Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1972 Gas chromatographic determination of lanthanide mixed-ligand complexes of 1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione Charles Allen Burgett Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Analytical Chemistry Commons Recommended Citation Burgett, Charles Allen, "Gas chromatographic determination of lanthanide mixed-ligand complexes of 1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione " (1972). Retrospective Theses and Dissertations. 5889. https://lib.dr.iastate.edu/rtd/5889 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. 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Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. university miuiuiiiiiia 300 North Zeeb Road Ann Arbor, Michigan 48106 A Xerox Education Company 73-3862 BURGETT, Charles Allen, 1947- GAS CHROMATOGRAPHIC DETERMINATION OF LANTHANIDE MIXED-LIGAND COMPLEXES OF 1,1,1,2,2,6,6,7,7,7- DECAFLUORO-3,5-HEPTANEDIONE. Iowa State University, Ph.D., 1972 Cnemistry, analytical University Microfilms, A XEROX Company, Ann Arbor, Michigan Gas chromatographic determination of lanthanide mixed-ligand complexes of 1,1,1,2,2,6,6,7, 7, 7-decafluoro-3, 5-heptanedione by Charles Allen Burgett A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Analytical Chemistry Approved: Signature was redacted for privacy. Major Work Signature was redacted for privacy. epartment Signature was redacted for privacy. Iowa State University Ames, Iowa 1972 PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company il Page TABLE OF CONTENTS L LITERATURE REVIEW AND THEORY 1 A. Introduction ^ B. Chemical Systems for the Gas Chromatography of Cationic 1 Species C. Gas Chromatographic Columns 9 1. Partitioning of molecules between the gas and the 12 liquid phase 2. Adsorption of solute molecules on the surface of the 12 liquid phase 3. Adsorption of solute molecules from the liquid solution 14 by the support surface 4. Adsorption of solute molecules from the gas phase 14 on the surface of the support 5. Change of composition and character of the liquid phase 15 caused by adsorption of its components D. Lanthanide Paramagnetic Shift Reagents 20 II. PURPOSE 23 III. AN INVESTIGATION OF GAS CHROMATOGRAPHIC SYSTEMS 24 USED IN DETERMINATION OF MIXED-LIGAND COMPLEXES A. Introduction 24 B. Experimental 24 1. Apparatus 24 a. Gas chromatograph 24 b. Spectrophotometers 25 c. Spectrometers 25 d. Thermogavimetric analyzer 25 e. pH meter 25 f. Automatic shaker 25 2. Reagents and materials 25 a. Lanthanides and yttrium 2 5 b. Cations 25 c - 1.].1.2.2.6 6.7.7. 7-derafluoro - 3. 5-heDtanedione . 26 H(FHD) d. Neutral donors 26 e. Solid supports 26 f. Liquid phases 26 g. Columns 26 h. Solvents 26 iii 3. Techniques 26 a. Preparation of stock solutions of cations 26 b. Preparation of buffer solution 27 c. Preparation of stock ligand solutions 27 d. Solvent extraction procedure 27 e. Sample injection 28 f. Preparation of column packing 28 g. Packing and conditioning of columns 28 4. Analytical determinations 29 a. Titration of cations 29 C. Results and Discussion 29 1. Synthesis of 1, 1, 1, 2, 2, 6, 6, 7, 7, 7-decafluoro-3, 5- 29 heptanedione, H(FHD) 2. Investigation of 1 anthanide H(FHD)-TBP mixed-ligand 37 complexes a. Thermal analysis of H(FHD)-TBP complexes of the 37 1anthanide s b. Elemental analysis of H(FHD)-TBP complexes of 43 the lanthanides and yttrium c. Evaluation of OF-1 as a liquid phase for the deter- 45 mination of lanthanide H(FHD)-TBP mixed-ligand complexes d. Evaluation of SE-30 as a liquid phase for the deter- 46 mination of lanthanide H(FHD)-TBP mixed-ligand complexes e. Evaluation of Dexsil 300 GC as a liquid phase for 49 the determination of lanthanide H(FHD)-TBP mixed- ligand complexes 3. Investigation of lanthanide