mK) 0,72
Xo(W/mK) 0.12
Ei (kJ/mol) 3.22
_____Eo (kJ/mol)______14.4
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.30 Thermal conductivity of amioca (starch) at various temperatures and

moisture contents.
Model Foods HYLON

Parameter Estimates
Xi (W/mK) 0.80
Xo(W/mK) 0.18
Ei (kJ/mol) 9.90
_____Eo (kJ/mol)______0.0
Temperature °C -j
• 40
1.0 10.0
Moisture (kg.kg db)
Figure 8.31 Thermal conductivity of hylon (starch) at various temperatures and

moisture contents.
344 Chapter 8
Model Foods STARCH

Parameter Estimates
Xi (W/mK) 0.62
Xo (W/mK) 0.24
Ei (kJ/mol) 0.32
____Eo (kJ/mol)_____0.4
Temperature °C -
• 40 M
1
• 60 IT
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.32 Thermal conductivity of starch at various temperatures and moisture

contents.
Dairy MILK
Parameter Estimates
Xi (W/mK) 0.67
Xo(W/mK) 0.21
Ei(kJ/mol) 1.73
_____Eo (kJ/mol)______1.9
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.33 Thermal conductivity of milk at various temperatures and moisture

contents.
346 Chapter 8
Cereal Products CORN

Parameter Estimates
Xi (W/mK) 0.47
Xo(W/mK) 0.31
Ei (kJ/mol) 0.00
____Eo (kJ/mol)_____9.0
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.34 Thermal conductivity of corn (grains) at various temperatures and

moisture contents.
Baked Products DOUGH

Relative Standard Deviation (rsd, %)_______0
Parameter Estimates
Xi (W/mK) 0.80
Xo (W/mK) 0.27
Ei(kJ/mol) 2.71
____Eo (kJ/mol)______0.0
0.1 1.0 10.0

Moisture (kg.kg db)
Figure 8.35 Thermal conductivity of dough at various temperatures and moisture

contents.
348 Chapter 8
_______________Meat____BEEF
Parameter Estimates
Xi (W/mK) 0.57
Xo (W/mK) 0.28
Ei(kJ/mol) 2.15
_____Eo (kJ/mol)______3.2
1.0 10.0
Moisture (kg.kg db)
Figure 8.36 Thermal conductivity of beef at various temperatures and moisture

contents.
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Heat and Mass Transfer Coefficients
in Food Systems
I. INTRODUCTION
Heat and mass transfer coefficients are used in the design, optimization, op-
eration and control of several food processing operations and equipment. They are
related to the basic heat and mass transport properties of foods (thermal conductiv-
ity and mass diffusivity), and they depend strongly on the food/equipment inter-
face and the thermophysical properties of the system. Table 9.1 shows some im-
portant heat transfer operations, which are used in food processing. In all of these
operations, heat must be supplied to or removed from the food material with an
external heating or cooling medium, through the interface of some type of process-
ing equipment. Some operations, such as evaporation, involve mass transfer, but
the controlling transfer mechanism is heat transfer (Heldman and Lund, 1992;
Valentas etal., 1997).
Table 9.2 shows some mass transfer operations that are applied to food
processing. They are characterized by the removal or separation of a component of
the food material by the application of heat, e.g. drying, or other driving potential,
such as osmosis, reverse osmosis, adsorption, or absorption (King, 1971;
Saravacos, 1995). Heat and mass transfer coefficients are empirical transfer con-
stants that characterize a given operation from theoretical principles, but they are
either obtained experimentally or correlated in empirical equations applicable to
particular transfer operations and equipment.
Heat transfer coefficients and heat transfer, in general, are used more exten-
sively than mass transfer data in most food processing operations. In many cases,
mass transfer correlations are similar to correlations developed earlier in heat
transfer. In some operations, simultaneous heat and mass transfer may control the
process, e.g. in the drying of solids.
359
360 Chapter 9
Table 9.1 Heat Transfer Operations in Food Processing

Operations____________Objective__________________
Blanching Enzyme inactivation
Pasteurization Inactivation of microorganisms and enzymes
Sterilization Inactivation of microorganisms
Evaporation Concentration of liquid foods
Refrigeration Preservation of fresh foods
Freezing Food preservation
Frying______________Food preparation______________
Table 9.2 Mass Transfer Operations in Food Processing

Operations_____________Objective_____________
Drying Food preservation
Extraction Recovery of components
Distillation Recovery of volatiles
Adsorption Removal/recovery of components
Absorption Absorption/removal of gases
Reverse osmosis Concentration, desalting
Crystallisation___________Purification of components____
The parallel treatment of heat and mass transfer coefficients is important,

since there is an analogy of the two transfer processes, evident in some systems,
e.g. air/water, which is based on the transport phenomena.
II. HEAT TRANSFER COEFFICIENTS
A. Definitions
The heat transfer coefficient h (W/m2K) at a solid/fluid interface is given by
the equation:
q/A=h(AT) (9-1)
where qlA is the heat flux (W/m2) and /IT is the temperature different (°C or K). A
similar definition is applicable to liquid/fluid interfaces.
Heat transfer is considered to take place by heat conduction through a film
of thickness L of thermal conductivity /I, according to the equation:
Heat and Mass Transfer Coefficients in Food Systems 361
q/A = QJL)(AT) (9-2)
Thus, the heat transfer coefficient is equivalent to h=UL. However, Eq. (9-2) is
difficult to apply, since the film thickness L cannot be determined accurately be-
cause it varies with the conditions of flow at the interface.
The overall heat transfer coefficient U (W/m2K) between two fluids sepa-
rated by a conducting wall is given by the equation
q/A = UAT (9-3)
where AT is the overall temperature difference (K).

The coefficient U is related to the heat transfer coefficients hi and h2 of the
two sides of the wall and the wall heat conduction x/X by the equation:
\/U=\/h,+x/X+l/h2 (9-4)
where x is the wall thickness (m), and X is the wall thermal conductivity (W/mK).
In industrial heat exchangers, the thermal resistance of fouling deposits must be
added in series to the resistances of Eq. (9-4).
The overall heat transfer coefficients are specific for each processing
equipment and fluid system, and it is determined usually from experimental meas-
urements.
B. Determination of Heat Transfer Coefficients

The heat transfer coefficient h at a given interface can be determined ex-
perimentally by various methods (Rahman, 1995). In the constant heating (steady
state) method, the heat flux q/A is measured (e.g. by electrical measurement) at a
given temperature difference AT, and the coefficient h is calculated from Eq. (9-1).
In the quasi-steady state method, the heat transfer coefficient is determined
from the slope of the heating line of a high conductivity solid, which is assumed to
heat uniformly. The heat transfer coefficient can be estimated from the analytical
or numerical solution of the heat conduction (Fourier) equation:
(9-5)
dt dX1
where a is the thermal diffusivity of the material.

The solution of Eq. (9-5) involves the Biot number for heat transfer, BiH =
(hL/X), from which the heat transfer coefficient can be estimated. The heat transfer
coefficient h at the interface of processing equipment can be measured by the heat
flux sensors method, which simultaneously measures the surface temperature and
the heat flux (Karwe and Godavarti, 1997). The sensors consist of a differential
362 Chapter 9
thermopile of thermal resistance with two inserted thermocouples. They are

mounted on the heat transfer surface by a high thermal conductivity paste.
Approximate values of h can be estimated indirectly by measuring the pa-
rameters of some physical processes, which involve heat transfer, such as the
freezing time of a material (Plank's equation) or the evaporation rate of a liquid in
a flat surface at a given temperature difference A T.
Special experimental arrangements are required for the estimation of the
heat transfer coefficients between particles and a liquid, both in motion, as in asep-
tic processing of food suspensions. The particle temperature may be measured by
a moving thermocouple or estimated from the change of color of special materials,
such as liquid crystals coated on acrylic spherical particles and observed through a
transparent flow tube.
C. General Correlations of the Heat Transfer Coefficient

Correlations of heat transfer data are useful for estimating the heat transfer
coefficient h in various processing equipment and operating conditions. These
correlations contain, in general, dimensionless numbers, characteristic of the heat
transfer mechanism, the flow conditions, and the thermophysical and transport
properties of the fluids. Table 9.3 lists the most important dimensionless numbers
used in both heat and mass transfer operations.
The Reynolds number (Re=uL/v) is used widely in almost all correlations.
In this number, the velocity u is in (m/s), the length I is in (m) and the kinematic
viscosity or momentum diffusivity (v=rj/p~) is in (m2/s). The length L can be the
internal diameter of the tube, the equivalent diameter of the noncircular duct, the
diameter of a spherical particle or droplet, or the thickness of a falling film. Some
dimensionless numbers, used in both heat and mass transfer correlations, are de-
noted by the subscripts H and M respectively, i.e. Bin Bi^, Stn, St^, JH andy^/-
Table 9.4 shows some heat transfer correlations of general applications. For
natural convection, the parameters a and m characterize the various shapes of the
equipment and the conditions of the fluid (McAdams, 1954; Perry and Green,
1984; Geankoplis, 1993; Rahman, 1995).
The ratio of tube diameter to tube length D/L is important in the laminar
flow (Re < 2100), but it becomes negligible in the tubular flow in long tubes (L/D
> 60). For shorter tubes, the ratio D/L should be included in the correlation.
The viscosity ratio r\/r]w refers to the different viscosity in the bulk of the
fluid 77 and at the tube wall t]w. This ratio becomes important in highly viscous
fluids, like oils, in which the viscosity drops sharply at the high wall temperatures,
increasing the heat transfer coefficients. Several other correlations have been pro-
posed in the literature for different heat transfer of fluid systems, like flow outside
tubes and flow in packed beds.
The heat transfer coefficients of condensing vapors have been correlated to

the geometry of the tubes and the properties of the liquid film or droplets. Very
high heat transfer coefficients are obtained by drop-wise condensation.
Table 9.3 Dimensionless Numbers in Heat and Mass Transfer Calculations

