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 ...... 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 LIST OF FIGURES (CONT*) Figure page 30 Crooeo Sulfate, -log a vs* log D at 25 C * ...... 205 31 Crooeo Sulfate, -log a va* log D at 15 C ...... 206 32 Flavo Sulfate, -log i ti.log D at 25 C* ... 207 33 Flavo Sulfate, -log s vs* log D at 15 C# •.* 208 34 Crooeo Iodate, -log e va. log D at 25 C* ••• 209 35 Crooeo Iodate, -log a va* log D at 15 C* ••• 210 36 Flavo Iodate, -log a vs* log D at 25 C ..... 211 37 Flavo Iodate, log a va* log D at 15 C ...... 212 38 Crooeo Dlnltrooxalatodlammine Cobaltate, -log a va* log D.at 25 C* ...... 213 39 Crooeo Dlnltrooxalatodlammine Cobaltate, -log a va* log D at 15 C* ...... 214 40 Flavo Dlnltrooxalatodlammine Cobaltate, -log a va* log D at 25 C* ...... 215 41 Flavo Dlnltrooxalatodlammine Cobaltate, -log a va* log D at 15 C ...... 216 42 Crooeo Iodate, -log a vs* l/D In water-dlox- ane at 15 C ...... 217 43 Crooeo Iodate, -log a vs* l/D In Water- Ethyl Alcohol at 15 C* ...... 218 44 Crooeo Iodate, -log a va* l/D In Water- Aoetone at 15 C ...... 219 45 Flavo Iodate, -log a va* l/D in Water- Dioxane at 15 ...... 220 46 Flavo Iodate, -log a vs. l/D In Water- Ethyl Alcohol at 15 C* ...... 221 47 Flavo Iodate, -log a va* l/D in Water- Acetone at 15 C* ...... 222 xi LIST OF FIGURES (CONT.) Figure Fag* 48 Flavo and Crooeo Iodate, -log a va. l/D In Water-Uioxana at 26 C...... 223 49 Crooao Iodate, -log a va. l/D In Water- Ethyl Alcohol and Water-Acetone at 25 C...... 224 50 Flavo Iodata, -log a va* l/D in Water- Ethyl Aloohol and Watar-Aoatone at 25 C ...... 226 51 Crooao Sulfate, -log a va. l/D in Water- Dioxane at 15 and 25 C...... 226 52 Crooao Sulfate, -log a va. l/D In Water- Ethyl Aloohol at 15 and 25 C. ••••••*.•«.•••.•• 227 55 Crooao Sulfata, -log a va. l/D In Watar- Aoetone at 15 and 25 C* ...... 228 54 Flavo Sulfata, -log a va. l/D in Water- Dloxana at 15 and 25 C ...... 229 55 Flavo Sulfata, -log a va. l/D in Water- Ethanol at 15 and 25 C ...... 230 56 Flavo Sulfata, -log a va. l/D in Water- Aoatona at 15 and 25 C...... 231 57 Crooao Dinltrooxalatodlawnine Cobaltate, -log a va. l/D in Water-Dioxane at 15 and 25 C ...... 232 58 Crooao Dlnltrooxalatodlammine Cobaltate, -log a va. l/D In Water-Ethyl Aloohol at 15 and 25 C...... 233 59 Crooao Dlnltrooxalatodlanalne Cobaltate, -log a va. l/D In Water-Acetone at 15 and 25 C ...... 234 60 Flavo DlnltrooxalatodlaBcnlne Cobaltate, -log a va. l/D in Water-Dioxane at 15 and 25 C ...... 235 61 Flavo Dinltrooxalatod lamina Cobaltate, -log a va. l/D in Water-Ethyl Alcohol at 15 and 25 C ...... 236 62 Flavo Dlnltrooxalatodiammine Cobaltate, -log a va. l/D In Water-Acetone at 15 and 25 C ...... 237 xll LIST OF FIGURES (COHT.) Figure Fag* 63 Flavo Sulfata, Salt Sffeota in Water ...... 238 64 Flavo Sulfata, Salt Effecta In Water-Dioxane .... 239 65 Flavo Sulfata, Salt Effecta In Water-Ethanol and Water-Aoeton#...... 240 66 Crooeo Sulfata, Salt Effacta in Water and Water-Dioxane ...... 241 67 Crooao Sulfata, Salt Effecta In Watar-Bthanol and Watar-Aoatone ...... 242 68 Flavo Iodate, Salt Effecta In Water, Water- Dioxane and Water-Acetone ...... 243 69 Flavo Iodate, Salt Effecta In Water-Dloxana and Water-Ethanol ...... 244 70 Flavo Iodata, Salt Effecta in Water-Ethanol and Water-Aoetona...... 245 71 Crooeo Iodate, Salt Effecta in Water, Water- Dloxana and Water-Aoetona...... 246 72 Crooeo Iodate, Salt Effecta In Water-Ethanol and Water-Dloxana ...... 247 73 Crooeo Iodate, Salt Effecta in Water-Acetone and Water-Ethanol...... 248 74 Flavo and Crooao Iodate Salt Effecta In Water- Ethanol ...... 249 75 Flavo Dlnltrooxalatodlainmlne Cobaltate, Salt Effecta in Water, Water-Dioxane and Water- Aoetona ...... 250 76 Flavo Dinitrooxalatodiammlne Cobaltate, Salt Effecta in Water-Ethanol...... 251 77 Crooeo Dinltrooxalatodiamnlne Cobaltate, Salt Effecta in Water, Water-Dioxane, Water-Ethanol and Water-Aoetona ...... 252
xill LIST OP FIGURES (COST.) Figure Pag* 78 Plavo Piorate, Salt Effects In Water and Water-Dioxane...... 253 79 Plavo Piorate, Salt Effects In Water-Dioxane •••• 254 80 Crooeo Piorate, Salt Effects In Water and Water-Dioxane ...... *...... 255 81 Flavo Sulfate, Heat of Solution vs. Dleleotrlo Constant ...... 256 82 Crooeo Sulfate, Heat of Solution vs* Dleleotrlo Constant ...... 257 83 Flavo Iodate, Heat of Solution vs* Dleleotrlo Constant ...... 258 84 Crooeo Iodate, Heat of Solution va* Dleleotrlo Constant ..... 259 85 Flavo Dlnltrooxalatodlammine Cobaltate, Heat of Solution vs. Dleleotrlo Constant ...... 260 86 Crooeo Dlnltrooxalatodlammine Cobaltate, Heat of Solution vs. Dleleotrlo Constant ...... 261
xiv THE SOLUBILITY OP SOME SALTS OP CIS- AND TRANS DINITROTETRAMMINE COBALT III IN MIXED SOLVENTS
INTRODUCTION
This work was dons to determine the variation of solu bility of some strong electrolytes with dielectric constant in mixed solvents, and to correlate the res tilts with ex isting theories of the solubility of electrolytes* Two simple predictions of the variation of solubility with dielectric constant were tested* The Born equation^*
(2)(t.303)KTr(i-i) which predicts that if the solvation radius and temperature are constant the logarithm of the solubility at zero Ionic
strength decreases linearly with the Inverse of the dielec tric constant* 2 The Rlccl-Davls empirical relation based on the as sumptions that the mean activity coefficient of a saturated solution of an electrolyte Is a constant Independent of sol vent and that the Debye-Huckel distance of closest approach is constant*
1 . It predicts the logarithm of the solubility to de crease linearly with the logarithm of the dielectric con stant with a slope of three* Bronsted, Delbanoo and Volquarts3 determined the solu bility of ois dlnltrotetrammine cobalt (III) tetranitro dlammine cobaltate in 10 pure solvents varying in dielectric constant from 20*8 for acetone to 84*7 for formamlde* They say The Born equation falls completely for this salt in the CQ 10 pure solvents tested. However, Bronstedwc quotes the same data to show the Born equation Is obeyed qualitative ly- 4 Bronsted and Williams find the solubility of trana dlnltrotetrammine cobalt III tetranitro dlammine cobaltate increases with decreasing dielectric constant in aqueous sugar solutions* Flatt and Jordan3 find the Born equation applies well to potassium, rubidium and cesium perchlorete in water- ethyl alcohol mixed solvents. The equation was verified exactly from D * 78 to 39, The valve of the radius was constant and approximately the same as the crystal radius* Dunning and 3hutte determined the solubilities of sil ver chloride and lead sulfate In water-glyclne (D * 78 to
96) and water-urea (D - 78 to 91). Both mixtures having a higher dielectric constant than water alone* The Born treatment gives a fair straight line for lead chloride but silver chloride shows a definite curvature* Pedersen53 determined the solubility of potassium acid tartrate, ammonium acid tartrate, thallium acid tartrate, potassium periodate, thallium iodate, oxalatotetramnine cobalt III iodate monohydrate, chloropentammlne cobalt
III iodate, hexanmlne cobalt III iodate, calcium iodate hexahydrate, barium Iodate monohydrate, lead chloride, chloropentammlne cobalt III chloride, sodium oxalate, and chloropentammlne cobalt III oxalate in both water-urea (D higher than water) and water-dloxane (D lower than wa ter) mixed solvents* The Born equation did no more than explain the magnitude of the effect of dielectric constant* It failed completely In the case of the sodium oxalate In water-urea where the solubility Increases with decreasing dielectric constant* 7 £1 Koizumi determined the solubility of lead sulfate in water-dioxane, water-glyoerine, water-ethyl alcohol, wa- cer-methyl aloohol and water-acetone at three dielectric constants at each of three temperatures. At25° C. the dielectric constants were 78.5 (water), 76.4 and 74.1. The Born solvation radii were approximately the same in all the mixed solvents except water-dioxane. The solubilities were not constant in the lsodlelectrlc solvents indicating other solvent effects* Rlccl^Davls and Sauter8 determined the solubilities of barium iodate monohydrate, silver aoetate and silver sulfate In water-dioxane mixed solvents from D » 78 to D = 12, and find the Born equation show definite curvature especially- below D * 50. Ricci and Davis® use the same data to show that the Rlcol-Davls empirical relation pre dicts the solubility better than the Born equation*
Ricci and Nesse® determined the solubility of potassium Iodate and of zinc iodate In water-dioxane mixed solvents
and find that the Rlcol-Davls empirical equation predicts the solubility better than the Born equation. They cor rected the solubility for the sorting of the mixed solvent molecules by the treatment of Debye^0 but this overcorrects
the Born equation. Mayper11 determined the solubility of both els and trans dlnltrotetrammine cobalt III sulfate In water-dioxane mixed solvents. Both salts diverge from the linear Born equation. The Riccl-Davls empirical equation predicts the experimental solubilities better than the Born equation. To this time the Rlcol-Davls empirical relation has been tested only in water-dioxane mixed solvents.
