Analytical SFE: Optimization and Applications Sohita Patel Seton Hall University

Seton Hall University eRepository @ Seton Hall Seton Hall University Dissertations and Theses Seton Hall University Dissertations and Theses (ETDs) Spring 5-1999 Analytical SFE: Optimization and Applications Sohita Patel Seton Hall University Follow this and additional works at: https://scholarship.shu.edu/dissertations Part of the Chemistry Commons Recommended Citation Patel, Sohita, "Analytical SFE: Optimization and Applications" (1999). Seton Hall University Dissertations and Theses (ETDs). 1256. https://scholarship.shu.edu/dissertations/1256 Analytical SFE: Optimization and Applications by Sohita Patel Dissertation Submitted to the Department ofChemistry of Seton Hall University in partial fulfillment ofthe requirements for the degree ofDoctor of Philosophy. May, 1999 We certify that we have read this thesis and that in our opinion it is adequate in scientific scope and quality as a dissertation for the degree ofDoctor ofPhilosophy. APPROVED Nichola . Snow, Ph. D. Research Mentor Joseph T Maloy, Ph.D. Member e Dissertation Committee u,..rv'___ / c:- John Richard D. Sheardy, Ph.D. Chairman, Department ofCheTnH' ITru Dedication To my parents, Manu and Shakuntla Patel. This work is also dedicated to my sister, Mohita Patel and brother, Dhaval Patel. iii Acknowledgements I would like to thank my mentor~ Dr. Nicholas H. Snow, for his support, advice, guidance, and willingness to let me work in his lab. Thank you Dr. Snow. I also like to thank. my parents who have supported me through out my carrier as student. I know this has not been a short period oftime. Thank you for your encouragement~ foresighted vision and wisdom, support and motivation. I would also like to thank members of my research group for their help, especially Cindy Mleziva Blake, who has proof read almost everything I have written for my thesis. Last but not least, I would like to thank is Dr. Issam El-Achkar. You have taught me a lot more then just math. Thank you for your support, advice and guidance. You are the one, who has helped me to tackle every problem that came upon during graduate school. I wonder ifI would have made through graduate school without your help. Thank you so much. Finally, I would like to thank the Seton Hall University Research Council, and Isco Inc. for providing the materials and instruments needed for the completion ofmy research. Many thanks to all ofyoul iv Contents Page Dedication iii Acknowledgement iv Contents v List ofFigures V111 List ofTables Xl Chapter 1 - Historical 1 Chapter 2 - Basic Principles and Introduction of 17 Supercritical Fluid Extraction (SFE) I. Introduction 17 II. Properties ofPhase Diagram 18 m. Definition ofSupercritical Fluid 23 IV. Selection ofthe Supercritical Fluid 24 V. Principles of SFE 28 VI. The practice ofSFE 29 VII. Effects ofModifiers 30 VIII. Instrumentation 31 A. Pump 34 B. Extraction vessels 35 C. Restrictors 35 1. Linear 37 a. Fused silica capillary 38 b. Stainless steel capillary 38 D. Collection Systems 38 1. Cryogenic trapping in an empty container 39 2. Deposition in a liquid solvent 40 3. Retention on a solid surface 41 IX. Factors effecting the extraction recovery of SFE 42 A. Spiking procedures 42 1. Fresh 42 2. Aged 42 3. Suspended 43 4. Supercritical 43 B. Sample size 44 C. Temperature and Pressure 44 D. Sample matrix effects in SFE 47 1. Physical matrix effects 48 2. Chemical changes in the sample matrix 48 v X. Impact of matrix on extraction kinetics 48 A Pawliszyns'model 49 Chapter 3 - Optimization ofconditions in 60 Supercritical Fluid Extraction I. Goal 60 II. Experimental 60 A. Reagents 61 B. Sample preparation 61 C. SFE conditions 61 D. GC conditions 63 III. Results and Discussion 64 A Non-polar analytes 67 1. Eicosane spiked onto ODS 67 2. Eicosane spiked onto silica gel 70 B. Polar acidic analytes 72 1. 0: - naphthol spiked onto ODS 72 2. 0: - naphthol spiked onto silica gel 75 C. Polar basic analytes 77 1. Propanolol spiked onto ODS 77 2. Propanolol spiked onto silica gel 78 IV. Conclusion 89 Chapter 4 - Determination ofCrude Fat in Food Products by 90 Supercritical Fluid Extraction and Gravimetric Analysis I. Introduction 90 n. Experimental 90 Ill. Results and Discussion 92 IV. Conclusion 97 Chapter 5 - Supercritical Fluid Extraction ofPeppermint Oil 98 from Toothpaste. VI I. Introduction. 98 II. Experimental. 99 III. Result and Discussion. 102 N. Conclusion. 113 Chapter 6- Extraction of Sulfur Containing Compounds using SFE 117 I. Introduction. 117 II. Experimental. 118 III. Result and Discussion. 120 IV. Conclusion. 125 Chapter 7- Conclusion. 133 References. 136 VB Figures Figures page Figure 1-1 - An example schematic ofthe 950 MDS-2000 3 instrument. Figure 1-2 - A schematic of solid phase microextraction 5 device. Figure 1-3 - A schematic ofa gas chromatograph 10 Figure 1-4 - A conceptual scheme for vapor phase analysis 14 by mass spectrometer. Figure 2-1 Phase diagram ofcarbon dioxide. 