THB SOLUBILITY OP 30MS SALTS OF CIS- AMD TRANS- DIN ITROTETRAMMINE COBALT III IM MIXED SOLVENTS DISSERTATION presented In Partial Fulfillment of the Requirements for the Degree Dootor of Philosophy In the Graduate School of The Ohio State University By HENRY LAWRENCE CLEVER. B.So#. M*SO The Ohio State University 1931 Approved byi AGKHOffLEDGUIBT I wish to express appr •olatloa to Dr* Frank Yerhoek for suggesting thla problem and for guidanoe and oounaal throughout tho work. I wish to express appreciation for the financial assistance of a fellowship g r suited t y the University Ooasdttee for the Allooatlon of Rose aroh Foundation Grants. TABLE OF CONTENTS Pag* INTRODUCTION ..................................... 1 EXPERIMENTAL ..................................... 6 Calibration of Glassware*................... 6 * Standardisations............................ 7 Cobalt Analysis............................. 11 Ansnonla Analysis......... 13 Solvents ............................. 21 Effsot of Tims and Light.................... 24 Tims and Saturation* ...... 20 Preparation of Compounds.................... 33 Solubility Determination Procedure.......... 47 Literature Densities of Mixed Solvents...... 50 Literature Dleleotrlo Constant of Mixed Solvinte........................... 51 CALCULATIONS AND DISCUSSION ..................... 129 Crooeo and Flavo Plcrate.................... 129 Solubility and Solvent Composition.......... 135 Solubility and Dleleotrlo Constant.......... 136 Comparison of Solubilities In Water......... 137 Heats of Solution* ......... 139 Test of the Born Equation................... 144 Debye-Huokel Limiting Law, Mean Activity Coefficient and Ricol-Davis finplrioal Relation.................................. 155 SUMMARY.......................................... 170 FIGURES .......................................... 175 BIBLIOGRAPHY .................................... 262 AUTOBIOGRAPHY.................................... 266 ill LIST OF TABLES Table Page I CALIBRATION OF GLASSWARS ................. 6 II STANDARDIZATION OF 0*005, 0*01 AND 0*05 N.HC1 ................................ 10 III TEST OF THE AMMONIA ANALYSIS PROCEDURE .**. 16 IV AMMONIA ANALYSIS OF CROCEO PICRATE AS A FUNCTION OF HYDROXYL CONCENTRATION....... 18 V ANALYSIS FOR AMMONIA IN BLANK SOLUTIONS CONTAINING PICRATE ION .................... 19 VI ANALYSIS OF CROCEO PICRATE IN 52£ DIOXANE ................................... 20 VII SAMPLES FOR STUDY OF THE EFFECT OF TIME AND LIGHT ON COBALTAMMINE SOLUTIONS...... 26 VIII EFFECT OF TIME AND LIGHT ON COBALTAMMINE SOLUTIONS ............................. ... 26 IX TIME AND SATURATION IN 40?£ D I O X A N E ....... 31 X SOLUBILITIES FROM OVER AND UNDER­ SATURATION ................................ 32 XI CONTROL OF CONSTANT TEMPERATURE BATH AT 25.0° C ................................. 49 XII DENSITIES OF WATER, DIOXANE, ETHYL ALCOHOL AND ACETONE FROM 20 TO 30° C............... 51 XIII DIELECTRIC CONSTANT OF DIOXANE-WATER, ETHYL ALCOHOL-WATER AND ACETONE-WATER MIXTURES AT 15*0° AND 25.0® C ............. 52 XIV SOLUBILITY OF CROCEO PICRATE IN DIOXANE- WATER AS SOLVENT AT 25.° C................. 53 XV SOLUBILITY OF FLAVO PICRATE IN DIOXANE- WATER AS SOLVENT AT 25* C .................. 