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High Pressure and Temperature Dependence of Thermodynamic Properties of Model Food Solutions Obtained from in Situ Ultrasonic Measurements

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High Pressure and Temperature Dependence of Thermodynamic Properties of Model Food Solutions Obtained from in Situ Ultrasonic Measurements HIGH PRESSURE AND TEMPERATURE DEPENDENCE OF THERMODYNAMIC PROPERTIES OF MODEL FOOD SOLUTIONS OBTAINED FROM IN SITU ULTRASONIC MEASUREMENTS By ROGER DARROS BARBOSA A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2003 Copyright 2003 by Roger Darros Barbosa To Neila who made me feel reborn, and To my dearly loved children Marina, Carolina and especially Artur, the youngest, with whom enjoyable times were shared through this journey ACKNOWLEDGMENTS I would like to express my sincere gratitude to Dr. Murat Ö. Balaban and Dr. Arthur A. Teixeira for their valuable advice, help, encouragement, support and guidance throughout my graduate studies at the University of Florida. Special thanks go to Dr. Murat Ö. Balaban for giving me the opportunity to work in his lab and study the interesting subject of this research. I would also like to thank my committee members Dr. Gary Ihas, Dr. D. Julian McClements and Dr. Robert J. Braddock for their help, suggestions, and words of encouragement along this research. A special thank goes to Dr. D. Julian McClements for his valuable assistance and for receiving me in his lab at the University of Massachusetts. I am grateful to the Foundation for Support of Research of the State of São Paulo (FAPESP 97/07546-4) for financially supporting most part of this project. I also gratefully acknowledge the Institute of Food and Agricultural Sciences (IFAS) Research Dean, the chair of the Food Science and Human Nutrition Department, the chair of Department of Agricultural and Biological Engineering at the University of Florida, and the United States Department of Agriculture (through a research grant), for financially supporting parts of this research. I am thankful to Dr. Miriam D. Hubinger, Dr. Florencia C. Menegalli and Dr. Antonio J. A. Meirelles, for the use of their laboratories at the Department of Food Engineering, at the State University of Campinas (UNICAMP), where some of the experiments at atmospheric pressure were conducted. I am indebted iv to my colleagues at the Department of Food Engineering and Technology at Paulista State University (UNESP). My accomplishments could not have been achieved without their support. I would also like to thank the staff and faculty of the Food Science and Human Nutrition Department (FSHN) and of the Department of Agricultural and Biological Engineering (AGEN), in particular the staff members of maintenance support (FSHN), and of the machine shop (AGEN), and the staff of the IFAS network computer office at the University of Florida for their help and support in many difficult situations. I am thankful to all my friends at the University of Florida, in special my friends at Dr. Balaban’s lab for their friendship, many helpful discussions, and cooperation. v TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................................................................................. iv LIST OF TABLES............................................................................................................. ix LIST OF FIGURES ........................................................................................................... xi LIST OF SYMBOLS .........................................................................................................xv ABSTRACT................................................................................................................... xviii CHAPTER 1 INTRODUCTION .........................................................................................................1 2 BACKGROUND AND LITERATURE REVIEW .......................................................6 High-Pressure Food Processing and Technology ......................................................... 6 The Role of Water in Food Systems under Pressure .............................................. 8 High Pressure as a Preservation Process for Foods .............................................. 10 End Effects of High Pressure on Foods and Food Components........................... 13 Thermodynamics of High Pressure............................................................................. 18 Compressibility..................................................................................................... 18 Adiabatic Thermal Pressure Coefficient............................................................... 19 Isobaric Heat Capacity and Thermal Expansion Coefficient................................ 20 Speed of Sound ..................................................................................................... 21 Thermodynamics of Solutions .............................................................................. 25 Equilibrium and Rate Processes............................................................................ 33 Methods of Measuring Thermodynamic Properties at High Pressure........................ 35 Density or Specific Volume and Compressibility Measurements ........................ 36 Sound Velocity Measurement............................................................................... 38 Objectives ................................................................................................................... 43 3 MATERIALS AND METHODS.................................................................................44 Pressure-Generating System ....................................................................................... 44 Sound-Velocity Measurement at High Pressures ....................................................... 50 Procedure for Collecting High-Pressure Ultrasonic Data........................................... 58 Preparation of Binary Aqueous Solutions................................................................... 62 Density and Heat-Capacity Measurements at Atmospheric Pressure......................... 63 vi Density Measurements.......................................................................................... 64 Heat-Capacity Measurements ............................................................................... 66 Summary of Conditions for the High-Pressure Experiments ..................................... 67 4 DATA PROCESSING AND ANALYSIS...................................................................68 Speed of Sound at High Pressures .............................................................................. 69 Density at Atmospheric Pressure................................................................................ 70 Isobaric Thermal-Expansion Coefficient at Atmospheric Pressure............................ 71 Isobaric Heat Capacity at Atmospheric Pressure........................................................ 71 From Ultrasonic Data to Thermodynamic Properties at High Pressures. Thermodynamic Approach ......................................................................................... 75 Mathematical Solution for the Set of Partial Differential Equations.......................... 77 Additional Thermodynamic Properties Derived......................................................... 82 Thermodynamics of Solution: Mixing Scheme and Solute Effect ............................. 83 Partial Molar Volumes.......................................................................................... 83 Partial Compressibilities ....................................................................................... 87 Water Activity from Solvent Partial Molar Volume: Thermodynamic Approach ..... 88 Error Analysis ............................................................................................................. 91 5 RESULTS AND DISCUSSION..................................................................................99 Sound Velocity at High Pressures............................................................................... 99 Density at Atmospheric Pressure.............................................................................. 103 Heat Capacity at Atmospheric Pressure.................................................................... 107 Thermodynamic Properties at High Pressures Derived from Ultrasonic Data......... 110 Thermodynamic Properties of Solution Components at High Pressures.................. 128 Partial Molar Volumes........................................................................................ 131 Partial Isentropic Compressibilities and Partial Specific Compressions ............ 137 Water Activity at High Pressures.............................................................................. 150 6 SUMMARY, CONCLUSIONS AND SUGGESTIONS FOR FUTURE STUDY ...155 APPENDIX A SELECTED THERMODYNAMIC RELATIONSHIPS AND DERIVATIONS .....163 B HIGH PRESSURE ULTRASONIC EXPERIMENTAL DATA...............................170 C DENSITY AND SPECIFIC HEAT CAPACITY EXPERIMENTAL DATA AT ATMOSPHERIC PRESSURE ..................................................................................176 D MATLAB PROGRAM FOR THE NUMERICAL ITERATIVE PROCEDURE TO COMPUTE THERMODYNAMIC PROPERTIES AT HIGH PRESSURE FROM ULTRASONIC DATA ..............................................................................................186 E THERMODYNAMIC PROPERTIES DERIVED FROM HIGH PRESSURE ULTRASONIC DATA. NUMERICAL VALUES...................................................203 vii LIST OF REFERENCES.................................................................................................221 BIOGRAPHICAL SKETCH ...........................................................................................247
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