(George D. Saravacos) Transport Properties of Food PDF

Transport
Properties of Foods
FOOD SCIENCE AND TECHNOLOGY

A Series of Monographs, Textbooks, and Reference Books
EDITORIAL BOARD
Senior Editors
Owen R. Fennema University of Wisconsin-Madison
Marcus Karel Rutgers University (emeritus)
Gary W. Sanderson Universal Foods Corporation (retired)
Pieter Walstra Wageningen Agricultural University
John R. Whitaker University of California-Davis
Additives P. Michael Davidson University of Tennessee-Knoxville
Dairy science James L. Steele University of Wisconsin-Madison
Flavor chemistry and sensory analysis John Thorngate University of
Idaho-Moscow
Food engineering Daryl B. Lund Cornell University
Health and disease Seppo Salminen University of Turku, Finland
Nutrition and nutraceuticals Mark Dreher Mead Johnson Nutritionals
Processing and preservation Gustavo V. Barbosa-Canovas Washington
State University-Pullman
Safety and toxicology Sanford Miller University of Texas-Austin
1. Flavor Research: Principles and Techniques, R. Teranishi, I. Hornstein,

P. Issenberg, and E. L. Wick
2. Principles of Enzymology for the Food Sciences, John R. Whitaker
3. Low-Temperature Preservation of Foods and Living Matter, Owen R.
Fennema, William D. Powrie, and Elmer H. Marth
4. Principles of Food Science
Part I: Food Chemistry, edited by Owen R. Fennema
Part II: Physical Methods of Food Preservation, Marcus Karel, Owen R.
Fennema, and Daryl B. Lund
5. Food Emulsions, edited by Stig E. Friberg
6. Nutritional and Safety Aspects of Food Processing, edited by Steven R.
Tannenbaum
7. Flavor Research: Recent Advances, edited by R. Teranishi, Robert A.
Flath, and Hiroshi Sugisawa
8. Computer-Aided Techniques in Food Technology, edited by Israel
Saguy
9. Handbook of Tropical Foods, edited by Harvey T. Chan
10. Antimicrobials in Foods, edited by Alfred Larry Branen and P. Michael
Davidson
11. Food Constituents and Food Residues: Their Chromatographic Determination, edited by James F. Lawrence
12. Aspartame: Physiology and Biochemistry, edited by Lewis D. Stegink
and L. J. Filer, Jr.
13. Handbook of Vitamins: Nutritional, Biochemical, and Clinical Aspects,
edited by Lawrence J. Machlin
14. Starch Conversion Technology, edited by G. M. A, van Beynum and J.
A. Roe Is
15. Food Chemistry: Second Edition, Revised and Expanded, edited by
Owen R. Fennema
16. Sensory Evaluation of Food: Statistical Methods and Procedures, Michael O'Mahony
17. Alternative Sweeteners, edited by Lyn O'Brien Nabors and Robert C.
Gelardi
18. Citrus Fruits and Their Products: Analysis and Technology, S. V. Ting
and Russell L. Rouseff
19. Engineering Properties of Foods, edited by M, A. Rao and S. S. H. Rizvi
20. Umami: A Basic Taste, edited by Yojiro Kawamura and Morley R. Kare
21. Food Biotechnology, edited by Dietrich Knorr
22. Food Texture: Instrumental and Sensory Measurement, edited by
Howard R. Moskowitz
23. Seafoods and Fish Oils in Human Health and Disease, John E. Kinsella
24. Postharvest Physiology of Vegetables, edited by J. Weichmann
25. Handbook of Dietary Fiber: An Applied Approach, Mark L. Dreher
26. Food Toxicology, Parts A and B, Jose M. Concon
27. Modern Carbohydrate Chemistry, Roger W. Binkley
28. Trace Minerals in Foods, edited by Kenneth T. Smith
29. Protein Quality and the Effects of Processing, edited by R. Dixon Phillips
and John W. Finley
30. Adulteration of Fruit Juice Beverages, edited by Steven Nagy, John A.
Attaway, and Martha E. Rhodes
31. Foodborne Bacterial Pathogens, edited by Michael P. Doyle
32. Legumes: Chemistry, Technology, and Human Nutrition, edited by Ruth
H. Matthews
33. Industrialization of Indigenous Fermented Foods, edited by Keith H.
Steinkraus
34. International Food Regulation Handbook: Policy Science Law, edited
by Roger D. Middlekauffand Philippe Shubik
35. Food Additives, edited by A. Larry Branen, P. Michael Davidson, and
Seppo Salminen
36. Safety of Irradiated Foods, J. F. Diehl
37. Omega-3 Fatty Acids in Health and Disease, edited by Robert S. Lees
and Marcus Karel
38. Food Emulsions: Second Edition, Revised and Expanded, edited by
Kare Larsson and Stig E. Friberg
39. Seafood: Effects of Technology on Nutrition, George M. Pigott and
Barbee W. Tucker
40. Handbook of Vitamins: Second Edition, Revised and Expanded, edited
by Lawrence J. Machlin
41. Handbook of Cereal Science and Technology, Klaus J. Lorenz and

Karel Kulp
42. Food Processing Operations and Scale-Up, Kenneth J. Valentas, Leon
Levine, and J. Peter Clark
43. Fish Quality Control by Computer Vision, edited by L. F. Pau and R.
Olafsson
44. Volatile Compounds in Foods and Beverages, edited by Henk Maarse
45. Instrumental Methods for Quality Assurance in Foods, edited by Daniel
Y. C. Fung and Richard F. Matthews
46. Listeria, Listeriosis, and Food Safety, Elliot T. Ryserand Elmer H. Marth
47. Acesulfame-K, edited by D. G. Mayerand F. H. Kemper
48. Alternative Sweeteners: Second Edition, Revised and Expanded, edited
by Lyn O'Brien Nabors and Robert C. Gelardi
49. Food Extrusion Science and Technology, edited by Jozef L. Kokini, ChiTang Ho, and Mukund V. Karwe
50. Surimi Technology, edited by Tyre C, Lanierand Chong M. Lee
51. Handbook of Food Engineering, edited by Dennis R. Heldman and Daryl
B. Lund
52. Food Analysis by HPLC, edited by Leo M, L. Nollet
53. Fatty Acids in Foods and Their Health Implications, edited by Ching
Kuang Chow
54. Clostridium botulinum: Ecology and Control in Foods, edited by Andreas
H. W. Hauschild and Karen L. Dodds
55. Cereals in Breadmaking: A Molecular Colloidal Approach, Ann-Charlotte
Eliasson and Kare Larsson
56. Low-Calorie Foods Handbook, edited by Aaron M. Altschul
57. Antimicrobials in Foods: Second Edition, Revised and Expanded, edited
by P. Michael Davidson and Alfred Larry Branen
58. Lactic Acid Bacteria, edited by Seppo Salminen and Atte von Wright
59. Rice Science and Technology, edited by Wayne E, Marshall and James
I. Wadsworth
60. Food Biosensor Analysis, edited by Gabriele Wagner and George G.
Guilbault
61. Principles of Enzymology for the Food Sciences: Second Edition, John
R. Whitaker
62. Carbohydrate Polyesters as Fat Substitutes, edited by Casimir C. Akoh
and Barry G. Swanson
63. Engineering Properties of Foods: Second Edition, Revised and
Expanded, edited by M. A. Rao and S. S. H. Rizvi
64. Handbook of Brewing, edited by William A. Hardwick
65. Analyzing Food for Nutrition Labeling and Hazardous Contaminants,
edited by Ike J. Jeon and William G. Ikins
66. Ingredient Interactions: Effects on Food Quality, edited by Anilkumar G.
Gaonkar
67. Food Polysaccharides and Their Applications, edited by Alistair M.
Stephen
68. Safety of Irradiated Foods: Second Edition, Revised and Expanded, J.
F. Diehl
69. Nutrition Labeling Handbook, edited by Ralph Shapiro
70. Handbook of Fruit Science and Technology: Production, Composition,

Storage, and Processing, edited by D. K. Salunkhe and S. S. Kadam
71. Food Antioxidants: Technological, Toxicological, and Health Perspectives, edited by D. L. Madhavi, S. S. Deshpande, and D. K. Salunkhe
72. Freezing Effects on Food Quality, edited by Lester E. Jeremiah
73. Handbook of Indigenous Fermented Foods: Second Edition, Revised
and Expanded, edited by Keith H. Steinkraus
74. Carbohydrates in Food, edited by Ann-Charlotte Eliasson
75. Baked Goods Freshness: Technology, Evaluation, and Inhibition of
Staling, edited by Ronald E. Hebeda and Henry F, Zobel
76. Food Chemistry: Third Edition, edited by Owen R. Fennema
77. Handbook of Food Analysis: Volumes 1 and 2, edited by Leo M. L.
Nollet
78. Computerized Control Systems in the Food Industry, edited by Gauri S.
Mittal
79. Techniques for Analyzing Food Aroma, edited by Ray Marsili
80. Food Proteins and Their Applications, edited by Srinivasan Damodaran
and Alain Paraf
81. Food Emulsions: Third Edition, Revised and Expanded, edited by Stig E.
Friberg and Kare Larsson
82. Nonthermal Preservation of Foods, Gustavo V. Barbosa-Canovas, Usha
R. Pothakamury, Enrique Palou, and Barry G. Swanson
83. Milk and Dairy Product Technology, Edgar Spreer
84. Applied Dairy Microbiology, edited by Elmer H. Marth and James L.
Steele
85. Lactic Acid Bacteria: Microbiology and Functional Aspects: Second
Edition, Revised and Expanded, edited by Seppo Salminen and Atte von
Wright
86. Handbook of Vegetable Science and Technology: Production, Composition, Storage, and Processing, edited by D. K. Salunkhe and S. S.
Kadam
87. Polysaccharide Association Structures in Food, edited by Reginald H.
Walter
88. Food Lipids: Chemistry, Nutrition, and Biotechnology, edited by Casimir
C. Akoh and David B. Min
89. Spice Science and Technology, Ken/7 Hirasa and Mitsuo Takemasa
90. Dairy Technology: Principles of Milk Properties and Processes, P. Walstra, T. J. Geurts, A. Noomen, A. Jellema, and M. A. J. S. van Boekel
91. Coloring of Food, Drugs, and Cosmetics, Gisbert Otterstatter
92. Listeria, Listeriosis, and Food Safety: Second Edition, Revised and
Expanded, edited by Elliot T. Ryser and Elmer H. Marth
93. Complex Carbohydrates in Foods, edited by Susan Sungsoo Cho, Leon
Prosky, and Mark Dreher
94. Handbook of Food Preservation, edited by M. Shafiur Rahman
95. International Food Safety Handbook: Science, International Regulation,
and Control, edited by Kees van der Heijden, /Waged Younes, Lawrence
Fishbein, and Sanford Miller
96. Fatty Acids in Foods and Their Health Implications: Second Edition,
Revised and Expanded, edited by Ching Kuang Chow
97. Seafood Enzymes: Utilization and Influence on Postharvest Seafood

Quality, edited by Norman F. Haard and Benjamin K. Simpson
98. Safe Handling of Foods, edited by Jeffrey M. Farber and Ewen C. D.
Todd
99. Handbook of Cereal Science and Technology: Second Edition, Revised and Expanded, edited by Karel Kulp and Joseph G. Ponte, Jr.
100. Food Analysis by HPLC: Second Edition, Revised and Expanded,
edited by Leo M. L. Nollet
101. Surimi and Surimi Seafood, edited by Jae W. Park
102. Drug Residues in Foods: Pharmacology, Food Safety, and Analysis,
Nickos A. Botsoglou and Dimitrios J. Fletouris
103. Seafood and Freshwater Toxins: Pharmacology, Physiology, and
Detection, edited by Luis M. Botana
104. Handbook of Nutrition and Diet, Babasaheb B. Desai
105. Nondestructive Food Evaluation: Techniques to Analyze Properties
and Quality, edited by Sundaram Gunasekaran
106. Green Tea: Health Benefits and Applications, Yukihiko Hara
107. Food Processing Operations Modeling: Design and Analysis, edited
by Joseph Irudayaraj
108. Wine Microbiology: Science and Technology, Claudio Delfini and
Joseph V. Formica
109. Handbook of Microwave Technology for Food Applications, edited by
Ashim K. Datta and Ramaswamy C. Anantheswaran
110. Applied Dairy Microbiology: Second Edition, Revised and Expanded,
edited by Elmer H. Marth and James L. Steele
111. Transport Properties of Foods, George D. Saravacos and Zacharias
B. Maroulis
112. Alternative Sweeteners: Third Edition, Revised and Expanded, edited
by Lyn O'Brien Nabors
Additional Volumes in Preparation

Food Additives: Second Edition, Revised and Expanded, edited by
Alfred Larry Branen, P. Michael Davidson, Seppo Salminen, and John
H. Thorngate
Control of Foodborne Microorganisms, edited by Vijay K. Juneja and
John N. Sofos
Handbook of Dietary Fiber, edited by Susan Sungsoo Cho and Mark
L. Ore her
Flavor, Fragrance, and Odor Analysis, edited by Ray Marsili
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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Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved.

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
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 engineering 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 engineering for simple gases and liquids, based on molecular dynamics and thermodynamics. However, the complex structure of solid, semi-solid, and fluid foods prevents the direct use of molecular dynamics for the prediction of the transport properties 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, especially 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 conductivity, and mass diffusivity of foods. One outcome of these projects was the importance of context (relevancy) of the measurement and sample conditions. This explains 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 (thermal conductivity or moisture diffusivity) of a given food or food class.
All transport properties are structure-sensitive at the three levels, i.e. molecular, 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 unified approach to the transport properties based on certain general principles. Chapter 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 treatment 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 diffusivity is presented in Chapter 6. The diffusion of solutes in food systems is discussed 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 University, 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 contributions 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
I. RHEOLOGICAL PROPERTIES
II. THERMAL TRANSPORT PROPERTIES
III. MASS TRANSPORT PROPERTIES
3
3
4
2. Transport Properties of Gases and Liquids
I. INTRODUCTION
II. ANALOGIES OF TRANSPORT PROCESSES
III. MOLECULAR BASIS OF TRANSPORT PROCESSES
A. Ideal Gases
B. Thermodynamic Quantities
C. Real Gases
IV. PREDICTION OF TRANSPORT PROPERTIES OF FLUIDS
A. Real Gases
B. Liquids
C. Comparison of Liquid/Gas Transport Properties
D. Gas Mixtures
V. TABLES AND DATA BANKS OF TRANSPORT PROPERTIES
7
8
9
9
10
12
14
15
16
18
19
19
3. Food Structure and Transport Properties

I. INTRODUCTION
II. MOLECULAR STRUCTURE
A. Molecular Dynamics and Molecular Simulations
29
29
29
29
vii
viii
Contents
B. Food Materials Science

C. Phase Transitions
D. Colloid and Surface Chemistry
III. FOOD MICROSTRUCTURE AND TRANSPORT PROPERTIES
A. Examination of Food Microstructure
B. Food Cells and Tissues
C. Microstructure and Food Processing
D. Microstructure and Mass Transfer
IV. FOOD MACROSTRUCTURE AND TRANSPORT PROPERTIES
A. Definitions
B. Food Macrostructure and Transport Properties
C. Determination of Food Macrostructure
D. Macrostructure of Model Foods
E. Macrostructure of Fruit and Vegetable Materials
30
30
31
32
32
32
34
34
36
36
40
45
46
50
4. Rheological Properties of Fluid Foods
63
I. INTRODUCTION
II. RHEOLOGICAL MODELS OF FLUID FOODS
A. Structure and Fluid Viscosity
B. Non-Newtonian Fluids
C. Effect of Temperature and Concentration
D. Dynamic Viscosity
III. VISCOMETRIC MEASUREMENTS
A. Viscometers
B. Measurements on Fluid Foods
IV. RHEOLOGICAL DATA OF FLUID FOODS
A. Edible Oils
B. Aqueous Newtonian Foods
C. Plant Biopolymer Solutions and Suspensions
D. Cloudy Juices and Pulps
E. Emulsions and Complex Suspensions
V. REGRESSION OF RHEOLOGICAL DATA OF FOODS
A. Edible Oils
B. Fruit and Vegetable Products
C. Chocolate
63
66
66
68
71
73
74
74
78
79
79
80
85
89
90
92
92
94
100
Contents
5. Transport of Water in Food Materials
ix
105
I. INTRODUCTION
II. DIFFUSION OF WATER IN SOLIDS
A. Diffusion of Water in Polymers
III. DETERMINATION OF MASS DIFFUSIVITY IN SOLIDS
A. Sorption Kinetics
B. Permeability Methods
C. Distribution of Diffusant
D. Drying Methods
E. Simplified Methods
F. Simulation Method
G. Numerical Methods
H. Regular Regime Method
I. Shrinkage Effect
IV. MOISTURE DIFFUSIVITY IN MODEL FOOD MATERIALS
A. Effect of Measurement Method
B. Effect of Gelatinization and Extrusion
C. Effect of Sugars
D. Effect of Proteins and Lipids
E. Effect of Inert Particles
F. Effect of Pressure
G. Effect of Porosity
H. Effect of Temperature
I. Drying Mechanisms
V. WATER TRANSPORT IN FOODS
A. Mechanisms of Water Transport
B. Effective Moisture Diffusivity
C. Water Transport in Cellular Foods
D. Water Transport in Osmotic Dehydration
E. Effect of Physical Structure
F. Effect of Physical/Chemical Treatments
G. Characteristic Moisture Diffusivities of Foods
105
106
107
109
110
114
118
120
123
124
124
12 5
126
127
127
13 0
133
13 5
137
138
140
141
143
144
144
145
146
147
150
152
155
6. Moisture Diffusivity Compilation of Literature

Data for Food Materials
163
I. INTRODUCTION
II. DATA COMPILATION
163
164
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
A. Diffusivity of Small Solutes
B. Measurement of Diffusivity
II. DIFFUSIVITY IN FLUID FOODS
A. Dilute Solutions
B. Concentrated Solutions
III. DIFFUSION IN POLYMERS
A. Diffusivity of Small Solutes in Polymers
B. Glass Transition
C. Clustering of Solutes in Polymers
D. Prediction of Diffusivity
237
237
239
241
241
242
243
244
246
247
248
IV. DIFFUSION OF SOLUTES IN FOODS

A. Diffusivity of Salts
251
251
B. Diffusivity of Organic Components
252
C. Volatile Flavor Retention

D. Flavor Encapsulation
V. PERMEABILITY IN FOOD SYSTEMS
A. Permeability
B. Food Packaging Films
C. Food Coatings
D. Permeability/Diffusivity Relation
254
258
259
259
261
262
263
8. Thermal Conductivity and Diffusivity of Foods

I. INTRODUCTION
II. MEASUREMENT OF THERMAL CONDUCTIVITY
AND DIFFUSIVITY
A. Thermal Conductivity
B. Thermal Diffusivity
III. THERMAL CONDUCTIVITY AND DIFFUSIVITY
DATA OF FOODS
269
269
270
270
273
275
Contents
A. Unfrozen Foods
B. Frozen Foods
C. Analogy of Heat and Mass Diffusivity
D. Empirical Rules
IV. MODELING OF THERMAL TRANSPORT PROPERTIES
A. Composition Models
B. Structural Models
V. COMPILATION OF THERMAL CONDUCTIVITY DATA OF FOODS
VI. THERMAL CONDUCTIVITY OF FOODS AS A FUNCTION OF
9. Heat and Mass Transfer Coefficients

in Food Systems
I. INTRODUCTION
II. HEAT TRANSFER COEFFICIENTS
A. Definitions
B. Determination of Heat Transfer Coefficients
C. General Correlations of the Heat Transfer Coefficient
D. Simplified Equations for Air and Water
III. MASS TRANSFER COEFFICIENTS
A. Definitions
B. Determination of Mass Transfer Coefficients
C. Empirical Correlations
D. Theories of Mass Transfer
IV. HEAT TRANSFER COEFFICIENTS IN FOOD SYSTEMS
A. Heat Transfer in Fluid Foods
B. Heat Transfer in Canned Foods
C. Evaporation of Fluid Foods
D. Improvement of Heat/Mass Transfer
V. HEAT TRANSFER COEFFICIENTS IN FOOD PROCESSING:
COMPILATION OF LITERATURE DATA
VI. MASS TRANSFER COEFFICIENTS IN FOOD PROCESSING:
xi
275
276
276
279
280
280
283
289
326
359
359
360
360
361
362
364
364
364
365
366
367
369
369
371
372
373
374
391
Appendix: Notation
403
Index
407
1
Introduction
The transport properties of momentum (flow), heat and mass of unit operations are an important part of the physical and engineering properties of foods,
which are necessary for the quantitative analysis, design, and control of food processes and food quality.
The transport of momentum (rheological properties) and heat (thermal conductivity) 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 transport phenomena have been advanced by a unified treatment of the three basic
transport processes (Brodkey and Hershey, 1988). The adoption of transport phenomena in food systems is expected to advance the emerging field of food engineering (Gekas, 1992). However, foods are complex heterogeneous and sensitive
materials, mostly solids or semisolids, and application of the principles of transport 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 considerable 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 liquids is based on molecular dynamics, experimental measurements are necessary
for the food materials and food processing systems.
Chapter 1
Theoretical analysis and experimental techniques of mass diffusion in polymeric 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 utilized 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 particularly 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 measurements 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 molecular, 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, demonstrating 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
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 cooling, 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 rheological 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 related 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 accurately 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 empirical 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 published data on mass transport in food systems refer to moisture (water) diffusivity
(Marinos-Kouris and Maroulis, 1995), since the transport of water is of fundamental 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 transfer 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 crystalline. 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 diffusivity, using an empirical model as a function of moisture content and temperature, 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 estimation 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 diffusivities are used in various food processes and food quality changes, like aroma retention (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 Structure of Starch Materials on Water Diffusivity. J Food Proc Preserv 15:183195.
Okos, M.R., ed. 1987. Physical and Chemical Properties of Foods. ASAE Publication 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: Aspen Publ.
Reid, R.C., Prausnitz, J.M., Poling, B.E. 1987. The Properties of Gases and Liquids. 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 Properties of Foods. 2nd ed. Rao, M.A., Rizvi, S.S.H. eds. New York: Marcel Dekker, 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 engineering (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. Molecular 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 importance 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 materials.
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 temperature (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 pressure 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
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 (Brodkey and Hershey, 1988). Thus, momentum transport is caused by the relative motion 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 obeying 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 equation (Brodkey and Hershey, 1988):
X =5/0=
"'
'
T
n*> 'l
(2-5)
where u is the mean velocity (m/s), 9 is the collision frequency (1/s), d is the molecular 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 proportional 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 constant 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 predict 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 correlations 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
11
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 degree 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 compared 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
For many fluids the normal boiling point is approximately equal to 0.7TC.
(2-18)
12
Chapter 2
Table 2.1 Critical Constants and Acentric Factors of Selected Fluids

Vc , crrrVmol
r c ,K
P c ,bar
Oxygen
73.4
154.6
50.4
Nitrogen
89.8
93.9
130.4
167.1
126.2
33.9
73.8
50.4
61.4
Fluid
Carbon Dioxide
Ethylene
Ethanol
Water
55.1
304.1
282.4
531.9
647.3
221.2
zc
0.288
0.290
0.274
0.280
0.240
0.235
CO
0.025
0.039
0.239
0.089
0.644
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 processes at the molecular level. Their origin and determination is treated in the specialized 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 parameters 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 spherical 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 distance.
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)
13
Table 2.2 Intermolecular Constants of Selected Components