Blosser^ determined the solubility of both cis and trans dlnltrotetrammine cobalt III plcrate in water-ethyl alcohol mixed solvents. There was no apparent relation be
tween solubility and dielectric constant. As the proportion of aloohol In the solvent is increased the solubility of 5 both compounds goes through a minimum, then a maximum, then decreases to a very lov solubility in the pure ethyl alcohol. The present research was done to obtain further infor mation on the variation of solubility with dielectric con stant. The work of Mayper1* was extended by determining the solubility of both ols and trans dlnltrotetramline co balt III sulfate in water-dioxane at lower dielectric con
stants at 25° C. and over the full range at 15° C., and in
water-ethyl alcohol and water-acetone mixed solvents at 15 12 and 25° C. The work of Blosser was extended by determining
the solubility of both cis and trans dinitrotetrammine co balt III plcrate in water-dioxane at both 15 and 25° C. and In water-acetone at 25° C. In addition the solubilities of the iodate and the dir dlnltrooxalatodlammine cobaltate of both cis dlnltrotetrammine cobalt III (flavo) and trans dlnltrotetrammine cobalt III (croceo) was determined in water-dioxane, water-ethyl alco hol and water-acetone at both 15 and 25° C. Hie cis and trans dlnltrotetrammine cobalt III univa lent cations were chosen becausi^^the solubilities of many of their salts is in the dilute range desirable in the studies of the properties of electrolytei2? The solubility
Is easily and accurately determined by a simple ammonia (g ) analysis and comparison of the solubilities of the geometri cal cis and trans Isomers should be of interest. EXPERIMENTAL
Calibration of Qlaaaware A buret and several plpets were calibrated by weighing the amount of water delivered* A 100 ml* volumetric flask was calibrated by weighing the amount of water contained* The temperature of the water was 22*5° C., density was taken as 0*99670* Results are summarized In Table 1* TABLE I CALIBRATION OP GLASSWARE
Glassware Volume Wa$er, Actual Correction Marked.ml* gr. volume .ml. ml. 3uret 0.0-10.00 9.3948 9.92 -0.08 0.0-20.00 19.8817 19.95 -0.05 0.0-30.00 29.8733 29.97 -0.03 0.0-40.00 39.8217 39.95 -0.05 0.0-50.00 49.6209 49.99 -0.01 Plpet - 1 25.00 24.9712 25.05 /0.05 24.9683 25.05 A). 05 Plpet - 2 25.06 24.6454 24.08 >0.08 24.9919 25.08 A). 08 Plpet - 3 25.00 24.784b 24.87 -0.13 24.7987 24.88 -0.12 Plpet - 1 50 .ob 46. 7*203 49.8b -b. 12 49.7172 49.88 -0.12 Volumetric 100.00 99.4149 49.99 -o.oi ..JlftijC . 99.6177 99.99 -0.01
The buret corrections were used but the plpet correc tions on plpets 1 and 2 25 ml* were Ignored* Kimball "normax”
6 7 burets supposedly off no more than 0*05 ml* In 50*00 ml* were used without calibration*
Standardizations A 0*01 N solution of NaOH was standardized against dry Mallinokrodt Analytical Reagent potassium acid phthalate by the procedure of Kolthoff and Sandell 13 Standardization 5 pts* 0.01 H NaOH 03U 3M 940 vs L1124 (0.01002) Number wt KHP Titration, Normality ST* ___ ml*____ 1 0.0665 32.94 0.00989 2 0*0654 31.42 0.01003 3 0.0436 21.78 0.00981 4 0.0837 40.74 0.01006 5 0.0742 36.01 0.01009 6 0*0940 45.47 0.01013 7 0.0685 33.40 0.01005 8 0.0887 43.42 0.01001 9 0.0918 45.29 0.00993 The lowest two standardizations and highest standardiza tion were Ignored, the ;remaining 6 gave a normality of 0.01003 which was used*
A solution of 0*01 N HgSO^ was standardized against the above standard base to the phenolphthalaln end point.
Standardization of 0*01 “_.h2304 acid, ml* base. ml. acid normality 49.99* 49.70 0.00997 49.99* 49.50 0.00993 49.88° 49.31 0.00992 49.88 49.28 0.00991 0.00&93 ave. a measured from calibrated buret b measured from calibrated plpet. The usual primary standard for acids Is sodium carbo nate which has the disadvantages of^ a low equivalent weight and^ Its solution must be boiled then cooled just before reaching the end point* According to both Hurley^-* and Kolthoff and Stenger^3 a more convenient primary standard is sodium tetraborate with 10 moles of water of crystallisation. Nag • lOHgO mol* wt* 381*43, rational equivalent weight 190.60, which can be titrated without boiling to the methyl red end point. Merck Analytical Reagent c*p. sodium tetraborate deca- hydrate was recrystallized, dried, and stored according to the procedure of Hurley^*. The bottle label gave the maximum limits of impurity as Insoluble material 0.005 As 0.0003 CO, 0.00 Ca 0.005 Cl3 0.001 Fe 0.0005 P0 4 0.001 Other 0.001 SO 4 0.005 heaven metals as Pb Re errstal11satIon about 50 g. sodium tetraborate deoahydrate was crushed in a mortar, dissolved completely in 200 ml* H©0 at 65° C* The solution was cooled to 42° C* where most of the material orystallized out* Note* Above 55° some penta- hydlrat e may form* The mixture was cooled to room tem perature, filtered by suction, washed with 2 25 ml* portions HgO, 2 30 ml* 9 portions of 95# ethyl aloohol and 2 30 ml. portions of diethylether. The 38 gr. of recrystallised ma terial was spread In a thin layer on two 6 inoh watchglasses and dried in air 24 hours* The salt was stored In a hydrostat over a water solvtion saturated with both sodium chloride and suo- crose* Note* This solution gives the correct humidity to maintain the salt as the deoahydrate. The salt Is stable In air as long as the water vapor pressure Is not less than 14 mm. of mercury at 25° C.^4 Standardizations of two 5 gallon lots of 0.01 N hydrochloric acid, 3 gallons of 0.05 N hydrochloric acid and one liter of 0*005 N hydrochloric acid were made with the above purified sodium tetraborate decahydrate* Results are summarized In Table II* 10 TABLE II STANDARDIZATION OP 0.005, 0.01 AND 0.05 N.HC1 wt. NaoBaO^ • 10 HgO Volume of HC1 to Normality dllutca to 100 ml. gr. bring 25 ml. all- of aold quot to methyl red end point, ml.______OSU Lot 3M 946 vs L128 (0.01025) 5 gallons 0.3229 41.53 0.01021 41.52 0.3869* 49.45 0.01026 49.49 0.3724 47.77 0.01022 47.80 a reason to suspect an error 0 .01022 In weighing, discarded. taken OSU Lot 3 M 945 vs L128 (0.01025) 5 gallons restandardization after exposure to n h 3 . 0.3052 39.46 0.010150 39.42 0.4404 56.70 0.010188 56.70 0.3336 42.88 0.010205 42.88 0.01018 taken OSU Lot 4M 76 vs 1525 (0.01001) 5 gallons 0.2873 37.82 0.009967 37.80 0.3815 50.48 0.009915 50.46 0.3166 41.90 0.009909 41.91 O.OOTST Discarded 1st taken 0.005 N HC1 1 liter 0.0811 8.60 (10 ml.allquot) 0.00484 8.61 it n 0.00484 8.60 n » 0.00484 0.0749 20.14 0 .00488 20.16 0.00488 0.00486 taken 11 TABLE II (CONT.) STANDARDIZATION OP 0.005, 0.01 AND 0.05 N.HC1
wt. NaoB.Or^ • 10 HqO Volume of HC1 to Normality diluted to 100 ml. gr. bring 25 ml. ali of a d d quot to methyl red end point, ml.