Number Applications
Reynolds Re=uL/v Flow processes
Nusselt Nu=hL/A Heat transfer
Prandtl Pr=v/a Heat transfer
Grashof Gr=L3g(Ap/p)/v2 Free convection
Graetz Gz=GACpM Heat transfer
Biot BiH=hm Heat transfer
Sherwood Sh=kcL/D Mass transfer
Schmidt Sc=v/D Diffusion processes
Stanton StH=h/G Cp Heat transfer
Stanton StM=kc/u Mass transfer
Lewis Le=a/D Heat/mass transfer
Peclet Pe=uL/D Flow/diffusion
Biot BiM=kcL/X Mass transfer
Heat Transfer Factor JH=StHPr2'^ Heat transfer
Mass Transfer Factor jM=StMSc /s Mass transfer
A, interfacial area (m2); L, length (m); a thermal diffusivity (m2/s); Cp, specific heat (J/kg K); D mass
diffusivity (m2/s); g acceleration of gravity (m2/s); G=up, mass flow rate kg/m2s; h, heat transfer coeffi-
cient (W/m2K); kc, mass transfer coefficient (m/s); 77 viscosity (Pas); p, density (kg/m3); u, velocity
(m/s)
Table 9.4 General Heat Transfer Correlations____________________________

Transfer System________________Correlation_____________
Natural convection Nu = a (Gr Pr)m
Laminar inside tubes Nu = l.B6[RePr(D/L)f\rj/rjwfu
Turbulent inside long tubes Nu = O.Q23Re°*Pr1'3 (rj/tjw}°M
Parallel to flat plate (laminar) Nu = 0.664/?e°5 Pr113
Parallel to flat plate (turbulent) Nu = 0.0366#e°8 Pr1'3
Past single sphere_______________Nu = 2.0 +0.60Re°'5 Pr113_______
Dimensionless numbers defined in Table 9.3. a and m, parameters of natural convection characteristic
of the system (Perry and Green, 1984); L, D length and diameter of tube. Long tubes L/D>60
364 Chapter 9
D. Simplified Equations for Air and Water
The heat transfer coefficients of air and water in some important operations
can be estimated from simplified dimensional equations, applicable to specific
equipment geometries and system conditions (Perry and Green, 1984; Geankoplis,
1993):
a. Natural convection of air:
Horizontal tubes, h = 1 .42 (A T/d0) 1/4 (9-6)
Vertical tubes, h=\A2 (AT/L)W (9-7)
b. Air in drying (constant rate):
Parallel flow, h = 0.0204G0'8 (9-8)
Perpendicular flow, h=l.ll G°'37 (9-9)
c. Falling films of water:
/j = 9150r 1/3 (9-10)
d. Condensing water vapors:
Horizontal tubes, h = 10800 / [(Nd0f\AT)l/3] (9-11)
Vertical tubes, h = 13900 / [Lw(AT)m] (9-12)
where AT is the temperature difference (K), d0 is the outside diameter (m), L is the
length (m), G is the mass flow rate (kg/m2s), F is the irrigation flow rate of the
films (kg/m s) and N is the number of horizontal tubes in a vertical plane.
III. MASS TRANSFER COEFFICIENTS
A. Definitions
Mass transfer in industrial and other applications is usually expressed by
phenomenological mass transfer equations, instead of the basic mass diffusion
model. The mass transfer equations use lumped parameters and average concentra-
tion, while the diffusion model has distributed parameters for the dependent vari-
able (concentration), which can vary with the independent variables of distance
and time (Cussler, 1997).
The mass transfer coefficients are functions of the mass diffusivity, the vis-
cosity, the velocity of the fluid, and the geometry of the transfer systems. The
mass diffusivity, in the diffusion model, is a fundamental property based on mo-
lecular interactions and on the physical structure of the material.
The mass transfer coefficient kc (m/s) in a process is defined in an analo-
gous manner with the heat transfer coefficient:
J = kcAC (9-13)
where J is the mass flux (kg/m2s) and AC is the concentration difference (kg/m3).
In contrast to heat transfer where the driving force is the temperature differ-
ence AT, m mass transfer the driving force can be expressed by the concentration
difference AC, the difference of mass fraction AY, or the pressure difference AP.
Thus, three mean mass transfer coefficients can be defined by the following equa-
tion (Saravacos, 1997):
J = kcAC = kYAY = kpAP (9-14)
The units of the three mass transfer coefficients depend on the units of AC, AY and
AP and they are usually kc (m/s), kY (kg/m2s) and kp (kg/m2sPa). In food engineer-
ing and especially in drying calculations, the symbol hM is used instead of kY, with
the same units (kg/m2s).
In an analogy with the overall heat transfer coefficient K, the overall mass
transfer coefficient is used to express mass transfer through the interface of two
fluids, according to the equation:
l/K=\fkci+\/kc2 (9-15)
where kcl and kC2 are the mass transfer coefficients of the two contacting fluids. It
should be noted that in mass transfer there is no wall resistance and the two fluids
at the interface are assumed to be in thermodynamic equilibrium.
Volumetric mass transfer coefficients (kcv) may be used in some industrial
operations, defined by the equation:
kcv=a.kc (9-16)
where a = A/Vis the specific surface of the transfer system (m2/m3). Thus the units
of kcv will be (1/s) and of h
B. Determination of Mass Transfer Coefficients
The mass transfer coefficients can be determined by direct or indirect meas-

urement of the mass transfer rates in a controlled experimental system.
The wetted wall column has been used to determine ^-values in liquid/gas
and liquid/vapor systems, like absorption of gas in aqueous solutions (Sherwood
et al., 1975; Brodkey and Hershey, 1988). The mass flux is measured at a given
driving force (AC, AY or AP) and the corresponding coefficients (kc, kY or kp) are
determined.
The mass transfer coefficients (kc or hM) during the constant rate period of
drying can be estimated from the drying rate of a known sample at well-defined
366 Chapter 9
drying conditions. As an illustration, the mass transfer coefficient in the air drying
of spherical starch samples 21 mm diameter at 60°C, 10% RHand 2 m/s air veloc-
ity was determined as kc= 34 mm/s (Saravacos et al, 1988).
It should be noted that the drying rate of wet high moisture samples is close
to the evaporation of water from a free surface. However, in drying food materials,
some resistance to mass transfer is usually present at the interface and in the inte-
rior of the product, resulting in significantly lower drying rates. Thus, the mass
transfer coefficient in drying grapes is lower, e.g. 7 mm/s or 13 mm/s, depending
on skin resistance to moisture transfer.
The mass transfer coefficient during drying kY or hM can be estimated simul-
taneously with the heat transfer coefficient h and the moisture diffusivity D from
drying data (Marinos-Kouris and Maroulis, 1995). The experimental drying data
are fitted by regression analysis to a heat and mass transfer model, assuming cer-
tain empirical relationships. The results, obtained for the heat and mass transfer
coefficients, are much lower than the values of evaporation of water from free
surfaces, since during drying the heat and mass transfer interface moves inside the
porous solid food material, becoming much larger than the outside surface of the
material.
C. Empirical Correlations
Tables 9.5 and 9.6 show some empirical correlations of the mass transfer
coefficient (kc) in fluid/solid and fluid/fluid systems. Fluid/solid systems are com-
mon in drying of solids, solvent extraction of solids and adsorption operations.
Fluid/liquid interfaces are important in aeration, de-aeration, and carbona-
tion/decarbonation of liquid foods.
Table 9.5 Mass Transfer Correlations for Fluid/Solid Interfaces

Transfer system_________________Correlation_______
Membrane Sh = 1
Laminar inside tubes Sh = 1.62 (cfuILD)1/3
Turbulent inside tubes Sh = 0.026 Re°8Sc1'3
Parallel to flat plate (laminar) Sh = 0.646 Re0'5 Sc>/3
Past single sphere Sh = 2.0 + 0.60 Re°'5Scl/3
Packed beds Sh=\.ll Re°A2 (1 /Sc)2/3
Spinning disc__________________Sh = Q.62Re°'5Sc1'3
Dimensionless numbers defined in Table 9.3.
Table 9.6 Mass Transfer Correlations for Fluid/Fluid Interfaces

