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A Thesis Entitled Mitigation of the Tomato Lye Peeling Process by Bradley S. Yaniga Submitted As Partial Fulfillment of the Requ

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A Thesis Entitled Mitigation of the Tomato Lye Peeling Process by Bradley S. Yaniga Submitted As Partial Fulfillment of the Requ A Thesis Entitled Mitigation of the Tomato Lye Peeling Process By Bradley S. Yaniga Submitted as partial fulfillment of the requirements for The Master of Science in Chemical Engineering _____________________________ Advisor: Constance A. Schall ______________________________ Advisor: Sasidhar Varanasi ______________________________ Committee Member: Dong-Shik Kim ______________________________ College of Graduate Studies The University of Toledo May 2007 The University of Toledo College of Engineering I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Bradley S. Yaniga ENTITLED Mitigation of the Tomato Lye Peeling Process BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science in Chemical Engineering Thesis Advisor: Constance A. Schall Thesis Advisor: Sasidhar Varanasi Recommendation concurred by Committee Committee Member: Dong Shik-Kim On Department Chairman: G. Glenn Lipscomb Final Examination Dean, College of Engineering Copyright © 2007 This document is copyrighted material. Under copyright law, no parts of this document may be reproduced without the expressed permission of the author. __________________________________ An abstract of Mitigation of the Tomato Lye Peeling Process Bradley S. Yaniga Submitted as partial fulfillment of the requirements for The Master of Science in Chemical Engineering The University of Toledo May 2007 Tomato lye peeling experiments were conducted to determine whether tomato maturity, post-harvest age, type of base, or the type of pretreatment has significant effects upon tomato peelability. Results show that tomatoes are significantly more difficult to peel as they mature on the vine. Similarly, increasing post-harvest ages make tomatoes more difficult to peel as well. No significant differences exist between tomato peelability for sodium hydroxide and an equimolar mixture of ammonium and potassium hydroxide at the same total hydroxide concentration. Thus, substituting sodium hydroxide for an equimolar mixture of potassium and ammonium hydroxide would produce statistically insignificant differences in tomato peeling. The best pretreatment for lye peeling was determined to be a mixture of water and octanoic acid provided that its presence is greater than its solubility point. Other functional groups such as aldehyde, ketones, and alcohols proved to be ineffective as a pretreatment. Mercerization and osmotic effects iv appear not to be mechanisms through which lye peeling occurs. Strong bases act to depolymerize pectin in the middle lamella, which separates the cuticle from the fruit. Applying advanced statistical principles of design of experiments to tomato lye peeling would greatly increase the validity of further experiments. Future work will include additional multifactor lye peeling experiments at the laboratory scale or pilot plant scale. v Dedication To my wife, Christina Yaniga, who has always been a support for me during my studies as a graduate student. vi Acknowledgements First, I would like to acknowledge my advisors, Dr. Constance A. Schall and Dr. Sasidhar Varanasi, for introducing me to the area of Food Science in Chemical Engineering. This is a truly interesting topic, and my experience as a graduate student at the University of Toledo has been greatly enhanced through my research. They have provided much guidance and insight during the course of my research. I would also like to acknowledge Dr. Dong-Shik Kim for his involvement in my thesis committee. I would like to acknowledge the following companies for their financial contributions to the project; the Center for Innovative Food Technology (CIFT) and the Hirzel Canning Company & Farms. Also, I would like to thank Hirzel Canning Company & Farms for providing us with tomatoes, constant temperature water baths, and the mechanical tumbler for tomato peelability experiments. Finally, I would like to acknowledge all those who helped me accomplish this project. Without these individuals, this project would not have been a success. William Hirzel, for his guidance throughout the project; Jeff Unkford, for acquiring and organizing tomatoes for vine-ripened studies in 2005 and 2006; and Glen Gibbs for acquiring tomatoes for picking and delivering tomatoes twice a week during the 2005 and 2006 peeling seasons. In addition, credit must also be given to the undergraduate students who helped design and conduct experiments in the lab. Jeremy Herman, for doing so much work in the lab at the start-up of the project and designing laboratory experiments; John Mehler, for his help in conducting experiments; and John Clements, for his help in conducting experiments and technical advice. vii Table of Contents Abstract iv Dedication vi Acknowledgements vii Table of Contents viii List of Tables xii List of Figures xviii I. Introduction 1 II. Literature Review 6 The Tomato Cuticle 9 Naringenin Chalcone 12 Cutin 13 Cell