OSU 3 M 988 vs 1213 (0.0507) 3 gallons 0.4331 45.00 (100 ml. aliquot) 0.05050 0.3982 4d;»6 " * 0.05052 0.4250 44.28 * * 0.05036 0.05046 taken
Cobalt Analysis Both Fairchild16 and Willard and Hall17 give a simple procedure for determining cobalt as oobaltoua sulfate when no other metals are present. The procedure used was es sentially that of Willard and Hall17 and is as follows! Procedure! Accurately weigh a sample containing the equivalent of 0.15 - 0.20 gr. oobaltous sulfate in a pre viously weighed porcelain crucible. Add 6-8 drops ltl nitric acid and 6-8 drops 111 sulfuric acid, heat gently without boiling on a hot plate until the sample Is decomposed. Increase heat and drive off all re maining sulfuric acid. Repeat the treatment with nitric and sulfurlo acids until the residue Is a uniform purple color. Place covered cruci ble in muffle furnace, heat 2 hours at 400-450° C., place in desiccator, cool, weigh calculate wt. % Co. 12 The time of heating was checked by analyzing two dif ferent samples of crooeo chloride, with the following re sults* ______Sample 6b Sample 6b3 Sample wt., gr. 0*2600 0*2606 0*2443 0*3824 0*3406 COSO* wt*, gr* 60 mln. 400-450° 0.1606 0*1608 0*1506 0*2344 0*2088 /30 mln. 400-460° 0*1604 0.1606 0.1505 0*2342 0.2086 /30 mln. 400-450° 0.1604 0.1606 0.1505 0.2341 0.2086 Co, wt. % 23*46 23*44 23.43 23*28 23*29 Theory Co, wt* % 23*16 Although the results were high, this Indicates 2 hours at 400-450° C. Is sufficient heating to bring the C0SQ4 to constant weight. Samples heated 1 hour at 600° C. definitely lost SO3 and gave low results*
The procedure was further checked by analyzing a sample of Malllnkrodt Analytical reagent cobaltous chloride hexahy- drate for cobalt. Ifce maximum limit of Impurities was given as Alkali Salta 0.25 % Co 0.002 Insoluble ma terial 0.01 Pe 0.001 Pb 0*005 Ni 0.15 No3 0.01 S°4 0.01 Zn* 0.05 0.49 % Cobaltous chloride hexahydrate loses its water of crys- tlllzatlon at 110° The water in the cobaltous chloride hexahydrate was determined by heating to constant weight of 125° C* 13 CoCl2 / 6Hg0, wt. gp. 0.3446 0.3759 CoCLg, wt. gr. 0.1389 0.2060 H20, wt. % 45.18 45.20 HgO Theory 45.43 CoClo / 6HgO, wt. gp. 0.5084 0.3411 0.4075 CoSCj wt. gp. 0.3337 0.2240 0.2682 Co. wt. 1) assuming 6H0 O (46*43/&20) 24.96 24.97 25.03 2) aasmnlng 45»195tfHoOi2^ 24.93 24.94 25.00 3} on dry basis 45.54 45.56 45.65 Theory 6Ho0 24.77 45.19 % HgO 24.88 dry basis 45.39 The cobalt analysis was used as a criterion or purity of the cobaltammine salts prepared and used in the solu bility determinations.
Ammonia Analysis The apparatus used is shown in figure 1. Analysis of known solutions of ammonium sulfate in water and croeeo sulfate in water gave best results with this apparatus as compared to other apparatuses which did not have the out let of the separatory funnel under the surface of the sodi um hydroxide solution, or the tube from the spray trap ex tending into the cold part of the condenser.
Wo tygon tubing was used where it could come in con tact with hot vapor. When tygon tubing was used to fasten an extension to the separatory funnel, blanks of 0.50 - 0.G5 ml. of 0.01 N sodium hydroxide were obtained.
Both the special receiver flask and the procedure are iq essentially that described by Rieman, Neuss and Haiman • 14 The re calving flask was made from a 500 ml* Krlenmeyer flask and a 100 ml* r*b* flask* The solutions used In the analysis are 1) Broa Cresol Oreen Indioator. 0*04 4. prepared as described In Merok Index p* 597 by OSU storeroom*
2) Borlo A d d Solution 0.6 a . dissolved 408 g* o*p* boric aold In 11 liters water* 3) Sodium Hydroxide Solution* 25i. prepared as needed by dissolving 700 g* o*p* sodium hydroxide In 8100 ml* water*
4) Standard Solutions of 0*005* 0*01 and 0*05 K hydrochloric aold. see section on standardizations* The procedure is as followss Procedure> Plaoe 25 ml* 25g sodium hydroxide plus 100 ml* water In a 500 ml* Kjedahl flask* Attach the special reoelvlng flask containing 50 ml* 0*6 m* borlo aold solution plus 5 drops of brom cresol green Indloator* Bring the sodium hy droxide solution to an even boll* Cautiously add the sample through the separatory funnel so no bub- bles escape through the borlo aold solution* Wash down the separatory funnel with 5 10 ml* portions of water* Distil over about 100 ml*, wash down condenser, titrate with standard hydrochloric aold until the oolor matches that of a blank of 50 ml* 0*6 m borlo aold plus 5 drops of brom cresol green indi cator plus a volume of water equal to that distilled over and that used In the titration* 16 The procedure waa checked with 26 ml* allquota aa the sample of both 0.6740 gr. dry e.p. amnonlum aulfata d Hu tad to 500 ml. (equivalent to 0.002660 m./l. of orooao aulfata or 0.0204 mill!equivalent of ammonia par ml.) and 0.5478 gr. orooao chlorlda diluted to 260 *1. water (0.006466 m./l. of orooao chloride or 0.0219 mllllequlvalents of ammonia par ml.). The lower limit of the ammonia analyaia was checked ualng aa aample 2 ml. of a solution of 0.1655 gr. ammonium aulfata diluted to 250 ml. of water (equivalent to 0.00125 m./l. of orooao aulfata or 0.010 mllllaqulvalenta of amnonia per ml.)# in the preaenca of both water and 100 ml. of 85jtf dloxane. The results which are summarized in
Table III ware satisfactory. The above procedure waa used in all analyses except those In which plorata ion waa pre sent. The procedure used when plorata Ion waa present la described on page *7 Horan and Eppig®® advise the uae of arsenlous oxide in the ammonia analysis to prevent the oxidation of some ammonia during the reduction of the trivalent cobalt of the complex to cobaltous ion.
Bloaser12 found araenloua oxide did not Improve the ammonia analyaia for either oroceo or flavo plorata. In the present research analysis of known solutions of oroceo sulfate varying In concentration from 0.001691 to 0.000074 m./l. both In the presence and absence of arsenlous oxide 16 TABLE III TEST OP THE AMMONIA ANALYSIS PROCEDURE
Sample Titration* Aold NR* Pound Units NH3 Pre ml* Normality sent 25 ml* 49*90 0*01022 0*002550 m*/l* cro- 0*002550 (NH*)2 SO* ceo- SO* soIn, I? 50*50 e 0*002570 " • 50*54 N 0.002572 " « 25 ml* oro ceo Cl 55*48 a 0*005447 m*/l* cro- 0*005446 Sola* ceo Cl 55*58 e 0*005437 ■ « 55.41 it 0*005440 " ** 2 ml* (NHa)o SO* 5*91 0 *00486 0*0190 m*eg* per 0*0200 soln* II* ml• NHj Blank 15 aa* HoO 0.14 0*00486 ---- 35 ml* dloxane 2 ml• (Nfl*)o 30* Soln* II 15 aa* RoO 4*08-0*14 0*00486 0.0191 " 0.0200 85 ml* dloxane
gave no significantly different results* The arsenlous oxide
was not used in analysing the solubility samples*
Check of Interference by Various Anions A* Plcrate Ion* In checking the purity of orooeo picrate by ammonia analysis results 2% high were obtained*
The cobalt analysis indicated a pure compound thus the am monia analysis was checked with known solutions of crooeo plcrate* Both the hydroxyl ion concentration and the volume 17 distilled from the KJedahl flask wsrs varied. The rssulta (see Table IV) Indloated ths analysis of oroceo plorata to be high and the error to depend on the hydroxyl ion con centration.