55 lv LIST OF TABLES (CONT.) Tab la Pag* XVI SOLUBILITY of CROCEO PICRATE IN DIOXANE- WATER AS SOLVENT AT 15.5° C............ 57 XVII SOLUBILITY OF FLAVO PICRATE IN DIOXANE- WATER AS SOLVENT AT 15.5° C. 58 XVIII SOLUBILITY OF CROCEO PICRATE IN ACETONB- WATER AS SOLV !NT AT 25.1° C............ 60 XIX SOLUBILITY OF FLAVO PICRATE IN ACETONB- WATER AS SOLV ENT AT 25.1° C. 61 XX SOLUBILITY OF CROCEO SULFATE DIOXANE- WATER AS SOLVENT AT 15 AND 25°P. C. 62 XXI SOLUBILITY OF FLAVO SULFATE IN DIOXANE- WATER AS SOLVENT AT 15 AND 25° C. 64 XXII SOLUBILITY OF CROCEO SULFATE IN KTHYL^ ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C« .. 66 XXIII SOLUBILITY IN FLAVO SULFATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. 68 XXIV SOLUBILITY OF CROCEO SULFATE IN ACETONE- WATER AS SOLVENT AT 15 AND 25° C. 70 XXV SOLUBILITY OF FLAVO SULFATE IN ACETONE- WATER AS SOLVENT AT 15 AND 25° C. 72 XXVI SOLUBILITY OF CROCEO IODATE IN DIOXANE* WATER AS SOLVIMT AT 15 AND 25° C. 74 XXVII SOLUBILITY OF FLAVO IODATE IN DIOXANE- WATER AS SOLVENT AT 15 AND 25° C, 77 XXVIII SOLUBILITY OF CROCEO IODATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. • * 80 XXIX SOLUBILITY OF FLAVO IODATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. • * 83 XXX SOLUBILITY OF CROCEO IODATE ACETONE- WATER AS SOLVENT AT 15 AND 25°3 C. 86 ▼ LIST OF TABLES (COHT.) Ftgt SOLUBILITY OF FLAVO IODATE IN ACETONB- WATER AS SOLVENT AT 15 AND 25° C...... 89 SOLUBILITY OF CROCEO DINITROOXALATO- DIAMMINE COBALTATE IN DIOXANE-WATER AS SOLVENT AT 16 AND 26° 0............. 92 SOLUBILITY OF FLAVO DINITROOXALATO- DIAMMINE COBALTATE IN DIOXANE-WATER AS SOLV BIT AT 15 AND 25° C............. 96 SOLUBILITY OF CFOCEO DINITROOXALATO- DIAMMINE COBALTATE IN ETHYL ALCOHOL- WATER AS SOLVENT AT 15 AND 25° C. ..... 99 SOLUBILITY OF FLAVO DINITROOXALATO- DIAMKINE COBALTATE IN ETHYL ALCOHOL- WATER AS SOLVENT AT 15 AND 25° C ...... 102 SOLUBILITY OF CROCEO DINITROOXALATO- DIAMKINE COBALTATE IN ACETONE-WATER AS SOLVENT AT 15 AND 25° C............. 105 SOLUBILITY OF FLAVO DINITROOXAIATO- DIAMKINE COBALTATE IN ACETONE-WATER AS SOLVENT AT 15 AND 25° C............. 108 SOLUBILITY OF CROCEO AND FLAVO PERMAN­ GANATE IN WATER AT 15 AND 25* C ....... 111 • T ■ - f-t EFFECT OF ADDED POTASSIUM CHLORIDE ON SOLUBILITY OF CROCEO SULFATE ......... 112 EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO SULFATE ...... 114 EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO DINITROOXALA- TODIAMKINE COBALTATE .................. 116 EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO DINITROOXALA- TODIAMMINE COBALTATE .................. 118 EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO IODATE ...... 120 vl LIST OF TABLES (GOST.) Tabla Pag* XLIII EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO IODATE............... 123 XLIV EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO P I C RATE.............. 126 XLV EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO PICRATE.............. 127 XLVI APPEARANCE OF CROCEO AND FLAVO PICRATE RESIDUES FROM SOLUBILITY DETERMINATION IN WATER-DIOXANE.......................... 