Transfer system____________Correlation________________
Gas bubbles in unstirred tank Sh = OA2 Gr1/45c"3
Gas bubbles in stirred tank Sh=l.62 [(P/V) cflpP3]1/4 5c1/3
Small liquid drops in unstirred solution Sh = 1.13 (dulD)°'%
Falling films______________Sh = 0.69 (zu/Df5_____________
Dimensionless numbers defined in Table 9.3; d, drop diameter (m); z, position along film (m); P/V
stirrer power per volume.
D. Theories of Mass Transfer

The empirical mass transfer data, used in various correlations can be inter-
preted in terms of approximate or exact theories of mass transfer. The mass trans-
fer theories were developed mainly for fluid/fluid systems. The most important
theories are briefly the following (Cussler, 1997).
1. Film Theory
The mass transfer coefficient kc is a function of the first power of the diffu-
sion coefficient £>:
hc =D/L (9-17)
where L (m) is the film thickness, which is difficult to determine accurately, since
it is a function of the flow conditions, the geometry of the system, and the physical
properties of the fluid.
2. Penetration Theory
The mass transfer coefficient kc is a function of the square root of the mass
diffusivity D:
kc=2(Du/nLf2 (9-18)
where L is the depth of penetration (m) and u is the velocity (m/s) of penetration.
The contact time between the diffusivity components and the fluid is defined as
u/L, and it is difficult to determine experimentally.
3. Surface Renewal Theory

The mass transfer coefficient kc is a function of the square root of mass dif-
fusivity D, in a similar manner with the penetration theory:
368 Chapter 9
kc=(Drf2 (9-19)
where T is the average time for a fluid element in the interface region.
4. Boundary Layer Theory

The boundary layer theory, applied primarily in fluid mechanism and heat
transfer, gives a more accurate correlation of the mass transfer coefficient kc in the
laminar flow. The kc is a function of the 2/3 power of mass diffusivity D.
The average mass transfer coefficient kc, past a flat plate of length L, is
given by the following empirical equation, which is analogous to the correspond-
ing heat transfer relationship:
kc = 0.00646 (D/L)RelK So213 (9-20)
where the Reynolds number is defined as Re=Lu/v.

The heat and mass transfer analogies are useful in evaluating the heat/mass
transfer mechanisms and in estimating and inter converting the heat and mass
transfer coefficients. The Chilton Colburn (or Colburn) analogy for heat and mass
transfer indicates that in fluid systems, under certain conditions, the heat and mass
transfer factors are equal (Geankoplis, 1993; Saravacos, 1997):
JH=JM (9-21)
where jH= 5^/'r2/3,yw= StMSc2n and StH= h/upCp, StM= kc/u or StM= hûp
The Colburn analogy in air/water mixtures (applications in drying and air
conditioning) is simplified, since the Pr and Sc are approximately equal (Pr = Sc
= 0.8). Therefore, we may have StH = StM or h/upCp = kC/u or h/pCp =kc,
In terms of the mass transfer coefficient hM, the last relationship becomes:
h/Cp = hM (9-22)
The specific heat of atmospheric air at ambient conditions is approximately

Cp = 1000 J/kgK. Therefore, Eq. (9-22) yields h = 1000hM, where h is in W/m2K
and hM in kg/m2s. If the units of hM are taken as g/m2s, the last relationship is writ-
ten as (Saravacos, 1997):
Atmospheric air, h (W/m2K) = HM (g/m2s) (9-23)
A similar relationship is obtained between the coefficients h and kc'.
Atmospheric air, h (W/m2K) = kc (mm/s) (9-24)

IV. HEAT TRANSFER COEFFICIENTS IN FOOD SYSTEMS

The heat and mass transfer coefficients in food systems are determined ex-
perimentally or correlated empirically from pilot plant and industrial data. They
are specific for each food process and processing equipment and are related to the
physical structure of the food materials.
Most of the literature data refer to heat transfer coefficients, since heat trans-
fer is the rate controlling mechanism in many processing operations. Mass transfer
coefficients can be related to heat transfer in some important operations, like dry-
ing, using the Colburn analogy of heat and mass transfer.
Typical values of heat transfer coefficients are shown in Table 9.7 (Hall-
strom et al., 1988; Perry and Green, 1997; Rahman, 1995; Saravacos, 1995). De-
tailed data and empirical correlations for both transfer coefficients are presented in
sections VI and VII of this chapter.
A. Heat Transfer in Fluid Foods

Heat transfer in viscous non-Newtonian fluids in laminar flow in tubes is
expressed by a correlation analogous to the equation for Newtonian fluids:
(9-25)
where the Graetz number Gz = GrCp/AL, and G is the mass flow rate (kg/m2s).
Table 9.7 Typical Heat Transfer Coefficient h and Overall Coefficients U in

Food Processing Operations_____________________ ______
Heat Transfer System h, W/m2K
Air/process equipment, natural convention 5 - 20a
Baking ovens 20 - 80a
Air drying, constant rate period 30 - 200a
Air drying, falling rate period 20 - 60
Water, turbulent flow 1000 - 3000
Boiling water 5000 - 10000
Condensing water vapor 5000 - 50000
Refrigeration, air cooling 20 - 200
Canned foods, retorts 150 - 500
Aseptic processing, particles 500 - 3000
Freezing, air/refrigerants 20-500
Frying, oil/solids 250 - 1000
Heat exchangers (tubular/plate) 500 - 3500 (overall U)
Evaporators____________________500 - 3000 (overall U)
' Similar numerical values for the mass transfer coefficients kc (mm/s) or hM (g/m2s), applying the
Colbum analogy.
370 Chapter 9
The apparent viscosities at the bulk of the fluid and at the wall tja and ^ are
determined for the given shear rate y using the Theological constants K and n of the
fluid for a mean temperature. Heat transfer in agitated vessels is expressed by the
empirical correlation (Saravacos and Moyer, 1967):
= CRe°'66Pr 1/3 Ola/Tlaw)',0.14 (9-26)
where the coefficient C = 0.55 for Newtonian and C = 1.474 for non-Newtonian
fluids.
The Reynolds number is estimated as Re = (d2Np)lrja where d is the diameter
of the impeller, and rja is the apparent viscosity estimated at the agitation speed TV
as r\a = Ky"'1 where K and n are the Theological constants of the fluid at the mean
temperature. The shear rate y for the pilot-scale agitated kettle, described in this
reference (0.40 m diameter, anchor agitator), was calculated from the empirical
relation 7= 13N.
The heat transfer coefficients h at the internal interface of the vessel for a
sugar solution and for applesauce increased linearly with speed of agitation
(RPM), as shown in Figure 9.1.
Figure 9.2 shows that the overall heat transfer coefficient U in the agitated
kettle decreases almost linearly when the flow consistency coefficient K is in-
creased.
10000
1000 --
Figure 9.1 Heat transfer coefficients in agitated kettle. S, sucrose solution 40° Brix;
A, applesauce; RPM, 1/min
1600
1300
1000
10
K (Pa s")
Figure 9.2. Overall heat transfer coefficient (U) of fruit purees in agitated kettle.
K, flow consistency coefficient.
B. Heat Transfer in Canned Foods

Several heat transfer correlations for canned foods are presented by Rahman
(1995). In most cases of heating/cooling of cans, the product heat transfer coeffi-
cient ht is controlling the transfer process, since the outside (heating/cooling me-
dium) coefficient and the heat conductance of the wall l/x are generally high (me-
tallic or glass containers). However, heat transfer in plastic containers may be con-
trolled by the wall thermal resistance, due to the low thermal conductivity and the
high wall thickness of the plastic material Eq. (9-4).
The Reynolds numbers for Newtonian fluids is estimated as Re =
where d is the can diameter and N is the speed of rotation (1/s) of the can. For non-
Newtonian fluids, the dimensionless numbers used are the following (Rao, 1999):
4n
Re = - (9-27)
l3n + l
372 Chapter 9
4n
Gr 22
-2 V ;
where K and n are the rheological constants of the fluid at a mean temperature, and
fi = (A V/AT)IV, 1/K (natural convection).
Heat transfer in cans in an agitated retort (Steritort) is considered as the sum
of the contributions of both natural and forced convection:
Nu = A[(Gr}(Prf + C^Re\Pr\D / L)]D (9-30)
where, for Newtonian fluids, A = 0.135, B = 0.323, C = 3.91xlO"3, and D = 1.369

and for non-Newtonian fluids, A = 2.319, B = 0.218, C = 4.1xlO'7, and D = 1.836
In end-over-end agitated cans the following correlations were obtained
(Rao, 1999):
Nu = 2 .9 Re°A36 Pr°2*7 for Newtonian fluids (9-3 1 )
Nu = Re°ABS Pr°'361 for non-Newtonian fluids (9-32)
Non-Newtonian biopolymers, when subjected to extreme heat treatment, suffer

significant losses in apparent viscosity.
C. Evaporation of Fluid Foods

Heat transfer controls the evaporation rate of fluid foods and high heat trans-
fer coefficients are essential in the various types of equipment. Prediction of the
heat transfer coefficients in evaporators is difficult, and experimental values of the
overall heat transfer coefficient U are used in practical applications.
The overall heat transfer coefficient is a function of the two surface heat
transfer coefficients //,• and h0, the wall thermal conductance MX, and the fouling
resistance Eq. (9-33):
-1 = 1 + - + — + FR (9-33)
U h k h,
The fouling resistance 7-7? becomes important in the evaporation of liquid foods
containing colloids and suspensions, which tend to deposit on the evaporator
walls, reducing significantly the heat transfer rate.
10000
Figure 9.3 Overall heat transfer coefficients U in evaporation of clarified CL and unfil-
tered UFT apple juice at 55°C.
Falling film evaporators are used extensively in the concentration of fruit

juices and other liquid foods because they are simple in construction and they have
high heat transfer coefficients. Figure 9.3 shows overall heat transfer coefficients
U for apple juices in a pilot plant falling film evaporator, 5 cm diameter and 3 m
long tube (Saravacos and Moyer, 1970).
Higher U values were obtained in the evaporation of depectinized (clarified)
apple juice (1200 to 2000 W/m2K) than the unfiltered (cloudy) juice, which tended
to foul the heat transfer surface as the concentration was increased. The U value
for water, under the same conditions was higher as expected: U= 2300 W/m2K.
D. Improvement of Heat / Mass Transfer