It was shown by analysis of blanks that the plorata ion alone, and not some combination of oobaltous ni trite ions from the complex with the plorata ion was re sponsible for the high results. (See Table V). When the plorata ion was present the sodium hydroxide solution turned a dark red after boiling, after standing oold sev eral days the oharaoterlstlo yellow plorata ion color re turned. To determine whether or not the plcrate Ion decomposed In the presence of low hydroxyl ion concentration a solu tion of 1.1583 g. oroceo plcrate in 250 ml. 51.8g dloxane was prepared and analysed using various sources and concen trations of OH” ion. The results are sunmarlzed in Table VI. Although the calolum hydroxide saturated solution had the lowest hydroxyl ion concentration it appeared to be satisfactory and was used aa a method of analysis for most of the solubility determinations of flavo and oroceo plorate. The good results might in part be due to the good boiling action, the excess calolum hydroxide acting as boiling ohlps. 18 T A B U IV AMMONIA ANALYSIS OF CR0CBO PICRAT2 AS A FUNCTION OF HYDROXYL CONCENTRATION
KJadahl Flask Voluma Distillad Titration Found, prasamt Contents ovar, ml* 0*01088 N m./l* m./l. HG1. ml* Crooso Chi or id# in watar 10 g. NaOH 80 50.90 *00520 •00547 120 ml« HgO 47 52*50 •00636 59 62*35 •00535 95 53.48 •00647 180 ♦59?47 4 g. BaOd 24 47.9i •06490 120 ml. HgO 54 51*19 •00523 77 53*18 •00544 -97 53*18 •00546 1 g. NaOi 62 55*86 *00544 120 ml* HgO 90 53*41 •00546 114 53.41 •00546 Crooao olorata in watar
10 g« m 6h 56 53.OS ' . 6 0 3 W •06545 120 ml* HgO 85 54*81 •00560 114 56*39 *00576 160 •00604 4 g* HaOrf 32 feo.lfe •00512 120 ml* HgO 68 52.97 *00541 104 53*42 •00546 138 53*82 •00550 1 g* VaOti 66 62*90 •06641 120 ml. HgO 94 52*90 *00541 _ 186 52*90 •00541 Crocao Dicrate In 63 wt. % Dloxana 10 g. NaOH 50 81*12 .00829 .00845 120 ml* HgO 82 84*90 •00868 118 88*86 •00908 l?f 90*96 •00930 4 g. JfaOk 38 81*25 •06830 120 ml* HgO 76 82.78 *00846 106 83*22 •00851 148 85.06 •00869 1 g* kaOH 60 80.12 •06819 120 HgO 108 82.56 •00844 .122 ...... 82*56 •00844 19 TABLE V ANALYSIS FOR AMMONIA IN BLANK SOLUTIONS CONTAINING PICRATE ION
Kjedahl Flask Volume Distilled Titration Contents over* ml. •01028 N HCl* ml. 10 g. NAOH 120 ml. HgO 97 8.67 0.1 g. Na plorata 1 g. NaOri 120 ml* HgO 77 1.26 0*1 g. Na plorats 118 2.36 1 g. fadtf 120 ml. HgO 120 0.26 0.045 a. fa nlorate 1 g. NaOH 120 ml. HgO Ca 100 0 .20 * 0.16 25 ml. 0.0161 m./l. plorata Ion dl%9?bui plus 0 .0& g. CoClg • 6HgO Ca 100 0.16 0.05 g. NafOg 10 g. NaOH 120 ml. HgO 25 ml. 0.0197 m./l. Ca 100 22.82 plorata ion in 63* dloxane 1 g. NaOH 120 ml. H©0 25 ml. 0.0197 m./l. Ca 100 0.32 * 0.25 plorata Ion In 63* dloxane _ 80 TABLE VI ANALYSIS OF CROCEO PICRATE IN 52* DIOXAHE
Contents of Ca * OH" oono. Crooeo plorata Crooeo plorata ----_ ___i. 10 g. NaOH 120 ml* HgO 8*0 0.01096 0.00998 0.01109 1 g. MaOH ...... o .m w s 6 .od098 180 ml. HgO 0.8 0.00994 120 aa. 0.1 molar 0.60987’ o.od99fl NaaP04 • 18 HgO 0.1 0.00989 9*1 g« O a l W g 180 ml. HgO 0.00994 (only 0.08 g. 0.02 0.00998 0.00998 needed to saturate soln.)
B. lodate Ion* The ammonia analyaia (p. 14 ) waa checked to dataralna whether or not the lodate ion inter- ferred. Sample Titration 0*00991 NHC1, ______s i * ______25 ml. 0.1 m 10. 0.0 25 ml. solution 24.70 85 na. solution and 24.50 25 ml. 0.1 m IO3 soln. 85 ml. flavo SO4 solution 49.65 25 na. flawo 30. soln. / 25 ml. 0.1 m. 10.t soln. 49.70
The lodate Ion did not Interfere in the analyaia of either ammonium sulfate or flawo sulfate solution and waa assumed not to Interfere In the analysis of flawo and crooeo lodate* 81 C« Permanganate lon« The asm on la analysis (p. 14 ) waa checked to determine whether or not tho permanganate ion In tar farad* 3 wapla Titration, 0*00991 H* ------BL 1______25 ml* 0*1 m Mn04~ 0*0 25 ml* (MH4 )9S0 * solution 24*70 25 ml* (NH4 J0SO4 solution / 25 ml* 0.1 m 8004* soln* 24*20 25 ml* flavo SO4 solution 49*65 25 ml* flavo 30a soln* / 26 ml* 0*1 ■ MnOj soln* 45*65
Ths parmanganate Ion does interfere, however a fairly satisfactory analysis can be made if tha permanganate is first reduced by hydrogen peroxide* This was confirmed b^ dissolving 0*2 g. sodium permanganate in 60 ml* of flavo
« sulfate solution, pipetting 25 ml* of the solution Into a mixture of 3 ml* 30£ hydrogen peroxide, 12 ml* water and 5 ml* 111 sulfurlo acid* After the permanganate color disappeared the sample was let into the Kjedahl flask and analysed* Titration was 48*60 ml* (The flavo sulfate may ha/e been diluted a little In the process*)
Solvents Water* The water used In the solubility measurements wak OSU triple distilled water with a specific conductance less than 0*99 micro mhos* Dloxane * The dloxane was a Carbon and Oarblde Co,* product purified by the method of Hess and Frahm^.to remove 88 any acetic acid, watar, peroxides and aoetal of dloxane that might be present. Seven 1500 ml. batches of dloxane were purified during the course of the work by the follow ing prooedure. Procedures Place 1500 ml. dloxane, 260 ml. water and 25 ml. 37jt hy drochloric aold in a r.b. flask, reflux 12 hours in an atmosphere of oxygen free nitrogen. Motes Oxygen removed from the nitrogen by bubbling through a solution of van adyl sulfate22, dissolving 2 g. vanadium pentoxlde in 10 ml. oono. sulfuric aold and 90 ml. water, pour on to 100 g. slightly amalga mated sine (amalgamate in saturated merourlo chloride solution of 50° C.) and bubble nitrogen through until the solution has a light clear purple color. Cool, add 200 gr. solid potassium hydroxide, shake vigorously, separate out the aqueous layer. Add a second 200 gr. KOH, shake, separate the aqueous layer. Place dloxane in atliter r.b. flask, add 20 gr. freshly out sodium, reflux 12 hours in an atmosphere of dry, oxygen free nitrogen, distill off the dl oxane through a 56 Inoh helix-packed column. Results of a typloal puriflostIon runt 83 Time Temp., Volume distilled -ffii______9ft t »l.t______8|45 A*M* 85 — 10145 99 85 2s 25 P.1I* 99*8 800") 5t 25 100*0 4001 Stored under 8 t 30 100*1 450 f inert atmos- 12 tOO midnight 100*3 800j phere In the dark The normal b*p* la 101*1 °C* at 760 mm* The above waa distilled at about 748 mm*
Water in the dloxane waa determined by FIsober reagent titration Purification 4 0.011 % HgO Purification 5 after standing several weeks 0*18 % HgO Bthyl Alcohol* The aloohol was 03U supply absolute alcohol* It waa purified by a single distillation through a 36 inch helix paoked column well protected from atmos pheric moisture* Two purifications were made* Purification b*p* Water by Fischer Reagent, %
1 77*3 0.87 8 77.3 0.46
Acetone* The acetone was Baker and Adamson ACS grade oode 1004 and was used with no purification* The following information was given on the label* 84 Bolling rang* 55*5-57.4° 0* Sp* gr* at 85° C* Not over 0*786 maxima* limit# of Impurities Non volatile 0*001 % Solubility In Hfl0 to pass tost Acids (as aoetliS) 0.003J* Alkaline sub* (as NH3 ) O.OOljf Aldehyde to pass test Substance reduolng KMnO* to pass teat Methanol Max* 0*1 % k titration with Flsoher reagent shoved 0*55 % water present*