Gas
Oxygen
Nitrogen
Air
Carbon Dioxide
Ethylene
Ethanol
Water
a, nm
0.35
0.38
0.37
0.39
0.42
0.45
0.26
/kB,K
106.7
71.4
78.6
195.2
224.7
362.6
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 potential 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
where 5* is the dipole dimensionless number, defined by the equation:
(2-23)
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] = 77rjq) 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 Hershey, 1988).
15
A. Real Gases
The transport properties of real gases, viscosity 77 (Pa s), thermal conductivity /I (W/m K), and mass diffusivity D (m2/s) can be predicted by the ChapmanEnskog equations, based on the intermolecular parameters (Brodkey and Hershey,
1988):
= 2.669x10"
(Mr)"
= 8.3224x10'
D = 1.883x10-
(2-26)
(2-27)
(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 diffusivity 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 +
cvIR
c IR-\
(2-30)
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 molecular parameters is difficult, and empirical relationships are normally used. Experimental measurements of the transport properties of liquids are necessary to validate 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 viscosity, 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.
17
2. Thermal Conductivity
The thermal conductivity of liquids can be estimated from empirical equations 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:
D=
If B T
(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 constant.
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 Arrhenius-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 diffusivity 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 DB 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 DAB 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 intermolecular 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 transport 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
DAB= 1.7x1 0"5m2/s

oxygen/water: DAB- 1.7x1 0"9m2/s
oxygen/air:
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)
19
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):
^=vayJy*+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 temperature 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. Extensive 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 properties (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 mainframe computers, are used in process equipment design and in processing operations. Software of selected physical properties for desktop computers and Windows 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 petrochemical industries. Limited information is available on food and biological
products, which are, for the most part, solid or semisolid materials.
Chapter 2
20
Tables 2.3 and 2.4 give some selected values of transport properties of simple 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 (25C)
Material
r|, mPa s
A., W/m K
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
Water vapor
0.025
0.015
0.010
0.020
Water
0.90
0.62
Ethanol
1.04
0.15
Gases
Liquids
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, 25C)
(dilute solutions, 25C)
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
2.1
2.0
-
1.3
Ethylene
Water
Salt (NaCl)
Source: Data from Perry, 1984 and Reid et al., 1987.
1.9
1.1
1.2
21
B.
0.01
0.001
200
300
400
Temperature (C)
Figure 2.1 Viscosity of air and water versus temperature. (Adapted from Pakowskietal., 1991.)
Chapter 2
22
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.)
23
A third degree polynomial was fitted to these data and the results are summarized 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 presented 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
Saturated Vapor
Superheated Vapor
Air
7.95E-03
8.07E-03
1.69E-02
4.49E-05
4.04E-05
4.98E-05
a2
-6.13E-08
1.24E-09
-3.19E-08
a3
1.44E-10
-1.21E-12
1.32E-11
Temperature (C)
0-300
100-700
0-1000
Saturated Water
ao
-1.07E+01
ai
1.97E-02
a2
-1.47E-05
a3
1.82E+03
Temperature (C)
0-350
5.70E-01
1.76E-02
1.77E-02
2.43E-02
1.78E-03
1.05E-04
6.01E-05
7.89E-05
-6.94E-06
-6.7 IE-07
9.5 IE-08
-1.79E-08
2.20E-09
3.07E-09
-3.99E-11
-8.57E-12
Temperature (C)
0-350
0-300
100-700
0-1000
2.16E-05
1.80E+00
-l.OOEOO
Thermal Conductivity
(W/m K)
Saturated Water
Saturated Vapor
Superheated Vapor
Air
Mass Diffusivitv
(m2/s)
D=ao(T+273)/273)ai P"2
Temperature (C)
Water Vapor in Air
Source: Data from Pakowski et al. (1991)
0-1200
Chapter 2
24
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 common gases of importance to food processes as a function of temperature.
25
percentage sucrose by weight = 60
50
100
Temperature (C)
Figure 2.4 Viscosity of aqueous sucrose solutions. (Adapted from Perry et al.,
1984.)
Chapter 2
26
0.070
0.060
0.050
a
a
e
(J
0.040
0.030
0.020
0.010
-200
200
Temperature (C)
Figure 2.5 Thermal conductivity of gases. (Adapted from Perry et al., 1984.)
600
27
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: Technical Data Services Inc.
Eckermann, R. 1983. Information systems for, and prediction of, physical properties 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. Intermolecular Forces. Their Origin and Determination. Oxford: Clarendon Press.
Millet, J., Dymond, J.H., Nieto de Castro, C.A. 1996. Transport Properties of Fluids. Their Correlation, Prediction and Estimation. Cambridge: Cambridge
University Press.
Pakowski, Z., Bartczak, Z., Strumillo, C., Stenstrom, S. 1991. Evaluation of Equations Approximating Thermodynamic and Transport Properties of Water,
Steam and Air for Use in CAD of Drying Processes. Drying Technol 9:753773.
Perry R.J., Green, J.H., Moloney, J.O. 1984. Perry's Chemical Engineers' Handbook. 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 Thermodynamics 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 macrostructure, used in engineering and processing applications, can be related to the recent
advances of food microstructure at the cellular level. Applications of food structural 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 thermodynamics. 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 analyze 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 structural, thermodynamic and transport properties are estimated (Theodorou, 1996).
Molecular simulations can produce polymer configurations based on equilibrium 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 applied 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 science 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 determination of mass transport (diffusion) of water and other solutes in food materials
(Vieth, 1991).
Food biopolymers of importance to transport properties are structural proteins (collagen, keratin, elastin), storage proteins (albumins, globulins, prolamins
and glutenins), structural polysaccharides (cellulose, hemicelluloses, pectins, seaweed, 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, texture 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 determined 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 WilliamsLandel-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 increased, 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 following 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 (x200500,000), 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 studies/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 characterize each material. The cells contain several components, which are essential in
living organisms, such as water, starch, sugars, proteins, lipids and salts. A schematic diagram of a plant parenchyma cell is shown in Figure 3.1.
33
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, surrounded 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 dehydration, 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 reduction), 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, lipids 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 diffusivity in the liquid solvent DL due to the complex structure of the material, according 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 tissues. 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 enzymatic treatment of the plant tissues, which break down, e.g. the pectins of the cell
walls.
35
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 equilibrium 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 components (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 Chapter 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 dehydration 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 transport (outside the cell membrane); b) symplasmatic transport through small channels (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 hydrodynamic 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 relation 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 dehydration 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) particulate 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 following 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, respectively (m3). The volume of air is referred to the internal pores only.
37
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 solids, combining Eqs. (3-5), (3-6), (3-7) and (3-9) results in:
38
Chapter 3
Pp=
lJrX
(3-11)
A..
Equation (3-11) shows the dependence of moisture content on true (particle) density.
Combining Eqs. (3-4), (3-7), (3-9) and (3-10) results in:
'iW
A,
P-12)
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
A
(3-13)
where L>O, and pbo are the specific volume and the apparent density at X = 0, respectively.
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\ +
IA
(3-15)
PL)
X +
Y
PL.
where pL is the oil density and 7 the oil content

Y=mL/ms
(3-17)
39
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 +
_____
j ___
P,
P,
(3-18)
I ___
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
(Xi)
Final
(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 conductivity 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 corresponding informational flow diagram is presented in Figure 3.4.
41
Table 3.1 Effective Thermal Conductivity Generic Model for Continuous Materials
Thermal Conductivity Structural Model
(2)
Volume Fraction of the Food Phases

/?,=!-
(4)
* =^
(5)
(6)
Density Structural Model
A,
P.
Chapter 3
42
pai, Xi,
O, al, a2, a3
Density
of Pure
Substances
Shrinkage
and
Porosity
Model
Eqs. (7) and (8)
ps, pw
pa, pt
Volume
Fraction
of Food
Components
Eqs. (4), (5)
and (6)
Thermal
es, e\v, ea
Conductivity
of Pure
Substances
Xs, Xw, Xa
Thermal
Conductivity
Structural
Model
Eqs. (1), (2)
and (3)
bo, bl, b2, b3
JXeff
Figure 3.3 Informational flow diagram for the model of Table 3.1. (Equation numbers
refer to those in Table 3.1.)
43
Table 3.2 Effective Thermal Conductivity Generic Model for Granular Materials
Thermal Conductivity Structural Model for Granular Material
*=l-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
___ I ___
P.
P.
(9)
^ '
Chapter 3
44
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
of Pure
Substances
Xs, Xw
Structural Model
for Granules (Particles)

Eqs. (4), (5)
and (6)
bo, bl, b2, b3
1 e
1
Xp
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.)
45
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.
2.
3.
Dimension measurement
Buoyant force determination
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 carbohydrates, proteins and lipids assembled in the form of a hydrated solid or a solidlike 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 content, 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 granular 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 densities of the material, are related to the changes of moisture diffusivity D during
the various drying and rehydration processes (see Chapter 5).
47
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 microscopic structure (see Chapter 8). Changes in porosity of granular starch struc-
tures by the incorporation of sugars, proteins, lipids, and inert particles are reflected in significant changes of the moisture diffusivity. Significant reduction of
the porosity of granular starch is obtained by mechanical compression (see Chapter 5).
Figure 3.8 shows schematically the macrostructure of dried granular and gelatinized starch materials. The spherical granular starch materials developed radial
channels through which water was transported by hydrodynamic flow during drying. The gelatinized starch suffered more shrinkage during drying with irregular
cracks in the dried matrix. These changes correspond to changes of moisture diffusivity 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 structure which had lower moisture and thermal diffusivity than the fibrous material.
The pore size distribution in granular, gelatinized and extruded starch materials, 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, developed for thermal conductivity, can be adapted to model the effective moisture diffusivity in granular starch materials (Vagenas and Karathanos, 1991). The pore
structure of extruded pasta has significant effect on the moisture sorption and diffusivity 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 developed 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). Developments 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).
49
a. Granular
b. Gelatinized
Figure 3.8 Macrostructure of air-dried spherical samples of corn starch (20 mm diameter).
O O Q
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 volume 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 physical 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 coefficient (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. Freezedried materials developed the highest porosity, whereas the lowest one was obtained using conventional air drying.
The above structural properties for the investigated materials were also examined during rehydration of dehydrated products, using the drying methods. The
same dehydrated products did not recover their structural properties after rehydration, due to structural damage that occurred during drying and the hysteresis phenomenon, which took place during rehydration. Porosity of the rehydrated products 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 parameters 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 investigated 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 conditions. The results showed that the porosity of french fries increases with increasing 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).
51
2.0 -
2.0 T
BANANA
A
APPLE
Dehydration
convective drying
vacuum drying
microwave drying
freeze drying
osmotic dehydration
calculated
Rehydration
convective drying
vacuum drying
micro\\ave drying
freeze drying
osmotic dehydration
- calculated
3
6
Moisture content (kg/kg db)
2.0 -
3
6
2.0 CARROT
3
6
3
6
Figure 3.10 Variation of true density with material moisture content for various drying
methods during dehydration and rehydration.
Chapter 3
52
2.0 -
o
o
D
Dehyd(ration
convei;tive drying
vacuuin drying
micro\vave drying
freeze drying
osmoti c dehydration
ited
RehydIration
convet;tive drying
vacuuin drying
microvvave drying
freeze drying
osmoti'c dehydration
0.0
CARROT
0.0
Figure 3.11 Variation of apparent density with material moisture content for various
drying methods during dehydration and rehydration.
53
Dehydration
1.0
BANANA
convective drying
vacuumdrying
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)

1,0 T
CARROT
Figure 3.12 Variation of porosity with material moisture content for various drying methods during dehydration and rehydration.
Chapter 3
54
15
Dehydration
convective drying
vacuum drying
microwave drying
freeze drying
osmotic dehydration
A
X
Rehydration
convective drying
vacuum drying
microwave drying
freeze drying
osmotic dehydration
o
A
X
0
D
15 -
Figure 3.13 Variation of specific volume with material moisture content for various drying
methods during dehydration and rehydration.
55
Table 3.4 Mathematical Model for Structural Properties of Foods
Structural properties
pp
pb
s
v
True density
Apparent density
Porosity
Specific volume
(L/kg db)
Moisture content
(kg/kg db)
(kg/L)
(kg/L)
Factors
Properties equations
1+ X
Pp
~ J_ A
Ps
P.
i +x
pb = t
Pbo
(2)
Pw
(3)
8 = 1-*-
Pp
u = + B'
Pbo
(1)
(4)
Pw
Parameters
pw
ps
pbo
/?'
Enclosed water density

Dry solid true density
Dry solid apparent density
Shrinkage or expansion coefficient
Factors affecting parameters

Material
Drying method
(kg/L)
(kg/L)
(kg/L)
Chapter 3
56
Table 3.5 Parameter Estimation of the Structural Properties Model

Material/Method
Ps
Rehydrat.
'c
Apple
Convective
Vacuum
Microwave
Freeze
Osmotic
Convective
Vacuum
Microwave
Freeze
Osmotic
Pbo
0.99
0.96
1.01
0.34
0.56
0.39
0.56
0.12
0.73
0.56
0.39
0.56
0.12
0.73
'- -g1.31
1.30
0.81
1.22
Banana
DC
B
'E>
Rehydrat.
it
c
'E>
O
u
B
>,
-C
BJD
C
'cEu
J>
Convective
Vacuum
Microwave
Freeze
Osmotic
Carrot
Convective
Vacuum
Microwave
Freeze
Convective
Vacuum
Microwave
Freeze
Potato
Convective
Vacuum
Microwave
Freeze
Convective
Vacuum
Microwave
Freeze
1.81
0.63
1.79
0.26
1.33
1.07 1.81
0.63
1.10
1.79
1.07
0.26
0.65
1.33
1.07
1.04
0.90
1.05
0.43
1.04
Convective
Vacuum
Microwave
Freeze
Osmotic
'
L9
1.75
L 2
1.02
0.99
0.94
0.30
1.02
1.05
1.20
0.22
1.60
1.03
1.03
0.81
0.29
1.02
1.05
1.07
0.74
1.60
0.92
0.53
0.14
12Q 1.60
0.92
0.53
0.14
1.50
1.29
0.44
0.18
10? 1.50
1.29
0.44
0.18
57
1.5 n
0.9
5
15
20
10
Time (min)
15
20
10
15
Time (min)
20
10
Time (min)
15
20
10
Time (min)
0.6
Figure 3.14
Effect of oil temperature on structural properties of french fries.
3.
a
o
s
I
01
CO
^
(Q
5"
x^
K)
O
<_ft
I5 "
re
<-/!
3
3 3
(-A
\
^
r>
'
UJ
1 I
1 1 1
\ | <
LK>
4^
Specific volume (I/kg)
Lft
'
<-*
Porosity
5"
Apparent density (kg/1)

o
o
True density (kg/1)
ff
O
39>
T3
CO
<n
59
1.5 -i
Concentration of
hydrogenated oil (%)

AO
50
100
15
20
10
15
Time (min)
20
10
10
15
Time (min)
20
10
15
Time (min)
20
Time (min)
0.
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 Techno!54(ll):56-65.
Aguilera, J.M., Stanley, D.W. 1999. Microstructural Principles in Food Processing
and Engineering. Gaithersburg, MD: Aspen Publishers.
Alien, T. 1997. Particle Size Measurement. Vol. 1. 5th ed. London: Chapman and
Hall.
Blonk, L.C.G. 2000. Viewing Food Microstructure presented at the ICEF 8. Puebla, Mexico.
Karathanos, V.T., Anglea, S.A., Karel, M. 1996a. Structure Collapse of Plant Materials during Freeze Drying. J of Texture Analysis 9:204-209.
Karathanos, V.T., Kanellopoulos, N.K. and Belessiotis, V.G. 1996b. Development
of Porous Structure During Air-Drying of Agricultural Plant Products. J Food
Sci 29:167-183.
Karathanos, V.T., Saravacos, G. D. 1993. Porosity and Pore Size Distribution of
Starch Materials. J Food Eng 18:254-280.
Krokida, M.K., Maroulis, Z.B. 1997. Effect of Drying Method on Shrinkage and
Porosity. Drying Technol 15 (10):2441-2458.
Krokida, M.K., Maroulis, Z.B. 2001a. Structural Properties of Dehydrated Products During Rehydration. International J of Food Sci and Technol 36:1-10.
Krokida, M.K., Maroulis, Z.B., Rahman, M.S. 200Ib. A Structural Generic Model
to Predict the Effective Thermal Conductivity of Granular Foods. Drying
Technol, in press.
Krokida, M.K., Oreopoulou, V., Maroulis, Z.B. 2000. Effect of Frying Conditions
on Shrinkage and Porosity of Fried Potatoes. J of Food Eng 43:147-154.
Krokida, M.K., Zogzas, N.P., Maroulis, Z.B. 1997. Modeling Shrinkage and Porosity During Vacuum Dehydration. International J of Food Sci and Technol
32: 445-458.
Lewicki, P. P., Lenart, A. 1995. Osmotic Dehydration of Fruits and Vegetables. In

Handbook of Industrial Drying. 2nd ed. Vol. 1. A.S. Mujumdar, ed. New
York: Marcel Dekker, pp. 691-713.
Levine, H., Slade, L. 1992. Glass Transitions in Foods. In: Physical Chemistry of
Foods, Schwartzberg, H.G. and Hartel, R., eds. New York: Marcel Dekker,
pp. 83-221.
Liu, H., Zhou, L., Hayakawa, K.I. 1997. Sensitivity Analysis for Hydrostress
Crack Formation in Cylindrical Food During Drying. J Food Sci 62:447-450.
Maroulis, Z.B., Krokida, M.K., Rahman, M.S. 2001. A Structural Generic Model
to Predict the Effective Thermal Conductivity of Fruits and Vegetables. J
Food Eng, in press.
Marousis, S.N, Karathanos, V.T., Saravacos, G.D. 1991. Effect of Physical Structure of Starch Materials on Water Diffusivity. J Food Proc Preserv 15:183195.
61
Marousis, S.N., Saravacos, G. D. 1990. Density and porosity in drying starch

materials. J Food Sci 55:1367-1372.
Perry, R.H., Green, D. 1997. Perry's Chemical Engineers' Handbook. 7th ed. New
York: McGraw-Hill.
Rahman, M.S., 1995. Food Properties Handbook. New York: CRC Press.
Rao, M.I., Hartel, R.W., eds. 1998. Phase/State Transition of Foods. New York:
Marcel Dekker.
Rassis, D., Nussinovitch, A., Saguy, I.S. 1997. Tailor-Made Porous Solid Foods.
Int J Food Sci Technol 32:271-278.
Reid, R.C., Prauznitz, J. M., Poling, B. E. 1987. The Properties of Gases and Liquids. 4th ed. New York: McGraw-Hill.
Roos, Y. 1992. Phase Transitions and Transformations in Food Systems. In:
Handbook of Food Engineering. Heldman, D.R., Lund, D.B., eds. New York:
Roos, Y. 1995. Phase Transitions in Foods. New York: Academic Press.
Rotstein, E. 1987. The Prediction of Diffusivity and Diffusion-Related Properties
in the Drying of Cellular Foods. In: Physical Properties of Foods 2. Jowitt, R.,
Escher, F., Kent, M., McKenna, B., Roques, M., eds. London: Elsevier Applied Science, pp. 131-145.
Saravacos, G.D. 1998. Physical Aspects of Food Dehydration. In: Drying '98 Vol.
A. Akritidis, C.A., Marinos-Kouris, D., Saravacos, G.D., eds. Thessaloniki,
Greece: Ziti Publ, pp. 35-46.
Schwartzberg, H. G. 1987. Leaching Organic Materials. In: Handbook of Separation Process Technology. Rouseau, R.W., ed. New York: Wiley, pp. 540-577.
Slade, L, Levine, H. 1991. A Polymer Science Approach to Structure / Property
Relationships in Aqueous Food Systems: Non-Equilibrium Behavior of Carbohydrate-Water Systems. In: Water Relationships in Foods, Levine, H.,
Slade, L., eds. New York: Plenum Press, pp. 29-101.
Spiess, W.E.L., Behsinlian, D. 1998. Osmotic Dehydration in Food Processing.
Current State and Future Needs. In: Drying '98 Vol. A. Akritidis, C.A., Marinos-Kouris, D., Saravacos, G.D., eds. Thessaloniki, Greece: Ziti Publ, pp. 4756.
Theodorou, T.N. 1996. Molecular Simulations of Sorption and Diffusion in
Amorphous Polymers. In: Diffusion in Polymers, Neugi, P., ed. New York:
Vagenas, O.K., Karathanos, V.T. 1991. Prediction of Moisture Diffusivity in
Granular Materials with Special Applications to Foods. Biotechnol Progr
7:419-426.
Vieth, W.R. 1991. Diffusion In and Through Polymers. Munchen, Germany: Hanser.
Willis, B., Okos, M., Campanella, O. 1999. Effect of Glass Transition on Stress
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AIChE, pp. 496-501.
62
Chapter 3
Xiong, X., Narsimhan, G., Okos, M. O. 1991. Effect of Composition and Pore
Structure on Binding Energy and Effective Diffusivity of Moisture in Porous
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Capillary Bodies During Intermittent Volumetric Thermal Drying. Drying
Technol 10:421-443.
Rheological Properties of Fluid Foods
I. INTRODUCTION
The viscosity of fluid foods is an important transport property, which is useful in many applications of food science and technology, such as design of food
processes and processing equipment, quality evaluation and control of food products, and understanding the structure of food materials. Due to the complex
chemical and physical structure of foods, viscosity can not be predicted by theoretical 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 characterization 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 continuous 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 computer modeling and simulation, require extensive data on the physical and engineering 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 viscoelasticity) 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 equivalent to the Newton Eq. (4-1) of shear flow. In most food applications, TJ is synonymous 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 useful 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 cylindrical 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 contraction in the third.
Figure 4.1 Shear viscosity in the x-direction.
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 models, 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 viscoelastic 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 allows the adding up of the three elements, i.e. the viscous, elastic, and inertial effects. 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 viscometric 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 proportional 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 complex hydrodynamic flow of the particle / solvent and particle / particle interactions.
The particle size, shape and concentration affect strongly the viscometric properties 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 particle-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 difficulty of rotating (flowing) in the suspension. The aspect (L/D) ratio of rodlike par-
67
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 exhibit 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 KriegerDougherty 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 crystals. 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-polymerization, 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 models 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 corresponds to the viscosity of Newtonian fluids.
The Herschel-Bulkley model is derived from the power-law model by adding a yield stress term r0:
69
(4-8)
T = Tn
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 equation, 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 timedependent rheology, i.e. their apparent viscosity at a given shear rate changes significantly 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 viscosity increases with the time of shearing. The time-dependent rheological behavior 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 rheopectic 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 equilibrium stresses as constants.
71
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 (nonNewtonian) 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 constant.
72
Chapter 4
In Newtonian fluid foods, the energy of activation has been found to increase 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 apparent 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 suspensions of fluid foods of high non-soluble solids concentration, like fruit or vegetable 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 Newtonian 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 Vitali 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 expressed by combining Eqs. (4-13) and (4-14):
K = K0 exp [ (Ea / RT) +BC]
(4-15)
The additive model assumes no temperature-solids concentration interaction. This may not be true when temperature affects the solids structure and particle 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.
73
D. Dynamic Viscosity
The rheological characterization of complex semisolid foods requires, in addition 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 (sinusoidally) 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, represents 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 frequency of oscillation (1/s), and A/, /L2 are time constants (s).
When the shear and dynamic viscosities of food suspensions, like mayonnaise and margarine, are plotted against shear rate or oscillation frequency on loglog 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 deformation 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 basically measure the shear stress versus shear rate at a given temperature. The external stress (force/area) is applied at steady state, usually stepwise, either in ascending 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 utilized to extract rheological data for the material under the specific measurement
conditions.
Three common types of viscometers are used in most fluid food applications, 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 processing. 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 circular 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 comparing 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)
75
AP
Q
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 circular 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 profile 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 applications. 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 cylinder 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
77
(4-25)
The shear rate of non-Newtonian fluids in rotational viscometers is estimated 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 relatively large fluid volumes, are used in many routine measurements of Newtonian
fluids. Such instruments are not suitable for non-Newtonian fluids, since the applied shear rate cannot be estimated accurately. However, in some systems, empirical relationships of rotational velocity Q and shear rate y can be used to construct the rheogram (T vrs. f) of the non-Newtonian fluid.
3. Cone-and-Plate Viscometer
The principle of cone-and-plate viscosimeter, or Weissenberger rheogoniometer, 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 observed 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 increasing shear or stress, the suspensions may break down gradually, especially at
low shear stresses. These changes are caused by breakdown of particle agglomerates 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 similar 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. Viscous heating during viscometric measurements of thick food fluids may result in
erroneous low viscosities. In general, temperature has little effect on the flow behavior 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 viscous 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.
79
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 solutions and clarified juices, suspensions of plant materials, and emulsions and complex 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, obtained in seven laboratories, using coaxial-cylinder and cone-and-plate viscometers at 25C, 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 depends 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 temperature range 25-50C 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
Temperature, C
Edible oil
23.9
Corn oil
Soybean oil
23.9
Olive oil
40.0
Cocoa butter
25.0
Viscosity, mPa s
52.3
54.3
36.3
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 50Brix sucrose solution at
25C (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 viscosity at higher temperatures, according to the Arrhenius equation. Concentration
has a strong positive effect on viscosity, and the combined temperature/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 60C. It appears that the viscosities of the two fluids are similar, except at
concentrations higher than 60Brix, 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 concentrations. This difference may be caused by the precipitation of some compounds of grape juice, which become insoluble at higher concentrations, for example tartrates. These compounds are known to precipitate during the storage of
grape juices and wines at low temperatures.
81
1000
ÊS:^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
20-60C. (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
40C. (From Saravacos, 1970, and Perry et al., 1984.)
82
Chapter 4
Figure 4.8 shows the energies of activation for viscous flow of sucrose solutions (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 energy of activation at 0Brix 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 expressed 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 values 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'\
f-^
sucrose solutions
grape juice
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).
83
Molasses (thick liquid residues of sugar manufacturing) have high viscosities, e.g. 6600 to 374 mPa s in the temperature range 21-66C (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 22-74Brix
and 5-70C 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 energies (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 3063.5Brix 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 particles 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 (20-79.7Brix) has viscosities ranging from 1 to 6000 mPa s in the range 3070C, 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 75-83Brix, and their viscosity at 20C is in the range of 4-20 Pa s. Temperature has a strong effect, with corresponding high energies of activation Ea.
Utilizing the viscosity-temperature data (10-80C) of five types of honey, published 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 (71.5-80.2Brix) and viscosities (0.33-6.30 Pa s at 20C) with estimated activation energies 60-65 kJ/mol.
Australian honeys have high sugar concentrations (82.4-83.3Brix) with high viscosities (about 100 Pa s at 10C), and a strong effect of temperature (Bhandari et
al., 1999).
Licorice extract of soluble solids concentration 3-50Brix exhibited Newtonian behavior in the temperature range of 10-60C, 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.
Chapter 4
84
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 20C 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 25C, 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 14-22C,
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 20C (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 2C (Hayes, 1987).
85
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 present, 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 (Prentice 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 constants 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 colloidal particles in the solution.
Table 4.2 Rheological Constants of 1% Food Gum Solutions at 25C
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
Chapter 4
86
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 25C. (Data from Prentice and
Huber,1983.)
1000
Carrageenan gum
solution
0.1
0.001
0.1
10
1000
100000
Shear Rate (1/s)
Figure 4.11 Rheological data of 1% carrageenan gum solution at 25C. (Data from Prentice and Huber, 1983.)
87
1000
0.001
0.1
10
1000100000
Shear Rate (1/s)
Figure 4.12 Rheological data of 1% xanthan gum solution at 25C. (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 25C. (Data from Prentice
and Huber, 1983.)
Chapter 4
88
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 25C (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 25-125C, 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 25-125C.
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 systems requires not only shear stress-shear rate data, but also viscoelastic measurements 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.)
89
D. Cloudy Juices and Pulps
The presence of hydrocolloids (gums) and suspended particles (e.g. granules or fibers) in fluid plant foods changes the rheological properties into nonNewtonian, 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 increased 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 increased from 8 to 54 kJ/mol when the sugar concentration increased from 21 to
51Brix (Guerrero and Alzamora, 1997). A similar change of the rheological properties and activation energy by glucose addition was observed on peach, papaya
and mango purees (Guerrero and Alzamora, 1998). The combined effect of concentration and temperature follows the generalized exponential model of Eq. (415).
Cloudy apple juice becomes a non-Newtonian fluid at concentrations higher

than 40Brix, 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 50Brix (Saravacos, 1970). A similar rheological behavior was observed on raspberry juice,
which changed from Newtonian to non-Newtonian above 25Brix, with = 0.900.60 (Ibarz and Pagan, 1987).
Ultrafiltration of orange juice removes part of the particles and hydrocolloids (pectin), decreasing the consistency coefficient K, and increasing the flow
behavior index n and the activation energy (Hernandez et al., 1995). This treatment increases significantly the heat transfer coefficient in the evaporation of orange 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); riceblackgram 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 (Bhattacharaya 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 received 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 32.6Brix (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" material. Thus, in the range 10-25Brix, the lvalue of the "cold break" tomato concentrates 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 coefficient K of tomato concentrates (Rao, 1999). An empirical rule is to scale the viscosity 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 indices 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 stabilized by adsorption of biopolymers (gums, proteins, lecithin) on the particle surfaces (Rao, 1999). Because of their structure, emulsions may exhibit timedependent theological properties, as well as viscoelastic behavior.
Addition of sugar to emulsions changes significantly their theological properties. 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 energy 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 0-80C (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 effect of temperature and concentration on the consistency coefficient K follows the
generalized model of Eq. (4-15). Freeze-concentrated milk showed a similar
91
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 activation energy increasing from 20 to 60 kJ/mol in the range of 20-40%TS.
Sodium caseinate suspensions behave as Bingham plastic materials, following an empirical model similar to Eq. (4-15). The activation energy of casein suspensions 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 viscoelasticity 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 25C increases sharply from 24 to 65 kJ/mol,
evidently due to action of thermophilic clotting bacteria (Benezech and Maingonnat, 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 25C________