Jet impingement ovens and freezers operate at high heat transfer rates, due
to the high air velocities at the air/food interface. Heat transfer coefficients of 250-
350 W/m2K can be obtained in ovens, baking cookies, crackers and cereals (Nitin
andKarwe, 1999).
Ultrasounds can substantially improve the air-drying rate of porous foods,
like apples (acoustically-assisted drying). Ultrasound of 155-163 db increased the
moisture diffusivity at 60°C from 7xlO' 10 to 14xlO'10 m2/s (Mulet et al., 1999).
374 Chapter 9
V. HEAT TRANSFER COEFFICIENTS IN FOOD PROCESSING: COM-

PILATION OF LITERATURE DATA
Recently reported heat transfer coefficient data in food processing were re-
trieved from the following journals (Krokida et al., 200 la):

• Transactions of the ASAE, 1975-1999
• International Journal of Food Properties, 1998-2000
A total number of 54 papers were retrieved from the above journals. The
data refer to 7 different processes (Table 9.8) and include about 40 food materials
(Table 9.9). Most of the data were available in the form of empirical equations
using dimensionless numbers. All available empirical equations were transformed
in the form of heat transfer factor versus Reynolds number (jH = aRe"). This equa-
tion was also fitted to all data for each process and the resulting equations charac-
terize the process, since they are based on the data from all available materials.
The results are classified by process and material and are presented in Table
9.10. All the equations are presented in Figure 9.4 to define the range of variation
of they'// and Re. The range of variation by process is also sketched in Figure 9.5.
The above results are presented analytically for each process in Figures 9.6-9.11.
The effect of food material is obvious in these diagrams. The results of fitting the
equation to all data for each process is summarized in Table 9.11 and in Figure
9.12.
Heat transfer coefficient values for process design can be obtained easily
from the proposed equations and graphs. The range of variation of this uncertain
coefficient can also be obtained in order to carry out valuable process sensitivity
analysis. Estimations for materials not included in the data can also be made using
similar materials or average values. It is expected that the resulting equations are
more representative and predict more accurately the heat transfer coefficients.
Table 9.8 Number of Available Equations for each Food Process
Process No. of equations

1 Baking
Forced convection 1
2 Blanching
Steam 1
3 Cooling
Forced convection 9
4 Drying
Convective 16
Fluidized bed 1
Rotary 4
5 Freezing
Forced convection 6
6 Storage
Forced convection 4
7 Sterilization
Aseptic 9
Retort 3
Total No. of equations 54
376 Chapter 9
Table 9.9 Number of Available Equations for each Food Material
Material No. of Equations

1 Apples 1
2 Apricots 1
3 Barley 2
4 Beef 1
5 Cakes 1
6 Calcium alginate gel 1
1 Canola seeds 1
8 Carrot 1
9 Corn 2
10 Corn starch 1
11 Figs 1
12 Fish 1
13 Grapes 3
14 Green beans 1
15 Hamburger 2
16 Maize 1
17 Malt 1
18 Meat carcass 1
19 Model food 4
20 Newtonian liquids 1
21 Non-food material 3
22 Particulate liquid foods 3
23 Peaches 1
24 Potatoes 2
25 Raspberries 1
26 Rice 1
27 Soya 2
28 Soybean 1
29 Strawberries 1
30 Sugar 1
31 Wheat 3
32 Spherical particles 1
33 Tomatoes 1
34 Corn cream 1
35 Rapeseed 1
36 Meatballs 1
Total No. of equations 54
Table 9.10 Parameters of the Equation jH = aRe" for each Process and each Mate-
rial
Process/product/reference a „ mm Re max Re
Baking
Cakes
Baiketal., 1999 0.801 -0.390 40 3,000
Blanching
Green Beans
Zhangetal., 1991 0.00850 -0.443 150 1,500
Cooling
Apples
Fikiinetal., 1999 0.0304 -0.286 4,000 48,000
Apricots
Fikiinetal., 1999 0.114 -0.440 2,000 25,000
Figs
Dincer, 1995 8.39 -0.492 3,500 9,000
Grapes
Fikiinetal., 1999 0.472 -0.516 1,300 17,000
Model Food
Alvarez et al., 1999 2.93 -0.569 2,000 12,000
Peaches
Fikiinetal., 1999 0.186 -0.500 3,700 43,000
Raspberries
Fikiinetal., 1999 0.0293 -0.320 1,300 16,000
Strawberries
Fikiinetal., 1999 0.136 -0.440 1,900 25,000
Tomatoes
Dincer, 1997 0.267 -0.550 1,000 24,000
378 Chapter 9
Table 9.10 Continued

Process/product/reference a n minRe ma\Re
Drying
Convective
Barley
Sokhansanj, 1987 3.26 -0.650 20 1,000
Canola Seeds
Langetal., 1996 0.458 -0.241 30 50
Carrot
Mulct etal., 1989 0.692 -0.486 500 5,000
Corn
Fortes etal., 1981 1.06 -0.566 400 1,100
Torrezetal., 1998 4.12 -0.650 20 1,000
Graves
Ghiausetal, 1997 0.665 -0.500 8 50
Vagenas et al, 1990 0.741 -0.430 1,000 3,000
Maize
Mourad et al., 1997 11.9 -0.901 150 1,500
Malt
Lopezetal., 1997 0.196 -0.185 60 80
Potatoes
Wangetal., 1995 0.224 -0.200 2,000 11,000
Rice
Torrezetal., 1998 4.12 -0.650 20 1,000
Soybean
Taranto et al., 1997 2.48 -0.523 200 1,500
Wheat
Langetal., 1996 149 -0.340 50 100
Sokhansanj, 1987 3.26 -0.650 20 1,000
Fluidized bed
Corn Starch
Shu-De etal., 1993 0.101 -0.355 3,200 13,000

Process/product/reference n min Re max Re
Rotary
Fish
Sheneetal, 1996 0.00160 -0.258 80 300
Soya
Alvarez et al., 1994 0.00960 -0.587 10 100
Sheneetal., 1996 0.000300 -0.258 20 80
Susar
Wangetal., 1993 0.805 -0.528 1,500 17,000
Freezing
Beet
Heldman, 1980 0.650 -0.418 80 25,000
Calcium alsinate sel
Sheng, 1994 48.6 -0.535 300 600
Hamburser
Floresetal, 1988 8.87 -0.672 7,500 150,000
Toccietal., 1995 4.67 -0.645 9,000 73,000
Meat carcass
Mallikarjunan et al., 1994 0.228 -0.269 1,800 20,000
Meatballs
Toccietal., 1995 0.536 -0.485 3,400 28,000
Storage
Potatoes
Xuetal., 1999 0.658 -0.425 70 90
Wheat
Changetal, 1993 0.0136 -0.196 1,500 10,000
380 Chapter 9

