A STUDY OF THE ADDITION COMPOUNDS OF TITANIUM TETRABROMIDE AND TITANIUM TETRAIODIDE WITH 1,4-DIOXANE, TETRAHYDROFURAN, AND TETRAHYDRQPYRAN DISSERTATION Presented in Partial Fulfillment of tha Requirements for the Degree Doctor of Philosphy in the Graduate School of The Ohio State University Robert Fredrick Rolsten, B.S. The Ohio State University 1955 Approved by: D r ACKNOWLEDGEMENTS The author wishes to express appreciation to Dr. Harry H. Sisler for his continued personal interest and guidance throughout the course of the investigation. Appreciation is also extended to Dr. Edward D. Loughran for his cooperation in the use of the infrared spectro­ photometer, to Dr. Preston M. Harris and Mr. Herbert W. Newkirk for contributing to the interpretation of the X-Ray data. The arrangement between Battelle Memorial Institute and the Graduate School of The Ohio State University with regard to tuition is gratefully acknowledged. I fully recognize the sacrifice my children have made in tolerating my necessary absence while attending school and which resulted in my failing of fatherly obligations. I sincerely hope the means has not destroyed the end. ii TABLE OF CONTENTS Page ACKNOWLEDGEMENTS ......................................... ...... ii LIST OF ILLUSTRATIONS .......................................... iv LIST OF TABIES ............................................. viii I. INTRODUCTION .................................. 1 II. HISTORICAL ............................................... 3 III. PREPARATION AND PURIFICATION OF REAGENTS ................ 25 IV. PREPARATION OF ADDITION COMPOUNDS ...................... 34 V. X-RAY DIFFRACTION ANALYSIS .............................. 55 VI. NEUTRALIZATION EQUIVALENT WEIGHT ....................... 136 VII. INFRARED ANALYSIS ........................................ 184 VIII. CRYOSCOPIC STUDY ......................................... 208 IX. REACTIONS OF TJ.I4 WITH EPOXY COMPOUNDS .................. 219 X. X-RAY DIFFRACTION ANALYSIS ........................ 232 XI. THEORETICAL DISCUSSION .................................. 255 XU. SUMMARY ................................................... 266 XIII. SUGGESTED RESEARCH PROBLEMS.... ........................... 268 APPENDIX I ..................................................... 269 APPENDIX II .................................................... 275 APPENDIX III ................................................... 278 APPENDIX IV ........ 280 AUTOBIOGRAPHY ................. V ................................ 283 iii LIST OF ILLUSTRATIONS Figure Page 1 Apparatus for Preparation of TiBr4 ........................ 27 2 Reaction Flask for The Preparation of TiBr^,.......... 29 3 Titanium Tetrabromide Storage Ampoules................. 30 4 Apparatus for Preparation of Addition Compounds. ....... 35 5 Purification of the Addition Compound, TiBr4 »C4Hg0 2 . ... 37 6 Photograph of TiBr4 and TiBr4 *C4 Hg0 2 ............ 40 7 Infrared Spectrogram of Tetra hydro fur an ......... 47 8 Infrared Spectrogram of Viscous Liquid As a Result of The Reaction of TiBr4 and Tetra hydro fur an............ 47 9 Infrared Spectrogram of TiBr4 *2Tetrahydrofuran'.in Nujol.. 49 10 Infrared Spectrogram of Water Insoluble Liquid....... 52 11 Infrared Spectrogram of Viscous Liquid After Passing Through a Column of Al2 0 3 »celite..................... 53 12 Geometrical Features of the Debye-Scherrer Technique. ... 57 13 X-ray Spectrometer Data for Ti0 2 - 78 14 X-ray Diffraction Patterns of Ti02 (Anatase)......... 79 15 Determination of Lattice Constant, a0, for Ti02 (Anatase) 80 16 Determination of the Lattice Constant, a0, for TiBr4 . ... 90 17 X-ray Diffraction Pattern of TiBr4 .................... 91 18 X-ray Diffraction Pattern of TiBr4 *Dioxane, Iron Radiation........... 106 19 X-ray Diffraction Pattern of TiBr4 *Dioxane, Cobalt Radiation................ 106 iv LIST OF ILLUSTRATIONS (Continued) Figure Page 20 X-ray Diffraction Pattern of TiBr4 *Dioxane, Copper Radiation. ....................... 106 21 Determination of the Lattice Constant, a0, for TiBr4 *Dioxane... ............................................ 107 22 X-ray Diffraction Pattern of TiBr4 *2Tetrahydropyran. ... 118 23 Determination of the Lattice Constant, a0 , for TiBr4 *2Tetrahydropyran.................. 119 24 Determination of the Lattice Constant a0 , for TiBr4 *Tetrahydrofuran (excess TiBr4 )......... 127 25 X-ray Diffraction Patterns of TiBr4 «2Tetrahydrofuran, Copper Radiation, Excess,TiBr4 ............ ................ 128 26 X-ray Diffraction Patterns of TiBr4 *2Tetrahydrofuran, Copper Radiation, Excess Tetrahydrofuran. ......... 128 27 Determination of the Lattice Constant, aQ, for TiBr4 *2Tetrahydrofuran (excess THF)....................... 134 28 Neutralization curve for TiBr4 (2.0283 grams)........ 