19 Figure 2-2 Clausius-Clapeyron plots for the vapor pressures 22 ofthe solid and liquid phases ofa pure substances. Figure 2-3 Schematic diagram of an off-line supercritical 32 fluid extraction apparatus. Figure 2-4 A schematic ofthe ISCO extraction vessel 36 Figure 2-5 Effect oftemperature and pressure on the 46 Hildbrand solubility parameter for supercritical carbon dioxide. Figure 2-6 Theoretical curve ofpercentage extraction versus 53 time. Figure 2-7 Theoretical curve for the hot-ball model. 56 Figure 2-8 Theoretical curves for SFE, including solvation 58 effects, for spherical matrix particles. Figure 3-1 - A typical chromatogram. 65 Figure 3-2 Theoretical dynamic extraction profile ofan 66 analyte from a solid matrix. Figure 3-3 Extraction recovery ofeicosane spiked on ODS 69 at a constant temperature. viii Figure 3-4 - Extraction recovery ofeicosane spiked on silica 71 gel at a constant temperature. Figure 3-5 - Extraction recovery ofa-naphthol spiked on ODS 74 at a constant temperature. Figure 3-6 - Extraction recovery ofa-naphthol spiked on 76 silica gel at a constant temperature. Figure 3-7 - Extraction recovery ofpropranolol spiked on 79 ODS at a constant temperature. Figure 3-8 - Extraction recovery ofpropranolol spiked on 81 silica gel at a constant temperature. Figure 3-9 - Extraction recovery ofeicosane spiked on ODS 83 at a constant pressure. Figure 3-10 - Extraction recovery ofeicosane spiked on silica 84 gel at a constant pressure. Figure 3-11 - Extraction recovery ofa-naphthol spiked on ODS 85 at a constant pressure. Figure 3-12 - Extraction recovery ofa-naphthol spiked on 86 silica gel at a constant pressure. Figure 4-1 - Fat recovery from Snickers bar versus carbon 94 dioxide extraction volume. Figure 5-1 - Calibration curve for menthoL 103 Figure 5-2 - An example total ionchromatogram ofpeppermint oil 104 standard. Figure 5-2A - Mass spectrum ofpeak at RT - 6.6 minutes. 105 Figure 5-2B - Matching library spectrum ofthe peak in Figure 5-2A. 105 Figure 5-3 - An example chromatogram ofthe extract ofbrand 106 1 toothpaste. Figure 5-3A - Mass spectrum ofthe peak at RT -7.6 minutes. 108 Figure 5-3B - Matching library spectrum ofthe peak in Figure 5-3A. 108 ix Figure 5-3C - Mass spectrum ofthe peak at RT - 8.0 minutes. 109 Figure 5-3D - Matching library spectrum ofthe peak in Figure 5-3C. 109 Figure 5-3E - Mass spectrum ofthe peak at RT - 8.2 minutes. 110 Figure 5-3F - Matching library spectrum ofthe peak in Figure 5-3E. 110 Figure 5-4 - An example chromatogram ofbrand 2 toothpaste. 111 Figure 5-4A - Mass spectrum ofthe peak at RT - 6.3 minutes. 112 Figure 5-4B - Matching library spectrum ofthe peak in Figure 5-4A. 112 Figure 5-5 - An example chromatogram ofthe brand 3 and 4. 114 toothpaste. Figure 5-5A - Mass spectrum ofthe peak at RT - 7.6 minutes. 115 Figure 5-5B - Matching library spectrum ofthe peak in Figure 5-5A. 115 Figure 6-1 - A chromatogram ofextract ofgarlic clove using SFE. 123 Figure 6-2 - Mass spectra ofAllyl methyl sulfide. 126 Figure 6-3(A) - Mass spectrum ofAllyl sulfide. 127 Figure 6-3(B) - Matching library spectrum ofthe peak in Figure 6-3A. 127 Figure 6-4(A) - Mass spectrum ofMethyl propenyl disulfide. 128 Figure 6-4(B) - Matching library spectrum ofthe peak in Figure 6-4A. 128 Figure 6-5(A) - Mass spectrum ofDiallyl disulfide. 129 Figure 6-5(B) - Matching library spectrum ofthe peak in Figure 6-5A. 129 Figure 6-6 - Mass spectum of3-vinyl-1,2-dithiin. 130 Figure 6-7 - Mass spectum of2-vinyl-1 ,3-dithiin. 131 Figure 6-8(A) - Mass spectrum ofAllyl trisulfide. 132 Figure 6-8(B) - Matching library spectrum ofthe peak in Figure 6-8A. 132 x Tables Tables Page Table 2-1 - Properties ofsupercritical fluids vs. gases 25 and liquids. Table 2-2 - Physical parameters ofcommonly used 26 supercritical fluids. Table 3-1 Characteristics ofthe analytes used. 62 Table 4-1 - Typical results offat extraction from candy 93 bar. Table 4-2 - Compiled results from crude fat extraction. 95 Table 5-1 - Conditions and parameters used for GCIMS. 101 Table 5-2 - Recovery ofmenthol from various toothpaste. 116 Table 6-1 - Sulfur containing compounds extracted by Deruaz 122 et at using headspace GC. Table 6-2 - Seven compounds detected from the extracts ofthe 124 garlic clove using SFE. xi Chapter 1 Historical There are three major steps in the analysis of any given sample: sample preparation, chemical reaction or separation, and detection. Over the past few decades, the technology for the latter two steps ofthe analysis process has advanced tremendously compared to the sample preparation methods. This step is still very time consuming and prone to inaccurate results. (1) The sample preparation techniques used today are primarily the same ones used many years ago: liquid-liquid extraction, liquid-solid extraction, and soxhlet extraction, etc., with very little or no modification.

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