Effect of Time and Light on Cobaltsaalnes In Solution* It was observed that solutions of oobaltammlnes de composed on standing* After several hours clear solutions becams cloudy and eventually a black precipitate formed which was assumed to be cobalt oxide* There was some evi dence that orooe* ohlorlde and sulfate recrystallized in the dark gave a slightly more nearly correct cobalt analysis than when reorystallized in the light* To study this effect further two 25 ml* samples eaoh of croceo sulfate, orooeo plcrate* flavo sulfate and flavo plcrate were prepared in 50 ml* g* s. weighing bottles* One solution of eaoh salt was kept in the light* the other was kept in complete darkness* The pH of eaoh solution was measured periodically on a Beckman model H pH meter* The instrument was calibrated against a pH 5*2 buffer bath be fore and after eaoh series of measurements* The results 85 are tabulated In Tables VII and VIII* Tha results of this experiment show oobaltaamlne solu tions decompose rapidly whan exposed to light but ara fair* ly stabla In tha dark* Tha flavo aalta seem to atart to deoompose a llttla aoonar than tha orooao aalta* Tha aul fata seemed to ba a llttla laaa atabla than tha plorata for both tha flavo and orooao aalt although thla might ba dua to tha faot tha oatlon concentration waa twloa aa great In tha aulfata aa In tha plorata aolutlona* To prevent decomposition of the orooao and flavo aalta all preparatlona and reoryatalllsatlons ware carried out
In aolutlona protected from direct light* With few excep tions, which ara mentioned In tha tabulated experimental results, tha solubility measurements ware oarrled out In sample tubas painted with two oo&ts of flat blaok paint* T A B U VII SAMPLES FOR STUDY OF THE EFFECT OF TIME AMD LIOHT ON COBALTAMMINE SOLUTIONS
Samp la Salt wt* Salt Conoantration # In 25 ml. solution, m./l* JBEx 1 0.0173 Orooao plorata .00149 2 0.0169 flavo plorata •00161 3 0.0179 Orooao aulfata •00162 4 0.0166 flavo aulfata .00141 5 0.0170 Orooao plorata •00146 6 0.0168 flavo plorata •00160 7 0.0179 Orooao aulfata .00162 8 0.0171 flavo aulfata •00146
T A B U VIII EFFECT OF TIME AND LIGHT ON COBALTAMMINE SOLUTIONS
Tima, Saapls PH Oomuant hour a # 0 1 6.6 Claar solution 2 6.9 m it 3 7.1 N it 4 7.1 m it 5 6.8 * n 6 6.7 NH 7 6.9 It II 8 7.1 * II
3* 3 Cloudy ap^earanes 4 •t 1 8.6 Slight cloudiness 2 8.6 it N 3 0.75 Slight brown ppt. — — 4 — — — — — — -8*7- 5 7.2 Clear solution 6 7.4 N n 87 TABLE VIII (CONT.) EFFECT OF TIKE AND LIGHT ON COBALTAMMINE SOLUTIONS
Time, 3uq>l« pH Comment hours______#______
81 1 8*7 Cloudy 8 8*6 Cloudy - soat brown ppt* 3 8*7 Solution brown fr< ppt* oxide 4 8*7 Solution brown fr< ppt* oxide 5 6*6 Clear solution 6 7.3 n m 7 6.9 tt N 8 7.4 • If 32} 1 8.7 Brown-black oxide ppt. 8 8.76 M If It It 3 8.8 it it tt it 4 8.9 « w w tt C 6.8 Clear solution 6 7.86 it tt 7 6.86 tt it 8 7*1 m it 43 1 8*6 3.2 ml. 0*01 N aold to bring to methyl Red end 8 8.6 3.3 • e l s e 3 8.7 g tt tt II tt H 4 8.8 7 it it tt « it End points faded badly, Vel*r poor titration 5 6.6 Clear solution 6 7.1 ■ tt 7 6.7 N tt 8 7.6 tt N 73 5 6.8 Clear Solution 6 6.8 tt tt 7 6.3 « « it n 8 ...... 7 d . TABLE VIII (CONT#) EFFECT OF TIKE AND LIGHT ON COBALTAMMINE SOLUTIONS
Tima. Staple PH OoHBtat hour* # 94 6 6*3 Claar solution 6 6*9 a a 7 6.5 a a a 7*3 a a 116* 5 6*2 a a 6 6.8 a a 7 6.4 a a 8 7.3 a a 146* 5 6.3 Claar solution 6 6.8 a a 7 6.4 a a 8 7.3 a a 164* 5 6.3 Claar solution 6 6.9 a a 7 6.4 a a 8 7.3 a a 165 (0 ) 10*30 A.M. Sat out is light. Cloudy dull daar. aast alndow. 165* (*) 7 Slightly oloudy 8 167 (2 ) 6 Slightly oloudy 7 almost opaqua 8 a a 167* (2*) 6 8.8 Claar solution 6 8.8 Cloudy 7 8.8 opaqua - dafinita blaok ppt. 8 8.9 opaqua - dafinita black ppt. 185 (24) 6 Solution olsar, but a small black ppt* 6 Cloudy solution, largi amt. blaok ppt. 7 Largs amount of ppt.# 8 supernatant liquid almost oolorlsss. 89 Motes About 90 ml* of 0*01 M HOI was added to aamplee 3 and 4 in which the supernatant liquid waa al most odorless* Vlthln a week the yellow oolor of a oobaltammlne returned in the solution and sons but not all of the oxide precipitate went baok into solution*
Time and Saturation Solutions of oobaltammlne salts ooae to saturation in a very short time* Bronsted and Latter**3 saturated wa ter solutions of oobaltaaimlnes at 15° C. by passing 500 ml* solvent through a column of the salt IQom* high and about 1 os in diameter in 24 hours. The solvent was probably not In contact with the solid for more than a few hours. Other solubility determinations of oobaltammlne salts in water and in 50% methyl alcohol by Bronsted and co-workers** ***• give no time of saturation but say the saturation was attained in a very short time* Mayper1* found water solutions of crooeo and flavo sulfate to be saturated in 8 hours or less* 12 Blosser determined solubility colorImetrlcally and found oobaltammlne solutions in water and 50% ethyl alcohol to be saturated within 2 to 4 hours*
The time of saturation in water waa assumed to be es tablished as probably no more than 8 hours* Time of satu ration in the organlo-water mixtures was ohecked by deter mining solubility both as a function of time and from under and over saturation* 30 Results of the solubility as a function of time for orooao and flavo sulfata In 39*7j£ dloxane and 38*2£dloxane ara sumnarlced In Tabla IX* Tha rasults indicata satu ration 1s attained in 8 - 9 hours or lass* Tha sample tubes used in these runs vara unpalnted and light nay have oaused some decomposition*
A solubility run vas made In vhloh tha solutions vara rotated 6 hours at 28° C., than 18 hours at 25*0° C* Tha samples vere analysed and results oompared with solubil ities taken from the solubility versus composition curve obtained at 25*0 i*e* undersaturation* The results ara summarized in Tabla X* Tha difference in tha solubility from oversaturation and undersaturation is expressed in both ml* of 0*01 X HC1 and as tha difference in velght per oant of organlo solvent necessary to bring tha over- saturation point onto the curve* The agreement is not as good as vas hoped it would be. Tha discrepancies may be due to a combination of tha follovlng affects* (1) Different amounts of solid equlll- brlated with the 40 ml* solvent, (2 ) different times in the bath, very likely some decomposition oocurs even in the dark, (3) errors in preparing tha mixed solvent (a) in under saturation runs the solvent vas mixed by volume;
then calculated aa velght par cant, in the over saturation the solvents vara prepared by direct weighing (b) tha TABLE IX TIME AMD SATURATION IN 40* DIOXANE
Crooeo Sulfate* Crooeo sulfate PlaTO Sulfate 39* 7* dloxane 38.2* dloxane 38.2* dloxane Tine in Rotated, Titration Solu- Rotated, Titration Solu- Rotated Titration Solu- bath, hra* hra. ml* blllty hr a* ml« blllty hrs* ml* bllitj ______m»/l# W l . 4 ll 30 3.88 •000197 ls55 9*70 •000496 8 4 . 3 2 •000211 9x00 4*32 •000221 8x00 9*18 •000458 4.34 •000212 15s 55 4*60 •000234 8 x00 9.58 •000489 a 4.45 •000219 32x15 4.28 •000219 14x55 9*00 •000449 94 4.48 •000220 14x55 9.45 •000483 24 4*31 •000211 50 4 .68 •000229 50 4*70 •000230 72 4*65 •000227 7 2 4.80 •000237 Maypera value •000225 •000251 •000528
e impure sample of oroceo sulfate. Probably contained some oobaltammlne vlth sulfate In the complex* TABLE X SOLUBILITIES FROM OVER AfiD UMDLRSATURATIOM
Solvent Organic Saturating Solubility Over or Difference, Different*, wt. % aalt Undar ■1*01 MHC1 wt.J< organle Saturation solvent
Dioxane- 58*3 Plavo Co(HHj)g(H02 )7(Cg04) ^ water Over / 0.27 0.7 •001650 under Croceo ii .000350 over / 0.30 2.1 Ethyl .000330 under alcohol 32.1 Flavo •000485 over / 0.75 3.3 -eater .000435 under Croceo « •000124 over / 0.22 4 •000109 under Acetone- 32.1 flavo a •001120 over / 0.30 0.7 eater •001100 under croceo ii •000223 over / 0*19 2.1 •000210 under Dioxmne- 50.8 Croceo I0s •002288 over / 1.80 1.3 eater •002108 under Ethyl 44.1 •001667 - 0*23 0.6 alcohol Croceo I03o over -eater •001690 under Acetone- / 0.63 0.4 eater 44.1 Croceo I03 •002109 over •002046 under Dloxane- 38.3 Flavo so4 •000485 over - 0.96 1.5 eater •000533* under Croceo S04 •000212 over - 0.46 1.3 .000235* under Ethyl Alcohol 32.1 flavo SO.9 .000295 over / 0.34 1*0 eater •000278 under TABLE X (CONT.)