Food emulsion
Consistency coefficient (K)
Flow behavior index (n)
Pas"
Mayonnaise
0.55
6.4
Mustard
0.39
18.5
0.074
Margarine
297.6
Peanut butter
0.065
501.1
Cream, 40% fat
1.0
0.0069 (40C)
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 (Prentice 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 products 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 Newtonian fluids. The reported viscosities ranged from 1.6 to 451 mPa s at temperatures from 0 to 121C. The viscosities are plotted versus the temperature in Figure
4.16.
The following form of the Arrhenius equation was applied for the calculation of the activation energy for viscous flow Ea:
93
(4-30)
77/ = 77
/ . exp[-(
^ ^ -)]
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 = 25C, the estimated viscosity of an "average" 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.
20
40
60
80
100
Temperature (C)
Figure 4.16 Regression line of viscosity data of edible oils.
120
140
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 22.5Brix (screen opening 0.6 mm) at 25C (Prentice
and Huber, 1983). The regression line of the power-law model yielded the following rheological constants: K= 26 A Pa s" and n = 0.286 (Figure 4.17).
1000
Apple Sauce
1
0.001
0.01 0.1
10
100
1000
Shear Rate (1/s)

Figure 4.17 Rheological data of applesauce at 25C. (Data from Prentice and Huber,
1983.)
95
2. Fruit /Vegetable Juices and Concentrates

Rheological data on tomato, orange, pear, and mango juices and concentrates, 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 concentration 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
B
Em kJ/mol
n0
Tomato
Orange
Pear
Mango
1.27
9.28
2.15
1.85
0.149
0.077
0.087
0.089
15.8
35.0
16.1
32.1
0.403
0.950
0.348
0.332
0.0028
0.0034
0.0000
0.0017
o'
OQ
o_
00
(Q
n
o
Flow Behavior Index (-)
to
H
o
Consistency Coefficient (Pa s")
T3
ff
J
u
to
(Q
C
8-
a
o
o>
n
o
\
\.
\
p
o
I
c
-a
y
\
\
Consistency Coefficient (Pa s")

o
o
a.
u>
O
o
in
O
fl>'
CO
TJ
D>
o'
(Q
o
o_
Chapter 4
98
.-*'^,
100 -
^^^' *^
e
J>
cu>
^^^
_^*
10 -
*^^-^^^ -^^^^^
Ift
ix^^^"*^
-^^
.^"^^^^'^
l
^<^c
r :
uo
Temperature (C)
40
60
n1.
20
40
60
Concentration (% solids)
i.o
8
_o
R
U
oa
20
40
Concentration (% solids)
Figure 4.20 Rheological data of pear juice and concentrates.
60
po
k)
(Q
C
I 8
sa
65
o
a
Consistency Coefficient (Pas )
to
to
Q.
(0
-n
o
o
OL
to'
to
<D
0)
o'
(Q
<D
O_
Chapter 4
100
C. Chocolate
The Theological data on chocolate at 40C, obtained in the COST 90 project,

were analyzed, assuming that the Casson model (Eq. 4-10) is applicable. The regression 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=
1000
CO
'I
0.001
0.01 0.1
10
100
1000
Shear Rate (1/s)

Figure 4.22 Rheological data of chocolate at 40C. (Data from Prentice and Huber,
1983.)
101
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Vitali, A.A., Rao, M.A. 1984b. Flow Properties of Low-Pulp Concentrated Orange
Juice: Serum Viscosity and Effect of Pulp Content. J Food Sci 49:876-881.
Whorlow, R.W. 1980. Rheological Techniques, Ellis Horwood, Chichester, U.K.
Yoo, B., Figueiredo, A.A., Rao, M.A. 1994. Rheological Properties of Mesquite
Seed Gum in Steady and Dynamic Shear. Lebens Wiss und Technol 27:1 SI157.
Yoo, B., Rao, M.A. 1994. Effect of Unimodal Particle Size and Pulp Content on
Rheological Properties of Tomato Puree. J Texture Studies 12:421-436.
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 mechanism in drying operations (Keey, 1972), and various techniques have been developed 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 transport in food materials, the diffusion model yields satisfactory results for engineering 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 measurement.
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 methods 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 mechanism of water transport in various food structures (Section IV). Characteristic
moisture diffusivities in the main classes of foods are given in tabular form in Section 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 predicted 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 hydrodynamic 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 molecular diffusion, i.e. the driving force is a concentration gradient (dC/dz) or the
equivalent moisture content gradient (dX/dz). For simplified analysis and calculations, one-dimensional diffusion is considered, and the Pick diffusion equation is
applied:
dt
dz
8z
(5-1)
The diffusion coefficient D of water in solids is usually defined as the effective 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 tortuosity 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 substantially during food processing and storage. For this reason, the effective moisture
diffusivity is determined directly by experimental techniques.
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 molecular 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 diffusivity D, which is proportional to the (3/2) power of the temperature equation (228).
Other diffusion mechanisms, which are of minor importance to food systems 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 effusion. 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 sorption 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 sorption 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 determine D.

The effective moisture diffusivity D depends strongly on the physical structure of the polymeric material. Thus, values of D of the order of 10'14 are characteristic 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 diffusional 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 values 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.
109
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 operations and applications, such as drying, adsorption, extraction, membrane separations, 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 earlier 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 mechanisms, but nevertheless convenient for obtaining quantitative data for such complex 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; Zogzas and Maroulis, 1996; Saravacos, 1995). As a general rule, the method of measurement should be related to the actual intended application, for example the drying
method is recommended for applications related to drying, sorption kinetics is applicable 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 practical 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 pressure 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 contains 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.
111
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):
dt ~ dz
Bz
(5-7)
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
Me
2 Z_i /^
. 1\2
~"~i"|
r2
>
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 instead 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 drying 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)
xL'
(5-9)
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.
113
1.0
M/Me
0.5
0.0
HE
2U/2
(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). Moisture equilibrium values Xe, at a given temperature, for various food materials can
be obtained from the isotherms, if available, of the specific material, from published compilations (Iglesias and Chirife, 1982; Wolf et al., 1985) or from empirical 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 chromatography (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 chromatography (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 0C, 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 concentration in the polymeric material and in the mobile phase, is given by the equation
Kf=(7psT)/273
(5-12)
where ps is the density of the polymeric material.

A technique of determining D of solutes in polymers, using IGPC, is described by Pawlisch and Laurence (1987).
Frontal Analysis (FA) may also be used in studying the transport mechanisms between the mobile and stationary phases in a chromatographic column
(Vieth, 1991). A mixture of carrier gas and probe vapor is forced through the column 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 linear (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 prepared 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 =-
(AP/Az)
(5-13)
115
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 inverse of the Henry's constant (S = 1/H). The constant S is also related to the dimensionless partition coefficient, defined as the ratio of concentrations of the solute 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 temperature. 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 timelag 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:
Chapter 5
116
I
~m www
AP
T
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 estimated.
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:
6D
-exp -
(5-16)
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:
6D
(5-17)
117
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 intercept (TL, time lag) on the t axis, given by Eq. (5-18), from which the diffusivity
D can be estimated.
TL--1L
6D
(5-18)
The time required to reach full steady-state diffusion has been found empirically 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 apparatus (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 diffuses into the polymer film until equilibrium is established.
The solubility of the gas S in the polymer is estimated from a material balance in the closed system, resulting in the equation:
118
Chapters
Fv 273(Pi-Pl
S =
-
r, T( P.
(5-19)
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 pressure Pt is applied, the chamber is evacuated by rapid pump down to a lower pressure, 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 conditions are met, and that diffusivity D is constant, the solution of the diffusion equation 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 concentration of the diffusant. The concentration of the component in the solid is measured at various distances from the surface as a function of time, obtaining the concentration-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 sections 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 plotting component concentration versus distance (Figure 5.5).
119
C,
Figure 5.5 Moisture concentration (C) - distance (z) curves in two contacted cylindrical samples.
The Pick diffusion equation for a semi-infinite solid yields the following
solution, assuming constant diffusivity (Crank, 1975):
-C
C
r = erfc
c-c.
(5-20)
where C0 is the initial concentration of the diffusant in the sample, C is the concentration 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 evaluation 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 separate 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 diffusivity of small molecules in solids, when diffusion is relatively slow, and thus concentration profiles can be determined within reasonable time intervals. It has the advantage of minimum disruption of the material structure during measurement, and it
has been applied to estimate the diffusivities of various components in food materials (see Chapter 7).
Application of this method to measurements of moisture diffusivity in food
systems presents experimental difficulties, mainly due to changes of moisture content during the analytical procedure (slicing, etc). The method can be used at higher
temperatures and pressures, where the usual methods are difficult to apply (Karathanos etal., 1991).
D. Drying Methods
The drying methods are used widely for the determination of moisture (water) 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, drying 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.
121
AIR
11
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 airdrying 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 outside 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 minimize 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 appropriate 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
- -
=JLy
; 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 expressed 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 sample during the drying process.
The first reported moisture diffusivities of food materials, obtained from drying data, assumed constant diffusivity (Saravacos and Charm, 1962a). However, it
was soon realized that diffusivity was a function of concentration (moisture content), 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 drying constant, defined by the equation:
X,)
at
(5-24)
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 humidity and air velocity) and sample thickness.
123
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 moisture ratio Y and the effective difrusivity is calculated from the equation
(dY/dt)
D = _1i2L
(dY/dFo),,
(5.26)
'
Chapter 5
124
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 (Karathanos 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 function of the moisture content X, and the diffusion equation (5-1) is fitted to the experimental 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)
125
where A' is the moisture content, Tis the temperature, and X0, T0 are adjustable constants.
A large number of drying data is obtained from drying experiments at fixed
drying conditions, and fitted simultaneously to the diffusion equation by a nonlinear regression technique. Two iterative methods of calculation can be used, i.e.
the finite differences of Crank-Nicolson (Crank, 1975) and the control volume (Patankar, 1980).
A numerical method, based on the exponential function of moisture diffusivity, (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 (Kiranoudisetal., 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 moisture 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 normally 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 converted 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 dryness, 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
where d is the fractal exponent, e.g. for drying of blanched potato d = 1.42.
(5-30)
127
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 physical 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 measurement (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 result, 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 during drying.
Figure 5.8 shows moisture diffusivities D in starch gels at 25C, obtained by
sorption kinetics. Thin films (1 mm) of potato starch gels were used, and the reported diffusivities were the mean values of adsorption and desorption measurements (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 macromolecular network. The thin samples of starch gel behaved like homogeneous polymer materials, and the small moisture diffusivities are of the same order of magnitude with the D values of small molecules through polymeric materials (Vieth,
1991).
Temperature has a positive effect on moisture diffusivity, following the Arrhenius 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 reduced, e.g. ED = 20 to 41 kJ/mol, at moisture contents X= 0.2 to 0.01, respectively.
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 glucose (50% dry basis) in the starch gel reduced significantly the moisture diffusivity.
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 diffusivity, 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 60C 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.
129
0.001
0.1
0.2
0.3
X (kg/kg dm)
Figure 5.8 Moisture diffusivity in potato starch gels. Sorption kinetics, 25C.
(Data from Fish, 1958.)
X (kg/kg dm)
Figure 5.9 Effective moisture diffusivity in drying slabs of starch gels at 40C.
S, starch; SG, starch glucose. (Data from Saravacos and Raouzeos, 1983.)
Chapter 5
130
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 60C. (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 different effect of gelatinization on moisture diffusivity was observed in highamylopectin (branched macromolecules) starch (AMIOCA), as shown in Figure
5.12(Saravacosetal., 1989).
131
The moisture diffusivity D in the gelatinized starch was reduced sharply, especially 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 60C. (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 60C. (Data from Saravacos et
al., 1989.)
50
40
EX
N 30
o
I 20
10
GEL
0.2
0.4
0.6
X (kg/kg dm)
Figure 5.13 Effective moisture diffusivity in drying of extruded (EX) and gelatinized (GEL) starch (AMIOCA) at 60C. (Data from Marousis et al.,1991.)
133
C. Effect of Sugars
Incorporation of small water-soluble molecules into the starch materials reduces, in general, the moisture diffusivity. The effect of sugars is more pronounced 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 60C. 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 proportional 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 untreated 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 diffusivity (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 "casehardening" 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).
Chapter 5
134
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 60C. S, starch; SG, starch/glucose; SD, starch/dextrin. (Data from Marousisetal., 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 60C. S, starch; SG, starch/glucose; SD starch/dextrose. (Data from
Marousis et al, 1989.)
135
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 60C. A similar effect was
observed with the addition of 25% lysozyme (Marousis, 1989).
Addition of proteins to amylose (linear macromolecule) reduced the D values to a lesser degree than amylopectin, presumably due to the weaker protein/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 manner 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 diffusivity 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 60C.
However, there is no significant change in D of gelatinized starches by the addition 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 physicochemical 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 water transport, e.g. by forming hydrophobic films in the starch network.
Chapter 5
136
0.2
0.4
0.6
X (kg/kg dm)
Figure 5.16 Effect of gluten (SP) on the moisture diffusivity (D) of granular amylopectin starch (S). Drying of spherical samples at 60C. (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 60C. (Data from Papantonis, 1991.)
137
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 diffusivity 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 60C. (Data from Leslie et al., 1991.)
138
Chapters
F. Effect of Pressure
Pressure has a significant effect on the moisture diffusivity of porous materials, 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 materials 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 temperature, 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 below 1 mbar (Saravacos and Stinchfield, 1965). The diffusion data were obtained
by the sorption kinetics method.
139
Figure 5.19 Effect of mechanical pressure on the moisture diffusivity of granular

starch (HYLON) at moisture X = 0.5. Drying at 60C. (Data from Marousis et al.,
1990.)
0.6
0.4
0.2
10
20
30
40
50
P (bar)
Figure 5.20 Effect of mechanical pressure on the porosity e of granular starch (HYLON) at moistureX= 0.5. (Data from Marousis et al., 1990.)
Chapter 5
140
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 60C. (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 experimental 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
141
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 properties 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 diffusion 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 various temperatures, is a good indication of the type of prevailing diffusion mechanism 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 Materials__________________________________________
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
Chapter 5
142
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, carboxy methyl cellulose. Y = (X-Xe)/(Xo-Xe). (Data from Saravacos, 1965.)
143
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 transport 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 transport 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 analogy.
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 water.
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 importance 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 approximate values of mass transport properties of broad classes of foods, e.g. porous, 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 experimental 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 structure, 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 Cooperative Project FAIR "DOPPOF").
A. Mechanisms of Water Transport
Most of the data on moisture diffusivity have been obtained from drying experiments, since mass transfer within the food material is the rate-controlling resistance. 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 internal 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 mechanisms are molecular diffusion (liquid and vapor), capillary flow, and hydrodynamic flow. Other mechanisms may be also involved, such as Knudsen diffusion,
surface diffusion, and thermal diffusion (Soret effect).
145
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 Section III of this chapter.
The drying curve (logY, t), obtained from drying experiments of specified
samples under controlled conditions, provides useful information on the mechanism 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 indication 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 resistance 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) Increasing 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 diffusivity 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 moisture 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
35C and air velocity of 3.7 m/s. Two effective moisture diffusivities were estimated 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 diffusion 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 35C. Slab thickness 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 nonliving food materials, i.e. the physiological processes of the living cells are neglected. 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 potential 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 gradient by the equation:
D = [Kfa)/pJ
(dn/cK)
147
(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 chemical 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 conductivities 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 product. 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 practice are sugar solutions, e.g. 65Brix 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 25C 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 temperature 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). Hydrodynamic 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 modeled 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 osmotic dehydration of fruit with sugars has significant effects on the moisture diffusivity in the dried product. Determination of moisture diffusivity D from airdrying 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 materials (Figure 5.14). The dissolved sugar molecules precipitate in the pores of the
fruit during drying, reducing significantly the porosity of the dried product (Chapter 3). Cylindrical apple samples 10 mm diameter were dried at 55C and 2 m/s air
velocity.
Sorption kinetics data show a similar effect of sugars on the moisture diffusivity 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 diameter in humidified air. The D values obtained from sorption experiments were
significantly lower than the data obtained by the drying method, in a similar manner with the data obtained on model food materials (see Section IV).
149
(S
X (kg/kg dm)
Figure 5.26 Effective moisture diffusivity in air-drying (55C) 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, osmotreated sample. (Data from Bakalis et al., 1994.)
150
Chapters
E. Effect of Physical Structure

As shown in model food systems, the physical and physicochemical structure 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 measurements in a vacuum sorption apparatus at 30C and increasing water vapor pressures. The obtained low values of moisture diffusivity are characteristic of sorption 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 porous 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 diffusion 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 30C. The D values of untreated samples 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).
151
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, 30C. 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. Sorption kinetics on thin samples, 30C. AD, air-dried; PD, puff-dried; FD, freezedried. (Data from Saravacos, 1967.)
Chapter 5
152
(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. Sorption kinetics on thin slices at 30C. (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 hydrophilic food components may reduce substantially the moisture diffusivity, due
primarily to the reduction of porosity. On the other hand, puffing (extrusion, explosion 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 moving 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).
153
Microwave or dielectric treatment of foods can substantially increase the

moisture diffusivity during drying at atmospheric pressure or in vacuum. Microwave 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 airdehydration 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 alkalitreated 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 water. 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 drying 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 treatment 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 60C. 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 60C of granular starch
(HYLON). CL, control; TR, treated 0.2% ethyl oleate. 7 = (X-Xe)f(Xo-Xe). (Data
from Saravacos et al., 1988.)
155
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 Products
Food Structure
Porosity
Activation energy
Diffusivity
______________%_______kJ/mol_________xlQ-'V/s
Highly porous
Freeze-dried
Puff-dried
Fibrous
90
10
50
Porous
Granular
Vacuum-dried
50
20
20
Low porosity
Compressed
20
30
Gelatinized
10
45
Starch/protein foods
10
50
0.1
Starch/lipid foods
10
60
0.01
Glassy-state foods
>60
0.0001
156
Chapters
Table 5.4 Typical Moisture Diffusivities of Cereal Grains and Rice at 30C
(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 30C
Diffusivity
Moisture
Food material
xlO'10m2/s
kg/kg dm
5.0
0.40
Dough
2.0
0.30
Bread
0.5
0.15
Cookie
0.3
0.15
Pasta
1.2
Puffed pasta
0.15
Table 5.6 Typical Moisture Diffusivities of Vegetable Products at 30C

Food material
Potato
Carrot
Peas
Onion
Soybeans
Moisture
kg/kg dm
0.30
0.30
0.10
0.10
0.20
Diffusivity
xlO-'W/s
5.0
2.0
3.0
0.5
0.8
157
Table 5.7 Typical Moisture Diffusivities of Fruit Products at 30C

Food material
Moisture
Diffusivity
_____________________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 30C

Food material
Minced beef
Pork sausage
Codfish
Herring
Mackerel
Hulibut
Moisture
kg/kg dm
0.60
0.20
0.50
0.50
0.40
0.40
Diffusivity
xlO-'W/s
1.0
0.5
2.0
0.8
0.5
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 diffusivity 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 content and temperature on this transport property. Porosity data, obtained from
measurements of bulk and particle densities (Chapter 3) at various moisture contents, 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 analyzed statistically to reveal the influence of material moisture content and temperature. 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 concerning 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 figures 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
Moisture
Temperature
IxlO' 1 2 -IxlO" 6 m 2 /s
0.01 - 15.0 kg/kg db
10-200C
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
J. Food
Engineering
Drying
Technology
165
J. of Food
Science
Trans of the
ASAE
Int. J, Food
Science and
Techn.
Figure 6.1 Number of papers on moisture diffusivity data in food materials published 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.
Chapter 6
166
l.E-03
l.E-06 - =
5 l.E-09
l.E-12
l.E-15
0.01
0.1
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.
167
The histogram in Figure 6.5 shows the distribution of the moisture diffusivity 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 publications 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
a
M
a
O
s
Z
10
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.
Chapter 6
168
Table 6.1 Literature for Moisture Diffusivity Data in Food Materials:

References and Number of Data Retrieved
Material Reference
Baked Products
Data
33
4
Biscuit
Balasubrahmanyam and Datta, 1993
Bread
Zhouetal., 1994
Cookie
Gekas, 1992
Lomauroetal, 1985
Crackers
Kirn and Okos, 1999

Dough
Kamthanos et al., 1995

Zanonietal, 1994
4
1
1
2
1
1
18
18
8
4
4
499
Cereal Products
16
Barley
Fasina et a!., 1998
Miketinac et al, 1992
Brown rice
Engelsetal, 1986
Gekas, 1992
Hendrickx et al, 1988
Lu and Siebenmorgen, 1992
Steffe and Singh, 1980
7
9
36
9
7
3
169
Table 6.1 Continued

Material Reference
Corn
Bakker-Arkema et a!., 1987
Galan-Domingo and Martinez-Vera, 1996
Gekas, 1992
Harosetal, 1995
Jumah and Mujumdar, 1996
Martinet- Vera eta!., 1 995
Mouradetal, 1996
Muthukumarappan and Gunasekaran, 1994a, b, c
Parti and Dugmanics, 1990
Patil, 1988
Shivhare et al, 1992
Syariefetal., 1987
Tolabaetal, 1989
Tolabaetal, 1990
Verma and Prasad, 1999
Waltonetal, 1988
Zahedetai, 1995
Malt
Lopezetal, 1997
Milled rice
Zhangetal, 1984
Paddy rice
Base et al, 1987
Parboiled brown rice

Igathinathane and Chattopadhyay, 1999a, b
Parboiled paddy rice

Parboiled rice
Chandra and Singh, 1984
Pasta
Litchfield and Okos, 1992
Meat et al, 1996
Waananen and Okos, 1996
Xiongetal, 1991
Data
168
6
3
3
9
6
5
17
40
8
8
10
9
8
4
7
20
5
4
4
2
2
3
3
6
6
6
6
12
6
6
51
11
4
30
6
Chapter 6
170
Table 6.1 Continued

Material Reference
Rice
Engelsetal, 1986
Galan-Domingo and Martinez-Vera, 1996
Gekas, 1992
Hendrickx et al, 1986
Hendrickx and Tobback, 1987

Hendrickx etal, 1988
Zahedetal, 1995
Rough rice
Bakker-Arkema et al, 1987

Chungu and Jindal, 1993
EceandCihan, 1993
Gekas, 1992
Lague andJenkins, 1991
Lu and Siebenmorgen, 1992
Sarkeretal, 1994
Suarezetal, 1982
Tang and Sokhansanj, 1993
Wheat
Bakker-Arkema et al, 1987

Bruin and Luyben, 1980
Chirife, 1983
Devahastin et al, 1998
Gekas, 1992
Giner and Calvelo, 1987
Gineretal, 1996
Gong etal, 1997

Igathinathane and Chattopadhyay, 1997
Jar os et al, 1992

Jayas et al, 1991
Lomauro et al, 1985
Sapru and Labuza, 1996
Suarezetal, 1982
Sun and Woods, 1994
Zahedetal, 1995
Wild rice
Gekas, 1992
Data
56
6
3
15
3
6
8
10
5
78
3
6
6
14
6
8
21
9
1
4
58
3
2
3
3
4
4
4
4
4
7
9
1
1
1
5
3
3
3
171
Table 6.1 Continued
Material Reference
Data
32
Dairy
Cheese
Change! al, 1998
Desobry and Hardy, 1994
Luna and Chavez, 1992
Dry milk
Gekas, 1992
Lomauroetal, 1985
Milk
Straatsmaetal., 1999
Skim milk
Ferrari et al, 1989
Kerkhof, 1994
9
2
5
2
2
1
1
6
6
15
9
6
63
Fish
Catfish
Chirife, 1983
Cod
Balaban and Pigott, 1988

Chirife, 1983
Dogfish
Chirife, 1983
Fish meal
Alvarez and Shene, 1996
Blasco and Alvarez, 1999
Haddock
Chirife, 1983
Halibut
Chirife, 1983
Herring
Chirife, 1983
Mackerel
Chirife, 1983
1
1
6
4
2
4
1
3
15
8
7
2
2
2
2
7
7
1
1
Chapter 6
172
Table 6.1 Continued

Material Reference
Data
12
Shark
Park, 1998
Squid
Teixeira and Tobinaga, 1995
Teixeira and Tobinaga, 1998

Swordfish
Chirife, 1983
Whiting
Chirife, 1983
12
6
1
5
4
4
3
3
268
Fruits
64
Apple
Chirife, 1983
Fuscoetai, 1991
Gekas, 1992
Lazarides et al., 1997
Lomauroetal, 1985
Nieto et al, 1998

Simaletal, 1997
Simaletal, 1998a, b
Apricot
Abdelhaq and Labuza, 1987
Vagenas and Marinos-Kouris, 1991

Avocado
Chirife, 1983
Gekas, 1992
Banana
Garciaetal, 1988
Gekas, 1992
Johnson et al, 1998
Mauro and Menegalli, 1995
Rastogietal, 1997
Son/cat el al., 1996

Waliszewskietal, 1997
Blueberries
Nsonzi and Ramas\vamy, 1998

Ramaswamy and Nsonzi, 1998
Coconut
Gekas, 1992
3
6
2
14
13
1
6
11
8
10
2
8
11
6
5
55
5
6
3
9
12
11
9
29
11
18
6
6
Table 6.1 Continued

Material Reference
Grapes
Alvarez and Legues, 1986
Gekas, 1992
Mahmutogluetal, 1996
Simaletal, 1996
Vagenasetal, 1990
Mulberry
Mas/can andGogus, 1998

Peach
Gekas, 1992
Pineapple
Azuaraetal, 1992
Beristainetal, 1990
Rastogi and Niranjan, 1998

Raisins
Gekas, 1992
Karathanos et al, 1995
Lomauro et al, 1985
Sapru and Labuza, 1996
Legumes
173
Data
52
18
4
16
8
6
9
9
1
1
20
6
9
5
11
1
8
1
1
29
Broad bean
Ptaszniketal, 1990
Fababean
Hsu, 1983a, b
Lentil
Tang and Sokhansanj, 1993
Navy beans
Radajewski et al, 1992
Meat
7
7
2
2
12
12
8
8
53
Beef
Gekas, 1992
Huang and Mittal, 1995
4
2
2
174
Chapters
Table 6.1 Continued

Material Reference
Beef carcass
Data
3
Mallikarjunan and Mittal, 1994
Broiled
McLendon and Gillespie, 1978

Bull
Gekas, 1992
Chicken
Ngadi et al, 1997
Ground beef
Gekas, 1992
Hallstrom, 1990
Lomauroetai, 1985
Heifer
3
3
3
3
3
6
6
19
1
17
1
7
Gekas, 1992
Pepperoni