132 XLVII CARBON AND HYDROGEN ANALYSIS OF CROCEO AND FLAVO PICRATE RESIDUES FROM VARIOUS MIXED SOLVENTS ............... „ 134 XLVII I RATIO OF FLAVO/CROCEO SOLUBILITY.......... 137 XLIX CKYSTALLOGRAPHIC R A D I I .................... 130 L CALCULATION OF ANION RADII FROM CRY3TALL0- GRAPHIC DATA ASSUMING SPHERICAL ANIONS .... 138 LI HEAT OF SOLUTION OF CROCEO AND FLAVO PICRATE IN DIOXANE-WATER.......................... 141 LII HEATS OF SOLUTION ......................... 142 LIII DIELECTRIC CONSTANT WHERE DEVIATION FROM BORN EQUATION STARTS ...... 148 LIV BORN EQUATION IONIC RADII ................. 150 LV DATA OF KOIZUMI ON SOLUBILITY OF PbSO* AT 25 C.................................... 154 LVI DIPOLE MOMENT AND DIELECTRIC CONSTANT OF THE PURS SOLVENTS USED IN PREPARING THE MIXED SOLVENTS ............................. 155 LVI I COMPARISON OF DEBYB-HUCKEL LIMITING LAW OBSERVED AND CALCULATED SLOPES ............ 159 LVIII MEAN ACTIVITY COEFFICIENT OF*SALT IN ITS SATURATED SOLUTIONS ....................... 162 ▼11 LIST OF TABLES (COHT.) Tabl# Pag# LIX SLOPES OF THE PLOT OF log ■ VS log D ..... 165 UE BJERKUM ION ASSOCIATION AND MINIMUM DISTANCE OF APPROACH................................. 168 ▼ill LIST OP FIGURES Figure Page 1 Ammonia Analysis Apparatus ............... 176 2 Sample Tube and Sampling M e t h o d ...... .... 177 3 Crooeo and Flavo Piorate, solubility vs. Solvent Composition In Water-Dioxane at 25 C. ...... 178 4 Crooeo and Flavo Picrate, Solubility vs. Solvent Composition in Water-Dioxane at 15*5 ..................................... 179 5 Crooeo and Flavo Piorate, Solubility vs. Solvent Composition in Water-Acetone at 25.1 C ..................................... 180 6 Crooeo Sulfate, Solubility vs. Solvent Composition at 25 C........................ 181 7 Crooeo Sulfate, Solubility vs. Solvent Composition at 15 C. ...................... 182 8 Flavo Sulfate, Solubility vs. Solvent Composition at 25 C. ..................... 183 9 Flavo Sulfate, Solubility vs. Solvent Composition at 15 C. ...............*...... 184 10 Crooeo Iodate, Solubility vs. Solvent Composition at 25 C....................... 185 11 Crooeo Iodate, Solubility vs. Solvent Composition at 15 C........................ 186 12 Flavo Iodate, Solubility vs. Solvent Composition at 25 C........................ 187 13 Flavo Iodate, Solubility vs. Solvent Composition at 15 C • ....... 188 14 Crooeo Dlnitrooxalatodlammlne Cobaltate, Solubility vs. Solvent Composition at 25 C ....................................... 189 lx LIST OF FIGURES (COST.) Figure Page 15 Crooeo Dlnltrooxalatodlammine Cobaltate, Solubility vs. Solvant Composition at 16 C ......................................... 190 16 Flavo Dlnltrooxalatodlammine Cobaltate, Solubility vs. Solvant Compoaltlon at 26 ......................................... 191 17 Flavo Dinitrooxalatodiammine Cobaltate, Solubility vs. solvant Composition at 15 C ......................................... 192 18 Crooao Sulfata, Solubility vs. Dlalaotrlo Constant at 26 C. ..................... 193 19 Crooao Sulfate, Solubility vs. Dleleotrlo Constant at 16 C. ......................... 194 20 Flavo Sulfate, Solubility vs. Dleleotrlo Constant at 26 ...........................