H{FHD)-DBS0 mixed-ligand 64 complexes a. Thermal analysis of H(FHD)-DBSO mixed-ligand 64 complexes of the lanthanides b. Elemental analysis of H(FHD)-DBSO complexes of 66 the lanthanides and yttrium c. Evaluation of OF-1 as a liquid phase for the deter- 68 mination of lanthanide H(FHD)-DBSO mixed-ligand complexes d. Evaluation of SE-30 as a liquid phase for the deter- 69 mination of lanthanide H(FHD)-DBSO mixed-ligand complexes e. Evaluation of Dexsil 300 GC as a liquid phase for 69 the determination of lanthanide H(FHD)-DBSO mixed- ligand complexes IV. AN INVESTIGATION INTO THE GAS CHROMATOGRAPHIC 90 COLUMN BEHAVIOR OF MIXED-LIGAND COMPLEXES iv A. Introduction 90 B. Experimental 90 1. Apparatus 90 a. Gas chromatograph 90 b. Fluorometer 90 2. Reagents and materials 90 a. Solid supports 91 b. Liquid phases 91 c. Columns 91 d. Solvents 91 3. Techniques 91 a. Preparation of column packing 91 b. Packing and conditioning of columns 91 c. Silanization of column materials 91 d. Sample collection 92 4. Analytical determinations 92 a. Determination of silicon liquid phases 92 b. Identification of eluted species 92 C. Results and Discussion 92 1. Partitioning of mixed-ligand complexes with various 92 liquid phases 2. Loading, displacement and other non-ideal column 100 behavior of mixed-ligand complexes V. AN INVESTIGATION OF THE ELECTRON CAPTURE 115 DETECTOR FOR THE DETERMINATION OF MIXED-LIGAND COMPLEXES A. Introduction 115 B. Experimental 115 1. Apparatus 115 a. Gas chromatograph 115 2. Mixed-ligand complexes 115 C. Results and Discussion 116 VI. AN INVESTIGATION INTO THE UTILITY OF LANTHANIDE - 118 FHD CHELATES AS PARAMAGNETIC SHIFT REAGENTS FOR NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY A. Introduction IIS B. Experimental 118 1. Apparatus 118 V a. Spectrometer 118 2. Reagents and materials 118 a. Lanthanides 118 b. Substrates 118 c. li Ij li 2, 2, 6, 6, 7, 7, 7-decafluoro-3, 5-heptane- 118 dione, H(FHD) 3, Techniques 118 a. Synthesis of shift reagents 118 C. Results and Discussion 119 Vn. SUMMARY 125 Vni. SUGGESTIONS FOR FUTURE WORK 127 IX. BIBLIOGRAPHY 128 X. APPENDIX 139 XI. ACKNOWLEDGEMENTS 143 1 1. LITERATURE REVIEW AND THEORY A. Introduction This thesis will report the comprehensive study of the various factors which contribute to the development of an analytical method for cationic species by gas chromatography. Synergistic solvent extraction systems which form mixed-ligand complexes suitable for gas chromato­ graphic determinations, various column phenomena, chromatographic detectors, and interferences have been studied. A new series of para­ magnetic shift reagents for nuclear magnetic resonance has been developed and systematically evaluated. The review of the literature will necessarily be restricted only to those areas directly pertinent to these topics. The vast majority of inorganic gas chromatography has been performed with systems involving metal chelates; for this reason the literature review will cover only such systems. This section will also include discussion of the literature and theory of solvent extraction as it applies to the mixed-ligand complexes evaluated in this study. The literature review and theory concerning gas chromatographic columns will be related only to the chromatography of metal complexes and the phenomena observed during metal analysis by gas chromatography. As a result of the voluminous literature concerning the application of paramagnetic shift reagents to nuclear magnetic resonance, this literature review will be restricted to the chemical nature of the shift reagents presently utilized. B. Chemical Systems for the Gas Chromatography of Cationic Species Since the initial studies of James and Martin (74,76), gas chroma­ tography has revolutionized separations in organic and biochemistry.