Chirife, 1983
Sausage
Dincer and Yildiz, 1996
Turkey
Chirife, 1983
Gekas, 1992
Model foods
7
5
3
2
1
1
2
1
1
202
Albumin-flour-bran
Strumitto et al, 1996

Amioca
Karathanos et al., 1990

Kostaropoulos and Saravacos, 1997
Marousisetal, 1989
Seowetal., 1999
Vagenas and Karathanos, 1993
Cellulose-oil-water
Chirife, 1983
Corn starch
Gekas, 1992
Flour
Gekas, 1992
Lomauroetai., 1985
27
27
59
16
4
20
10
9
1
1
2
2
3
1
2
175
Table 6.1 Continued_________________________________

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

Material Reference
Coffee
Data
3
Gekas, 1992
Egg
Kincal, 1987
Sunflower seeds
Rovedo et al, 1993
Toria
Raoetal, 1992
Vegetables
3
6
6
4
4
4
4
470
Beet
Chirife, 1983
Broccoli
Sanjuanetal, 1999
Simaletal, 1998a, b
Carrot
Cordova-Quirozet al, 1996

Gekas, 1992
Kiranoudis et al, 1992
Kiranoudis et al., 1993
Kompany et al., 1993

Mabrouk and Belghith, 1995
Markov/ski, 1997
Muletetal., 1987
Mulet et al, 1989
Mulet, 1994
Rastogi and Raghavarao, 1997
Stapley et al, 1995
Cassava
Chavez-Mendez et al, 1998
Fuscoetal, 1991
Garlic
Madambaetal, 1996
Pezzutti and Crapiste, 1997
Pinagaetal, 1984
Vazquezetal, 1999
Okra
Gogus and Maskan, 1999
1
1
22
10
12
106
1
4
9
15
10
8
12
7
12
6
12
10
10
2
8
22
5
6
5
6
6
6
177
Table 6.1 Continued

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

Material Reference
Soya meal
Alvarez and Blasco, 1999
Alvarez and Shene, 1996
Soybean
Barrozo et al, 1998
Deshpande et al., 1994

Gekas, 1992
Hsu, 1983a, b
Misra and Young, 1980
Oliveira and Haghighi, 1998
Suarezetal, 1982
Sugar beet
Data
18
12
6
19
3
1
1
8
4
1
1
7

Chirife, 1983
Fuscoetal, 1991
Tapioca
Chirife, 1983
Tomato
Dincer and Dost, 1995
Hawladeretal., 1991
Karatas and Esin, 1994
Turnip
Lomauro et al., 1985
Moreiraetal, 1993
Yam
Hawladeretal, 1999
2
3
2
4
1
3
16
3
8
5
10
1
9
2
2
179
Table 6.2 Moisture Diffusivity of Foods Versus Moisture and Temperature:
Average Values of Available Data

Material
Diffusivity
(m2/s)
Moisture
(kg/kg db)
Temperature
(C)
33
Baked Products
Biscuit
fondant coated
Bread
Cookie
oatmeal
Crackers
Dough
-
4
5.26E-09
0.12
85
5.00E-08
0.67
80
3.99E-12
0.18
25
6.08E-10
0.08
63
4.89E-10
0.48
122
4
1
1
2
2
18
18
8
8
492
Cereal Products
Barley
kernel
Brown rice
bran
endosperm
kernel
testa
Corn
dent
endosperm
flint
germ
grains
hard endosperm
kernel
pericarp
semident
shelled
soft endosperm
without pericarp
No. of
Data
9
1.85E-10
0.23
49
2.64E-10
2.59E-11
6.68E-11
4.36E-11
4.46E-11
0.19
0.22
0.24
0.24
0.24
40
45
40
40
40
3.27E-07
3.40E-10
1.08E-10
3.20E-11
1.31E-10
6.04E-10
1.72E-11
4.49E-11
1.09E-11
4.54E-11
1.01E-10
2.96E-11
4.06E-13
0.34
0.28
0.20
0.50
0.14
0.28
0.09
0.35
0.19
0.50
0.19
0.06
0.21
41
60
40
55
35
48
33
49
38
55
71
33
33
9
36
18
9
3
3
3
168
31
15
3
3
11
28
4
25
13
3
20
4
8
Chapter 6
180
Table 6.2 Continued

Material
Malt
Milled rice
Paddy rice
grains
Diffusivity
(m2/s)
Moisture
(kg/kg db)
Temperature
(C)
8.73E-08
0.45
50
No. of
Data
4
4
2
1.31E-10
0.32
60
1.53E-11
0.11
50
Parboiled brown rice
2
3
3
6
6
6
6
12
6
bran
3.52E-11
0.33
75
Parboiled paddy rice

husk
Parboiled rice
1.01E-IO
0.30
75
endosperm
long grain
short grain
3.21E-10
6.05E-11
1.37E-10
0.52
0.50
0.50
75
60
60
1.94E-11
4.76E-11
1.21E-10
0.16
0.13
0.12
63
81
68
21
18
12
56
4.49E-1 1
4.13E-09
9.94E-11
1.05E-10
1.20E-11
1.21E-10
4.43E-11
0.26
37
130
39
61
45
40
40
13
3.71E-09
8.68E-12
1.73E-10
1.30E-11
1.06E-11
2.56E-11
1.62E-08
0.19
0.15
0.15
0.15
0.23
0.15
0.28
Pasta
dense
porous
Rice
cooking
endosperm
grains
hull
kernel
testa
Rough rice
bran
endosperm
grains
hull
husk
kernel
3
3
51
0.23
0.26
0.23
49
43
47
41
45
45
60
2
21
3
2
12
3
78
35
8
6
1
9
7
12
181
Table 6.2 Continued

Material
Wheat
bran
endosperm
flakes
grains
hard
kernel
shredded
soft
Wild rice
broken
unprocessed
whole
Dairy
Cheese
Dry milk
nonfat
Milk
powder
Skim milk
-
Diffusivity
(m2/s)
1.45E-10
1.73E-10
1.91E-10
8.33E-14
3.69E-11
2.02E-09
6.54E-11
5.53E-12
1.51E-10
Moisture
(kg/kg db)
0.23
0.35
0.50
0.50
0.15
0.17
0.16
0.11
0.15
Temperature
No. of
(C)
Data
49
30
30
25
66
20
63
25
50
25
20
20
7.00E-13
4.00E-13
2.00E-13
32
9
2.02E-08
0.58
2.12E-11
0.12
25
6.58E-10
0.30
40
1.36E-10
0.56
46
9
2
2
6
6
15
15
30
63
1
1
Fish
Catfish
Cod
muscle
Dogfish
Fish meal
-
Haddock
muscle
58
26
2
2
1
10
2
11
1
3
3
1
1
1
8.00E-1 1
2.78E-10
3.40E-10
3.00
30
1.48E-10
7.97E-10
6.00E-11
3.30E-10
42
30
0.40
118
30
30
6
5
1
4
4
15
15
2
1
1
Chapter 6
182
Table 6.2 Continued

Material
Halibut
muscle
Herring
Mackerel
Shark
muscle
Squid
mantle
Swordflsh
salted
Whiting
muscle
Diffusivity
Moisture
Temperature
No. of
(m2/s)
(kg/kg db)
(C)
Data
5.80E-11
2.50E-10
30
30
6.53E-11
30
3.50E-11
30
1.80E-10
1.31
30
8.91E-11
1.50
34
3.45E-10
2.95E-10
48
48
4.80E-11
1.76E-10
30
28
Fruits
2
1
1
7
7
1
1
12
12
6
6
4
2
2
3
1
2
268
Apple
-
6.64E-10
2.80
47
Apricot
-
1.39E-07
2.88
53
64
10
10
50
11
11
Avocado
Banana
plantain
ripe
Blueberries
Coconut
Grapes
red
seedless
Mulberry
-
64
6.35E-10
1.4 IE-09
6.51E-10
1.43E-09
1.63
0.90
3.00
53
55
60
2.12E-10
1.75
45
9.77E-10
0.60
83
1.37E-10
1.79E-10
2.03E-10
1.49
53
60
60
1.18E-09
1.50
70
55
49
3
3
29
29
6
6
52
18
2
32
9
9
183
Table 6.2 Continued

Material
Diffusivity
(mVs)
Peach
Pineapple
Raisins
-
Moisture
(kg/kg db)
Temperature
(C)
30
8.00E-12
1.47E-09
4.50
40
1.67E-10
0.37
37
Legumes
6.53E-07
0.26
30
Fababean
-
1.78E-07
0.75
30
Lentil
cotyledons
hilum
seedcoat
2.25E-11
7.22E-09
1.57E-12
0.13
0.15
0.18
40
40
40
Navy beans
4.56E-08
0.28
50
Meat
Beef
raw
Beef carcass
bone
fat
muscle
Broiled
waste
Bull
-
Ground beef
heat treated
raw
Data
1
1
20
20
11
11
29
Broad bean
seeds
meatball
No. of
1.40
30
140
30
9.81E-06
0.30
21
7.40E-1 1
0.76
27
3.03E-11
1.48E-10
8.61E-11
0.16
0.80
1.13
25
51
43
5.56E-10
3.20E-10
l.OOE-11
5.48E-12
3.07E-11
5.83E-10
7
7
2
2
12
3
3
6
8
8
53
4
1
2
1
3
1
1
1
3
3
3
3
19
2
8
9
184
Chapter 6
Table 6.2 Continued

Material
Heifer
heat treated
raw
Pepperoni
sausage
Sausage
Turkey
-
Diffusivity
Moisture
(m2/s)
(kg/kg db)
(C)
Data
1.69E-10
8.33E-11
1.00
1.00
51
43
5.20E-11
5.33E-11
0.19
12
12
1.31E-07
0.32
180
8.00E-15
0.04
22
4
3
5
2
3
1
1
2
2
Temperature
Model foods
Albumin-flour-bran
mixture!
mixture 2
mixtures
Amioca
gel
hydrated
Cellulose-oil-water
Corn starch
Flour
Glucoose-starch
Gluten-starch
gelatinized
ungelatinized
Hylon-7
gel
hydrated
Polyacrylamide gel
Potato starch
.
No. of
202
1.45E-09
1.0 IE-09
7.70E-10
0.43
0.49
0.49
92
92
92
2.26E-09
8.20E-10
1.90E-09
0.36
0.33
0.33
74
60
60
3.10E-09
68
2.25E-10
30
2.26E-1 1
0.12
25
2.27E-10
0.60
39
3.33E-11
2.67E-11
0.14
0.14
74
74
2.09E-09
2.06E-09
2.27E-09
0.30
0.44
0.33
63
60
60
1.52E-10
0.90
40
6.91E-12
25.28
25
27
9
9
9
59
49
5
5
1
1
2
2
3
3
7
7
6
3
3
59
48
6
5
6
6
4
4
185
Table 6.2 Continued

Material
Rice starch
full heated
Diffusivity
Moisture
(m2/s)
(kg/kg db)
Temperature
nonheated
9.75E-10
2.1 IE-09
1.63
1.50
50
57
Starch
-
4.23E-10
0.60
42
2.32E-12
0.05
281
shelled
unshelled
4.03E-09
6.16E-09
0.15
0.15
55
55
hull
kernel
4.69E-11
7.28E-11
0.60
0.60
35
35
Peanuts
-
4.00E-11
0.10
50
Peanut pods
embryo
kernel
3.58E-09
5.09E-09
0.02
0.02
80
80
Chocolate
dark
Coffee
1.03E-13
2.00
20
extract
1.08E-10
50
1.44E-11
1.61E-11
1.00
0.80
36
36
4.40E-10
1.20E-10
0.07
0.07
45
45
9.80E-11
0.10
65
Sunflower seeds
hull
kernel
Toria
seeds
2
2
12
6
6
64
32
32
1
1
45
Other
Canola
incubated
23
13
10
5
5
79
Nuts
Almond
Hazelnuts
Egg
fresh
No. of
(C)Data
24
12
12
4
4
3
3
6
3
3
4
2
2
4
4
186
Chapter 6
Table 6.2 Continued

Material
Diffusivity
(mVs)
Moisture
(kg/kg db)
No. of
Temperature
Data
(C)
Vegetables
Beet
-
1.50E-09
Broccoli
stems
1.29E-09
8.80
62
Carrot
Cassava
2.05E-09
4.60
53
roots
6.30E-10
0.63
67
Garlic
-
1.74E-10
0.80
50
2.24E-09
2,00
70
1.0 IE-09
1.65
64
Okra
Onion
Paprika
Pea
-
Pepper
redpo-wder
Pigeon pea
kernel
Potato
restructured product
tissue
Soya meal
Soybean
grains
Sugar beet
roots
Tapioca
roots
65
48
2.17E-10
2.74E-10
0.97
48
6.22E-09
2.09E-10
3.70
0.06
70
49
5.07E-11
0.20
70
1.32E-09
2.02E-09
1.67E-09
3.17
1.85
58
105
65
1.16E-08
0.10
162
9.0 IE-08
1.12E-09
0.56
0.60
47
48
6.59E-10
2.60
57
6.00E-10
1.05
78
467
1
1
22
22
106
106
10
10
22
22
6
6
31
31
3
3
9
9
14
9
5
5
5
165
148
16
1
18
18
16
13
2
7
7
4
4

Table 6.2 Continued
Material
Tomato
concentrate droplets
Turnip
Yam
_
Diffusivity
(m2/s)
187
Moisture
(kg/kg db)
Temperature
(C)
7.57E-10
1.87E-09
10.00
0.50
64
77
1.64E-09
6.33
57
1.27E-09
0.10
45
No. of
Data
16
11
5
10
10
2
2
188
Chapter 6
Table 6.3 Moisture Diffusivity of Foods Versus Moisture and Temperature:

Variation Range of Available Data
Temperature
Material
min
Diffusivity
(m2/s)
max
Baked Products
3.97E-I2
5.00E-08
0.03
0.67
15
203
4.06E-09
4.06E-09
5.00E-08
5.00E-08
3.97E-12
3.97E-12
1.40E-11
1.40E-11
1.30E-10
1.30E-10
6.29E-09
6.29E-09
5.00E-08
5.00E-08
4.00E-12
4.00E-12
1.81E-09
1.81E-09
l.OOE-09
l.OOE-09
0.03
0.03
0.39
77
77
80
80
25
25
40
40
15
15
91
91
80
80
25
25
90
90
203
203
8.33E-14
4.04E-06
6.52E-10
6.52E-10
3.94E-09
3.94E-09
4.07E-11
9.64E-11
7.25E-11
9.31E-11
4.04E-06
4.04E-06
1.48E-09
2.01E-10
4.50E-11
8.42E-10
6.1 IE-09
2.06E-1 1
1.14E-10
7.37E-11
6.80E-11
2.23E-10
3.72E-11
5.50E-13
Biscuit
fondant coated
Bread
Cookie
oatmeal
Crackers
Dough
-
Cereal Products
Barley
kernel
Brown Rice
bran
endosperm
kernel
testa
Corn
dent
endosperm
flint
germ
grains
hard endosperm
kernel
pericarp
semident
shelled
soft endosperm
without pericarp
1.31E-11
1.31E-11
1.81E-12
1.81E-12
1.48E-11
4.36E-11
2.00E-11
1.25E-11
9.72E-14
2.33E-11
2.39E-11
3.61E-11
1.90E-11
5.28E-12
5.24E-11
1.29E-11
1.11E-11
9.72E-14
2.50E-11
2.16E-11
2.12E-11
2.56E-13
Moisture
(db)
(C)
min
max
min
max
0.67
0.67
0.18
0.18
0.03
0.03
0.20
0.20
0.39
0.67
0.67
0.18
0.18
0.14
0.14
0.60
0.60
0.02
0.56
150
0.10
0.27
0.27
0.25
0.25
0.24
0.24
0.24
0.24
0.56
0.50
0.50
0.30
0.50
0.30
0.40
0.10
0.56
0.30
0.50
0.19
0.07
0.23
30
30
12
12
35
30
30
30
10
10
30
40
45
25
10
25
25
25
45
38
25
25
70
70
120
120
55
50
50
50
120
120
90
40
65
40
120
40
90
60
65
104
40
40
0.10
0.16
0.16
0.21
0.24
0.24
0.24
0.06
0.10
0.10
0.10
0.50
0.10
0.10
0.07
0.12
0.10
0.50
0.19
0.06
0.19
189
Table 6.3 Continued

Diffusivity
Material
min
Malt
Milled Rice
Paddy Rice
grains
Parboiled Brown Rice
bran
Parboiled Paddy Rice
husk
Parboiled Rice
endosperm
long grain
short grain
Pasta
dense
porous
Rice
cooking
endosperm
grains
hull
kernel
testa
Rough Rice
bran
endosperm
grains
hull
husk
kernel
1.11E-08
1.1 IE-08
8.33E-11
8.33E-11
2.28E-12
2.28E-12
1.15E-11
1.15E-11
3.43E-11
3.43E-11
2.38E-11
2.12E-10
2.62E-11
2.38E-11
1.55E-12
1.55E-12
9.40E-12
2.43E-11
3.30E-12
3.30E-12
1.92E-09
4.40E-11
6.67E-11
4.00E-12
5.19E-11
1.20E-11
7.56E-13
7.56E-13
4.03E-12
9.86E-11
1.30E-11
4.08E-12
1.11E-11
4.75E-12
(m2/s)
max
2.14E-07
2.14E-07
1.78E-10
1.78E-10
3.44E-11
3.44E-11
6.26E-11
6.26E-11
1.80E-10
1.80E-10
4.84E-10
4.84E-10
1.02E-10
2.98E-10
3.42E-10
4.84E-1 1
1.06E-10
3.42E-10
6.33E-09
1.17E-10
6.33E-09
1.98E-10
1.48E-10
2.00E-11
2.28E-10
9.30E-11
1.68E-07
2.64E-08
2.21E-11
2.20E-10
1.30E-11
3.59E-11
4.41E-11
1.68E-07
Moisture
(db)
min
max
0.45
0.45
0.13
0.13
0.11
0.11
0.30
0.30
0.28
0.28
0.50
0.51
0.50
0.50
0.02
0.02
0.05
0.04
0.10
0.10
0.45
0.45
0.50
0.50
0.11
0.11
0.36
0.36
0.33
0.33
0.53
0.53
0.50
0.50
0.32
0.32
0.23
0.21
0.35
0.35
0.20
0.22
0.25
0.30
0.23
0.24
0.05
0.10
0.15
0.15
0.15
0.22
0.15
0.05
0.50
0.33
0.15
0.15
0.15
0.24
0.15
0.50
Temperature
(C)
min
max
20
20
60
60
40
40
50
50
50
50
40
50
40
40
40
40
40
40
8
20
110
8
61
35
30
30
12
12
25
30
41
35
30
38
80
80
60
60
60
60
100
100
100
100
100
100
80
80
122
85
122
105
150
55
150
55
61
55
50
50
120
120
60
60
41
55
60
82
Chapter 6
190
Table 6.3 Continued

Diffusivity
Moisture
(m2/s)
Material
Wheat
bran
endosperm
flakes
grains
hard
kernel
shredded
soft
Wild Rice
broken
unprocessed
whole
Dairy
Cheese
Dry Milk
nonfat
Milk
powder
Skim Milk
Fish
Catfish
Cod
muscle
(db)
Temperature
(C)
max
min
min
max
min
max
8.33E-14
6.07E-12
1.68E-10
1.91E-10
8.33E-14
1.50E-11
3.30E-IO
1.15E-11
5.53E-12
2.98E-11
2.00E-13
7.00E-13
4.00E-13
2.00E-13
3.70E-09
5.30E-10
1.78E-10
1.92E-10
8.33E-14
7.94E-1 1
3.70E-09
1.43E-10
5.53E-12
3.19E-10
7.00E-13
7.00E-13
4.00E-13
2.00E-13
0.10
0.17
0.35
0.50
0.50
0.10
0.13
0.10
0.11
0.15
0.50
0.30
0.35
0.50
0.50
0.20
0.20
0.30
0.11
0.15
5
5
30
30
25
40
20
40
25
30
20
25
20
20
86
85
30
30
25
86
20
80
25
70
25
25
20
20
2.10E-11
5.60E-11
9.00E-08
0.12
0.80
9.00E-08
0.80
9.00E-08
2.13E-11
2.13E-11
1.83E-09
1.83E-09
2.56E-10
2.56E-10
0.80
0.12
0.12
0.40
0.40
0.80
0.80
0
0
25
25
10
10
30
30
70
13
5.60E-11
2.10E-11
2.10E-11
3.50E-11
3.50E-11
2.51E-11
2.51E-11
0.35
0.35
0.12
0.12
0.20
0.20
0.20
0.20
1.30E-11
1.89E-09
0.33
3.00
20
8.00E-11
8.00E-11
8.10E-11
8.10E-11
3.40E-10
8.00E-11
8.00E-11
5.13E-10
5.13E-10
3.40E-10
3.00
3.00
3.00
3.00
13
25
25
70
70
70
70
30
170
30
30
30
30
30
30
60
60
30
191
Table 6.3 Continued

Material
Dogfish
Fish Meal
-
Haddock
muscle
Halibut
muscle
Herring
Mackerel
-
Shark
muscle
Squid
mantle
Swordfish
salted
Whiting
muscle
Fruits
Apple
Apricot
Avocado
-
Banana
plantain
ripe
min
Diffusivity
(m2/s)
max
8.30E-11
8.30E-11
1.95E-11
1.95E-11
6.00E-11
6.00E-1 1
3.30E-10
5.80E-11
5.80E-11
2.50E-10
1.30E-11
1.30E-11
3.50E-11
3.50E-11
8.70E-11
8.70E-11
8.30E-11
8.30E-11
2.60E-10
3.00E-10
2.60E-10
4.80E-11
4.80E-11
8.20E-11
2.20E-10
2.20E-10
1.89E-09
1.89E-09
3.30E-10
6.00E-11
3.30E-10
2.50E-10
5.80E-11
2.50E-10
1.90E-10
1.90E-10
3.50E-11
3.50E-11
2.85E-10
2.85E-10
1.09E-10
1.09E-10
3.90E-10
3.90E-10
3.30E-10
2.70E-10
4.80E-11
2.70E-10
4.00E-13
Moisture
(db)
min
max
Temperature
(C)
max
min
30
30
65
65
30
30
30
30
30
30
30
30
30
30
20
20
34
34
40
40
40
25
30
25
30
30
0.33
0.33
0.55
0.55
1.18
1.18
0.50
0.50
1.42
1.42
2.50
2.50
6.10E-07
0.00
8.70
15
110
4.00E-12
6.40E-09
8.70
4.00E-12
l.OOE-11
l.OOE-11
1.10E-10
1.10E-10
1.60E-10
1.60E-10
3.16E-10
5.50E-10
6.40E-09
6.10E-07
6.10E-07
1.80E-09
1.80E-09
3.40E-09
3.40E-09
1.15E-09
2.66E-09
0.00
0.00
0.50
0.50
0.25
0.25
0.90
3.00
3.00
3.00
0.90
3.00
20
20
40
40
31
31
25
25
40
60
90
90
80
80
60
60
110
110
70
60
8.70
3.48
3.48
170
170
30
30
30
30
30
30
30
30
30
30
40
40
34
34
55
55
55
30
30
30
Chapter 6
192
Table 6.3 Continued

Material
Blueberries
Coconut
-
Grapes
red
seedless
Mulberry
Peach
Pineapple
Raisins
~
Legumes
Broad Bean
seeds
Fababean
Lentil
cotyledons
hilutn
seedcoat
Navy Beans
min
Diffusivity
(mVs)
max
3.80E-11
5.10E-10
3.80E-11
4.60E-10
4.60E-10
4.83E-11
4.85E-11
5.80E-11
4.83E-11
2.32E-10
2.32E-10
8.00E-12
8.00E-12
5.38E-10
5.38E-10
4.00E-13
4.00E-13
5.10E-10
1.28E-09
1.28E-09
9.28E-10
4.20E-10
3.00E-10
9.28E-10
2.76E-09
2.76E-09
8.00E-12
8.00E-12
2.64E-09
2.64E-09
4.80E-10
4.80E-10
2.06E-14
3.66E-07
3.66E-07
1.28E-07
1.28E-07
2.06E-14
1.43E-11
4.58E-09
2.06E-14
3.33E-08
3.33E-08
5.48E-12
l.OOE-11
1.17E-05
5.56E-10
5.56E-10
2.50E-10
l.OOE-11
5.56E-10
3.90E-10
l.OOE-11
Moisture
Temperature
(db)
(C)
min
max
min
max
0.50
0.50
0.60
0.60
0.39
4.00
37
60
4.00
0.60
0.60
2.35
0.39
0.50
0.50
2.35
3.00
3.00
3.80
3.80
0.15
0.15
5.00
5.00
0.60
0.60
37
45
45
30
50
50
30
60
60
30
30
30
30
15
15
60
110
110
75
70
70
75
80
80
30
30
50
50
1.07E-06
0.12
1.00
20
65
1.07E-06
1.07E-06
2.27E-07
2.27E-07
1.02E-08
3.17E-11
1.02E-08
4.03E-12
5.56E-08
5.56E-08
0.17
0.37
20
40
0.17
0.50
0.50
0.12
0.13
0.15
0.12
0.15
0.15
0.37
1.00
1.00
0.24
0.13
0.15
0.24
0.40
0.40
20
30
30
30
30
30
35
35
40
30
30
50
50
50
50
65
65
0.04
2.45
10
180
1.40
1.40
140
1.40
1.40
30
30
140
30
30
70
70
"
Meat
Beef
meatball
raw
30
140
30
193
Table 6.3 Continued