Process/product/reference // min Re max Re
Sterilization
Aseptic
Model food
Balasubramaniam et al, 1994 0.500 -0.507 5,000 20,000
Sastryetal., 1990 0.448 -0.519 2,400 45,000
Zuritzetal, 1990 3.42 -0.687 2,000 11,000
Non-food material
Kramers, 1946 0.748 -0.512 3,000 85,000
Ranzetal.,1952 0.662 -0.508 3,000 85,000
Whitaker, 1972 0.517 -0.441 3,000 85,000
Paniculate liquid foods
Mankadetal., 1997 0.225 -0.400 140 1,500
Sannervik et al., 1996 0.0493 -0.199 1,800 5,200
Spherical particles
Astrometal., 1994 2.26 -0.474 4,300 13,000
Retort
Newtonian liquids
Anantheswaran et al., 1985 2.74 -0.562 11,000 400,000
Particulate liquid foods
Sablanietal, 1997 0.564 -0.403 30 1,600
Corn cream
Zamanetal., 1991 0.108 -0.343 130,000 1,100,000
Table 9.11 Parameters of the Equation jH = a Re" for each Process
Process a « mm Re max Re
Baking 0.80 -0.390 40 3,000
Blanching 0.0085 -0.443 150 1,500
Cooling 0.143 -0.455 1,000 48,000
Drying /convective 1.04 -0.455 8 11,000
Drying /fluidized bed 0.10 -0.354 3,200 13,000
Drying /rotary 0.001 -0.161 10 300
Freezing 1.00 -0.486 80 150,000
Storage 0.259 -0.387 70 10,000
Sterilization /aseptic 0.357 -0.450 140 45,000
Sterilization /retort 1.034 -0.499 30 110,000
The data of Tables 9.10 and 9.11 demonstrate the importance of the flow
conditions (Reynolds number, Re) and the type of food process and product on the
heat transfer characteristics (heat transfer factor, jH). As expected from theoretical
considerations and experience in other fields, the heat transfer factor, jH decreases
with a negative exponent of about -0.5 of the Re. The highest jH values are ob-
tained in drying and baking operations, while the lowest values are in storage and
blanching. Granular food materials, such as corn and wheat appear to have better
heat transfer characteristics than large fruits (apples).
Regression analysis of published mass transfer data show the similarity be-
tween the heat transfer factory'// and the mass transfer factor jM (see section VI of
this chapter).
382 Chapter 9
JH
0.01
0.001
0.0001
0.00001
1 10 100 1000 10000 100000 1000000 10000000
Re
Figure 9.4 Heat transfer factor jH versus Reynolds number Re for all the examined proc-
esses and materials.
JH 0.01
0.001
0.0001
10 1 000 10 000 100 000 1 000 000
Re
Figure 9.5 Ranges of variation of the heat transfer factor^ versus Reynolds number Re
for all the examined processes.
384 Chapter 9
0.001
1 000 10000 Re 100000
Figure 9.6 Heat transfer factory'// versus Reynolds number Re for cooling process and
various materials.
JH 0.1
0.01
10 100 1000 10000
Re
Figure 9.7 Heat transfer factor jH versus Reynolds number Re for convective drying
process and various materials.
386 Chapter 9
J H 0.l
0.01
0.001
100 000
Figure 9.8 Heat transfer factor jH versus Reynolds number Re for freezing process and
various materials.
Storage i
0.1
JH
0.01
WlhesiT
0.001
10 100 1000 10000 100000
Re
Figure 9.9 Heat transfer factory'// versus Reynolds number Re for storage process and
various materials.
388 Chapter 9
0.1
Sterilization Aseptic
Spherical
Parti i :les
JH
0.01
Non-Foa4
Matcri
Partiqulatg Upii
Fo )di
V
Moi lei F( od
0.001
1000 10000 100 000
Re
Figure 9.10 Heat transfer factory'// versus Reynolds number Re for sterilization aseptic
0.1
Sterilization Retort
\
Part culat? Lii
Fi oils
JH 0.01
0.001
100 1000 10000 100000 1000000
Re
Figure 9.11 Heat transfer factory// versus Reynolds number Re for sterilization retort
390 Chapter 9
JH
0.01
0.001
0.0001
10 100 1000 10000 100000 1000000
Re
Figure 9.12 Estimated equations of heat transfer factory'// versus Reynolds number Re for
all the examined processes.
VI. MASS TRANSFER COEFFICIENTS IN FOOD PROCESSING:

COMPILATION OF LITERATURE DATA
Recently reported mass transfer coefficient data in food processing were re-
trieved from literature following the same procedure described in Section V for
heat transfer coefficient data (Krokida et al., 2001b).
A total number of 15 papers were retrieved from the above journals. The
data refer to 4 different processes (Table 9.12) and include about 9 food materials
(Table 9.13). All available empirical equations were transformed in the form of
mass transfer factor versus Reynolds number (JM = aRen).
The results are classified by process and material and are presented in Ta-
bles 9.14 and 9.15. All the equations are presented in Figure 9.13 to define the
range of variation of the jM and Re. The range of variation by process is sketched
in Figure 9.14. The above results are presented for convective drying process in
Figure 9.15. The effect of food material is obvious in this diagram. The results of
fitting the equation to all data for each process is summarized in Table 9.14 and in
Figure 9.16.
Mass transfer coefficient values for process design can be obtained easily
form the proposed equations and graphs. The range of variation of this uncertain
coefficient can also be obtained in order to carry out valuable process sensitivity
analysis.
Table 9.12 Number of Available Equations for each Food Process
_____Process____________No. of Equations
1 Drying
Convective 6
Spray 1
2 Freezing
Forced Convection 6
3 Storage
Forced Convection 1
4 Sterilization
______Forced Convection________________1^
_____Total No. of Equations__________15
392 Chapter 9
Table 9.13 Number of Available Equations for each Food Material
Material No. of Equations

1 Com 1
2 Grapes 2
3 Maize 1
4 Meat 6
5 Model food 1
6 Potatoes 1
7 Rice 1
8 Carrots 1
9 Milk 1
Total No. of Equations 15
Table 9.14 Parameters of the Equation/^ = aRe" for each Process
Process a n mm Re max Re
Drying/convective 23.5 -0.882 5 5,000
Drying/spray 2.95 -0.889 1 2
Freezing 0.10 -0.268 2,500 70,000
Storage 0.67 -0.427 50 55
Sterilization 11.2 -1.039 6,500 26,000

Table 9.15 Parameters of the Equation jM = aRe" for each Process and each Ma-
terial
Process/product/reference a /; min Re max Re
Drying
Convective
Corn
Torrezetal., 1998 5.15-0.575 20 1,000
Graves
Ghiausetal., 1997 0.004 -0.462 10 40
Vagenasetal, 1990 0.741-0.430 900 3,000
Maize
Mouradetal., 1997 34.6 -1.000 5 15
Rice
Torrezetal., 1998 5.15-0.575 20 1,000
Carrot
Muletetal., 1987 0.69 -0.486 500 5,000
Spray
Milk
Straatsma et al., 1999 2.947 -0.890 1 2
Freezing
Meat
Toccietal., 1995 2.496 -0.495 2,500 70,000
Storage
Potatoes
Xuetal.,1999 0.667 -0.428 50 55
Sterilization
Model food
Fuetal.,1998 11.220 -1.039 6,500 26,000
394 Chapter 9
10
^
V
\\ V
Sr—
"*^ N^
% 5fc
s
»
s,,v
\
k
Nt,""•
'V
ss
ss S
*^
0.1 0
JM-1.llRe' '
x^
•^
^
N.
JM ;., ^
»' ^"V
0.01 1s ^
— S iir-5*
!l ^*;-
\__ 5 _ *
«^s
^> sS <v s
*','^n
0.001 \ ^
_ __ . , __
-^
\
S
V
0.0001
1 10 100 1 000 10 000 100 000
Re
Figure 9.13 Mass transfer factory^ versus Reynolds number Re for all the examined
processes and materials.
10
TJfyfitg
\ Con-wclti
0.1 \
JM
nezjir
0.01
0.001
izat
0.0001
10 100 1000 10 000 100 000
Re
Figure 9,14 Ranges of variation of the mass transfer factor JM versus Reynolds number
Re for all the examined processes.
396 Chapter 9
10
Convective Drying
\Miize
0.1
JM
5 Gra«s
0.01
0.001
10 100 1000 10000
Re
Figure 9.15 Mass transfer factor jM versus Reynolds number Re for convective drying
process and for various materials.
10
\s I\
t
j
sTa I> ing H -J ^.

It II BCtlV
)i ing
5
1
^1 s, V—— j 1
\ i
\
s. ^> j 1
=
i
0.1 St nv>r a
ST _ . ——— —— J
*"*"-^
: ^1
\ =f-
\V F •e izil 2(
1 1 1 i j
JM
i
1 S
0.01
1
1 1
0.001
1
V"
\
X
y
I
1 ..tod \'n ttrJ
0.0001
1 10 100 1000 10000 100000
Re
Figure 9.16 Estimated equations of mass transfer factory^ versus Reynolds number Re
for all the examined processes.
398 Chapter 9
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Appendix: Notation
A transport area, m
a constant of Redlich-Kwong Eq. (2-12)
Bi Biot number
b constant of Redlich-Kwong Eq. (2-12)
cp heat capacity at constant pressure kJ/kmol K
cv heat capacity at constant volume kJ/kmol K
C concentration, kg/rrr3
D mass diffusivity, m2/s
D diameter, m
d diameter, m
De Deborah number
DPM dipole moment, debye
E modulus of elasticity, Pa
E activation energy, kJ/kmol
ED energy of activation for diffusion, kJ/mol
Ea activation energy for viscous flow, kJ/mol
F force, N
Fo Fourier number
G shear modulus, Pa
G' storage modulus, Pa
G " loss modulus, Pa
G mass flow rate, kg/m2s
Gz Graetz number
h height, m
h heat transfer coefficient, W/m K
JA mass flux of A, kg/m2s or kmol/m2s
JH heat transfer factor
JM mass transfer factor
K flow consistency coefficient, Pa sn
K drying constant, 1/s
Kp partition coefficient
kB Boltzmann constant, kB= R/N= 1.38xlO"23 J/molecule K
kc mass transfer coefficient, m/s
L length, m
M mass, kg
M torque, N m
M molecular weight, kg/kmol
MA molecular weight of A
N Avogadro's number, 6.022xl023 molecules/mol
Nu Nusselt number
n flow behavior index
403
404 Appendix: Notation
n index
P pressure, Pa or bar
P permeability, kg / m s Pa
PM permeance, kg/ m2s Pa
Pr Prandtl number
Q volumetric flow rate, m3/s
Q accumulated quantity, kg/m2
q heat transport rate, W
r radius, m
R gas constant, 8.314 kJ/kmol K
Re Reynolds number
rt inside radius, m
r0 outside radius, m
5 solubility, kg/m3Pa
Sh Sherwood number
t time, s
T temperature, K, C
f kBT/s
Tg glass transition temperature, K, °C
U velocity, m/s
M velocity, m/s
u(r) potential energy (Lennard-Jones potential), J
V molar volume, cm3/mol, m3/mol
V volume, m3
W weight, kg
WVTR water vapor transmission rate, kg/m s
X transport property
X moisture content, kg/kg dm
compressibility factor
Greek
a thermal diffusivity, m2/s
a relative volatility
Y activity coefficient
F film flow rate, kg/m s
3.141
Y shear rate, 1/s