152 29 Volume of NaOH versus A pH/0.1 ml.; sample: TiBr4(2.0283 grams). ..................................... 154 30 Neutralization curve for T H 4 (2.1067 grams).......... 156 31 Neutralization Curve for TH 4 (1.6805 grams)............. 158 32 Neutralization Curve for Til4 (2.4927 grams).......... 160 33 Neutralization Curve for TiBr4 »Dioxane (0.4762 grams). 162 34 Neutralization Curve for TiBr4 *Dioxane (0.4102 grams). .. 164 35 Neutralization Curve for TiBr4 *2Tetrahydrofuran (2.3092 grams) Prepared from Excess TiBr4 ................ 166 36 Neutralization Curve for TiBr4 »2Tetrahydrofuran (1.3734 grams) prepared from Excess TiBr4 ................ 168 37 Neutralization Curve for TiBr^*2Tetrahydrofuran (0.1644 grams) prepared from Excess Tetrahydrofuran. ... 170 v LIST OF ILLUSTRATIONS (Continued) Figure Page 38 Neutralization Curve for TiBr4 *2Tetrahydrofuran (0.2872 grams) Prepared from Excess Tetrahydrofuran 172 39 Neutralization Curve for TiBr4 *2Tetrahydropyran (0.3335 grams).............................................. 174 40 Neutralization Curve for TiBr4 *2Tetrahydropyran (0.3826 gram)............................................ 177 41 Neutralization Curve for TiBr4 *2Tetrahydropyran (0.9934 grams)............................................. 179 42 Neutralization Curve for TiBr4 *2Tetrahydropyran (0.6743 grams). ....................................... 181 43 Neutralization Equivalent Weight Apparatus. ............. 182 44 Infrared Spectrogram of Tetrahydrofuran............... 187 45 Infrared Spectrogram of 1,4-Dioxane. ............ 188 46 Infrared Spectrogram of Tetrahydropyran; Cell Thickness, Plate to Plate. .......................... 189 47 Modes of Vibration of the Imaginary CH£ Molecule. ...... 19U 48 Infrared Spectrogram of Nujol; Cell Thickness, Plate to Plate.......... .......... ....................... 194 49 Infrared Spectrogram of TiBr4 «Dioxane Mulled in Nujol; Cell Thickness, Plate to Plata................... 194 50 Infrared Spectrogram of TiBr4 *2Tetrahydropyran Mulled in Nujol; Cell Thickness, Plate to Plate. .......... 195 51 Infrared Spectrogram of TiBr^»2Tetrahydrofuran in Nujol.. 196 52 Freezing Point Cell..................................... 212 53 Typical Cooling Curve............................. 214 54 Molality Versus Molecular Weight of Addition Compound. 216 55 Apparatus for Preparation of Titanium Tetraiodide by Direct Synthesis................................ 220 vi LIST OF ILLUSTRATIONS (Continued) Figure Page 56 Apparatus for Preparation of Titanium Tetraiodide by Disproportionation of Titanium Triiodide. ..... 222 57 Purification of Til4 « .............. 223 58 Apparatus for Preparation of Tilg....................... 226 59 Needles of Titanium Triiodide.............................. 228 6 u Infrared Spectrogram of the Til4 »Tetrahydrofuran oil. Cell thickness: Plate to Plate. ............. 231 61 Determination of the Lattice Constant, a0, for TH 4 . ... 241 62 X-ray Diffraction Patterns of Til4 ................ 242 63 X-ray Diffraction Patterns of Til4 , Iron Radiation. .... 242 64 X-ray Diffraction Patterns of Tilg, Copper Radiation. .. 253 65 X-ray Diffraction Patterns of Tilg, Iron Radiation. 253 66 Determination of Lattice Constant, a 0 for Tilg............ 254 67 Graphical Determination Sf/S^................... 274 68 Mole Fraction of ®r2(j£) -^Br4(j0 as a Function of Temperature (Pressure c 760 mm.). 277 vii LIST OF TABLES Interplaner Spacings (ASTM) for T 3.O2 as Obtained From a G. E. Spectrometer............. .................... 65 Interplaner Spacings for Ti02 as Obtained From a Philips X-ray Spectrometer. ................... ..... 66 Measurement of Ti02 Film, Molybdenum Radiation........... 67 Measurement of Ti02 Film, Copper Radiation. ......... 68 Measurement of Ti02 Film, Copper Radiation. ......... 70 Measurement of Ti02 Film, Copper Radiation. ........... 71 Measurement of Ti02 Film, Iron Radiation. .......... 73 Measurement of Ti02 Film, Iron Radiation. .... 74 Calculation of Absorption Effects for Anatase (Ti02). ...76 Calculation of Absorption Effects for Anatase (Ti02) ao/co B 0.39779... ......... ..................... ...... 77 Interplaner Spacings (ASTM) for TiBr4 .............. ...... 84 Measurement of TiBr4 Film, Iron Radiation. ............. 85 Measurement of TiBr4 Film, Iron Radiation........ 86 Calculation of Absorption Effects for TiBr4 ........ 87 Calculation of Absorption Effects for TiBr4 « .......... 88 Calculation of Absorption Effects for TiBr4 , a 0s 11.292$. 89 Measurement of TiBr4 *Dioxane Film, Cobalt Radiation. ... 95 Measurement of TiBr4 »Dioxane Film, Copper Radiation. ... 97 Measurement of TiBr^Dioxane Film, Copper Radiation. ... 99 Measurement of TiBr4 *Dioxane Film, Iron Radiation. ..... Measurement of TiBr4 *Dioxane