SOLUBILITIES FROM OVER AND UNDERSATURATION
Solvent Organic Saturating Solubility Over or Difference9 Difference9 wt? i aalt Under ■1.01 KHC1 vt.jf organic Saturation solvent
Ethyl 32.1 Croceo SO* .000191 over / 0.36 1.0 Aleohol •000173 under -eater Aoetone- 32*1 flavo 30* •000560 over - 0 .5 0 0.7 eater *000586 under Croceo SO* •000259 over - 0.26 1.0 •000272 under Dloxane- 38.3 Flavo plcrate •003528 over / 0 . 3 3 0.5 eater •003495 under Ethyl alcohol 32.1 Flavo plcrate •001594 over - 0*51 1.0 -eater .001645** under
• Mayper's data* ** Blosscr'o data*
**» very flat portion of curve. amount of watar In tha orgaalo aolrant may have inoraaaad causing some arror In tha calculated weight par cent* On tha basis of thasa results ona must conclude that the results ara significant only to three figures*
Preparation of Compounds Tha following compounds ware prepared. Carbonato tetrammlne cobalt III sulfate, ammonium tetranltrodlamina cobaltate, ammonium dlnltrooxalatodlammlne cobaltate, flavo (cis-dinitrotetrammine cobalt III) nitrate, orooao (trans din ltrotetr amine cobalt III) chloride and the plcrate, sul- fata, lodate, permanganate o# dl-dlnltrooxalatodlammlne co- baltata of both tha orooao and flavo Ions* Carbonatotetramlne cobalt III sulfate [ i f Co( N H j ) 4COJ 2SO4 • The compound was prepared by tha method of Jorgensen***** and Damon®® say tha most Important part of tha procedure Is to keep a good excess of amonlum oarbonate present at all times. This was found to be very true, and In preparations when an excess of amonlum oarbonate Is not present the pro duct Is oontamlnated with an Insoluble pink paste containing about 1$( cobalt. The carbonatotetramlne oobalt III sul fate Is unstable In both aold and basic solutions* Reorys- talllsatlon from ammonium sulfate solution which Is slightly acidic, but not acidic enough to decompose carbonatotetram mlne oobalt III sulfate, was unsuccessful because the pink paste became very soluble In the presence of the ammonium sulfate. 9 4 Large, deep purple, apparently pura oryatala of
£co(NH^)0 C0J 2 a04 * 3 H2° Obtalnad by tha follow* lng procedure*
Prooodor#t Dissolve 220 g* eobaltous oarbonate In 1200 ml* hot 6 V sulfuric aold, filter to remove any oobalt oxldo or undlssolved cobaltous car bonate and pour the flltrato Into a solution of 1000 gr* asmonlum oarbonate, 4 0 0 0 ml* water and 2 3 0 0 ml* oono* ammonium hydroxide* Bub* ble air rapidly through the solution for 5 hours* Flaoe the solution on steam bath and evaporate to about 9 0 0 0 ml*, add 10 gr* asanonlum ear* bonate every 90 minutes during the evaporation* filter the solution to remove sny oxide present, con tinue bath evaporation of the fil trate and additions of ammonium oarbonate until crystals Just be* gan to form* Set the solution aside to oeol to rooai temperature* Filter by suction, wash the crys tals with 100 ml* portions of 95% ethyl alcohol, dry In air* Evaporate the filtrate until a second batch of oryatals form, fil ter as before, and oomblne oryatals with the first batch*
The above procedure gave about 400 gr* of material which was used In the subsequent preparation of cis- dlnltrotetrammlne oobalt (III) nitrate* The cobalt analysis was 22*6, 22mQ%l theory 22*5%. £2*22 (cla-dlnltrotatrammlne oobalt H i) t» £co( NH5 )^(N0g) J HOg* The flavo nitrate was prepared by the method of Jfergensen3^* Ihe following procedure was used* 35 Prooadwai Dissolve 20 g* car- bonatotetraamlne oobalt III aul fata* KotaI ImportantI Use only large, purpla orys- tala of oarbonatotetram- mine oobalt (III) aul fata* If any "pink paste* la praaant tha flavo nltrata will hava a red-orange color and will ba aa mueh aa low In oobalt* In 200 ml* watar* Add 25 ml* 40jC nitrlo aold, whan Oog a vo lution oaaaaa add 40 gr* aolld aodium nitrite, heat tha solu- tlon 15 mlnutea on tha ateam bath (or until flavo nltrata cryatala bagln to aeparata out wall), oool in an loa bath, add 250 ml* 40J< nitrlo aold of auoh a rata that tha temperature doea not go above 10° C* Let stand In an loa bath aavaral hours* Filter by suotlon through a sintered glass filter, wash with 4 30 ml* portions of 40jt nitrlo aold, then with 90% ethyl al- oohol until the washings ara aold free* Dry In vaouum dealocator over phosphorlo anhydride* Obtain about 16- 20 gr* of a yellow powder* About 90 gr* of flavo nitrate waa prepared, combined 12 with 50 gr. flavo nltrata prepared by Phyllis Bloaser t and recrystallised In 3 batches by the following procedure* Prooeduret Dissolve 45 g* flavo nitrate In 500 ml* 0*1 N acetic aold solution at 45° C*, filter, oool the filtrate alowly to 12- 16° C* Than plaoe in an loa bath* Slowly add 130 ml* 95^ ethyl aloohol, filter, wash with 1 36 16 ml* portion of loo water and 3 60 ml. portion* of 90% ethyl aloohol. Dry in vacuum deslo- oator. Solution* w*r* prot*otod from diroot light* The 110 gr. of orgnge oryatala vac analysed for co balt.
I II III Sample wt. gr* 0*3076 0*3329 0*2912 0*2260 0*3023 COS04 wt* gr* 0*1726 0*1848 0 . 1 6 1 8 0*1245 0*1681 Co, wt. % 21*24 21*11 21*13 2 0 * 9 6 21*15 Theory 20*97 The flavo nitrate was used in subsequent preparations of flavo salts* Croceo (trana-dlnltrotctrammlne cobalt III) chloride (co(nh3 )4 (no2 ) g]ci* The croceo chloride was prepared by a method which was essentially that of Jorgensen*®^ The procedure was as follows I Prooedurei Dissolve 120 gr* oobaltoua ohlorlde hexahydrate in 225 ml* water, pour into a solution of 136 gr* sodium nitrite, 100 gr* ammonium chloride* and 150 ml* oonc* ammonium hydroxide in 300 ml* of water* Bubble air rapidly through the solution for 5 hours, fil ter, wash the preolpltate with 8 50 ml* portions of water then 3 50 ml* portions of 95% ethyl alcohol* Dry 24 hours In vacuum desiccator* Two runs gave 172 gr. of yellow crystals which were raorystalllsed In 10-12 gr* lots by applying the following procedure 15 times*
Procedural Dissolve 10 gr* croceo chloride In 260 ml* 0.1 N aoetlo acid at 65° 0* Filter, cool the filtrate slowly to 10° 0*, add 70 ml* 95% ethyl aloohol over a 1 hour period* Filter by suotlon, wash with 9 portions loe water, then 3 portions 96)C ethyl aloo hol* Dry in vacuum deelooator over phosphoric anhydride* All solutions were protected from direct light* The material was analysed for both cobalt and ammonia* Cobalt 23*44, 23*42, 23*24 theory 23*16 Ammonia 26*72, 26*80, 26*83 theory 26*76 No improvement In cobalt content was noted when small amounts of the reorystalllsed croceo chloride was recryatal- lized a second time from either o.l N acetic acid or 0*08 N HC1 acid solution* The croceo ohlorlde was used in the subsequent preparations of orooeo salts* Ammonium tetranltrodlamnlne cobaltate (Erdmans salt) NH^[bo( NH^JgfNOg) J • The preparation was essentially that of Jorgensen* v Procedural Dissolve 90 gr* of oo- Daltous chloride hexahydrate in 250 ml* water, pour into a solution of 135 gr* sodium nitrite, 100 gr* ammonium chloride and 26 ml* oono* ammonium hydroxide In 760 ml* of water* Bubble air through the solu tion 2 hours* Let the solution stand with a gentle stream of air over the surface to hasten evapo ration* Filter every 24 to 48 hours and then continue evapora tion of the filtrate* Three applications of the above procedure yielded 273 gr. of a heavy dark brown orystalllne material contaminated with a small amount of an insoluble bright yellow powder* 38 The materiel was r•crystallised as follows* Reorvstalllsatlont Dissolve 275 gr* material in is liTTers water of 45° C*, filter, oool the filtrate to room temperature, and filter again* Let solution stand 5 days with a gentle stream of air over the surface, filter out 93 gr* material, let filtrate evaporate a second 5 days, filter out 83 gr* material* Thomas3^* says the yellow impurity is a polynoclear
