East Tennessee State University Digital Commons @ East Tennessee State University Electronic Theses and Dissertations Student Works 12-2018 Relative Permittivity As A Function of Co-Solvent and Impedance Spectroscopy for Quantifying Anions in Solution Yahya Sami Alseiha East Tennessee State University Follow this and additional works at: https://dc.etsu.edu/etd Part of the Analytical Chemistry Commons Recommended Citation Alseiha, Yahya Sami, "Relative Permittivity As A Function of Co-Solvent and Impedance Spectroscopy for Quantifying Anions in Solution" (2018). Electronic Theses and Dissertations. Paper 3510. https://dc.etsu.edu/etd/3510 This Thesis - Open Access is brought to you for free and open access by the Student Works at Digital Commons @ East Tennessee State University. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ East Tennessee State University. For more information, please contact [email protected]. Relative Permittivity as a Function of Co-solvent and Impedance Spectroscopy for Quantifying Anions in Solution ________________________________________________ A thesis presented to the faculty of the Department of Chemistry East Tennessee State University In partial fulfillment of the requirements for the degree Master of Science in Chemistry ______________________ by Yahya Sami Alseiha December 2018 _____________________ Dr. Dane W. Scott Dr. Gregory Bishop Dr. Catherine McCusker Keywords: Relative Permittivity, Impedance Spectroscopy, Nyquist Plot, Resistivity and Conductivity ABSTRACT Relative Permittivity as a Function of Co-solvent and Impedance Spectroscopy for Quantifying Anions in Solution by Yahya Sami Alseiha This work measured relative permittivity from 15.0 to 55.0 °C of aqueous solutions containing acetone or tetrahydrofuran using a BI 870 dielectric meter. A cubic polynomial fit resulted in coefficients for calculating permittivity as a function of temperature and mole fraction. Literature values for other co-solvent system resulted in similar polynomial coefficients. Using BI 870, permittivity measurements of ionic solutions were not possible because of high conductivity. A simple method using impedance spectroscopy measured these solutions. Impedance decreases with increasing temperature and decreases with increasing ionic strength. Due to the temperature dependence of impedance, all measurements were at 25.0 °C. Anions including bicarbonate, sulfate, acetate, and carbonate were determined using this method. Detection limits were at parts per trillion (ppt) levels. A simple sensor based on smaller stainless steel cylinders and a circuit to determine impedance is currently being developed in combination with an anion exchange column. 2 DEDICATION This work is dedicated to my parent, my wife, my parent-in-laws, my kids, my siblings, my aunts, my uncles, my cousins, and my grandparents and all my friends. 3 ACKNOWLEDGEMENTS First and foremost, I would like to thank God for giving me the knowledge, strength, opportunity and ability to accomplish this research satisfactorily. Without his blessings, this work would not be possible. I would like to express my profound gratitude to my research advisor Dr. Dane Scott. This journey to complete this research would not be possible without him. Also, I would like to thank my committee members Dr. Bishop and Dr. McCusker for their suggestions and comments resulting this thesis. I also thank the East Tennessee State University Office of Sponsored Research and Programs. 4 TABLE OF CONTENTS Page ABSTRACT .................................................................................................................................... 2 DEDICATION ................................................................................................................................ 3 ACKNOWLEDGEMENTS ............................................................................................................ 4 LIST OF TABLES .......................................................................................................................... 7 LIST OF FIGURES ...................................................................................................................... 10 LIST OF ABBREVIATIONS ....................................................................................................... 11 Chapter 1. INTRODUCTION .................................................................................................................... 12 Purpose of Research .......................................................................................................... 12 Relative Permittivity .......................................................................................................... 13 The Relative Permittivity of Pure Water Compared to Other Solvents ................... 13 Temperature and Relative Permittivity .................................................................... 14 Relative Permittivity Measurements of Water Co-Solvent Systems ....................... 16 Relative Permittivity and Ionic Strength .................................................................. 16 Electrochemical Impedance Spectroscopy ........................................................................ 18 Current Applications of EIS ..................................................................................... 20 Resistivity and Impedance of Pure Water and Ions in Solutions ............................. 21 2. EXPERIMENTAL .................................................................................................................... 23 Materials and Equipment ................................................................................................... 23 Relative Permittivity Measurements ................................................................................. 24 5 Impedance Methods .......................................................................................................... 24 3. RESULTS AND DISCUSSION ............................................................................................... 26 Relative Permittivity of Pure Water .................................................................................. 26 Relative Permittivity Using Acetone as a Co-Solvent ...................................................... 27 Trends Among the Polynomial Coefficients ..................................................................... 29 Impedance of Pure Water as a Function of Temperature .................................................. 30 Calibration and Detection Limits ...................................................................................... 32 Effect of 1:1 and 2:1 Electrolytes ...................................................................................... 34 4. CONCLUSION ......................................................................................................................... 37 REFERENCES ............................................................................................................................. 39 APPENDICES .............................................................................................................................. 45 APPENDIX A: Relative Permittivity Values for Mole Fractions of Acetone in Water as a Function of Temperature ................................................................................. 45 APPENDIX B: Relative Permittivity Values for Mole Fractions of Tetrahydrofuran in Water as a Function of Temperature ................................................. 48 APPENDIX C: Polynomial Coefficients Other Aqueous Co-Solvent Systems ................ 51 APPENDIX D: Impedance Measurements for Pure water as a Function of Temperature ...................................................................................................................... 54 APPENDIX E: Impedance Measurements for Salts in Aqueous Solution as a Function of Temperature ................................................................................................... 55 VITA ............................................................................................................................................. 57 6 LIST OF TABLES Table Page 1. Relative permittivity of pure water and solvents at 20.0 °C12,13 ....................................... 14 2. Relative permittivity of water at different temperatures listed in the CRC Handbook13,15 .................................................................................................................... 15 3. Values for α and β and legend for each temperature in Figure 2 ..................................... 18 4. Relative permittivity of pure water vs temperature .......................................................... 26 5. Polynomial coefficients a-d of relative permittivity of acetone in water using mole fraction ..................................................................................................................... 28 6. Detection limits for anion concentrations measured at 25.0 °C ....................................... 34 7. Specific ion conductivities values in S·cm2/mole 46,47 ...................................................... 34 8. Experimental and calculated real impedance for 1.0 ´ 10-5 M solutions at 25.0 °C35,49 .................................................................................................................... 35 9. Relative permittivity of 0.60 mole fraction of acetone in water