Walls 14 Cellulose 17 Pectin 22 Growth & Development 26 Vine-Ripened Development 26 Post-Harvest Development 30 Tomato Peeling 33 Lye Peeling 34 Wastes from Lye Peeling 37 Steam Peeling 38 viii Research in Lye Peeling 39 Surfactants 40 Research Goals 43 III. Experimental Procedures: Lye Peeling Protocols 45 Equipment 47 Chemical Reagents 48 Tomato Peeling 49 Tomato Selection 49 Peeling Process 50 Pretreatment 50 Pretreatment Reaction Time 51 Base Dip 51 Base Reaction Time 51 Mechanical Peeling 52 Scoring 52 Statistics 53 IV. Vine-Ripened & Post-Harvest Age Studies 54 Vine-Ripened Study 54 Post-Harvest Study 63 V. Process Parameters Controlling Lye Peeling 67 Temperature, Concentration and Time Study 68 Type of Base 76 VI. Role of Caustic in Tomato Peeling 84 ix Chemical Reagents 85 Mercerization Studies 85 Cellulose II Standards 86 13C Solid State CP-MAS NMR 87 X-Ray Diffraction 88 VII. Pretreatment with Organic Solvents: Preliminary Studies 98 VIII. Solvent Pretreatments Used in Lye Peeling 109 Experimental Methods 110 Variation of Functional Group 111 Carboxylic Acids Above & Below Solubility 112 Effectiveness of Ketones 116 Temperature Variation with Carboxylic Acids 116 Carboxylic Acids at Room Temperature 120 IX. Conclusions 125 Age Studies 125 Base Selection 126 Solvent Studies 127 Role of Caustic in Tomato Peeling 128 X. Future Work 131 Vine-Ripened and Post-Harvest Changes 131 Solvent Studies 131 Design of Experiments 132 XI. References 134 x XII. Appendices 143 Appendix A – Robbins Chart 143 Appendix B – Scoring of Tomatoes 144 Appendix C – Part Drawing for X-Ray Diffraction Sample Holder 147 Appendix D – X-Ray Diffraction Patterns for Cellulose 148 xi List of Tables Table 1. ANOVA analysis for the vine-ripened study in 2005. Tomato variety was H9423. No pretreatment was used. NaOH concentration was 3.0 N. NaOH dip time and reaction time were 45 and 60 seconds, respectively. NaOH temperature was 85±2°C. 57 Table 2. ANOVA analysis for the vine-ripened study in 2006. Tomato variety was 696. Water pretreatment was used for 60 seconds. NaOH concentration was 3.0 N. NaOH dip time and reaction time were 60 seconds for both. Temperatures of water pretreatment and NaOH treatment were 80±1°C. 57 Table 3. ANOVA analysis for the post-harvest study in 2006. Tomato variety was TSH- 8. Pretreatment was water Pretreatment dip time and reaction were 60 and 30 seconds, respectively. NaOH concentration was 3.0 N. NaOH dip time and reaction time were 60 seconds for both. Temperature was 80±1°C. 64 Table 4. Time and Temperature Studies Using NaOH from 2005. Tomato variety was H9704. No pretreatment or pretreatment reaction time was used. NaOH concentration was 3.0 N. NaOH dip time and reaction time was 60 seconds. 69 Table 5. Experimental design for three-factor factorial experiment. Treatment totals refers to the total sum of all six duplicated replicates. Tomato variety was TSH-8. Water pretreatment reaction time was 30 seconds. NaOH reaction time was 60 seconds. Pretreatment and NaOH temperatures and times were the same and are xii listed below. Each replicate was a duplicated measurement in which the response was the average score of the three tomatoes. 70 Table 6. Three-way ANOVA analysis for lye peeling study. Tomato variety was TSH-8. Water pretreatment was used with a 30 second reaction time. NaOH reaction time was 60 seconds. Temperatures and times were adjusted for both pretreatment and caustic dips. Each replicate was a duplicated measurement in which the response was the average score of the three tomatoes. 71 Table 7. A list of the four bases used to determine if the type of base has an affect upon tomato peelability. Tomato variety was TSH-8. 76 Table 8. ANOVA analysis for type of base study. Tomato variety was TSH-8. Pretreatment was water. Pretreatment dip time and reaction time were 60 and 30 seconds, respectively. Base concentration was 4.0 N. Base dip time and reaction time were 60 seconds each. Pretreatment and NaOH temperatures were 80°C. 77 Table 9. Comparisons of average tomato score for base study. Tukey’s value, T0.05, was found to be 0.96. Tomato variety was TSH-8. Pretreatment was water. Pretreatment dip time and reaction time were 60 and 30 seconds, respectively. Base concentration was 4.0 N. Base dip time and reaction time were 60 seconds each. Pretreatment and NaOH temperatures were 80°C. 78 Table 10. Experimental design and results for an unbalanced factorial study between NaOH and NH4OH. An ANOVA analysis revealed no significant differences between the type of base tested. Pretreatment was water. Pretreatment dip time and reaction time were 60 and 30 seconds, respectively. Base dip time and xiii reaction time were 60 seconds each. Pretreatment and NaOH temperatures were 80°C. 81 Table 11. ANOVA analysis for effect of type of base and concentration for results in Table 10 and Figure 20. Tomato varieties were 9423 and TSH-8. Pretreatment was water. Pretreatment dip time and reaction time were 60 and 30 seconds, respectively. Base dip time and reaction time were 60 seconds each. Pretreatment and NaOH temperatures were 80°C. 82 Table 12. Experimental design for mercerization experiments 90 Table 13.
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