Y strain (relative deformation)
S generalized transport coefficient
S" dimensionless dipole moment
AP pressure drop, Pa
s interaction energy parameter, J
Appendix: Notation 405
s porosity
rj viscosity, Pa s
rj shear viscosity, Pa s
77' dynamic viscosity, Pa s
T;,, apparent viscosity, Pa s
77,. relative viscosity
9 collision frequency, 1/s
9 angle of cone/plate
/I thermal conductivity, W/m K
Am mean free path, m
ju chemical potential, kJ/mol
v momentum diffusivity (kinematic viscosity), m2/s
p density kg/m3 or mol/m3
<r collision diameter, m
T tortuosity
r shear stress, Pa
TO yield stress, Pa
<j) interaction parameter
<j> volume fraction
W generalized transport rate
co acentric factor
or frequency of oscillation. 1/s
/2 collision integral
/3 rotational velocity, 1/s
Subscripts
A component A(diffusant)
B component B (medium)
b boiling
c critical
D diffusion
e equilibrium
G gas
id ideal
K Knudsen
L liquid
0 dilute, initial
P particle
r reduced
res residual
V viscosity
Index
Ash, 281
Avocado, 172, 182, 191
B
Absorption, 228, 234, 360 Baking, 373, 377, 381
Acentric factor, 11-12 Baking ovens, 369
Acetic acid, 242, 267 Banana, 50-56, 182, 191, 201, 215,
Activation energy, 72, 82-84, 91, 95, 306,318
198,249,253 Barley, 179, 188, 302, 314, 378
Adsorption, 113,228,231,360 Beef, 183, 192, 275, 307, 319, 329,
Agar, 298, 299, 309, 312, 321, 324 348, 354, 379
Agitated kettle, 370, 371 Beef carcass, 183, 192
Albumen, 313, 325 Beer, 84
Albumin, 184, 193 Beeswax, 263
Albumine, 313, 325 Beet, 186, 195,300,311,323
Almond, 175, 185, 194,226 Bentonite, 298, 355
Amioca, see Amylopectin Bilberry, 296, 306, 318
Ammonia, 241 Bingham plastic, 68-69, 91
Amylopectin (Amioca), 128-132, Biopolymers, 30, 150, 254, 372
140,184, 193,201-204,308, Biot number, 145, 273, 363
320, 342 Bird-Carreau model, 73
Amylose (Hylon), 128-132, 134, Biscuit, 168, 179, 188,302,314
137,154,184,193,201-204, Blanching, 360, 375,377, 381
308, 320, 343 Bluebenies, 172, 182, 191
Apparent viscosity, 69,79, 370 Boiling water, 369
Apparent density, 50, 55 Boltzmann constant, 9, 17, 241
Apple, 50-56, 149-151,182, 191, Boundary layer theory, 368
201,213,253,275,305,317, Bread, 156, 168, 179, 188, 293, 302,
329, 337, 377 314
Apple juice, 80-82, 373 Brine, 252
Apple sauce, 72, 89, 92, 94 Broad bean, 173, 183, 192
Apple slices, 253 Broccoli, 176, 186, 195
Apricots, 157, 172, 182, 191, 377 Broiled meat, 173, 183, 192
Arrhenius equation, 16, 71, 78-80, Brown rice, 168,169, 179,180,
82,93, 128, 141,245,260 188-189
Aseptic processing,369, 375, 381 Bull, 174, 183, 192
407
408 Index
Buoyant Force, 46 Codfish fillet, 145-146, 157

Butanol, 255 Coffee, 194,253,312,324
Butanone, 255 Colburn analogy, 368, 369
Butter, 92, 294, 304, 316 Collapse, 31,50, 60, 152,259
Buttermilk, 91,101 Collision, 9, 12, 13, 15
Butyric acid, 242 Colloid / Surface Chemistry, 31
c Compressibility factor, 11
Condensing water vapor, 364, 369
Cake, 295,302, 314, 377 Condensing water vapors, 364
Calamari, 305, 317 Controlled release, 258
Calcium alginate gel, 376, 379 Cookie, 156, 168, 179, 188
Canned foods, 369, 371 Cooling, 3, 227, 245, 350-351, 359,
Canola, 185, 194,378 371,375,377,381,384
Capillary tube vicometer, 74-77 Corn, 156, 179, 188, 201, 209-210,
Carbohydrate, 281 221-224, 264, 302-303, 314-315,
Carbon dioxide, 12-13, 20, 241 329, 346, 378, 380, 393,
Carp, 295,305, 317 Corn cream, 376, 380
Carrageenan gum, 85-86 Corn meal, 303,315
Carrot, 50-56, 186, 195, 201, 217, Corn oil, 79
310,322,378,393 Corn pericarp, 156, 234, 264
Cassava, 186, 195,310,322 Corn Starch, 127, 162, 174, 184,
Catfish, 181 193,353,376,378
Celery, 300,311,323 Cottonseed oil, 253
Cellophane, 264 Crackers, 179, 188
Cellulose gum, 298, 309, 321 Cracks, 47, 114, 127-128, 130, 141,
Cellulose-oil-water, 174, 184, 193 143,253,260
Cereal products, 168, 179, 188,201, Cream, 92, 303-304, 315-316
293,302,314,329 Critical conditions, 11-12,14-15
Chapman-Enskog equation, 12, 15 Crystallization, 30, 33, 360
Cheese, 171, 181, 190,227,230, Cucumber, 301,311, 323
251,303,315
Chemical potential, 105, 109,146- &
147, 244 Dairy products, 181, 190,303,315,
Cherry, 83, 306, 318 329
Chicken, 174, 231, 297, 307, 319 Data banks, 7, 19, 29, 269, 275
Chlorine, 241 Database, 27, 144, 161, 164
Chocolate, 70, 92, 100, 175, 185, Deborah number, 73, 108
194,226,262-264 Diaphragm cell, 238-239
Chromatographic method, 110, 113 Dickerson method, 273, 351
Clustering of solutes, 247 Dietary fibers, 89
Coating, 258-260, 262-264 Diethyl ketone, 255
Cocoa, 79 Diffusivity, mass
Coconut, 182, 191,312,324 determination, 109-123
Cod, 181, 190,304,316 sorption kinetics, 110
Index 409
[Diffusivity, mass]
permeability methods, 114
distribution of diffusant, 118 Edible oils, 72, 78-79, 92-93
drying methods, 120 Egg, 175, 185, 194,229
flavors, 254-258 Einstein equation, 66
in fluid foods, 241-243 Elastic materials, 65, 244
in polymers. 243 Empirical rules, 279
organic components, 252 Emulsions, 90, 92, 262
salts, 251 Enclosed water density, 50, 55
small solutes, 237 Enzyme inactivation, 360
Diffusivity, moisture Ethanol, 12, 13, 17, 20, 84, 241-242,
baked products, 168, 179, 188 255
cereal products, 168,179,188, 201, Ethyl acetate, 255
209-212 Ethyl butyrate, 255
dairy products, 171,181, 190 Ethyl oleate, 153, 154
fish, 171,181, 190 Ethylene, 12-13, 20, 241
fruits, 172, 182, 191, 201, 205, 206 Eucken factor, 15
legumes, 173, 183, 192 Evaporation, 254-257, 360, 372
meat, 173, 183, 192 Evaporators, 369
model foods,127-143,174, 184, Excess contributions, 14
193,201,203,204 Extensional viscosity, 64
nuts, 175, 185, 194 Extraction, 33-34, 252-253, 360
other, 175, 185, 194 Extrusion, 130-131
vegetables, 176, 186, 195,201 Eyring theory, 16, 18
Dilatant fluid, 69
Dimensional equations, 363 Fababean, 173, 183, 192
Dimensionless numbers, 14, 362, Falling films, 364, 367
363,366-367,371,374 Falling rate period, 120-122, 144-
Distillation, 266, 360 145,369
Distribution of diffusant, 110, 118 Fat, 232-233, 281, 304, 307, 316,
Dogfish, 171, 181, 190 319,355
Dough, 168, 179, 188,229,293, Fiber, 101,281
302,314,329,347,352-353, Fibrinogen, 242
356 Pick diffusion equation, 8, 106, 118-
Dried fruit, 275 119,145-147,237,243
Dry milk, 181,190 Fickian diffusion, 107-108, 243,
Dry solids apparent density, 55 250,260
Dry solids true density, 55 Figs, 376-377
Drying Kinetics, 110, 159-160, 162, Fish, 122, 145,157,181,190,252,
227, 230-232, 234 275,304,316,379
Dual-sorption model, 248, 262 Flavor, 254-259, 261-262
Dynamic viscosity, 73 Flavor encapsulation, 258
410 Index
Flour, 184, 193, 302-303, 314-315, Grapes, 191,201,296,306,318,