Material
Beef Carcass
bone
fat
muscle
Broiled
waste
Bull
Ground Beef
heat treated
raw
Heifer
heat treated
raw
Pepperoni
sausage
Sausage
Turkey
Model Foods
Albumin-Flour-Bran
mixture!
mixlure2
mixtures
Amioca
gel
hydrated
Cellulose-oil-water
Corn Starch
.
min
Diffusivity
(mVs)
max
5.48E-12
5.48E-12
3.07E-11
5.83E-10
8.06E-06
8.06E-06
6.30E-11
6.30E-11
3.00E-11
3.00E-11
7.50E-11
4.00E-11
5.40E-11
1.30E-10
5.40E-11
4.70E-11
4.70E-11
4.70E-1 1
1.3 IE-07
1.3 IE-07
8.00E-15
8.00E-15
5.83E-10
5.48E-12
3.07E-11
5.83E-10
1.17E-05
1.17E-05
8.20E-11
8.20E-11
2.30E-10
3.07E-11
2.30E-10
1.70E-10
2.14E-10
2.14E-10
1.20E-10
5.70E-11
5.70E-11
5.70E-11
1.3 IE-07
1.3 IE-07
8.00E-15
8.00E-15
l.OOE-14
2.25E-08
5.80E-10
1.15E-09
8.00E-10
5.80E-10
6.13E-11
6.13E-11
5.50E-10
1.40E-09
3.10E-09
3.10E-09
1.89E-10
1.89E-10
1.85E-09
1.85E-09
1.26E-09
1.05E-09
7.30E-09
7.30E-09
1.20E-09
2.40E-09
3.10E-09
3.10E-09
2.60E-10
2.60E-10
Moisture
(db)
Temperature
min
max
min
0.30
0.30
0.76
0.76
0.16
0.16
0.60
0.60
1.00
1.00
1.00
0.19
0.30
0.30
0.76
0.76
1.60
0.16
1.00
1.60
1.00
1.00
1.00
0.19
10
0.19
0.32
0.32
0.04
0.04
0.19
0.32
0.32
0.04
0.04
10
20
20
25
25
30
30
30
30
30
12
12
12
180
180
22
22
0.02
0.08
80.00
20
0.83
0.08
0.13
0.10
0.02
0.02
0.07
0.05
0.82
0.83
0.80
0.93
0.93
0.75
0.75
75
75
75
75
20
20
60
60
68
68
30
30
(C)
max
32
32
30
30
75
25
75
60
75
75
60
12
12
12
180
180
22
22
105
105
105
105
105
100
100
60
60
68
68
30
30
194
Chapter 6
Table 6.3 Continued

Material
Flour
Glucoose-Starch
Gluten-Starch
gelatinized
ungelatinized
Hylon-7
gel
hydrated
Polyacrylamide Gel
Potato Starch
-
Rice Starch
full heated
non-heated
Starch
~
Nuts
Almond
Hazelnuts
shelled
unshelled
Peanut Pods
hull
kernel
Peanuts
.
min
Diffusivity
(m2/s)
max
3.86E-12
3.86E-12
6.60E-11
6.60E-11
1.90E-11
2.20E-1 1
1.90E-11
2.48E-10
2.48E-10
8.00E-10
1.70E-09
8.77E-12
8.77E-12
l.OOE-14
l.OOE-14
8.48E-11
8.48E-11
3.92E-10
1.50E-10
1.50E-10
Moisture
(db)
Temperature
min
max
min
(C)
max
3.20E-11
3.20E-11
5.90E-10
5.90E-10
4.00E-11
4.00E-1 1
3.20E-11
2.25E-08
2.25E-08
3.70E-09
2.70E-09
3.00E-10
3.00E-10
2.40E-11
2.40E-1 1
4.62E-09
2.84E-09
4.62E-09
6.90E-10
6.90E-10
0.07
0.07
0.60
0.60
0.09
0.09
0.09
0.03
0.03
0.05
0.05
0.10
0.10
0.80
0.80
0.67
0.67
0.67
0.60
0.60
0.17
0.17
0.60
0.60
0.20
0.20
0.20
1.00
0.90
1.00
0.75
2.00
2.00
80.00
80.00
4.00
4.00
2.33
0.60
0.60
25
25
30
30
74
74
74
20
20
60
60
40
40
25
25
25
25
25
30
30
25
25
50
50
74
74
74
100
100
60
60
40
40
25
25
80
80
80
50
50
4.36E-13
1.24E-08
27
281
2.39E-12
2.39E-12
1.24E-08
8.39E-09
1.24E-08
2.36E-10
1.17E-10
2.36E-10
4.00E-11
4.00E-11
0.05
0.05
0.60
2.24E-12
2.24E-12
1.48E-09
1.48E-09
3.65E-09
4.36E-13
4.36E-13
8.52E-12
4.00E-11
4.00E-11
281
281
30
30
30
27
27
27
50
50
281
281
80
80
80
43
43
43
50
50
0.05
0.15
0.15
0.15
0.60
0.60
0.60
0.10
0.10
0.05
0.05
0.15
0.15
0.15
0.60
0.60
0.60
0.10
0.10
195
Table 6.3 Continued

Diffusivity
Moisture
(mVs)
Material
(db)
min
max
min
max
0.00
0.00
2.00
0.00
0.00
2.00
2.00
0.05
0.05
2.00
2.00
8.20E-14
6.60E-09
Canola
2.10E-09
6.60E-09
embryo
kernel
2.10E-09
3.70E-09
8.20E-14
8.20E-14
5.00E-11
5.00E-11
1.03E-11
1.03E-11
1.39E-11
7.00E-11
1.70E-10
7.00E-1 1
2.85E-11
2.85E-11
5.20E-09
6.60E-09
1.33E-13
1.33E-13
1.65E-10
1.65E-10
2.03E-11
2.03E-11
1.90E-11
7.10E-10
7.10E-10
1.70E-10
2.08E-10
2.08E-10
0.80
1.00
0.80
0.07
0.07
0.07
0.08
0.08
2.20E-12
3.05E-07
0.03
1.50E-09
1.50E-09
1.50E-09
1.78E-10
1.78E-10
2.20E-12
2.20E-12
1.07E-10
1.07E-10
1.14E-11
1.14E-11
4.28E-10
4.28E-10
1.38E-11
1.38E-11
5.80E-11
5.80E-11
1.10E-10
1.10E-10
1.50E-09
3.41E-09
3.41E-09
7.46E-09
7.46E-09
2.15E-09
2.15E-09
4.18E-10
4.18E-10
6.80E-09
6.80E-09
6.60E-09
6.60E-09
4.08E-10
4.08E-10
4.40E-10
4.40E-10
Other
Chocolate
dark
Coffee
extract
Egg
fresh
incubated
Sunflower Seeds
hull
kernel
Toria
seeds
Vegetables
Beet
Broccoli
stems
Carrot
-
Cassava
roots
Garlic
Okra
Onion
-
Paprika
Pea
.
0.05
1.00
1.00
0.80
0.07
0.07
0.07
0.12
0.12
15.00
13.93
2.00
2.00
0.10
0.10
0.60
0.60
0.10
0.10
2.00
2.00
0.10
0.10
13.93
15.00
15.00
0.64
0.64
1.50
1.50
2.00
2.00
10.00
10.00
0.50
0.50
1.50
1.50
Temperature
(C)
max
min
20
80
80
80
80
80
20
20
30
30
33
33
33
40
40
40
50
50
80
80
20
20
70
40
40
40
50
50
50
80
80
20
300
65
65
65
25
25
20
20
55
55
22
22
60
60
40
40
25
25
30
30
65
90
90
100
100
90
90
90
90
80
80
80
80
70
70
65
65
70
Chapter 6
196
Table 6.3 Continued

Moisture
(db)
Diffusivity
Material
Pepper
redpowder
Pigeon Pea
kernel
Potato
restructured product
tissue
Soya Meal
Soybean
grains
Sugar Beet
roots
Tapioca
roots
Tomato
concentrate droplets
Turnip
Yam
.
min
5.86E-11
1.85E-09
5.86E-11
2.88E-11
2.88E-11
8.00E-12
8.00E-12
7.30E-10
1.67E-09
1.47E-10
1.47E-10
9.30E-11
9.30E-11
9.30E-11
1.96E-10
1.96E-10
3.50E-10
3.50E-10
1.52E-10
1.52E-10
1.69E-10
7.61E-12
7.61E-12
7.30E-10
7.30E-10
(m2/s)
max
1.16E-08
1.16E-08
4.08E-10
7.70E-11
7.70E-11
1.25E-08
1.25E-08
4.52E-09
1.67E-09
4.01E-08
4.01E-08
1.17E-05
3.05E-07
2.15E-09
1.30E-09
1.30E-09
9.00E-10
9.00E-10
6.46E-09
2.36E-09
6.46E-09
3.62E-09
3.62E-09
1.81E-09
1.81E-09
Temperature
CO
min
max
min
max
0.06
0.10
0.06
0.20
0.20
0.10
0.10
10.00
10.00
0.06
0.20
0.20
10.00
10.00
1.85
0.03
0.03
0.19
0.19
0.20
2.21
2.21
1.05
1.05
0.50
10.00
0.50
0.31
0.31
0.06
0.06
1.85
0.22
0.22
1.00
1.00
1.00
3.00
3.00
1.05
1.05
10.00
10.00
0.50
7.00
7.00
0.14
0.14
25
60
25
50
50
24
24
105
65
65
65
20
20
25
40
40
55
55
40
40
60
20
20
40
40
80
80
70
90
90
185
185
105
65
300
300
95
95
72
81
81
97
97
100
80
100
100
100
50
50
197
III. MOISTURE DIFFUSIVITY OF FOODS AS A FUNCTION OF

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 detail 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, regardless 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 uniform mixture of two different materials: (a) a dried material and (b) a wet material
with infinite moisture. Moisture diffusivity is, generally, different for each material. The diffusivity of the mixture could be estimated using a two-phase structural
model:
l +X
"
l +X
(6-1)
where D (m2/s) the effective moisture diffusivity, DXo (m2/s) the moisture diffusivity 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 material temperature.
Assume that the diffusivities of both phases depend on temperature by an
Arrhenius-type model:
= u exp -
R(T
(6-2)
198
Chapters
x,
, -r
(6-3)
where Tr= 60C 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 60C was chosen as a typical temperature of air-drying of
foods.
Thus, the moisture diffusivity for every material is characterized and described by four parameters with physical meaning:
D0 (m2/s)
Dj (m2/s)
E0 (kJ/mol)
Ei (kJ/mol)
diffusivity at moisture X = 0 and temperature T = Tr

diffusivity at moisture X = oo and temperature T - Tr
activation energy for diffusion in dry material at X = 0
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 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 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.
199
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 moisture 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 statistical 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 accuracy and general applicability.
The diffusivity parameters D0 and Z)/ of the proposed model, shown in Figure 6.6, vary in the range of 10~10 to 10~8 m2/s. It should be noted that the selfdiffusivity 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 materials. 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 content. Temperature has a positive effect, which depends strongly on the food material. 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 expected for porous foods, where vapor diffusion is important. In general, temperature has a stronger effect on diffusivity in the liquids and solids than in the gas
state (see Chapter 2).
Chapter 6
200
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
where
D (m2/s)
X (kg/kg db)
r(C)
Tr = 60C
R = 0.0083143 kJ/mol K
l +X
RT T
\+x
exp
RT
the moisture diffusivity,

the material moisture content,
the material temperature,
a reference temperature, and
the ideal gas constant.
Adjustable Model Parameters
D0 (m2/s)
D, (m2/s)
E0 (kJ/mol)
EI (kJ/mol)
diffusivity at moisture X = 0 and temperature T = Tr

diffusivity at moisture X = oo and temperature T = T.
activation energy for diffusion in dry material at X = 0
activation energy for diffusion in wet material at X = oo
201
Table 6.5 Parameter Estimates of the Proposed Mathematical Model

Material
No. of No. of
Papers Data
Di
(m2/s)
Do
Ei
Eo
(mVs) (kJ/mol) (kJ/mol)
sd
(m2/s)
Cereal products
Corn
dent
grains
kernel
pericarp
4
3
3
4
3
26
15
28
25
13
4.40E-09
1.19E-08
1.15E-09
5.87E-10
1.13E-09
O.OOE+00
O.OOE+00
6.66E-11
5.32E-10
O.OOE+00
0.0
49.4
10.2
0.0
10.0
10.4
73.1
57.8
33,8
5.0
1.48E-10
3.30E-10
3.17E-10
1.88E-11
2.34E-11
Pasta
-
21
1.39E-09
O.OOE+00
16.2
2.0
7.71E-12
12
9.75E-09
O.OOE+00
12.5
2.0
5.52E-11
35
2.27E-09
O.OOE+00
12.7
0.7
3.66E-11
22
1.94E-09
1.30E-09
0.0
46.3
9.53E-11
39
7.97E-10
1.16E-10
56.6
1.92E-10
34
2.03E-09
4.66E-10
9.9
4.6
1.77E-10
32
5.35E-09
O.OOE+00
34.0
10.4
1.45E-10
10
8.11E-10
1.05E-10
21.4
50.1
6.88E-11
49
1.52E-08
1.52E-08
0.0
33.3
1.02E-09
48
1.96E-08
1.96E-08
0.0
24.2
3.87E-09
90
2.47E-09
1.54E-09
13.9
11.3
1.69E-09
22
5.33E-10
1.68E-11
15.4
7.1
7.43E-11
31
1.45E-08
O.OOE+00
70.2
10.4
1.58E-09
16
106
1.57E-09
4.31E-10
44.7
76.9
4.02E-10
Rice
kernel
Rough rice
Wheat
-
Fruits
Apple
Banana
Grapes
seedless
Raisins
-
16.7
Model foods
Amioca
Hvlon-7
-
Vegetables
Carrot
Garlic
Onion
Potato
-
Chapter 6
202
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
8 1 11
o-
3 |
JJ
T S .a a a
= t = ! a
i a o o ,2
100
Moisture = infinite
13 Moisture = zero
E
i-:
^
>.
I
.
*
o
Figure 6.6 Parameter estimates of the proposed mathematical model.
I 1
o S.
l.E-06
l.E-07
Moisture (kg/kg db)
Figure 6.7 Predicted values of moisture diffusivity of model foods at 25C.
203
204
Chapter 6
.E-06
Model foods
:ratuie (C) = 60
.E-07
-f
l.E-08
Hylon-7
.|" l.E-09
Amioca
l.E-10
.E-ll
l.E-12
0.1
1
Moisture (kg/kg db)
Figure 6.8 Predicted values of moisture diffusivity of model foods at 60C.
10
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 25C.
205
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 60C.
207
l.E-06
1
Vegetables
Tempera ture i C) = 25
l.E-07
l.E-08
l.E-12
10
0.1
Moisture (kg/kg db)
Figure 6.11 Predicted values of moisture diffusivity of vegetables at 25C.
Chapter 6
208
l.E-06
l.E-07
l.E-12
0.1
1
Moisture (kg/kg db)
Figure 6.12 Predicted values of moisture diffusivity of vegetables at 60C.
10
209
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 25C.
Chapter 6
210
l.E-06
h-
Jtr
60
f
|Cere al products (corn)
r
Temperature (C) =
.E-07
l.E-12
0.1
Moisture (kg/kg db)
Figure 6.14 Predicted values of moisture diffusivity of corn at 60C.
211
Garlfc.E-06
real products
| C(
t~r
Temperature (C) = 25
i
.E-07 -
.E-08 -
.E-09 -
Rice kernel
Corn
^^ "
.E-10 -j
r^j i Vheat
"^^
j
Lx^' Rough rice
'
X ^|x.E-ll -^^^r F asta

^^^
Pact n
F.n a
0.1
10
Moisture (kg/kg db)
Figure 6.15 Predicted values of moisture diffusivity of cereal products at 25C.
Chapter 6
212
l.E-06
Cereal products
1^--MI
Temperature (C) = 60
.E-07
l.E-08
l.E-09
' Rice kernel
l.E-10 -I
wheat
Rough rice
Pasta
l.E-11
l.E-12
0.1
10
Moisture (kg/kg db)
Figure 6.16 Predicted values of moisture diffusivity of cereal products at 60C.
Fruits
213
Apple
Total Number of Papers

Total Experimental Points
8
64
Points Used in Regression Analysis

Standard Deviation (sd, rti'/s)
36
Relative Standard Deviation (rsd, %)

Parameter Estimates
Di (m2/s)
Do (mj/s)
Ei (kJ/mol)
Eo (kJ/mol)
(56%)
1.92E-10
457
7.97E-10
1.16E-10
16.7
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

