THE SOLUBILITY OF SOME SALTS OF CIS AND TRANS DINITROTETRAMMINE COBALT III IN MIXED SOLVENTS

281 Pages·011.054 MB·English

by  CLEVER, HENRY LAWRENCE

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 gr suited t y the University
Ooasdttee for the Allooatlon of Rosearoh 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?£ DIOXANE....... 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-
P.
WATER AS SOLVENT AT 15 AND 25° 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 3 ACETONE-
WATER AS SOLVENT AT 15 AND 25° 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 PICRATE.............. 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 RADII.................... 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 Method...... .... 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 ............................ 195
21 Flavo Sulfate, Solubility vs. Dleleotrlo
Constant at 15.C........................... 196
22 Crooao Iodate, Solubility vs. Dleleotrlo
Constant at 25 C. ......................... 197
23 Crooeo Iodate, Solubility vs. Dleleotrlo
Constant at 15.C........................... 198
24 Flavo Iodate, Solubility vs. Dleleotrlo
Constant at 25 C........................... 199
25 Flavo Iodate, Solubility vs. Dleleotrlo
Constant at 15.C........................... 200
26 Crooeo Dinitrooxalatodiaimnine Cobaltate,
Solubility vs. Dleleotrlo Constant at 25 C.« 201
27 Crooeo Dlnltrooxalatodlammine Cobaltate,
Solubility vs. Dleleotrlo Constant at 15 C.. 202
28 Flavo Dlnltrooxalatodlammine Cobaltate,
Solubility vs. Dleleotrlo Constant at 25 C.. 203
29 Flavo Dlnltrooxalatodlaanilne Cobaltate,
Solubility vs. Dleleotrlo Constant at 15 C.. 204
x