324 377-378, 393
Flow behavior index, 68, 72, 76, 78, Grashof number, 363
80, 85, 88-92, 95 Gravimetric method, 110
Flow consistency coefficient, 68, Green beans, 376-377
370-371 Green olives 251
Fluidisedbeds, 375, 378, 381 Ground beef, 174, 183, 192
Food coatings, 262-263 Guar gum, 85-86
Food Materials Science, 2, 30 Guarded hot plate, 270-271
Food preparation, 360
Food preservation, 360 H
Food rheology, 3, 63 Haddock, 171, 181, 190
Free convection, 363 Halibut, 171, 182, 191
Free-volume model, 249 Hamburger, 303, 315, 376, 379
Freeze-dried gel, 275 Hazelnuts, 175, 185, 194
Freezing, 379,381,391-393 HOPE, 261-262, 264
Fructose, 242, 266 Heat capacity, 8, 15
Fruits, 50, 94, 146-152,157, 182, Heat exchangers, 369
191,201,205-206,305-306, Heat transfer coefficients,
317-318,329,331-332,373 determination, 361
Frying, 35, 360, 369 baking, 375, 377, 381
blanching, 375, 377, 381
G cooling, 375, 377, 381,384
Gamma function, 125 drying, 375, 378, 381,385
Garlic, 186, 195, 201, 219, 310,322, freezing, 375, 379,381,387
Gas bubbles, 367 storage, 375, 379, 381, 387
Gas constant, 16, 71, 93, 198, 200, sterilization, 375, 380, 381, 388-
249, 326, 328 389
Gas pycnometer method, 46 Heat transfer correlations, 362-363,
Gelatin, 281, 298, 309-310, 321-322 371
Gelatinized starch,130, 141, 275, Heat transfer factor, 363, 374, 382,
281 384-389
Gelatin, 298, 309-310, 321-322 Heated probe, 270-274
Glass transition, 30-31, 244-247 Heifer, 184, 193
Glucose, 242, 312, 324 Hemoglobin, 242
Gluten, 174, 184, 193,263-264 Herring, 157, 182,191,251
Glycerin, 242, 263, 298, 310, 322 Herschel-Bulkley equation, 68-69,
Glycine, 242 75,91,95
Graetz number, 363, 369 Hexane, 253
Granular materials, 36, 61, 133, 135, Hexanol, 255
285 Honey, 78, 80, 83, 299, 313, 325
Granular starch, 130, 133-135, 137- Horizontal tubes, 364
141, 150, 154,275,284 Huggins equation, 65
Hydrodynamic flow, 147
Index 411
Hydrogen, 241 Mass transfer correlations, 359, 362,

Hylon, see Amylose 366-367
Mass transfer factor, 363, 368, 391,
I 395-398
Ice, 33, 47, 276, 281, 292, 325, 327 Mass transfer operations, 109, 359-
Idli Batter, 293, 303, 315 360, 362
J Mayonnaise, 90, 92
Juices, 80-83, 89-90, 92, 95-99, 305- Meat, 157,183, 192, 251, 307, 319,
306,311,317-318,323,373 329, 379, 393
Meat Carcass, 376, 379
K Meat Muscle, 251
Karaya gum, 85, 87 Meatballs, 376, 379
Kidney bean, 301,311,323 Membrane, 366
Kinematic viscosity, 8, 362 Methane, 241
Methanol, 255
L Method of slopes, 123-124
Lactoglobulin, 242 Methyl anthranilate, 255
Lard, 299, 312, 324 Microstructure, 2, 5, 29, 31-35, 60,
LDPE, 261-262, 264 114,243,261
Legumes, 173, 183, 192, 296, 306 Milk, 90-91, 181, 190, 275-276,
Lentils, 183, 192,306,318 304,312,316,324,329,345,
Lewis number, 363 393
Lewis-Squires equation, 16, 72 Milled Rice, 169, 180, 189
Licorice extract, 83 Mixed model, 283-284
Lipid films, 264 Mizrahi-Berk model, 70
Liquid diffusion, 141, 143 Model food, 346-49,142, 203
Liquid displacement method, 46 Molecular diameter, 9, 12
M Molecular diffusion, 4, 106-107,
144, 147, 238, 244, 260, 263
Macadamia, 298, 310, 322
Molecular effusion, 107
Mackerel, 157, 182, 191, 304, 316
Molecular simulation, 2, 5,29- 30,
Macrostructure, 2-4, 29, 35, 40, 45-
61,248,250,253,268
47, 49-50
Mulberry, 182, 191,231
Maize, 303, 315, 378, 393
Mushrooms, 301, 311, 323, 357
Malt, 180, 189,230,376,378
Mustard, 92
Maltose, 242
Mutton, 297, 308, 320
Mango, 89, 90, 92, 95, 99, 101-102
Margarine, 33, 73, 92 N
Mass transfer coefficients Natural convection, 363-364, 369
determination, 365 Navy beans, 183, 192,232
drying, 392-394, 397, 397 Nernst-Haskel equation, 18
freezing, 391-393, 397 Newton equation, 8, 64, 65, 73
storage, 391-393, 397 Newtonian foods, 69, 72, 380
sterilization, 391-393, 397 Nitrogen, 12-13,20,241
412 Index
Non-Newtonian foods, 68, 372 Penetration theory, 367

Nuclear magnetic resonance, 75 Pepper, 177, 186, 195
Numerical methods, 124-125 Pepperoni, 174, 184, 193, 308, 320
Nusselt number, 351, 363, 399 Permeability, 110, 114-117,237-
Nuts, 175,185, 194, 298, 310, 322 238, 243-244, 248-249, 259-264
o Permeance, 260
Perpendicular flow, 364
Oat, 294, 303, 315 Phase transition, 30, 61
Okra, 176, 186, 195,228 Pickles, 251,267
Olive oil, 79 Pigeon pea, 177, 186, 195,233
Onion, 156, 186, 195, 201, 218, 310, Pineapple, 173, 183, 192, 226, 232
322 Plant cells, 32-33
Orange, 83, 89, 95, 97, 306, 318, Plant hydrocolloids, 85
329,338 Plantain, 306, 318
Osmotic dehydration, 35, 147 Plasticization, 128, 244
Ovalbumin, 242, 281, 309, 321 Poiseuille equation, 74
Overall heat transfer coefficient, Polyacrylamide gel, 175, 184, 193
371-373 Polymer Science, 30, 65,110, 244
Oxygen, 12-13,20,241,262 Polysaccharide films, 264
P Pork, 157, 265, 297, 308, 320, 355
Packaging, 259-264 Potatoes, 50, 54, 150, 151, 156, 184,
Packed beds, 366 186,193, 195,201,216,275,
Paddy Rice, 180, 189 297,310,322,329,340,378-
Palm kernel, 299, 312, 324 379, 392-393
Paprika, 176, 186, 195, 227 Potato starch, 158, 175, 184, 193,
Parallel flow, 364 297, 309, 321
Parallel model, 65, 283, 284 Power-law model, 68-69, 71, 75, 85,
Parboiled Rice, 169, 180, 189,227 88-89, 91, 94-95
Parsley, 300, 311,323 Prandtl number, 363
Parsnip, 301,311,323 Propanol, 255
Past single sphere, 363, 366 Protein films, 264
Pasta, 156, 169, 180, 189, 201, 225 Proteins, 135-136, 155,262-264,
Pasteurization, 360 280-281
Peas, 177, 186, 195, 300, 310, 322 Pseudoplastic fluids, 69, 85, 88-89,
Peaches, 183, 192, 306, 318, 377 252
Peanuts, 175, 185, 194,253 Puffing, 127,152,231,275
Peanut butter, 92 PVC, 261-262, 264
Peanut oil, 253 R
Peanut pods, 175, 185, 194,227 Radish, 301,311,323
Pear, 95, 98, 102, 306, 318, 329, 339 Raisins, 157, 183, 192, 201, 306 318
Peclet number, 363 Rapeseed, 312, 324, 329
Pectin, 33, 88-89, 127, 256-257, Raspberries, 376-377
298,309-310,321-322 Raspberry, 89, 102, 295, 306, 318
Index 413
Real gases, 11-12, 15 Simplified methods, 110, 123, 125