cobalt complex* Ammonium dlnltrooxalatodlaaralne oobaltate NH4 [co(NH3 )2 (NOgJ^CCgO^ The preparation was essentially that of Jorgensen32* Prooedurei Dissolve 20 gr* ammonium tetranltrodlammlne oobaltate In 100 ml* water at 60° C*, pour into a solution of 10 gr* oxalic acid In 60 ml* of water at 50° C., maintain this temperature several hours, oool In ice bath, filter, wash precipitate with water, dry In air* The prooedure was applied twloe, onoe with doubled amounts, and 37 gr* of product obtained* According to Thomas33 the produot Is a mixture of the relatively soluble
ammonium trans-dlnltrooxalato-ols-diamnlne oobaltate and the relatively Insoluble dl* ammonium ols-dlnltrooxalato- cia-diammine oobaltate* The product was recrystallised In such a manner that only the more insoluble dl-ammonium cls- dlnitrooxalato-ols-dlammlne oobaltate was recovered* Recrystaillsatloni Dissolve 9 gr* crude produot In 800 ml* water at 39 50° 0* Filter. oool tho filtrate to rooa temperature and Til tor* Obtain about 3 gr* from each re- orystalllsatlon. Total recovered 18 sr. Crooeo and flavo sulfate £co( NH3 )^( 2S04* The orooeo sulfate was prepared by adding a solution of 10 gr. ammonium sulfate In 60 ml. water to a solution of 10 gr. orooeo ohlorlde In 400 ml. water at 66° C. TOie mixture was cooled to 80° C*. filtered by suotlon and washed with 4 25 ml. portions of water. The orooeo sulfate was rotated In a sample tube with successive 80 ml. por tions of water until a fairly oonstant solubility was ob tained on suooesslve runs. The remaining solid (oa. 8 gr.) was filtered out. dried In air and analysed for cobalt and ammonia. Sample wt*. gr. 0.3010 0.5352 C0SO4 . gr. 0.1762 0 . 1 9 4 0 Co. w t . % 22.26 22.01 Theory 2 2 . 0 7 Ammonia, found 2 5 . 3 9 . 25.35. theory 2 5 . 5 0 . The flavo sulfate was prepared by the procedure given by llayper.** Procedure! Dissolve 35 gr. oarbonato te trasnnTne oobalt III sulfate In 400 ml. water, add 80 gr. sodium nitrite, filter. To the filtrate add 10 ml. 6 X sulfurlo aold and then heat 10 minutes on a steam bath. Cool In an loe bath to 10° C. and slowly add 100 ml. 6 V sulfurlo aold at suoh a rate that the temperature does not go above 10° 0. Let stand In loe bath over night. Filter, wash pro- duot with 8 30 ml* port Iona of water, then 8 30 ml* portions 70% ethyl alcohol, dry la air* Two lota of flavo 80^ were prepared # 1 19 gr*, # 8 17 gr* The material was recrystallised In 3 gr* batches* Reorvstal11satIoni Dissolve 3 gr* flavo sulfate fn 350 ml* 0 . 0 8 N sulfurlo aold at 66° 0 * for 6 min utes • Filter, oool filtrate to loe temperature, add 80 ml* ab- solute aloohol over a 1 hour period* Filter, wash crystals several times with 70% ethyl aloohol* Dry In air*
Recovered 17 gr# of # 1 and 13 gr* # 2 by this prooedure*
The two lots of crystals were rotated In a 120 ml* sample tube with suooesslve 80 ml* portions of water until suc cessive determinations gave a fairly constant solubility* The solubilities at 26*0° C*
# 1 0 * 0 0 3 6 4 4 0*003598 0*003648 0*003602 0*003614 0*003664 0*003656 ave* <5.o6fcSO Ave* The remaining solids were filtered out and analysed for oobalt*
# 1 # 2 sample wt* gr* 0*3244 0*3155 0*3290 0*3241 CoS04 wt* gr* 0*1898 0*1836 0*1930 0*1683 Co^ wt. % 28*18 82*13 22*31 22*09 Theory 22*07
The # 8 preparation was used In solubility measurements# 41 OrQo.o and fl»TO ploraf C c o d ^ t U O g l j f o C g H g d O g ^ .
The orooeo plorate preparation was tha s u m at used by P. ¥. • Bloaaer*12 and la at follows. Prooadurai Dlaaolva 15 gr, orooao chloride In 550 ml* water at 40° C., filter, pour filtrate Into a solu- tlon of 15 gr. picric aold and 3 gr. Ha-CO, In 350 ml. water at 40° C. Stir vigorously 1 0 - 1 5 minutes, let atand at room tem perature an hour and filter. Waah the oryatala with several 25 ml. portions of distilled water, dry In air. About 10 gr. of the material waa rotated with 7 suc cessive 100 ml. portions of water. Solubilities from the last three portions were determined using 1 gr. NaOH plus 120 ml. water In the EJedahl flask (see section on ammonia analysis). The results were Rotated, hrstmln Solubility, m ./l. 8 I00 0.007532 8 100 0.007628 14130 0 . 0 0 7 6 0 9 14130 0 . 0 0 7 4 5 6 * 28|00 0.007550 28|00 0.007852 (T) *# 28tOO 0 . 0 0 7 6 1 8 0.0&T5&? ' average • KJedahl flask oraoked and leaked *# not In average The remaining orooeo plcrate was filtered and dried In air. It was used In the solubility determinations In dioxane- water. The orooeo plerate used In the aoetone-water solvent waa not purified by suooesslve rotations in water. The orooeo plorate Is In the form of the monohydrate. The product was analysed for cobalt. 48 Sample wt, gr. 0.8689 0.3884 C0SO4 wt, gr. 0.0898 0.1107 Co, wt. % 18.70 18.88 Theory 18.67
The flavo plorate woo prepared by the m u m prooedure as used by P. II. Blosser.*8 Prooeduret Dissolve 10 gr. flavo nitrate in 800 ml. water at 36° C., filter, pour filtrate Into a fil tered solution of 12 gr. plorle aold plus 8 gr. sodium oarbonate In 300 ml. water at 43° C. Stir the mixture vigorously for 10 minutes, then Intermittently for 30 minutes. Filter, wash crys tals with 2 20 ml. portions of water, dry In air. Two preparations by the above procedure gave about
35 gr. of a yellow-orange dry powder. About 10 gr. of the material was rotated with suooesslve 100 ml. portions of water until successive determinations gave fairly constant solubility values. The solubility in water was 0.001717 0.001730 0.001718 0.001701 0.001715 average The remaining solid was filtered, dried In air. It was used In the solubility determinations In dioxane-water. That used In aoetone-water had not been rotated In water first. The flavo plorate oomes out of solution with no water of hydration. Cobalt analysis gave the following results. 4 3 Sample wt, gr* 0*8201 0*8267 CoSO^ wt, gr* 0.0797 0*0791 Co, wt % 13*29 13*33 Theory 13*18 As observed by Blosser^ both the orooeo end flevo picrate first separated as a gelatinous aass shloh changed to a crystallne form after being stirred a few minutes* Croceo and flavo lodate £bo( J I0 3* The orooeo lodate was prepared by the following prooedure* Procedure1 Dissolve 8*4 gr* potassium lodate In 60 ml• water at 46° C«, pour Into a solution of 5 gr* orooeo ohlorlde In 175 ml* water at 50° C. Cool slowly to 20° C*, filter, wash crystals with 3 26 ml• portions of water. Dry In air* The prooedure gives about 5 gr* of yellow crystals* The prooedure was repeated with quadrupllled amounts* Yield 21 gr. (26 gr* total)* The flavo lodate was prepared by the following proce dure* Prooedure1 Dissolve 7.6 gr. potassium lodate In 50 ml* water at 50° C«, pour Into a solution of 6 gr* flavo nitrate In 100 ml* water at 50° C* Cool to 10° C., soratoh side of beaker to start precipitation* Filter, wash crystals with 3 20 ml* portions of loe water* Dry In air* The above prooedure gives about 5 gr* crystals* The prooedure was repeated with 6 fold amounts* Obtained 29 orooeo flavo Sample wt, gr* 0*1833 0*2274 0.2432 0.1668 CoS04 wt, gr* 0.1179 0.1469 0.1547 0.1060 Go, wt. % 24.46 24.56 24*19 24*17 Theory 23*95 About 0.5 gr. samples of each salt was rotated with successive 50 ml* portions of water and the solubility de termined. Results were as follows* ______Orooeo ___ Flavo ___ Time ro- H-0 vol., Titra- Solu- Time ro- HgO Titra- Solubil- tated, ml* tlon bil- tated, vol., tlon, ity hrs* ity, ml* ml* ml* m./l* _ m./l. 8 s 30 50 8.14 *000554 8l45 50 31.30 .002124 OslO 50 . . . - - - OslO 50 ...... OslO 50 . . . ------OslO 50 ... OllO 50 — - — . OslO 50 ...... 