Standard Deviation (sd, rrrVs)
3
32
20
1.45E-10
1 31
seedless
(63%)
Parameter Estimates
Di(m 2 /s)
Do (m2/s)
Ei (kJ/mol)
Eo(kJAnol)
5.35E-10
O.OOE+00
34.0
10.4
1 F-Ofi ;
Tem perat ure (C)
l.E-07 -
l.E-08 -
40
60
A 80
_L
h-
f l.E-09 -
1
-1
^>
1
i
l.E-10 1
^^
=^
~~~~
*
^ ! *
1
-_
=1IE I
J r^
~*
^^
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.
215
Fruits
Banana
49

Standard Deviation (sd, rrvVs)
Parameter Estimates
Di (m'Vs)
Do(m'Vs)
Ei (kJ/mol)
15
1.77E-10
15
(31%)
2.03E-09
4.66E-10
9.9
Eo (kJ/mol)
4.6
l.F-06
Tern perature (C)
'
60
-4-
l.E-07 -
A 80
(i
Sm.
MD
h=Hs_^M
^s.
BH
Si
-1f
I
"
0
hn
^-
Diffusivity (m2/s)
l.E-08 -
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.
Chapter 6
216
Vegetables
Potato

13
148
66
(45%)
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
A SO
l.E-07
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.
217
Vegetables
Carrot
12

106
98
1.69E-09
(92%)
Relative Standard Deviation (rsd, %)_____18699

Parameter Estimates
Di (m"/s)
2.47E-09
1.54E-09
Do(rrrVs)
Ei (kJ/mol)
Eo(kJ/mol)
13.9
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.
Chapter 6
218
Vegetables

Standard Deviation (sd, m'Vs)
Onion
4
31
22
1.58E-09
575
Parameter Estimates
Di (m"/s)
Do (mVs)
Ei (kJ/mol)
Eo (kJ/mol)
1.45E-09
O.OOE+00
70.2
10.4
(71%)
1.E-06
l.E0.1
1.0
10.0
Moisture (kg/kg db)
Figure 6.22 Moisture diffusivity of onion at various temperatures and moisture

contents.
219
Vegetables
Garlic

Parameter Estimates
Di (m"/s)
Do(nWs)
Ei(kJ/moI)
Eo(kJ/mol)
4
22
19
7.43E-1 1
385
(86%)
5.33E-10
1.68E-11
15.4
7.1
l.E-06 -
Tern perat ure(C) =

40
60
A 80
l.E-07 -
re
=P
l.E-08 W5
"E,
f l.E-09 -
la
5
rr*~m
3 i~~*
~
*?
* ^ -}
l.E-10 ,
if* *
1
*~\fff* ^*^

l.E-11 -
l.E-12 0.1
1
1
- - - - -
1.0
10.0
Moisture (kg/kg db)
Figure 6.23 Moisture diffusivity of garlic at various temperatures and moisture
contents.
Chapter 6
220
Cereal Products
Wheat

5
26
15
(58%)
9.53E-1 1
54
Parameter Estimates
Di(m"/s)
Do(mVs)
Ei (kJ/mol)
Eo (kJ/mol)
1.94E-10
1.30E-10
0.0
46.3
1 ,F,-06 i i
B40
60
A 80
l.E-07 -
tfi
l.E-08 1
1" l.E-09 V)
4,
*- k
A I\
l.E-10 -
^fc
f
J
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
221
Corn

Standard Deviation (sd, rrrVs)
dent
3
15
15
3.30E-10
343
(100%)
Parameter Estimates
Di(rrrVs)
Do (m"/s)
Ei (kJ/mol)
1.19E-09
O.OOE+00
49.4
Eo(kJ/mol)
73.1
l.E-06 peral ure CC)

40
60
A80
l.E-07 -
i
l.E-08 5"
=
+*
_>1
^^
f l.E-09 -- .^T *
M
**?- < k
^*
\*
a
L****T
l.E-10
^M
;\^^j^^
i
1
1
t11
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 moisture contents.
Chapter 6
222
Cereal Products
Corn

grains
3
28
26
3 . 1 7E- 1 0
1 53
(93%)
Parameter Estimates
Di(m<Vs)
Do (m'Vs)
Ei (kJ/mol)
Eo(kJ/mol)
1.15E-09
6.66E-11
10.2
57.8
l.F-06 ,
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
f l.E-09 1
r^
^^
li
Jj
1
l.E-10 -
"*
=>
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
223
Corn

Standard Deviation (sd, nWs)
Parameter Estimates
Di(m'Vs)
Do(m'Vs)
Ei (kJ/mol)
Eo (kJ/mol)
kernel
3
25
21
1.88E-1 1
32
(84%)
5.87E-11
5.32E-11
0.0
33.8
I P-flfi r-i
tE
CO =E ~ q
B40
60
A 80
l.E-07 -
l.E-08 -
f l.E-09 -
ia
4
l.E-10 - -f-
^Ît 4=^
=^1
J
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.
Chapter 6
224
Cereal Products
Corn

13
12
Standard Deviation (sd, nTVs)
pericarp
(92%)
2.34E-1 1
7558
Parameter Estimates
Di(m 2 /s)
Do (nrVs)
Ei (kJ/mol)
Eo (kJ/mol)
l.E-06 -
1.13E-10
O.OOE+00
10.0
5.0
Temperat ure(C) =g= q

- 40
60
-p A 80
l.E-07 -
l.E-08 :
ff>
(S
f l.E-09 -
'
l.E-10 -
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.
225
Cereal Products
Pasta
3
21
17
7.71E-12
36
(81%)
Parameter Estimates
Di(m 2 /s)
1.39E-10
Do(m 2 /s)
-1.6 IE-21
Ei(kJ/mol)
Eo (kJ/mol)
16.2
2.0
i F-Ofi
~ 1_ f
Tern perat ure(C) =t4=

40
60
A 80
l.E-07 -
_ . ^rj^
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, organic acids, flavor components, salts, preservatives, and gases (e.g. oxygen, carbon 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 extraction (e.g. sugar/water), ion exchange (e.g. de-acidification and de-bittering of
juices), reverse osmosis, and ultrafiltration. Mass diffusivity is the basic component of permeability of packaging films and food coatings, which are used as barriers to water, oxygen, and carbon dioxide transport in food materials.
Theoretical prediction of solute diffusivity in solid and semisolid food materials 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 diffusion model, in general, is used in modeling mass transport of water and small solutes within foods, since solid and semisolid food materials have complex structures 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 empirical correlations are essential.
Although small solutes can be transported in food systems by different
mechanisms, molecular diffusion is generally accepted as the basic transport process, in a similar manner with the transport of water (see Chapter 5). Thus, the effective 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 solids (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
Liquids
Polymers (rubbery)
Polymers (glassy)
IxlO' 5
IxlO' 9
IxlO' 14 - IxlO' 10
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 coefficients 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 concentrations, using magnetic stirring. The fritted glass diaphragm may be replaced by a
piece of filter paper for faster measurement.
magnetic
stirrer
glass
"frit
stirring
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 diaphragm, 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 compartments, 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 compartments, 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 (Cussler, 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 differential refractometry) over a period of time and the concentration profile is determined. 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.
241
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 unsteadystate profile of the refractive index of two solutions in a transparent system, diffusing 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 concentrations (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 25C 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 solutions, 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 components, 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 25C
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
Ammonia
1.49
1.64
242
Chapter 7
Table 7.3 Diffusivities of Solutes in Dilute

Water Solutions at 25C
Solute
D, x 10-'m2/s
Ethanol
8.40
Acetic acid
12.1
Butyric acid
Glycine
Sucrose
Glucose/fructose
Maltose
Glycerol
Hemoglobin
Fibrinogen
Lactoglobulin
Ovalbumin
9.20
10.6
5.40
6.90
4.80
9.20
0.69
0.20
0.70
0.78
The diffusivity of solutes in dilute water solutions can be predicted by empirical 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 independent 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 concentration, sometimes with maximum or minimum values at certain concentrations.
The D can be estimated from the diffusivity at infinite dilution Dm using a correction 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)
243
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 corresponding 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 concentration.
III. DIFFUSION IN POLYMERS
The sorption and transport of small molecules (solutes) in polymeric materials 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 mechanism, although in some cases other mechanisms may be involved. Solution of the
diffusion equation (7-1) forms the basis of mathematical analysis of the experimental 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 synthesis (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 experimental measurements and phenomenological correlations from various systems (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 driving force is the concentration gradient. The Fickian diffusion is applicable to low
concentrations (infinite dilution) of the solute, which is the case of most applications 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 determination 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 transition 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 matrix. 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 stretching (induced orientation) of the polymers can reduce solute diffusivity. Liquids
and vapors may cause swelling of the glass polymeric matrix, facilitating the diffusion 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
245
l.E-14
30
35
40
Temperature (C)
Figure 7.2 Arrhenius plots of diffusivity of solutes (water and carbon dioxide) in a polymeric 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 Arrhenius equation. However, in the temperature range Tg to (rg+100C) the Williams-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 temperature is increased immediately above Tg, e.g. the viscosity decreases 3 to 5 orders of magnitude at temperatures 20-3 0C 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 0C as the moisture content is increased.
Figure 7.3 schematically shows the change of Tg of a food biopolymer as a function of moisture content (Roos, 1992).
247
V
>w
X
X.
x^
cmpcraturc (C)
\.
x^
^\^^
%v
0 -
î
r
10
15
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 particular interest to food systems. The clustering theory of Zimm and Lundberg is
based on the statistical mechanics of fluctuations, and a simplified version of clustering 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 calculation 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). Negative 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 polymer, 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 approaches have been used for this purpose, i.e. the dual-sorption model, the freevolume model, and the molecular simulation method.
1. Dual-Sorption Model
This model has been applied to the sorption and diffusion of small molecules (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", representing the ratio of rate constants of gas adsorption and desorption in microcavities.
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 dissolved state DD and in the holes DH by the overall flux equation:
J= - D (dCI dz) = - DD(dCDl dz) - DH (dCHl dz)
(7-14)
249
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 volume 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 exponential 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 coefficient (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 increased from 0.2 to 0.8 (at 25C). 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 mechanism 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, thermodynamic and transport properties can be extracted. Molecular dynamics (MD) assumes 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 computer time required for the extensive computations can be reduced by certain approximations, 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 selfdiffusion 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 separation and barrier properties.
251
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 concentration 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 decreased 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 (20C)
Material
D, x 10"' m2/s
Agar gel, 3 % solids
12.0
Pickles
11.0
Swiss cheese
1.90
Meat muscle, fresh

Meat muscle, thawed
4.00
Herring
2.30
Green olives, fresh
0.38
1.95
Green olives, treated
2.20
252
Chapter 7
The salt diffusivity in fresh meat muscle is 2.2 x 10"' m2/s, while it is considerably 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 (Drusasetal., 1988).
The diffusivity of sodium hydroxide in tomato skin, measured with a modified 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 diffusivity 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 viscosity 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 (Loncin, 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 concentration 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
253
of significant open space in food solids, such as pores, cracks, and channels, complicates 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 diffusivity 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 materials, which are useful in calculations involving solvent extraction (leaching) and
liquid infusion operations (Schwartzberg and Chao, 1982). The diffusivity of sugars 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 dilute 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
Sugar beets
Sucrose
Water
Sugar cane
Sucrose
Water
Apple slices
Sugars
Water
Coffee beans
Coffee solubles
Water
Soybean flakes
Soybean oil
Cottonseed oil
Cottonseed oil
Hexane
Hexane
Peanuts
Peanut oil
Hexane
r,c
65
75
75
98
69
69
25
7,
D, x 10'10 m /s
6.80
2.00
11.5
1.00
1.00
0.27
0.006
254
Chapter 7
The free water fraction in the solid can be estimated from the moisture content and the sorption isotherm, but the tortuosity factor must be estimated indirectly from the measured D. Both parameters are not constant during food processing 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 vaporliquid 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)
255
The activity coefficients of aroma components in water and aqueous foods

are very high, especially for partially soluble organic flavor components, like esters 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 considerably the activity coefficient (Saravacos et al., 1990; Sancho and Rao, 1997).
Table 7.6 shows some typical relative volatilities of volatile flavor compounds in dilute water solutions (Saravacos, 1995; Chandraskaren and King,
1972).
The relative volatility of these compounds in aqueous solutions of 60% sucrose is 20 to 10 times higher than in water, due to the strong interactions of the 3component 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 established. 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 mechanically 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 (25C)
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
2-Butanone
Diethyl ketone
Ethyl acetate
Ethyl butyrate
31.0
76.0
77.0
205
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 water. The mass transport of volatiles should be considered as a ternary diffusion
process, with three binary diffusivities, i.e. water/solids, volatile/water and volatile/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 solution reduces the volatile loss and increases its retention. A higher retention is obtained by freeze-drying.
Volatile retention during spray drying depends not only on the relative volatility 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 concentration is increased from 0 to 70% (Voilley and Simatos, 1980; Voilley and
Roques, 1987).
50
257
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 volatile retention in spray- and freeze-drying (Coumans et al., 1994b). Atomization
and evaporation of water/volatiles from drops control flavor retention in spraydried particles (King, 1994; Hecht and King, 2000).
Retention of charactertistic aroma during storage of dried fruits can be improved 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 pharmaceuticals, 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 enzymes 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 matrices, or by incorporation in liposomes (e.g. lecithin).
Release of encapsulated solutes is achieved by temperture and moisture control, 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
259
temperature" is related to T& and both temperatures decrease as the moisture content 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 reduces 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 packaging 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 diffusivity 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 relation to water transport. Conversion of solubility S and diffusivity D data to permeability P though Eq. (7-23) is possible, when the material behaves like a homogeneous 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 pressure 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 permeabilities and the thicknesses of the individual films (P, z/) by the equation (Cookseyetal., 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)
261
Table 7.7 Conversion Factors to SI Permeability Units (g/m s Pa)

Conversion from / to (g / m s Pa)
3
cm (STP) mil /100 in day atm

3
Multiplying factor
6.42 x 10'17
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
1.16x10""
gmm/m daykPa
2
g mil/m day atm
2.90 x 10"15
g mil/m2 day (mm Hg)
2.20 x 10'12
g mil/m day (90 % RH, 100 F)

g mil/100 in2 day (90 % RH, 100 F)
4.50 x 10'14
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 100F,
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 (Hernandez, 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 (nontoxicity), 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, solute 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 25C (Miltz, 1992; Hernandez, 1997).
262
Chapter 7
Table 7.8 Permeabilities of Packaging Films to Water

Vapor and Oxygen (25C)
Permeability, x 1 0 - 1 2 g / m s P a
Packaging film
Water vapor
Oxygen
1.40
0.031
LDPE
0.007
0.20
HDPE
1.00
0.010
PP
3.00
0.005
PVC
12.0
0.018
PS
1.40
0.0006
PET
0.002
0.0004
Nylon
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 diffusivity 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 25C 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 oxygen), flavor components and lipids in food systems. Edible coatings, used as barriers in foods, include proteins (wheat gluten, caseinates, whey protein, corn zein),
polysaccharides (starch, dextrins), pectins, lipids, and chocolate. Composite coatings, containing a food biopolymer (e.g. protein) and a hydrophobic material, like
lipid, fatty acid, chocolate, and beeswax, usually have very low water permeabilities.
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 mechanical properties of the coating. They are applied to the various fresh and processed 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):
263
Table 7.9 Water Vapor Permeabilities P

of Food Coatings (25C)
P, xlO- 1 0 g/msPa
Food coating
6.10
Gluten-glycerine
7.20
Whey protein-sorbitol
1.00
Zein-glycerine
4.20
Sodium casemate
0.12
Chocolate
0.006
Beeswax
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 polymer 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 molecular 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 comparison 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 permeability 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 20C. 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 20C (p0 = 2340 Pa), and Ap =
234Pa. The concentration of water in the chocolate material is converted to consistent (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 concentration in the chocolate becomes C = (1.7/0.0625) = 27.2 kg/m3, and the solubility S = 27.2/232= 0.116 kg/m3 Pa.
Using the measured diffusivity of the system (D = 1 x 10~13 m2/s), the permeability 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
0.005
0.002
HDPE
LDPE
0.010
0.014
PP
0.010
0.010
0.041
0.050
PVC
1.00
Cellophane
3.70
Protein films
0.100
0.10-10.0
0.100
0.10-1.00
Polysaccharide films
0.010
Lipid films
0.003-0.100
Chocolate
0.001
0.11
Gluten
1.00
5.00
Com pericarp
0.10
1.60
LPDE = low density polyethylene, HDPE = high density polyethylene,
PP = polypropylene, PVC = polyvinyl chloride
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268
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8
Thermal Conductivity and Diffusivity
of Foods
I. INTRODUCTION
The thermal transport properties, thermal conductivity and thermal diffusivity of simple gases and liquids can be predicted by molecular dynamics and semiempirical 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 possible explanation of the heat transport mechanisms.
The thermal conductivity (X) of a material is a measure of its ability to conduct 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 material normal to the direction of heat flow (m2). The S.I. units of A are W/mK. Equation (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 electrical 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 comprehensive 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 steadystate 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 assured 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 relatively 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. Assuming 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
quard rings
f'H.4.-^ *-:; -a.-^:-; "'. s-y " ' %-'-"-'"- <<.': ":-
81_ AAAAAA^
/ , sample
/
cold plate
Jjpyjij*
iffigam
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 semilog 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.
273
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 unsteady-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 semiempirical 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 cylindrical solid:
AT= (q/4aX) [-0.58/2 -
where j3 = r/2(af)1'2
! - (34/4x2!
(8-11)
275
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 accuracy 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: Kostaropoulos (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 (25C)
% Moisture
Food material
A, W/mK
0.620
100
Water
0.567
Sucrose solution
85
0.110
Granular starch
15
0.547
Gelatinized starch
85
0.533
82
Potato
0.513
85
Apple
0.550
65
Tomato paste
0.452
74
Beef
0.460
80
Fish
0.530
Milk
85
0.180
Vegetable oil
0.237
18
Dried fruit
0.041
Freeze-dried gel
4
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 Pilsworth, 1965). An analogous effect was noticed in the drying rates of the two materials (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% moisture content decreases gradually from about 1.5 W/mK at -40C to 0.5 W/mK at
0C, as shown in the diagram of Figure 8.5. A sharp drop of A is observed near
0C, due to the melting of ice.
An analogous variation of the thermal diffusivity a of the frozen foods is observed below the freezing point (Figure 8.6). The a of a typical frozen food decreases from about 1x10'6 m2/s at -40C to 1x10'7 m2/s above 0C. The sharp drop
near the freezing point is due to the sharp increase of cp, which incorporates the
heat of melting, near 0C (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 extrusioncooked 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 increases gradually at moistures higher than 35% (Figure 8.7).
277
0.050
0.000
10
0.1
100
1000
Pressure (mbar)
Figure 8.4 Effect of air pressure on thermal conductivity of porous food material.
-40
-30
-20
-10
10
Temperature (C)
Figure 8.5 Thermal conductivity of frozen food material.
20
30
40
Chapter 8
278
l.OE-06
-40
-30
-20
-10
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.
279
D. Empirical Rules
A preliminary checking of thermal transport property data can be made, using 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, respectively.
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 conductivity 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 models, 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 25C. The temperature effects of the major food components are summarized by
Rahman (1995) in Table 8.2 and in Figure 8.8.
281
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
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
Ice
2.22E+00
-6.25E-03
1.02E-04
-4.33E-06
2.20E-09
Chapter 8
282
0.75
I
u
3
U
B
O
"5
E
0.25
50
Temperature (C)
Figure 8.8 Effect of temperature on the major food components.
100
283
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 electricity, Luikov et al. (1968) initially used the idea of an elementary cell, as representative 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 mixtures 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 assumes 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 assumed 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 temperature,
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, randomly 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. Figure 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 thermal 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. Consequently, 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 granule. It has been shown that the parallel model is the best model for both the granular starch and the starch granule (Maroulis et al., 1990). These results led to simultaneous 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.
285
286
Chapter 8
Table 8.3 Structural Models for Thermal Conductivity
Series
1
\-e)
Random
Mixed (Krischer )
287
0.125
Parallel
Maxwell (Continuous phase 1)

Random
Maxwell (Continuous phase 2)

Series
0.025
0.00
0.25
0.50
Void Fraction
Figure 8.11 Structural models for porous materials.
0.75
Chapter 8
288
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.
289
V. COMPILATION OF THERMAL CONDUCTIVITY DATA OF FOODS
There is a wide variation of the reported experimental data of thermal conductivity 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 property.
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 retrieved from the literature, and they were classified and analyzed statistically to
reveal the influence of material moisture content and temperature. Structural models, relating thermal conductivity to material moisture content and temperature
were fitted to all examined data for each material. The data were screened carefully, using residual analysis techniques. The most promising model was proposed, 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 content.
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 material.
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 according to the distribution presented in Figure 8.13. The accumulation of the papers versus the publishing time is presented in Figure 8.14. The search resulted in
1210 data concerning the thermal conductivity in food materials.
Chapter 8
290
J. Food
Engineering
J, of Food
Science
Drying
Technology
Trans of the Int. J. Food International

ASAE
Science &
Journal of
Techn.
Food
Properties
Figure 8.13 Number of papers on thermal conductivity data in food materials published 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.
291
0.001
0.01 0.1
10
100
Moisture (kg/kg db)
Figure 8.15 Thermal conductivity data for all foods at various moistures.
0.01
0.1
10
100
1000
Temperature (oQ
Figure 8.16 Thermal conductivity data for all foods at various temperatures.
Chapter 8
292
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

0.01-65 kg/kg db
Moisture
-43 -160 C
Temperature
The histogram in Figure 8.17 shows the distribution of the thermal conductivity 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 25C)
are characteristic of frozen foods of high moisture content, since the thermal conductivity 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 categories. 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 corresponding 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
3.00 1.00
0.30
Thermal Conductivity Values (W/mK)
Figure 8.17 Histogram of observed values of thermal conductivity in food materials.
293
Table 8.4 Literature for Thermal Conductivity Data in Food Materials:

References and Number of Data Retrieved
Material
Reference
Data
60
Baked products
14
Bread
Zanonietal, 1995
Zanonietal., 1994
Goedeken et a!., 1998

Dough
Bouvier et al, 1987
Zanonietal, 1995
Griffith etal., 1985
Soy flour
Maroulisetal.,1990
Wallapapan et al., 1982
Cake
Zanonietal., 1995
Yellow batter
Baiketal, 1999
Cup batter
Baiketal., 1999
Cereal products
5
3
6
20
3
8
9
11
7
4
2
2
1
1
12
12
76
9
Barley
Alagusundaram et al., 1991

Corn
Bekeetal, 1994
Changetal, 1980
Okos etal, 1986
Rice
Okos etal, 1986

Ramesh, 2000
Wheat
Changetal., 1980