Recovery of volatiles, 360 Simulation, 29-30, 124, 232, 250,
Refrigeration, 360, 369 253
Regular regime theory, 125-126 Skim milk, 101, 171, 181, 190, 352
Retorts, 375, 380-381 Sodium caseinate, 101, 263
Reverse Osmosis, 360 Solid displacement method, 46
Rheological properties (viscosity) Solubility, 115, 117-118,248-249,
aqueous Newtonian, 80 259-260, 262-263
chocolate, 100 Sorbitol, 263
cloudy juices/pulps, 89 Sorghum, 299, 313, 325
edible oils, 79 Sorption kinetics, 107-111, 127,
emulsions, 90 129, 148,150-152,244
fruit and vegetable juices, 95 Soy flour, 293, 302, 314
plant biopolymer solutions, 85 Soya, 177, 186, 195,376,379
Rheology, 3, 5, 63, 66, 70, 72-74, Soya meal, 177, 186, 195
90, 101-103 Soybean, 152, 156, 186, 195,312,
Rice, 156, 179-180, 185, 188-189, 324, 378
201,303,315,378,393 Soybean flakes, 253
Rice Starch, 185, 194 Soybean oil, 79,253
Rotary drying, 375, 379, 381 Soybeans, 150, 152, 156,161
Rotational viscometer, 75-76 Specific volume, 55
Rough Rice, 180, 189, 201, 233 Spinach, 301, 311,323, 351
Rubbery state, 108, 238, 244 Spinning disc, 366
Rutabagas, 301,311 Squid, 191,305,317
Stanton number, 363
5 Starch gel, 49, 127-129, 131
Salad, 90 Steam, 19, 27, 226, 352, 375
Salmon, 91, 101,295,305,317 Sterilization, 360, 380-381, 388-
Salt, 18, 20, 84, 133, 146-147, 237, 389, 392-394
251-252 Stokes diaphragm cell, 239
Sausage, 157,184, 193, 308, 320 Stokes-Einstein equation, 17,241,
Scanning microscopes, 31-32 242, 252
Schmidt number, 363 Storage, 30-32, 257, 379, 381 387,
Shark, 171, 182, 191 391-393
Shear rate, 31, 64-66, 68-76, 78-80, Strawberries, 295, 306, 318, 351,
85,88,91,94,370 376-377
Shear stress, 8, 64-66, 68-71 74-76, Structural models, 40, 47, 50, 163,
78, 85, 88, 94 197,280,283,284,287,326
Sherwood number, 120-121, 126, Structural properties, 55
161,363,365 Sucrose, 24-25, 80-83, 133, 147-
Shrimp, 305,317 148,242,253,258,281,309-
Shrinkage, 36-37, 39-40, 47, 50, 55, 310,312,321-322,324,371
60, 126, 137, 150 Sucrose solution, 275
Shrinkage coefficient, 55
414 Index
Sugar Beets, 178, 186, 195,253, Transport coefficients, 144

300,311,323 Transport gradient, 8
Sugar solutions, 80 Transport Phenomena, 5, 7, 27, 158,
Sunflower seeds, 185, 194 228, 257, 265, 354
Surface renewal theory, 367 True density, 55
Surfactants, 153 Turbulent flow, 363, 366, 369
Surimi, 305, 317 Turkey, 184, 308, 320
Swiss cheese, 251,267 Turnip, 187, 196,311,323
Swordfish, 172, 182, 191 Tylose, 309,321
T u
Tailor-made porous solid foods, 47, Unsteady-state method, 110, 117-
60 118,273-274
Tapioca, 178, 186, 195
Taylor dispersion method, 238, 240 V
Texture, 3, 29, 31, 33, 60, 64, 101, Vapor diffusion, 106, 109, 141, 143,
102-104,266 163, 199
Thermal conductivity of foods Variable Diffusivity, 110, 123, 226
determination, 270-273 Vegetable oil, 275
baked products, 293, 302, 314, 329 Vegetables, 35, 50, 95, 150, 156,
cereal products, 293, 302, 314, 329 176,186, 195,201,207-208,
dairy products, 294, 303, 314, 329 333-334
fish, 294, 304, 316 Vertical tubes, 364
fruits, 295, 305, 317, 329, 331-332 Viscometers
legumes, 296, 306, 318 capillary tube, 74
meat, 296, 307, 319,329 rotational, 75
model foods, 297, 308, 320, 329 cone-and-plate, 76
nuts, 298, 310, 322 Viscosity, see Rheological proper-
other, 299, 312, 324, 329 ties
vegetables, 300, 310, 322, 329, Volatile compounds, 255, 266
333-334 Volume displacement method, 46
Thermal diffusion, 107, 145
Thermal diffusivity, 269, 273-279
w
Weissenberger rheogoniometer, 76
Thermodynamics, 7, 10, 27, 29, 158,
Wheat, 135, 156, 181, 190,201,
266-267
220,302-303,315,378-379
Thixotropic fluids, 70-71, 91
Whey, 263, 294, 304,316
Time lag method, 110, 117
Whiting, 172, 182, 191
Tobacco, 299, 312,324, 350
Wild rice, 170, 181, 190
Tomato, 67-68, 90, 95-96, 187, 196,
Wilke-Chang equation, 241-242,
252,311,323,329,341,377
252
Tomato paste, 275
Williams-Landel-Ferry equation, 31,
Torque, 74, 76
245
Tortuosity, 106, 147, 250, 254
Wine, 84, 102
Index 415
x y
Xanthan gum, 85, 87 Yam, 187, 196, 311, 323, 355
Yellow batter, 293
Yogurt, 91, 101, 294, 304, 316, 353

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Transport

MARCEL DEKKER, INC. NEW YORK • BASEL

This book is printed on acid-free paper.

Eastern Hemisphere Distribution

World Wide Web

Copyright © 2001 by Marcel Dekker, Inc. All Rights Reserved.

Current printing (last digit):

PRINTED IN THE UNITED STATES OF AMERICA

5. Transport of Water in Food Materials 105

6. Moisture Diffusivity Compilation of Literature

ture, as related to transport properties are reviewed in Chapter 3. A unified treat-

2. Transport Properties of Gases and Liquids 7

3. Food Structure and Transport Properties 29

B. Food Materials Science 30

4. Rheological Properties of Fluid Foods 63

III. MOISTURE DIFFUSIVITY OF FOODS AS A FUNCTION OF

7. Diffusivity and Permeability of Small Solutes

8. Thermal Conductivity and Diffusivity of Foods 269

A. Unfrozen Foods 275

9. Heat and Mass Transfer Coefficients

Appendix: Notation 403

Theoretical analysis and experimental techniques of mass diffusion in poly-

II. THERMAL TRANSPORT PROPERTIES

Thermal conductivity represents the basic thermal transport property, and it

III. MASS TRANSPORT PROPERTIES

II. ANALOGIES OF TRANSPORT PROCESSES

<p = -S(dy/8x) (2-1)

where fx is the transport rate, 8 is the transport coefficient or property, and

r» = -T] (du/dx) (2-2)

(q/A\ = -A (dT/dx) (2-3)

(j/A)x = -D (dC/dx) (2-4)

The basic transport properties, defined by the last equations, are:

v = Tj/p: momentum diffusivity or kinematic viscosity (m2/s)

a = ^1 p cp : thermal diffusivity (m2/s)

III. MOLECULAR BASIS OF TRANSPORT PROCESSES

Molecular dynamics, which is concerned with intermolecular forces and

^mP = constant (2-6)

), = cvi] = pcvD (2-10)

pr = p/pc, v, = V/Vc, Tr = T/Tc (2-15)

where z = PV/RTis the compressibility factor, which expresses the non-ideality

a> = 1.0-log(P,)rr.,7 (2-18)

Table 2.1 Critical Constants and Acentric Factors of Selected Fluids

Oxygen 73.4 154.6 50.4 0.288 0.025

where cr is the characteristic collision diameter, similar to molecular diameter d of

Table 2.2 Intermolecular Constants of Selected Components

s/kBTc =0.17915 + 0.169o> (2-21)

where T" = TkB/ sis the reduced temperature.

IV. PREDICTION OF TRANSPORT PROPERTIES OF FLUIDS

X(p,T)=X.(T) + AX(p,T) + A* (p,T) (2-25)

The heat capacities cv and cp are related by the equation:

where R = 8.314 kJ/kmol K is the gas constant.

where A and B are empirical constants for the particular liquid.

where the constants A, B, C, D are given in tables (Reid et al., 1987).

where A is a constant and ED is the energy of activation for diffusion (kJ/kmol).

C. Comparison of Liquid/Gas Transport Properties

• air: 77 = 0.017 mPas, A = 0.025 W/m K

tljjj0 = A t / A G = 10 to 1000, DJDG si/10000 (2-39)

V. TABLES AND DATA BANKS OF TRANSPORT PROPERTIES

Table 2.3 Viscosity 77 and Thermal Conductivity A of

Table 2.4 Mass Diffusivity (DAB)

Source: Data from Pakowski et al. (1991)

Figure 2.4 shows the viscosity of aqueous sucrose solutions as a function of

percentage sucrose by weight = 60