Okos etal., 1986
Corn meal
Laietal, 1992
Kumaretal, 1989
9
21
9
3
9
13
4
9
10
3
7
7
4
3
Chapter 8
294
Table 8.4 Continued

Material
Reference
Data
4
Iclli batter
Murthyetal, 1997
Maize
Halltdayetal, 1995
Tolabaetal.,1988
Oat
Okosetal.,1986
4
11
9
2
1
1
136
Dairy
Cheese
Lunaetal., 1985
Tavmanetal., 1999
Milk
Duaneetal., 1992
Duaneetal, 1993
Duaneetal, 1994
Me Proud eta!., 1983
Hori, 1983
Zieglereta!., 1985
Ready etal, 1993
Tavmanetal, 1999
Okosetal.,1986
Cream
Duaneetal, 1998
Butter
Tavmanetal, 1999
Okosetal.,1986
Yogurt
Kirn etal, 1997

Tavmanetal., 1999
Whey
Okosetal.,1986
23
1
22
84
1
1
1
1
6
3
9
9
53
1
1
5
2
3
19
9
10
4
4
295
Table 8.4 Continued

Material
Reference
Fish
Data
83
Cod
Sam et a!., 1987
Mackerel
Sametal., 1987
Squid
Rahman et al, 1991

Rahman, 1991
Carp
Hung el al., 1983

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

Material
Reference
Peach
Okosetal.,1986
Strawberry
Delgado et al, 1997

Bhumbla et al., 1989
Okosetal.,1986
Raspberry
Bhumbla etal, 1989
Okosetal.,1986
Grape
Bhumbla et al, 1989
Okosetal.,1986
Plantain
Njieetal, 1998
Raisin
Vagenas et al., 1990
Pear
Matteaetal, 1989
Rahman, 1991
Dincer, 1997
Mattea et al., 1986
Okosetal.,1986
Orange
Telis-Romeroetal, 1998
Bhumbla etal, 1989
Ziegler et al, 1985
Okosetal.,1986
Bilberry
Bhumbla et al, 1989
Okosetal.,1986
Cherry
Bhumbla etal, 1989

Okosetal.,1986
Data
1
1
5
3
1
1
2
1
1
8
1
7
6
6
4
4
15
3
2
1
3
6
15
9
1
4
1
2
1
1
2
1
1
Legumes
Lentils
Alagusundaram et al, 1991
297
Table 8.4 Continued

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

Laietal, 1992
Drouzasetal, 1991
Maroulis et al, 1991
Drouzasetal, 1988
Hylon-7
Maroulis etal, 1990

Laietal, 1992
Drouzasetal, 1988
51
7
18
8
9
9
43
9
19
9
6
Chapter 8
298
Table 8.4 Continued

Material
Reference
Potato starch
Okosetal.,1986
Starch
Renaudetal, 1991
Njieetal, 1998
Morley et al, 1997
Wangetal.,1993
Lanetal, 2000
Sucrose
Renaudetal., 1991
Ziegleretai., 1985
Gelatin
Renaudetal, 1991
Okosetal.,1986
Ovalbumin
Renaudetal, 1991
Cornillon et al, 1995
Tylose
Phametal, 1990
Agar-water
Delgado et al, 1997
Barringer et al, 1995
Bentonite-water
Sheen et al, 1993

Gelatin-water
HalUdayetal.,1995
Amylose
Voudouris et al, 1995
Cellulose gum
Saravacos et al,1965
Pectin 5%
Saravacos et al.,1965
Pectin 10%
Saravacos el al.,1965
Pectin 5%-glucose 5%
Saravacos et al.,1965
Gelatin-sucrose-water
Hallidayetal, 1995
Glycerin
Ryniecki et al, 1993
Data
2
2
61
24
1
6
6
18
6
33
30
3
26
24
2
36
24
12
6
6
2
1
1
1
1
1
1
4
4
2
2
2
2
2
2
2
2
2
2
3
3
299
Table 8.4 Continued

Material
Reference
Nuts
Macadamia
Rahman, 1991
Data
1
1
1
134
Other
Coconut
Duane et a!., 1995
Chenetal, 1998
Coffee
Sagaraetal., 1994
Soybean
Okos et al, 1986
Palm kernel
Duane etal, 1996
Lard
10
1
9
10
10
12
12
1
1
1
Duane et al., 1997
Agar-water
Wang etal, 1992
Water-NaCI
Lucas etal, 1999
Water-sucrose
Lucas etal, 1999
Rapeseed
Bilanskietal, 1976
Moyseyetal, 1977
Okos eta!., 1986
Tobacco
Casadaetal, 1989
Sorghum
Changetal, 1980
Okos etal. ,1986
Sugar
Okos etal, 1986

Albumen
Okos etal, 1986

NaCl
Okos etal, 1986
1
52
18
10
24
3
3
7
3
4
15
15
2
2
3
3
Chapter 8
300
Table 8.4 Continued

Material
Reference
Honey
Okos et al.,1986
Albumine
Okos eta!., 1986
Vegetables
Data
12
12
3
3
154
Carrot
Niesteruk, 1998
Njie et al, 1998
Rahman, 1991
Buhri et al, 1993
Cassava
Njieetal, 1998
Garlic
Madamba et al, 1995
Onion
Rapusasetal, 1994
Pea
Sastry et al, 1983

Alagusundarametal, 1991
Potato
Niesteruk, 1996
Niesteruk, 1997
Niesteruk, 1998
Hungetal.,1983
Luelal, 1999
Njieetal, 1998
WangetaL, 1992
Rahman, 1991
Matteaetal, 1986
Hallidayetal, 1995
Madamba eta!., 1995
Buhri eta!., 1993
Cratzeketal.,1993
Sugar beet
5
1
1
2
1
6
6
3
3
7
7
12
3
9
45
1
1
1
2
1
2
16
2
3
9
2
1
4
7
Niesteruk, 1998
Okos etal, 1986
Turnip
Buhri et al, 1993
4
3
1
1
Table 8.4 Continued

Material
Reference
Yam
Njieetal., 1998
Beetroot
Niesteruk, 1998
Parsley
Niesteruk, 1998
Celery
Niesteruk, 1998
Tomato
Dincer, 1997
Choietd.,1983
Filkovaetal, 1987
Okos eta!., 1986

Drouzasetal., 1985
Cucumber
Dincer, 1997
Spinach
Delgado et al, 1997

Mushrooms
Shrivastavaetal, 1999
Rutabagas
Buhri et al, 1993
Radish
Buhrietal, 1993
Parsnip
Buhri etai, 1993
Kidney bean
Zuritz et al, 1989
301
Data
6
6
2
2
1
1
1
1
31
1
9
3
9
9
1
1
10
10
9
9
1
1
1
1
1
1
4
4
Chapter 8
302
Table 8.5 Thermal Conductivity of Foods Versus Moisture and Temperature:

Average Values of Available Data
Temperature
(W/mK)
Moisture
(kg/kg db)
(C)
Data
Baked products
0.34
0.57
46
60
Conductivity
Material
Bread
0.23
0.39
44
14
0.27
0.35
47
Crust
0.06
0.00
68
Crumb
0.26
0.76
17
Dough
0.34
0.89
60
20
Wheat bread
0.41
0.78
23
Rye bread
0.47
1.06
20
Biscuit
0.40
0.07
20
Soy
0.35
0.33
150
Soy flour
0.22
0.21
27
11
Defatted
0.44
0.36
25
Dry defatted
0.12
0.00
40
Cup cake batter
0.17
0.63
15
0.17
0.63
15
Yellow cake batter
0.22
0.71
20
0.22
0.71
20
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
Seeds
0.20
0.18
Corn
0.39
1.55
36
21
Dent
0.16
0.20
36
Shelled
0.55
0.73
30
Dust
0.09
0.15
22
Syrup
0.43
4.16
52
303
Table 8.5 Continued

Conductivity
Material
(W/mK)
Moisture
(kg/kg db)
Temperature
(C)
Data
13
Rice
0.15
0.22
48
Paddy
0.15
0.22
48
13
Wheat
0.26
0.13
26
10
Dust
0.07
0.15
22
Hard red spring
0.16
0.17
-3
Soft white
0.13
0.13
16
Flour
0.59
0.10
56
Corn meal
0.36
0.27
88
0.36
0.27
88
Idli batter
0.45
1.71
16
0.45
1.71
16
Maize
0.27
0.32
62
11
Kernel
0.17
0.16
50
Grits
0.29
0.36
65
Oat
0.13
0.14
27
White
0.13
0.14
27
Dairy
0.45
3.78
38
136
Cheese
0.42
1.20
22
23
Cheddar
0.35
0.56
23
Mozzarella
0.38
0.80
23
Cuartirolo Argentina
0.37
1.20
15
Hamburger
0.39
0.69
23
Old Kashkaval
0.38
0.69
23
Tulum
0.38
0.69
23
Fresh Kashkaval
0.40
0.78
23
Buffet Kashkaval
0.41
0.99
23
Fresh cream
0.43
1.29
23
Spreadable cheese
0.49
1.54
23
Labne
0.47
2.24
23
Low fat labne
0.55
2.94
23
Chapter 8
304
Table 8.5 Continued

(W/mK)
Moisture
(kg/kg db)
Temperature
(C)
Data
Milk
0.46
4.02
46
84
0.46
4.00
20
Conductivity
Material
Fresh
0.57
9.00
23
Powder
0.11
25.33
25
Whole
0.46
3.04
53
18
Skim
0.57
6.33
36
15
Concentrated
0.41
0.92
50
Condensed
0.49
4.01
54
Half-half
0.54
5.11
40
Baby food
0.55
0.03
50
Powdered
0.30
0.05
54
11
Butter
0.22
0.20
21
0.23
0.18
23
Fat
0.21
0.21
20
Yogurt
0.45
3.60
31
19
0.56
6.25
21
Plain
0.33
2.05
40
Strained
0.54
2.88
23
Pasterized
0.58
4.71
23
Light
0.58
4.54
23
Extra light
0.59
6.58
23
Whey
0.59
9.00
40
0.59
9.00
40
Cream
0.13
44.00
25
Powder
0.13
44.00
25
Fish
0.79
3.29
83
Cod
1.23
4.88
-10
Perpendicular
1.23
4.88
-10
Mackerel
0.80
3.42
Perpendicular
0.80
3.42
305
Table 8.5 Continued

Temperature
(W/mK)
Moisture
(kg/kg db)
(C)
Data
Conductivity
Material
Squid
0.35
2.36
26
16
Fresh
0.50
5.04
30
Mantle
0.50
3.83
15
3
2
Dried
0.24
0.87
30
Tentacle, arrow
0.48
3.56
15
Tentacle
0.50
3.56
15
Carp
1.21
0.83
1.21
0.83
Surimi
0.78
4.02
14
30
0.85
4.08
-2
6% cryoprotectant cone
0.87
4.08
-2
12% cryoprotectant cone
0.86
4.08
-2
Pacific whiting
0.59
3.88
53
Cake
0.10
0.00
15
Pressed
0.10
0.00
15
Shrimp
1.03
3.24
-8
13
peeled and head removed
1.03
3.24
-8
13
Calamari
0.51
4.04
15
mantle
0.51
4.04
15
Salmon
1.06
2.40
-12
Perpendicular
1.06
2.40
-12
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
Green
0.41
0.14
45
Golden delicious
0.41
4.89
18
Granny Smith
0.19
2.17
25
37
47
Juice
0.53
3.81
Sauce
0.59
10.11
Chapter 8
306
Table 8.5 Continued

Moisture
Conductivity
(W/mK)
(kg/kg db)
Temperature
(C)
0.48
3.12
20
Dessert
0.48
3.12
20
Peach
0.04
Freeze-dried
0.04
35
1
1
1
1
Plantain
0.37
0.98
30
Fruits
0.37
0.98
30
Pear
-
0.49
3.22
34
15
0.47
2.85
24
Material
Banana
35
Data
Green
0.52
7.41
15
Juice
0.51
2.60
50
Williams
0.45
2.17
25
Orange
0.41
4.28
27
15
Juice
0.41
4.28
27
15
Bilberry
0.55
8.52
18
Juice
0.55
8.52
18
Cherry
0.55
6.52
18
Juice
0.55
6.52
18
Grape
0.52
4.08
42
0.52
3.60
50
Juice
0.55
5.54
18
Raspberry
0.55
7.70
18
Juice
0.55
7.70
18
Strawberry
0.63
8.44
14
Juice
0.57
11.05
18
Tioga
0.67
6.70
11
Raisin
0.23
1.35
45
0.23
1.35
45
Legumes
0.22
0.18
Lentils
0.22
0.18
Seeds
0.22
0.18
307
Table 8.5 Continued

Material
Conductivity
Moisture
Temperature
(W/mK)
(kg/kg db)
(C)
Data
Meat
0.71
2.40
16
134
Beef
0.63
2.22
28
75
0.54
2.43
Fat
0.28
0.14
Lean
1.03
0.63
Ground
1.01
0.75
Minced
0.56
1.96
11
Muscle semitendinosus
0.31
0.99
20
Dryfiber
0.21
1.03
25
Boneless
1.03
3.31
-4
20
Ground round
0.51
2.53
60
Whole round
0.49
2.32
60
Ground shank
0.51
2.45
60
Ground brisket
0.44
2.38
60
Whole rib steak
0.50
1.84
60
Ground sirloin tip
0.49
2.35
60
Whole sirloin tip
0.48
2.27
60
Ground rib
0.41
1.11
60
Ground s\viss steak
0.51
2.90
60
Whole swiss steak
0.49
2.82
60
Loaf, uncooked
0.40
2.58
15
Loaf heated
0.47
1.96
60
Chicken
1.05
3.46
-9
Boneless
0.97
3.00
-4
White
1.33
5.10
-25
Chapter 8
308
Table 8.5 Continued

Conductivity
Material
(W/mK)
Sausage
0.42
Moisture
(kg/kg db)
Temperature
(C)
Data
1.02
18
13
0.33
1.24
22
Italian
0.93
0.64
Salami cooked
0.37
1.70
22
Lebanon bologna
0.36
1.63
22
Salami cotto
0.37
1.33
22
Thuringer
0.35
0.96
22
Salami Genoa
0.30
0.56
22
Salami hard
0.32
0.52
22
Pepperoni
0.28
0.37
22
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
Boneless
0.93
3.25
-4
0.93
3.25
-4
11
11
Pork/soy
0.05
3.41
25
Unprocessed
0.05
3.17
25
Processed
0.05
3.64
25
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
Granular
0.34
0.12
40
309
Table 8.5 Continued

Conductivity
(W/mK)
Moisture
(kg/kg db)
Hylon-7
0.33
5.08
60
43
Gelatinized
0.22
5.99
85
16
0.53
1.90
46
15
Powder
0.13
15.55
48
Granular
0.34
0.12
40
Material
Temperature
(C)
Data
Potato starch
0.04
0.08
41
Gel
0.04
0.08
41
Starch
0.68
4.71
42
61
0.10
0.00
25
Gel
1.02
8.80
29
Gelatinized
0.34
0.10
50
Hydrated
0.38
0.28
47
Granular
0.09
0.20
45
Gels
0.50
1.65
100
18
Sucrose
0.85
3.57
-1
33
0.48
3.72
20
Gel
Gelatin
0.89
3.56
-4
30
0.96
7.92
26
Gel
0.96
7.92
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
Gel
0.99
3.35
Agar-water
0.61
36.95
25
Gel
Gelatin-water
-
0.61
36,95
25
0.59
65.67
25
0.59
65.67
25
Amylose
0.53
3.50
30
Gel
0.53
3.50
30
Chapter 8
310
Table 8.5 Continued

Conductivity
Material
(W/mK)
Moisture
(kg/kg db)
Temperature
(C)
Data
Cellulose gum
0.06
0.08
41
Freeze-dried gel
0.06
0.08
41
Pectin 5%
0.04
0.08
41
Freeze-dried gel
0.04
0.08
41
Pectin 10%
0.05
0.08
41
Freeze-dried gel
0.05
0.08
41
Pectin 5%-glucose 5%
0.05
0.08
41
Freeze-dried gel
0.05
0.08
41
Glycerin
0.47
3.79
20
0.47
3.79
20
0.44
1.44
15
0.44
1.44
15
Nuts
0.22
0.02
15
Macadamia
0.22
0.02
15
Integrifolia
0.22
0.02
15
Vegetables
0.43
3.81
39
154
Carrot
0.48
5.85
22
0.45
3.82
27
Large
0.52
8.91
15
Cassava
0.47
1.22
30
Roots
Gelatin-sucrose-water
"
0.47
1.22
30
Garlic
0.36
0.80
15
0.36
0.80
15
Onion
.
0.42
2.05
32
0.42
2.05
32
311
Table 8.5 Continued

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

(W/mK)
Moisture
(kg/kg db)
Temperature
(C)
Data
Mushrooms
0.37
3.27
55
Pleurotusflorida
0.37
3.27
55
Rutabagas
0.45
0.08
45
0.45
0.08
45
Radish
0.50
0.06
45
0.50
0.06
45
Parsnip
0.39
0.21
45
0.39
0.21
45
Kidney bean
0.15
0.24
20
0.15
0.24
20
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
10
Solutions
Conductivity
Material
0.21
1.62
10
Soybean
0.09
0.14
34
12
Powder
0.08
0.10
36
Whole
0.11
0.13
36
Crushed
0.10
0.11
36
Flour
0.05
0.22
26
Palm kernel
0.10
26.00
25
Milkpowder
0.10
26.00
25
Lard
0.12
32.00
25
Milkpowder
0.12
32.00
25
Water-Nad
0.46
4.00
10
Solution
0.46
4.00
10
Water-sucrose
0.32
0.67
10
Solution
0.32
0.67
10
313
Table 8.5 Continued

Material
Conductivity
(W/mK)
Moisture
(kg/kg db)
Temperature
(C)
Data
Rapeseed
0.11
0.10
14
52
mole
0.13
0.11
17
21
Ground
0.07
0.11
16
Torch
0.10
0.10
-4
Midas
0.09
0.01
19
Crushed
0.13
0.11
18
12
Agar-water
0.62
19.90
30
Gel
0.62
19.90
30
Tobacco
0.06
0.26
15
0.06
0.26
15
Sugar
0.52
4.32
42
15
Glucose
0.54
4.80
44
Cane sugar
0.51
4.00
40
Albumen
0.04
0.08
41
Freeze-dried gel
0.04
0.08
41
Sorghum
0.24
0.17
21
Rs610
0.14
0.22
NC+RS66
0.56
0.16
36
Grain dust
0.09
0.15
22
NaCl
0.61
4.00
43
Solution
0.61
4.00
43
Honey
0.53
4.83
36
12
Albumine
0.53
4.83
36
12
0.41
0.67
60
Solution
0.41
0.67
60
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)

Max
Min
Min
Max
Min
Max
15
150
0.82
15
120
0.79
25
100
0.00
0.00
15
120
0.72
0.82
15
18
0.04
1.17
20
150
0.00
1.17
0.055
0.650
0.530
0.00
0.080
0.530
0.05
Crust
0.055
0.066
Crumb
0.232
0.298
Dough
0.230
0.600
Baked products
0.048
Bread
-
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
315
Table 8.6. Continued

Material

Max
Min
Max
Min
Max
Min
0.366
0.11
0.082
0.366
0.067
0.689
Dust
0.067
Hard red spring
0.144
Soft white
0.118
Rice
0.082
Paddy
Wheat
70
0.43
20
0.11
0.43
20
70
0.01
0.29
-3
66
0.073
0.10
0.20
22
22
0.166
0.05
0.29
-3
-3
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
90
Cheese
0.345
0.548
0.56
2.94
15
30
Cheddar
0.345
0.351
0.56
0.56
15
30
Mozzaretta
Cuartirolo ArgenTino
0.380
0.383
0.80
0.80
15
30
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
0.78
15
30
Fresh Kashkaval
0.403
0.403
0.78
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
Chapter 8
316

Material

Min
Max
Min
Max
Min
Max
Milk
0.112
0.686
0.02
30.00
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
90
Skim
0.481
0.646
1.50
19.00
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
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
55
0.525
0.603
6.25
6.25
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
87
0.547
0.642
9.00
9.00
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
Perpendicular
0.549
1.543
4.88
4.88
-22
Mackerel
Perpendicular
0.409
1.428
3.42
3.42
-20
20
0,409
1.428
3.42
3.42
-20
20
317

Material

Min
Max
Max
Min
Max
Min
Squid
0.040
0.507
0.10
Fresh
0.490
0.500
Mantle
0.483
0.507
Dried
0.040
0.440
Tentacle, arrow
0.475
0.475
Tentacle
0.501
0.501
5.20
15
30
4.75
5.20
30
30
3.83
3.83
15
15
0.10
2.86
30
30
3.56
3.56
15
15
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
Peeled and head
removed
0.490
1.600
1.00
4.20
-30
30
0.490
1.600
1.00
4.20
-30
30
4.04
4.04
15
15
Calamari
0.508
0.517
Mantle
0.508
0.517
4.04
4.04
15
15
Salmon
0.497
1.245
2.03
2.70
-24
Perpendicular
0.497
1.245
2.03
2.70
-24
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

Material

Max
Min
Min
Max
Min
Max
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
62
Juice
0.290
0.560
0.64
19.00
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
319

Material
Meat
Min
Max
Min
Max
Min
Max
0.049
1.660
0.01
5.10
-40
90
Beef
0.095
1.650
0.01
3.69
-30
90
Fat
Lean
0.454
0.622
2.28
2.57
-18
20
0.264
0.311
0.10
0.16
-10
15
0.510
1.550
0.63
0.63
-15
15
Ground
0.400
1.620
0.75
0.75
-15
15
Minced
Muscle semitendinosus
0.360
0.844
1.11
3.44
-5
30
0.01
2.84
20
20
25
30
0,095
0.490
Dry fiber
0,140
0.243
0.38
2.30
25
Boneless
0.429
1.650
2.92
3.69
-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
90
Ground rib
0.368
0.450
0.78
1.37
30
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
Material

Min
Min
Max
Max
Max
Min
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
Boneless
0.490
1.660
2.85
2.85
-24
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
321

Material
Min
Max
Min
Max
Min
Max
Hylon-7
0.100
0.661
0.00
Gelatinized
0.442
0.661
0.01
20.00
20
150
4.00
20
70
Powder
0.100
0.160
11.10
Granular
0.227
20.00
25
70
0.01
0.23
20
0.454
Potato starch
0.039
0.041
60
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
Chapter 8
322

Material

Min
Max
Max
Min
Min
Max
Cellulose gum
0.056
Freeze-dried gel
0.056
0.063
Pectin 5%
0.038
0.039
0.063
0.14
41
41
0.02
0.14
41
41
0.02
0.14
41
41
0.02
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
0.04S
0.050
0.02
0.14
41
41
41
Pectin 5%-glucose
5%
Freeze-dried gel
0.048
0.050
0.02
0.14
41
Glycerin
0.450
0.490
3.35
4.26
20
20
0.450
0.490
3.35
4.26
20
20
Gelatin-sucrosewater
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
9.00
15
45
8.91
15
15
0.182
0.605
0.15
Large
0.509
0.532
8.91
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
0.520
0.32
4.15
31
33
0.290
323

Material

Min
Max
Min
Max
Min
Max
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
20
45
Roots
0.448
0.589
1.50
4.00
20
Turnip
0.480
0.480
0.08
0.08
45
45
30
0.480
0.480
0.08
0.08
45
Yam
0.160
0.600
0.19
3.76
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
2.40
30
50
22
22
Paste
0.460
0.660
1.16
Cucumber
0.621
0.621
24.00
24.00
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
Chapter 8
324

Material
Mushrooms

Min
Min
Max
Max
Min
Max
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
20
20
Kidney bean
0.103
0.201
0.12
0.41
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
325

Material
Min
Max
Min
Max
Min
Max
Rapeseed
0.060
0.155
0.01
0.24
-26
32
Whole
0.108
0.155
0.06
0.15
32
Ground
0.062
0.088
0.07
0.15
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
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
80
Glucose
0.450
0.637
1.50
8.09
80
Cane sugar
0.382
0.637
0.67
9.00
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
36
Rs6lO
0.130
0.150
0.15
0.28
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
71
0.440
0.618
1.50
9.00
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 25C) are characteristic of frozen
foods of high moisture content, since the thermal conductivity of ice is about 2 W/mK
Chapter 8
326
VI. THERMAL CONDUCTIVITY OF FOODS AS A FUNCTION OF

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 uniform 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
:(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 temperature by an Arrhenius-type model:
= A0 exp
exp
R(T
(8-14)
(8-15)
where Tr =60C 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 60C was chosen as a typical temperature of
air-drying of foods. Thus, the thermal conductivity for every material is characterized and described by four parameters with physical meaning:
327
/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 moisture 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
X0exp
where
RT
T,
X .
+X.exp
l +X
RT T
/i (W/mK) the thermal conductivity,

X (kg/kg db) the material moisture content,
T(C) the material temperature,
Tr = 60C 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
329
Table 8.8. Parameter Estimates of the Proposed Mathematical Model

4,
E;
E0
(W/mK) (kJ/mol) (kJ/mol)
sd
(W/mK)
7.2
5.0
0.047
0.287
0.106
0.270
2.4
1.3
2.4
11.7
0.0
1.9
0.114
0.007
0.016
0.718
0.623
0.800
0.120
0.243
0.180
3.2
0.3
9.9
14.4
0.4
0.037
0.006
0.072
37
28
0.611
0.680
0.049
0.220
0.0
0.2
47.0
5.0
0.059
0.047
33
0.665
0.212
1.7
1.9
0.005
Beef
37
0.568
0.280
2.2
3.2
0.017
Other
Rapeseed
35
0.239
0.088
3.6
0.6
0.023
15
0.800
0.273
2.7
0.0
0.183
Papers
No. of
Data
15
1.580
0.070
12
4
5
68
13
15
0.589
0.642
0.658
5
4
3
29
24
21
12
5
No. of
Material
4
(W/mK)
Cereal products
Corn
Fruits
Apple
Orange
Pear
Model foods
Amioca
Starch
Hylon
Vegetables
Potato
Tomato
Dairy
Milk
Meat
Baked products
Dough
Chapter 8
330
I Moisture=infinite
Moist ure=zero
.t!
0,1
I
u
a
a
o
0.01
100
Moisture=infinite
0 Moisture=zero
e 10
&
<u
.2
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 25C.
331
Chapter 8
332
Moisture (kg/kg db)
Figure 8.20 Predicted values of thermal conductivity of fruits at 60C.
Moisture (kg/kg db)
Figure 8.21 Predicted values of thermal conductivity of vegetables at 25C.
333
Chapter 8
334
Moisture (kg/kg db)
Figure 8.22 Predicted values of thermal conductivity of vegetables at 60C.
1.0
335
10.0
Moisture (kg/kg db)
Figure 8.23 Predicted values of thermal conductivity of miscellaneous foods at

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

60C.
Fruits
Standard Deviation (sd, W/mK)

Parameter Estimates
APPLE
12
73
68
0.11
142
Xi (W/mK)
Xo (W/mK)
Ei (kJ/mol)
_____Eo (kJ/mol)
337
(93%)
0.59
0,29
2.45
11.7
1.0
10.0
Moisture (kg.kg db)
Figure 8.25 Thermal conductivity of apple at various temperatures and moisture

contents.
Chapter 8
338
Fruits
ORANGE
4

15
13

Parameter Estimates
(87%)
0.01
2
Xi (W/mK)
0.64
/u>(W/mK.)
Ei(kJ/mol)
0.11
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
339
PEAR
5

Parameter Estimates
Xi (W/mK)
Xo (W/mK)
15
15
(100%)
0.02
10
0.66
0.27
Ei (kJ/mol)
Eo(kJ/mol)
2.45
1.9
1
Temperature C 40
A
A
**
V s^ +*
s+
i
E
I
60
A80
,L i
^
<:&?
u-E
& ->
"5
a
a
o
i
0.1 - -
0.1
- -r -
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
12
45
37
(82%)
0.06
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.
341
Vegetables
TOMATO
31

28
(90%)
0.05
25
Parameter Estimates
Xi (W/mK)
0.68
Xo (W/mK)
Ei(kJ/mol)
0.22
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.
Chapter 8
342
Model Foods
AMIOCA
5

51
29
(57%)
0.04
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
343
HYLON

3
43
21
(49%)
0.07
9
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.
Chapter 8
344
Model Foods
STARCH
55

24
(44%)
0.01
0
Parameter Estimates
Xi (W/mK)
Xo (W/mK)
Ei (kJ/mol)
0.62
0.24
0.32
____Eo (kJ/mol)_____0.4
Temperature C 40 M
1
0.1
60
1.0
IT
10.0
Moisture (kg.kg db)
Figure 8.32 Thermal conductivity of starch at various temperatures and moisture

contents.
345
Dairy
MILK
5
84
33
(39%)
0.01
Parameter Estimates
Xi (W/mK)
Xo(W/mK)
Ei(kJ/mol)
0.67
0.21
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.
Chapter 8
346
Cereal Products
CORN

3
28
15
(54%)
0.05
Parameter Estimates
Xi (W/mK)
Xo(W/mK)
0.47
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
347
DOUGH

3
20
15
(75%)
0.18
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.
Chapter 8
348
_______________Meat____BEEF
6
75
37
(49%)
0.02
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
contents.
Thermal conductivity of beef at various temperatures and moisture
349
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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, operation and control of several food processing operations and equipment. They are
related to the basic heat and mass transport properties of foods (thermal conductivity and mass diffusivity), and they depend strongly on the food/equipment interface and the thermophysical properties of the system. Table 9.1 shows some important 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 processing 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 constants 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 extensively 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
q/A = QJL)(AT)
361
(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 because it varies with the conditions of flow at the interface.
The overall heat transfer coefficient U (W/m2K) between two fluids separated 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 measurements.
B. Determination of Heat Transfer Coefficients
The heat transfer coefficient h at a given interface can be determined experimentally 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:
dt
dX1
(9-5)
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 parameters 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 aseptic 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 denoted 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 proposed in the literature for different heat transfer of fluid systems, like flow outside
tubes and flow in packed beds.
363
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
Flow processes
Re=uL/v
Reynolds
Heat transfer
Nu=hL/A
Nusselt
Heat transfer
Pr=v/a
Prandtl
Free convection
Gr=L3g(Ap/p)/v2
Grashof
Graetz
Heat transfer
Gz=GACpM
Heat transfer
BiH=hm
Biot
Mass transfer
Sh=kcL/D
Sherwood
Diffusion processes
Sc=v/D
Schmidt
Heat transfer
Stanton
StH=h/G Cp
Stanton
Mass transfer
StM=kc/u
Heat/mass transfer
Le=a/D
Lewis
Flow/diffusion
Pe=uL/D
Peclet
Mass transfer
BiM=kcL/X
Biot
Heat transfer
JH=StHPr2'^
Heat Transfer Factor
Mass transfer
Mass Transfer Factor
jM=StMSc /s
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 coefficient (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/?e5 Pr113
Parallel to flat plate (turbulent)
Nu = 0.0366#e8 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
Vertical tubes, h=\A2 (AT/L)W
(9-6)
(9-7)
b. Air in drying (constant rate):
Parallel flow, h = 0.0204G0'8

Perpendicular flow, h=l.ll G'37
(9-8)
(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]
Vertical tubes, h = 13900 / [Lw(AT)m]
(9-11)
(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 concentration, while the diffusion model has distributed parameters for the dependent variable (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 viscosity, 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 molecular interactions and on the physical structure of the material.
The mass transfer coefficient kc (m/s) in a process is defined in an analogous manner with the heat transfer coefficient:
J = kcAC
(9-13)
365
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 difference 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 equation (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 engineering 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 measurement 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 60C, 10% RHand 2 m/s air velocity 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 interior 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 simultaneously 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 certain 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 common in drying of solids, solvent extraction of solids and adsorption operations.
Fluid/liquid interfaces are important in aeration, de-aeration, and carbonation/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 Re8Sc1'3
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 ReA2 (1 /Sc)2/3
Spinning disc__________________Sh = Q.62Re'5Sc1'3
Dimensionless numbers defined in Table 9.3.
367
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 interpreted in terms of approximate or exact theories of mass transfer. The mass transfer 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 diffusion 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 diffusivity 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 corresponding 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 written 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)
369
IV. HEAT TRANSFER COEFFICIENTS IN FOOD SYSTEMS
The heat and mass transfer coefficients in food systems are determined experimentally 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 transfer is the rate controlling mechanism in many processing operations. Mass transfer
coefficients can be related to heat transfer in some important operations, like drying, using the Colburn analogy of heat and mass transfer.
Typical values of heat transfer coefficients are shown in Table 9.7 (Hallstrom et al., 1988; Perry and Green, 1997; Rahman, 1995; Saravacos, 1995). Detailed 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.
Chapter 9
370
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 increased.
10000
1000 --
Figure 9.1 Heat transfer coefficients in agitated kettle. S, sucrose solution 40 Brix;
A, applesauce; RPM, 1/min
371
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 coefficient ht is controlling the transfer process, since the outside (heating/cooling medium) coefficient and the heat conductance of the wall l/x are generally high (metallic or glass containers). However, heat transfer in plastic containers may be controlled 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 nonNewtonian fluids, the dimensionless numbers used are the following (Rao, 1999):
Re = -
4n
l3n + l
(9-27)
372
Chapter 9
4n
Gr
22
-2
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 ReA36 Pr2*7 for Newtonian fluids
(9-3 1 )
Nu = ReABS 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 transfer 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
U h k h,
(9-33)
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.
373
10000
Figure 9.3 Overall heat transfer coefficients U in evaporation of clarified CL and unfiltered UFT apple juice at 55C.
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 250350 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 60C from 7xlO' 10 to 14xlO'10 m2/s (Mulet et al., 1999).
374
Chapter 9
V. HEAT TRANSFER COEFFICIENTS IN FOOD PROCESSING: COMPILATION OF LITERATURE DATA
Recently reported heat transfer coefficient data in food processing were retrieved 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 equation was also fitted to all data for each process and the resulting equations characterize 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.
375
Table 9.8 Number of Available Equations for each Food Process
Process
Baking
Forced convection
Blanching
Steam
Cooling
Forced convection
Fluidized bed
Rotary
4
6
Storage
Forced convection
16
1
Freezing
Forced convection
Drying
Convective
No. of equations
Sterilization
Aseptic
Retort
Total No. of equations
54
376
Chapter 9
Table 9.9 Number of Available Equations for each Food Material
Material
Apples
2 Apricots
3 Barley
4 Beef
5 Cakes
6 Calcium alginate gel
1
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Canola seeds
Carrot
Corn
Corn starch
Figs
Fish
Grapes
Green beans
Hamburger
Maize
Malt
Meat carcass
Model food
Newtonian liquids
Non-food material
Particulate liquid foods
Peaches
Potatoes
Raspberries
Rice
Soya
Soybean
Strawberries
Sugar
Wheat
Spherical particles
Tomatoes
Corn cream
Rapeseed
Meatballs
Total No. of equations
No. of Equations
1
1
2
1
1
1
1
1
2
1
1
1
3
1
2
1
1
1
4
1
3
3
1
2
1
1
2
1
1
1
3
1
1
1
1
1
54
377
Table 9.10 Parameters of the Equation jH = aRe" for each Process and each Material
mm Re
Process/product/reference
a
max Re
Baking
Cakes
Baiketal., 1999
0.801
-0.390
40
3,000
Green Beans
Zhangetal., 1991 0.00850
-0.443
150
1,500
Cooling
Apples
Fikiinetal., 1999
0.0304
-0.286
4,000
48,000
0.114
-0.440
2,000
25,000
8.39
-0.492
3,500
9,000
0.472
-0.516
1,300
17,000
2.93
-0.569
2,000
12,000
0.186
-0.500
3,700
43,000
0.0293
-0.320
1,300
16,000
0.136
-0.440
1,900
25,000
0.267
-0.550
1,000
24,000
Blanching
Apricots
Fikiinetal., 1999
Figs
Dincer, 1995
Grapes
Fikiinetal., 1999
Model Food
Alvarez et al., 1999
Peaches
Fikiinetal., 1999
Raspberries
Fikiinetal., 1999
Strawberries
Fikiinetal., 1999
Tomatoes
Dincer, 1997
Chapter 9
378
Table 9.10 Continued

Drying
minRe
ma\Re
3.26
-0.650
20
1,000
0.458
-0.241
30
50
0.692
-0.486
500
5,000
1.06
4.12
-0.566
-0.650
400
20
1,100
1,000
0.665
0.741
-0.500
-0.430
8
1,000
50
3,000
11.9
-0.901
150
1,500
0.196
-0.185
60
80
0.224
-0.200
2,000
11,000
4.12
-0.650
20
1,000
2.48
-0.523
200
1,500
149
3.26
-0.340
-0.650
50
20
100
1,000
0.101 -0.355
3,200
13,000
Convective
Barley
Sokhansanj, 1987
Canola Seeds
Langetal., 1996
Carrot
Mulct etal., 1989
Corn
Fortes etal., 1981
Torrezetal., 1998
Graves
Ghiausetal, 1997
Vagenas et al, 1990
Maize
Mourad et al., 1997
Malt
Lopezetal., 1997
Potatoes
Wangetal., 1995
Rice
Torrezetal., 1998
Soybean
Taranto et al., 1997
Wheat
Langetal., 1996
Sokhansanj, 1987
Fluidized bed
Corn Starch
Shu-De etal., 1993
379

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

//
min Re
max Re
0.500
0.448
3.42
-0.507
-0.519
-0.687
5,000
2,400
2,000
20,000
45,000
11,000
0.748
0.662
0.517
-0.512
-0.508
-0.441
3,000
3,000
3,000
85,000
85,000
85,000
0.225
0.0493
-0.400
-0.199
140
1,800
1,500
5,200
2.26
-0.474
4,300
13,000
2.74
-0.562
11,000
400,000
0.564
-0.403
30
0.108
-0.343 130,000
Sterilization
Aseptic
Model food
Balasubramaniam et al, 1994
Sastryetal., 1990
Zuritzetal, 1990
Non-food material
Kramers, 1946
Ranzetal.,1952
Whitaker, 1972
Paniculate liquid foods
Mankadetal., 1997
Sannervik et al., 1996
Spherical particles
Astrometal., 1994
Retort
Newtonian liquids
Anantheswaran et al., 1985
Particulate liquid foods
Sablanietal, 1997
Corn cream
Zamanetal., 1991
1,600
1,100,000
381
Table 9.11 Parameters of the Equation jH = a Re" for each Process
Process
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
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 obtained 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 between the heat transfer factory'// and the mass transfer factor jM (see section VI of
this chapter).
Chapter 9
382
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 processes and materials.
383
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.
385
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.
387
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.
Chapter 9
388
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
389
0.1
Sterilization Retort
\
Part culat? Lii
Fi oils
JH 0.01
0.001
100
1000
10000
Re
100000
1000000
Figure 9.11 Heat transfer factory// versus Reynolds number Re for sterilization retort
Chapter 9
390
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.
391
VI. MASS TRANSFER COEFFICIENTS IN FOOD PROCESSING:

Recently reported mass transfer coefficient data in food processing were retrieved 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 Tables 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
Spray
2 Freezing
Forced Convection
3 Storage
Forced Convection
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
1
2
3
4
5
6
7
8
9
No. of Equations
1
Com
Grapes
Maize
Meat
Model food
Potatoes
Rice
Carrots
2
1
6
1
1
1
1
1
Milk
Total No. of Equations
15
Table 9.14 Parameters of the Equation/^ = aRe" for each Process

Process
Drying/convective
Drying/spray
mm Re
max Re
23.5 -0.882
5,000
2.95
-0.889
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
393
Table 9.15 Parameters of the Equation jM = aRe" for each Process and each Material
/;
min Re
5.15-0.575
20
-0.462
0.004
0.741-0.430
10
900
40
3,000
Mouradetal., 1997
34.6 -1.000
15
Rice
Torrezetal., 1998
Carrot
5.15-0.575
20
Muletetal., 1987
0.69 -0.486
500
5,000
max Re
Drying
Convective
Corn
Torrezetal., 1998
Graves
Ghiausetal., 1997
Vagenasetal, 1990
Maize
1,000
1,000
Spray
Milk
Straatsma et al., 1999
2.947
-0.890
Meat
Toccietal., 1995
2.496
-0.495
2,500
70,000
Storage
Potatoes
Xuetal.,1999
0.667
-0.428
50
55
11.220
-1.039
6,500
26,000
Freezing
Sterilization
Model food
Fuetal.,1998
394
Chapter 9
10
^
\\
Sr
"*^
N^
5fc
s
%
\
s,,v
0.1
Nt,""
0
'V
JM-1.llRe' '
ss
ss
*^
x^
^
N.
JM
;., ^
' ^"V
1s ^
0.01
S iir-5*
!l
^*;-
\__ 5 _ *
^s
^> sS <v s
*','^n
0.001
_ __
. , __
-^
S
V
0.0001
10
1 000
100
10 000
100 000
Re
Figure 9.13 Mass transfer factory^ versus Reynolds number Re for all the examined
processes and materials.
395
10
TJfyfitg
Con-wclti
0.1
nezjir
JM
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
Gras
0.01
0.001
10
100
Re
1000
10000
Figure 9.15 Mass transfer factor jM versus Reynolds number Re for convective drying
process and for various materials.
397
10
1
\s
I\
t
sTa
I>
ing
H -J
It II BCtlV
5
)i ing
^.
^1 s, V
\
St
0.1
1
JM
nv>r
s.
^> j
ST _ .
1 1
^1
i
j
\V
0.01
*"*"-^
=f-
F e izil 2(
0.001
V"
\
y
I
..tod
\'n ttrJ
0.0001
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
a
Bi
b
cp
cv
C
transport area, m
constant of Redlich-Kwong Eq. (2-12)
Biot number
constant of Redlich-Kwong Eq. (2-12)
heat capacity at constant pressure kJ/kmol K
heat capacity at constant volume kJ/kmol K
concentration, kg/rrr3
mass diffusivity, m2/s
D
d
De
DPM
E
E
ED
Ea
F
Fo
G
G'
G "
G
Gz
h
h
JA
JH
JM
K
K
Kp
kB
kc
L
M
M
M
MA
N
Nu
n
diameter, m
diameter, m
Deborah number
dipole moment, debye
modulus of elasticity, Pa
activation energy, kJ/kmol
energy of activation for diffusion, kJ/mol
activation energy for viscous flow, kJ/mol
force, N
Fourier number
shear modulus, Pa
storage modulus, Pa
loss modulus, Pa
mass flow rate, kg/m2s
Graetz number
height, m
heat transfer coefficient, W/m K
mass flux of A, kg/m2s or kmol/m2s
heat transfer factor
mass transfer factor
flow consistency coefficient, Pa sn
drying constant, 1/s
partition coefficient
Boltzmann constant, kB= R/N= 1.38xlO"23 J/molecule K
mass transfer coefficient, m/s
length, m
mass, kg
torque, N m
molecular weight, kg/kmol
molecular weight of A
Avogadro's number, 6.022xl023 molecules/mol
Nusselt number
flow behavior index
403
Appendix: Notation
404
n
P
P
PM
Pr
Q
Q
q
r
R
Re
rt
r0
5
Sh
t
T
f
index
pressure, Pa or bar
permeability, kg / m s Pa
permeance, kg/ m2s Pa
Prandtl number
volumetric flow rate, m3/s
accumulated quantity, kg/m2
heat transport rate, W
radius, m
gas constant, 8.314 kJ/kmol K
Reynolds number
inside radius, m
outside radius, m
solubility, kg/m3Pa
Sherwood number
time, s
temperature, K, C
Tg
U
M
u(r)
V
V
W
WVTR
kBT/s
glass transition temperature, K, C
velocity, m/s
velocity, m/s
potential energy (Lennard-Jones potential), J
molar volume, cm3/mol, m3/mol
volume, m3
weight, kg
water vapor transmission rate, kg/m s
transport property
moisture content, kg/kg dm

compressibility factor
Greek
a
a
Y
thermal diffusivity, m2/s

relative volatility
activity coefficient
film flow rate, kg/m s
3.141
Y
Y
S
S"
AP
s
shear rate, 1/s

strain (relative deformation)
generalized transport coefficient
dimensionless dipole moment
pressure drop, Pa
interaction energy parameter, J
Appendix: Notation
s
rj
rj
77'
T;,,
77,.
9
9
/I
Am
ju
v
p
<r
T
r
TO
<j)
<j>
W
co
or
/2
/3
porosity
viscosity, Pa s
shear viscosity, Pa s
dynamic viscosity, Pa s
apparent viscosity, Pa s
relative viscosity
collision frequency, 1/s
angle of cone/plate
thermal conductivity, W/m K
mean free path, m
chemical potential, kJ/mol
momentum diffusivity (kinematic viscosity), m2/s
density kg/m3 or mol/m3
collision diameter, m
tortuosity
shear stress, Pa
yield stress, Pa
interaction parameter
volume fraction
generalized transport rate
acentric factor
frequency of oscillation. 1/s
collision integral
rotational velocity, 1/s
Subscripts
A
B
b
c
D
e
G
id
K
L
0
P
r
res
V
component A(diffusant)
component B (medium)
boiling
critical
diffusion
equilibrium
gas
ideal
Knudsen
liquid
dilute, initial
particle
reduced
residual
viscosity
405
Index
Ash, 281
Avocado, 172, 182, 191
Absorption, 228, 234, 360
Acentric factor, 11-12
Acetic acid, 242, 267
Activation energy, 72, 82-84, 91, 95,
198,249,253
Adsorption, 113,228,231,360
Agar, 298, 299, 309, 312, 321, 324
Agitated kettle, 370, 371
Albumen, 313, 325
Albumin, 184, 193
Albumine, 313, 325
Almond, 175, 185, 194,226
Amioca, see Amylopectin
Ammonia, 241
Amylopectin (Amioca), 128-132,
140,184, 193,201-204,308,
320, 342
Amylose (Hylon), 128-132, 134,
137,154,184,193,201-204,
308, 320, 343
Apparent viscosity, 69,79, 370
Apparent density, 50, 55
Apple, 50-56, 149-151,182, 191,
201,213,253,275,305,317,
329, 337, 377
Apple juice, 80-82, 373
Apple sauce, 72, 89, 92, 94
Apple slices, 253
Apricots, 157, 172, 182, 191, 377
Arrhenius equation, 16, 71, 78-80,
82,93, 128, 141,245,260
Aseptic processing,369, 375, 381
B
Baking, 373, 377, 381
Baking ovens, 369
Banana, 50-56, 182, 191, 201, 215,
306,318
Barley, 179, 188, 302, 314, 378
Beef, 183, 192, 275, 307, 319, 329,
348, 354, 379
Beef carcass, 183, 192
Beer, 84
Beeswax, 263
Beet, 186, 195,300,311,323
Bentonite, 298, 355
Bilberry, 296, 306, 318
Bingham plastic, 68-69, 91
Biopolymers, 30, 150, 254, 372
Biot number, 145, 273, 363
Bird-Carreau model, 73
Biscuit, 168, 179, 188,302,314
Blanching, 360, 375,377, 381
Bluebenies, 172, 182, 191
Boiling water, 369
Boltzmann constant, 9, 17, 241
Boundary layer theory, 368
Bread, 156, 168, 179, 188, 293, 302,
314
Brine, 252
Broad bean, 173, 183, 192
Broccoli, 176, 186, 195
Broiled meat, 173, 183, 192
Brown rice, 168,169, 179,180,
188-189
Bull, 174, 183, 192
407
408
Buoyant Force, 46
Butanol, 255
Butanone, 255
Butter, 92, 294, 304, 316
Buttermilk, 91,101
Butyric acid, 242
c
Cake, 295,302, 314, 377
Calamari, 305, 317
Calcium alginate gel, 376, 379

Canned foods, 369, 371
Canola, 185, 194,378
Capillary tube vicometer, 74-77
Carbohydrate, 281
Carbon dioxide, 12-13, 20, 241
Carp, 295,305, 317
Carrageenan gum, 85-86
Carrot, 50-56, 186, 195, 201, 217,
310,322,378,393
Cassava, 186, 195,310,322
Catfish, 181
Celery, 300,311,323
Cellophane, 264
Cellulose gum, 298, 309, 321

Cellulose-oil-water, 174, 184, 193
Cereal products, 168, 179, 188,201,
293,302,314,329
Chapman-Enskog equation, 12, 15
Cheese, 171, 181, 190,227,230,
251,303,315
Chemical potential, 105, 109,146147, 244
Cherry, 83, 306, 318
Chicken, 174, 231, 297, 307, 319
Chlorine, 241
Chocolate, 70, 92, 100, 175, 185,
194,226,262-264
Chromatographic method, 110, 113
Clustering of solutes, 247
Coating, 258-260, 262-264
Cocoa, 79
Coconut, 182, 191,312,324
Cod, 181, 190,304,316
Index
Codfish fillet, 145-146, 157

Coffee, 194,253,312,324
Colburn analogy, 368, 369
Collapse, 31,50, 60, 152,259
Collision, 9, 12, 13, 15
Colloid / Surface Chemistry, 31
Compressibility factor, 11
Condensing water vapor, 364, 369
Condensing water vapors, 364
Controlled release, 258
Cookie, 156, 168, 179, 188
Cooling, 3, 227, 245, 350-351, 359,
371,375,377,381,384
Corn, 156, 179, 188, 201, 209-210,
221-224, 264, 302-303, 314-315,
329, 346, 378, 380, 393,
Corn cream, 376, 380
Corn meal, 303,315
Corn oil, 79
Corn pericarp, 156, 234, 264
Corn Starch, 127, 162, 174, 184,
193,353,376,378
Cottonseed oil, 253
Crackers, 179, 188
Cracks, 47, 114, 127-128, 130, 141,
143,253,260
Cream, 92, 303-304, 315-316
Critical conditions, 11-12,14-15
Crystallization, 30, 33, 360
Cucumber, 301,311, 323
&
Dairy products, 181, 190,303,315,
329
Data banks, 7, 19, 29, 269, 275
Database, 27, 144, 161, 164
Deborah number, 73, 108
Diaphragm cell, 238-239
Dickerson method, 273, 351
Dietary fibers, 89
Diethyl ketone, 255
Diffusivity, mass
determination, 109-123
sorption kinetics, 110
Index
[Diffusivity, mass]
permeability methods, 114
distribution of diffusant, 118
drying methods, 120
flavors, 254-258
in fluid foods, 241-243
in polymers. 243
organic components, 252
salts, 251
small solutes, 237
Diffusivity, moisture
baked products, 168, 179, 188
cereal products, 168,179,188, 201,
209-212
dairy products, 171,181, 190
fish, 171,181, 190
fruits, 172, 182, 191, 201, 205, 206
legumes, 173, 183, 192
meat, 173, 183, 192
model foods,127-143,174, 184,
193,201,203,204
nuts, 175, 185, 194
other, 175, 185, 194
vegetables, 176, 186, 195,201
Dilatant fluid, 69
Dimensional equations, 363
Dimensionless numbers, 14, 362,
363,366-367,371,374
Distillation, 266, 360
Distribution of diffusant, 110, 118
Dogfish, 171, 181, 190
Dough, 168, 179, 188,229,293,
302,314,329,347,352-353,
356
Dried fruit, 275
Dry milk, 181,190
Dry solids apparent density, 55
Dry solids true density, 55
Drying Kinetics, 110, 159-160, 162,
227, 230-232, 234
Dual-sorption model, 248, 262
Dynamic viscosity, 73
409
Edible oils, 72, 78-79, 92-93

Egg, 175, 185, 194,229
Einstein equation, 66
Elastic materials, 65, 244
Empirical rules, 279
Emulsions, 90, 92, 262
Enclosed water density, 50, 55
Enzyme inactivation, 360
Ethanol, 12, 13, 17, 20, 84, 241-242,
255
Ethyl acetate, 255
Ethyl butyrate, 255
Ethyl oleate, 153, 154
Ethylene, 12-13, 20, 241
Eucken factor, 15
Evaporation, 254-257, 360, 372
Evaporators, 369
Excess contributions, 14
Extensional viscosity, 64
Extraction, 33-34, 252-253, 360
Extrusion, 130-131
Eyring theory, 16, 18
Fababean, 173, 183, 192
Falling films, 364, 367
Falling rate period, 120-122, 144145,369
Fat, 232-233, 281, 304, 307, 316,
319,355
Fiber, 101,281
Fibrinogen, 242
Pick diffusion equation, 8, 106, 118119,145-147,237,243
Fickian diffusion, 107-108, 243,
250,260
Figs, 376-377
Fish, 122, 145,157,181,190,252,
275,304,316,379
Flavor, 254-259, 261-262
Flavor encapsulation, 258
Index
410
Flour, 184, 193, 302-303, 314-315,

324
Flow behavior index, 68, 72, 76, 78,
80, 85, 88-92, 95
Flow consistency coefficient, 68,
370-371
Fluidisedbeds, 375, 378, 381
Food coatings, 262-263
Food Materials Science, 2, 30
Food preparation, 360
Food preservation, 360
Food rheology, 3, 63
Free convection, 363
Free-volume model, 249
Freeze-dried gel, 275
Freezing, 379,381,391-393
Fructose, 242, 266
Fruits, 50, 94, 146-152,157, 182,
191,201,205-206,305-306,
317-318,329,331-332,373
Frying, 35, 360, 369
G
Gamma function, 125
Garlic, 186, 195, 201, 219, 310,322,
Gas bubbles, 367
Gas constant, 16, 71, 93, 198, 200,
249, 326, 328
Gas pycnometer method, 46
Gelatin, 281, 298, 309-310, 321-322
Gelatinized starch,130, 141, 275,
281
Gelatin, 298, 309-310, 321-322
Glass transition, 30-31, 244-247
Glucose, 242, 312, 324
Gluten, 174, 184, 193,263-264
Glycerin, 242, 263, 298, 310, 322
Glycine, 242
Graetz number, 363, 369
Granular materials, 36, 61, 133, 135,
285
Granular starch, 130, 133-135, 137141, 150, 154,275,284
Grapes, 191,201,296,306,318,
377-378, 393
Grashof number, 363
Gravimetric method, 110
Green beans, 376-377
Green olives 251
Ground beef, 174, 183, 192
Guar gum, 85-86
Guarded hot plate, 270-271
H
Haddock, 171, 181, 190
Halibut, 171, 182, 191
Hamburger, 303, 315, 376, 379
Hazelnuts, 175, 185, 194
HOPE, 261-262, 264
Heat capacity, 8, 15
Heat exchangers, 369
Heat transfer coefficients,
determination, 361
baking, 375, 377, 381
blanching, 375, 377, 381
cooling, 375, 377, 381,384
drying, 375, 378, 381,385
freezing, 375, 379,381,387
storage, 375, 379, 381, 387
sterilization, 375, 380, 381, 388389
Heat transfer correlations, 362-363,
371
Heat transfer factor, 363, 374, 382,
384-389
Heated probe, 270-274
Heifer, 184, 193
Hemoglobin, 242
Herring, 157, 182,191,251
Herschel-Bulkley equation, 68-69,
75,91,95
Hexane, 253
Hexanol, 255
Honey, 78, 80, 83, 299, 313, 325
Horizontal tubes, 364
Huggins equation, 65
Hydrodynamic flow, 147
411
Index
Hydrogen, 241
Hylon, see Amylose
I
Ice, 33, 47, 276, 281, 292, 325, 327
Idli Batter, 293, 303, 315

J
Juices, 80-83, 89-90, 92, 95-99, 305306,311,317-318,323,373
K
Karaya gum, 85, 87
Kidney bean, 301,311,323
Kinematic viscosity, 8, 362
L
Lactoglobulin, 242
Lard, 299, 312, 324
LDPE, 261-262, 264
Legumes, 173, 183, 192, 296, 306
Lentils, 183, 192,306,318
Lewis number, 363
Lewis-Squires equation, 16, 72
Licorice extract, 83
Lipid films, 264
Liquid diffusion, 141, 143
Liquid displacement method, 46
M
Macadamia, 298, 310, 322
Mackerel, 157, 182, 191, 304, 316
Macrostructure, 2-4, 29, 35, 40, 4547, 49-50
Maize, 303, 315, 378, 393
Malt, 180, 189,230,376,378
Maltose, 242
Mango, 89, 90, 92, 95, 99, 101-102
Margarine, 33, 73, 92
Mass transfer coefficients
determination, 365
drying, 392-394, 397, 397
freezing, 391-393, 397
storage, 391-393, 397
sterilization, 391-393, 397
Mass transfer correlations, 359, 362,

366-367
Mass transfer factor, 363, 368, 391,
395-398
Mass transfer operations, 109, 359360, 362
Mayonnaise, 90, 92
Meat, 157,183, 192, 251, 307, 319,
329, 379, 393
Meat Carcass, 376, 379
Meat Muscle, 251
Meatballs, 376, 379
Membrane, 366
Methane, 241
Methanol, 255
Method of slopes, 123-124
Methyl anthranilate, 255
Microstructure, 2, 5, 29, 31-35, 60,
114,243,261
Milk, 90-91, 181, 190, 275-276,
304,312,316,324,329,345,
393
Milled Rice, 169, 180, 189
Mixed model, 283-284
Mizrahi-Berk model, 70
Model food, 346-49,142, 203
Molecular diameter, 9, 12
Molecular diffusion, 4, 106-107,
144, 147, 238, 244, 260, 263
Molecular effusion, 107
Molecular simulation, 2, 5,29- 30,
61,248,250,253,268
Mulberry, 182, 191,231
Mushrooms, 301, 311, 323, 357
Mustard, 92
Mutton, 297, 308, 320
N
Natural convection, 363-364, 369
Navy beans, 183, 192,232
Nernst-Haskel equation, 18
Newton equation, 8, 64, 65, 73
Newtonian foods, 69, 72, 380
Nitrogen, 12-13,20,241
Index
412
Non-Newtonian foods, 68, 372

Nuclear magnetic resonance, 75
Numerical methods, 124-125
Nusselt number, 351, 363, 399
Nuts, 175,185, 194, 298, 310, 322
o
Oat, 294, 303, 315
Okra, 176, 186, 195,228
Olive oil, 79
Onion, 156, 186, 195, 201, 218, 310,
322
Orange, 83, 89, 95, 97, 306, 318,
329,338
Osmotic dehydration, 35, 147
Ovalbumin, 242, 281, 309, 321
Overall heat transfer coefficient,
371-373
Oxygen, 12-13,20,241,262
P
Packaging, 259-264
Packed beds, 366
Paddy Rice, 180, 189
Palm kernel, 299, 312, 324
Paprika, 176, 186, 195, 227
Parallel flow, 364
Parallel model, 65, 283, 284
Parboiled Rice, 169, 180, 189,227
Parsley, 300, 311,323
Parsnip, 301,311,323
Past single sphere, 363, 366
Pasta, 156, 169, 180, 189, 201, 225
Pasteurization, 360
Peas, 177, 186, 195, 300, 310, 322
Peaches, 183, 192, 306, 318, 377
Peanuts, 175, 185, 194,253
Peanut butter, 92
Peanut oil, 253
Peanut pods, 175, 185, 194,227
Pear, 95, 98, 102, 306, 318, 329, 339
Peclet number, 363
Pectin, 33, 88-89, 127, 256-257,
298,309-310,321-322
Penetration theory, 367

Pepper, 177, 186, 195
Pepperoni, 174, 184, 193, 308, 320
Permeability, 110, 114-117,237238, 243-244, 248-249, 259-264
Permeance, 260
Perpendicular flow, 364
Phase transition, 30, 61
Pickles, 251,267
Pigeon pea, 177, 186, 195,233
Pineapple, 173, 183, 192, 226, 232
Plant cells, 32-33
Plant hydrocolloids, 85
Plantain, 306, 318
Plasticization, 128, 244
Poiseuille equation, 74
Polyacrylamide gel, 175, 184, 193
Polymer Science, 30, 65,110, 244
Polysaccharide films, 264
Pork, 157, 265, 297, 308, 320, 355
Potatoes, 50, 54, 150, 151, 156, 184,
186,193, 195,201,216,275,
297,310,322,329,340,378379, 392-393
Potato starch, 158, 175, 184, 193,
297, 309, 321
Power-law model, 68-69, 71, 75, 85,
88-89, 91, 94-95
Prandtl number, 363
Propanol, 255
Protein films, 264
Proteins, 135-136, 155,262-264,
280-281
Pseudoplastic fluids, 69, 85, 88-89,
252
Puffing, 127,152,231,275
PVC, 261-262, 264
R
Radish, 301,311,323
Raisins, 157, 183, 192, 201, 306 318
Rapeseed, 312, 324, 329
Raspberries, 376-377
Raspberry, 89, 102, 295, 306, 318
Index
Real gases, 11-12, 15

Recovery of volatiles, 360
Refrigeration, 360, 369
Regular regime theory, 125-126
Retorts, 375, 380-381
Reverse Osmosis, 360
Rheological properties (viscosity)
aqueous Newtonian, 80
chocolate, 100
cloudy juices/pulps, 89
edible oils, 79
emulsions, 90
fruit and vegetable juices, 95
plant biopolymer solutions, 85
Rheology, 3, 5, 63, 66, 70, 72-74,
90, 101-103
Rice, 156, 179-180, 185, 188-189,
201,303,315,378,393
Rice Starch, 185, 194
Rotary drying, 375, 379, 381
Rotational viscometer, 75-76
Rough Rice, 180, 189, 201, 233
Rubbery state, 108, 238, 244
Rutabagas, 301,311
5
Salad, 90
Salmon, 91, 101,295,305,317
Salt, 18, 20, 84, 133, 146-147, 237,
251-252
Sausage, 157,184, 193, 308, 320
Scanning microscopes, 31-32
Schmidt number, 363
Shark, 171, 182, 191
Shear rate, 31, 64-66, 68-76, 78-80,
85,88,91,94,370
Shear stress, 8, 64-66, 68-71 74-76,
78, 85, 88, 94
Sherwood number, 120-121, 126,
161,363,365
Shrimp, 305,317
Shrinkage, 36-37, 39-40, 47, 50, 55,
60, 126, 137, 150
Shrinkage coefficient, 55
413
Simplified methods, 110, 123, 125
Simulation, 29-30, 124, 232, 250,
253
Skim milk, 101, 171, 181, 190, 352
Sodium caseinate, 101, 263
Solid displacement method, 46
Solubility, 115, 117-118,248-249,
259-260, 262-263
Sorbitol, 263
Sorghum, 299, 313, 325
Sorption kinetics, 107-111, 127,
129, 148,150-152,244
Soy flour, 293, 302, 314
Soya, 177, 186, 195,376,379
Soya meal, 177, 186, 195
Soybean, 152, 156, 186, 195,312,
324, 378
Soybean flakes, 253
Soybean oil, 79,253
Soybeans, 150, 152, 156,161
Specific volume, 55
Spinach, 301, 311,323, 351
Spinning disc, 366
Squid, 191,305,317
Stanton number, 363
Starch gel, 49, 127-129, 131
Steam, 19, 27, 226, 352, 375
Sterilization, 360, 380-381, 388389, 392-394
Stokes diaphragm cell, 239
Stokes-Einstein equation, 17,241,
242, 252
Storage, 30-32, 257, 379, 381 387,
391-393
Strawberries, 295, 306, 318, 351,
376-377
Structural models, 40, 47, 50, 163,
197,280,283,284,287,326
Structural properties, 55
Sucrose, 24-25, 80-83, 133, 147148,242,253,258,281,309310,312,321-322,324,371
Sucrose solution, 275
414
Sugar Beets, 178, 186, 195,253,

300,311,323
Sugar solutions, 80
Sunflower seeds, 185, 194
Surface renewal theory, 367
Surfactants, 153
Surimi, 305, 317
Swiss cheese, 251,267
Swordfish, 172, 182, 191
Index
Transport coefficients, 144

Transport gradient, 8
Transport Phenomena, 5, 7, 27, 158,
228, 257, 265, 354
True density, 55
Turbulent flow, 363, 366, 369
Turkey, 184, 308, 320
Turnip, 187, 196,311,323
Tylose, 309,321
Tailor-made porous solid foods, 47,

60
Tapioca, 178, 186, 195
Taylor dispersion method, 238, 240
Texture, 3, 29, 31, 33, 60, 64, 101,
102-104,266
Thermal conductivity of foods
determination, 270-273
baked products, 293, 302, 314, 329
cereal products, 293, 302, 314, 329
dairy products, 294, 303, 314, 329
fish, 294, 304, 316
fruits, 295, 305, 317, 329, 331-332
legumes, 296, 306, 318
meat, 296, 307, 319,329
model foods, 297, 308, 320, 329
nuts, 298, 310, 322
other, 299, 312, 324, 329
vegetables, 300, 310, 322, 329,
333-334
Thermal diffusion, 107, 145
Thermal diffusivity, 269, 273-279
Thermodynamics, 7, 10, 27, 29, 158,
266-267
Thixotropic fluids, 70-71, 91
Time lag method, 110, 117
Tobacco, 299, 312,324, 350
Tomato, 67-68, 90, 95-96, 187, 196,
252,311,323,329,341,377
Tomato paste, 275
Torque, 74, 76
Tortuosity, 106, 147, 250, 254
Unsteady-state method, 110, 117118,273-274
V
Vapor diffusion, 106, 109, 141, 143,
163, 199
Variable Diffusivity, 110, 123, 226
Vegetable oil, 275
Vegetables, 35, 50, 95, 150, 156,
176,186, 195,201,207-208,
333-334
Vertical tubes, 364
Viscometers
capillary tube, 74
rotational, 75
cone-and-plate, 76
Viscosity, see Rheological properties
Volatile compounds, 255, 266
Volume displacement method, 46
Weissenberger rheogoniometer, 76
Wheat, 135, 156, 181, 190,201,
220,302-303,315,378-379
Whey, 263, 294, 304,316
Whiting, 172, 182, 191
Wild rice, 170, 181, 190
Wilke-Chang equation, 241-242,
252
Williams-Landel-Ferry equation, 31,
245
Wine, 84, 102
Index
415
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

FOOD SCIENCE AND TECHNOLOGY

1. Flavor Research: Principles and Techniques, R. Teranishi, I. Hornstein,

41. Handbook of Cereal Science and Technology, Klaus J. Lorenz and

70. Handbook of Fruit Science and Technology: Production, Composition,

97. Seafood Enzymes: Utilization and Influence on Postharvest Seafood

Additional Volumes in Preparation

Flavor, Fragrance, and Odor Analysis, edited by Ray Marsili

National Technical University of Athens

MARCEL DEKKER, INC.

NEW YORK BASEL

This book is printed on acid-free paper.

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

Current printing (last digit):

2. Transport Properties of Gases and Liquids

3. Food Structure and Transport Properties

B. Food Materials Science

4. Rheological Properties of Fluid Foods

5. Transport of Water in Food Materials

6. Moisture Diffusivity Compilation of Literature

III. MOISTURE DIFFUSIVITY OF FOODS AS A FUNCTION OF

7. Diffusivity and Permeability of Small Solutes

IV. DIFFUSION OF SOLUTES IN FOODS

B. Diffusivity of Organic Components

C. Volatile Flavor Retention

8. Thermal Conductivity and Diffusivity of Foods

9. Heat and Mass Transfer Coefficients

II. THERMAL TRANSPORT PROPERTIES

Thermal conductivity represents the basic thermal transport property, and it

Transport Properties of Gases and

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

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

momentum diffusivity or kinematic viscosity (m2/s)

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

Transport Properties of Gases and Liquids

III. MOLECULAR BASIS OF TRANSPORT PROCESSES

Transport Properties of Gases and Liquids

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

Table 2.1 Critical Constants and Acentric Factors of Selected Fluids

ource: Data from Reid et al., 1987.

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

Transport Properties of Gases and Liquids

Table 2.2 Intermolecular Constants of Selected Components

Source: Data from Reid et al., 1987. Inm = 10A = 1 0 m

s/kBTc =0.17915 + 0.169o>

where T" = TkB/ sis the reduced temperature.

where 5* is the dipole dimensionless number, defined by the equation:

IV. PREDICTION OF TRANSPORT PROPERTIES OF FLUIDS

Transport Properties of Gases and Liquids

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

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

Transport Properties of Gases and Liquids

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

DAB= 1.7x1 0"5m2/s

tljjj0 = A t / A G = 10 to 1000, DJDG si/10000

Transport Properties of Gases and Liquids

The viscosity of steam/air mixtures, which is important in retort processing

V. TABLES AND DATA BANKS OF TRANSPORT PROPERTIES

Table 2.3 Viscosity 77 and Thermal Conductivity A of

Source: Data from Perry, 1984 and Reid et al., 1987.

Table 2.4 Mass Diffusivity (DAB)