13s 45 50 8*20 *000556 12S 40 50 31.21 .002118 There was no appreciable change in solubility whloh Indicates no soluble impurity was being removed* The salts were used in the solubility determinations without further purification* Croceo and flavo permanganate £co( KH3 )4 ( *102)2] **n0 4 . The croceo permanganate was prepared as follows* 4 6 ProoedureI Dissolve 5*8 gr. sodium permanganate la 40 ml. water at room temperature, pour Into a solution of & gr. orooeo ohlorlda In 166 ml. of water at 60° C. Oool slowly to 25° C., than plaoa in loa bath 16 minutes• Filter, wash orystals with 3 20 ml. portions of loa oold water. Dry In air. Obtain about 6} gr. fine black crystals. Repeated the above prooedure with double amounts, obtained 11} gr. (total 17 gr.) The flavo permanganate was prepared as follows. Procedural Dissolve & gr. sodium permanganate In 30 ml. water at room temperature, pour Into a solu tion of 4 gr. flavo nitrate In 95 ml. water at 50° 0. Oool slowly to 25° C., then plaoe In Ice bath 15 minutes, filter, wash crystals with 3 16 ml. portions of loe cold water. Dry In air. Obtain about 3.6 gr. blaok plate-like crystals. The prooedure was repeated with 4 fold amounts obtained 22.5 gr. material# The orooeo and flavo permanganate were analyzed for ammonia after first reduolng the 1(0 0 4 " with HgOg. Flavo Mn0 4 Orooeo MnO^ Sample wt, gr. 0.1179 0.1261 Titration, 0.06046 II HOI ml. 27.38 29.60 NH3, wt. % 19.96 20.10 Theory 20.15 The solubility of both orooeo and flavo permanganate was determined only In water at 15.0 and 26.0° C. The com- 47 pound decomposed T « r y badly in dloxane-water solvents end It was assumed thsy would also decompose in ethyl aloohol* water solvents* Hers and Knooh3* determined the solubility of KXnO^ in acetone-water solvents at 13° C* and found a maximum in the solubility versus solvent oomposltlon curve at 70 volume per oent acetone* It might have been possible to determine the solubility of crooeo and flavo permanganate In acetone* water but no attempt to do so was made* Unsuccessful Preparations Several attempts were made to prepare crooeo and flavo methyl sulfonate using methane sulfonic aold (CH3 SO3H) both a s the aold and as the sodium salt* The product was very Impure and different preparations gave widely different solubilities in water* Attempts to prepare orooeo and flavo periodate were * unsuccessful because the only source of periodate ion was the Insoluble potassium periodate* Solubility Determination Procedure Preparation of the mixed solvent* In the solubility determination the mixed solvent was prepared by accurately measuring a volume of both water and the organlo solvent at a known temperature from a buret directly into a dry sample tube* The weight per oent composition of the sol* vent was calculated from literature densities* For the salt 48 effect data a large amount of advent waa prepared by direct w e i g h i n g and 40*00 ml* of the nixed aolvent measured by buret Into a dry sample tube containing an accurately weighed amount of potaaalun ohlorlde* A weighed amount of the aatu- r a t i n g salt waa placed In the solvent* Sample Tubes* The aample tubes were made by the glass b l o w e r to the specifications of figure 8 * The sample tubes w e r e sealed with paraffin and attached to a shaft in the c e n t e r of the constant temperature bath by phosphor bronse clips* The shaft was rotated at 14 rpm tumbling the aample tubes end over end until saturation was reached* To protect t h e saturated solutions from light the sample tubes were p a i n t e d with two coats of black paint* Constant Temperature Bath* The constant temperature b a t h was a copper container 18 inches deep and 24 Inches in diameter set In a sawdust Insulated box* Hie water was stirred by a Inch diameter 4 blade stirrer on a & inch brass shaft rotated at 1725 rpm by a 1/5 hp* else trio motor* T h e stirrer was located at the bottom of a 4 Inoh copper pipe that extended from 2 inches below the top of the bath to 2 Inches from the bottom of the bath* This provided a rapid and efficient mixing of the water In the bath* The temperature was maintained at 25*0° C* by a 250 watt heater w h i c h was controlled by a mercury-tolwene thermoregulator a n d an FO-57 thyratron oircult* In warm weather it was 4 9 necessary to have a fan dlreoted continuously on the sur face of the water. An indication of the temperature control is given In Table XI. TABLE XI CONTROL OF CONSTANT TEMPERATURE BATH AT 25.0° C. Date Hour Beokman Date Hour Beckman ______B s e & a s ______30 Nov. 9120 P.M. 3.120 6 Deo. 10(30 A.M. 3.120 1 Deo»10t45 A.M. 3.120 5(10 P.M. 3.120 2110 P.M. 3.120 7 Deo. 8(15 A.M. 3.119 5 tOO P.M. 3.120 2(10 P.M. 3.120 *10(30 P.M. 3.119 8 Deo. 11(30 A.M. 3.117 2 Deo.l0(45 A.M. 3.120 5(30 P.M. 3.119 10(15 P.M. 3.120 10 Deo. 2(30 P.M. 3.118 3 Deo. 1(55 P.M. 3.122 5(00 P.M. 3.114 7(30 P.M. 3.121 11 Deo. 11(13 A.M. 3 .115 9(30 P.M. 3.120 5(00 P.M. 3.115 4 Deo. 9(45 A.M. 3.120 12 Deo. 9(00 A.M. 3.119 9(30 P.M. 3.120 Notes Zero on this Beokman 5 Deo. 8(30 A.M. 3.112 at the top of the aoale. 4(30 P.M. 3.118 Lowest terns, during period 3.122 11(00 P.M. 3.119 (25.078)* Highest temp, during period 3.112 (25.088) * The temperature waa adjusted to 25.00 for the solubility runs. To maintain the temperature at 15.0° C. a circulating pump was added to the thyratron circuit so when the temper ature went above 15.0° water was pumped from the bath through an ioe bath and back Into the bath. Considerable difficulty was experienced with this set-up when the room tesg>erature o went over 28 C. which necessitated cutting some runs shorter than was desired. Temperature was controlled to_£ 0.01° C. at 26° and 50 £ 0.05° C. at 15.0° 0. inft» Samples vara plpattad by forcing tha saturated solution into a plpat through a pyrex M filter- atick* by air praasura exerted on tha aurfaoa of tha solu- tion. See figure 8 * Generally 85 ml. aamplaa vara taken and plpattad directly Into tha aeparatory funnel of tha ammonia apparatua. (Sea figure 1 and aeotlon on ammonia analysis*) Some time a 10, 50 or 100 ml* samples vara taken depending on tha concentration of the aaturated aolutlon* All solubility and salt effect data are summarized in Tables XIV to XLV. Denaitiea The solvent mixtures vera prepared on a volume basis, then converted to a valght per oent basis. The densities used in the calculation are suimnarlzed in Table XII. Water densities are data of P. Chappuia33. Dioxane densities at 20, 25 and 30° are the data of Hovorka, Schaefer and Drelsbaoh* The other values are from a linear extrapolation of their data* The ethyl aloohol densities are from the Handbook of Chemistry and P h w i o ..87 The acetone densities vera calculated from tha equa tion d* v 0.81245 - 1.1142 x 10~3 t - 0*315 x 10"6 t2 . 38 ♦Corning Glass Works, Coming, N* Y* Catalog No* LP-31, p. 161, Item No, 39535, coda vork HEJOF. 61 TABLE XII d e n s i t i e s o f w a t e r , d i o x a n e , e t h y l a l o o h o l a n d a c e t o n e FROM 20 TO 90° C* Temperature Water Dioxane Ethyl Acetone 0 C. (35) (36) Aloohol (37) (38) 20 0*99023 1*03318 0*78445 0.7901 21 0*99802 1*03206 0*78860 0*7890 22 0*99780 1*03096 0.78775 0.7879 23 0.99767 1*02986 0*78691 0*7868 24 0*99733 1.02876 0*78606 0*7856 25 0*99708 1*02766 0*78522 0*7844 26 0*99682 1*02649 0.78437 0*7833 27 0*99666 1.02534 0*78352 0*7822 28 0*99627 1*02419 0*78267 0.7811 29 0*99598 1*02304 0*78182 0.7800 30 0*99568 1*02189 0.78097 0.7788 Dielectric Constant Data The dielectric oonstant value of dioxane-water mix* tures at 15*0° and 25.0° C. waa calculated from the equation of Akerlof and Short®® log D s log a - bt The dielectric oonstant value of ethyl alcohol-water mixtures at 15*0 and 25*0° C. waa calculated from the equa tion of Akerlof*® log* D - log a - b(t - 2 0 ) The dielectric constant value of acetone-water mixtures at 25,0° C. was from the data of Akerlof**0 The values at 15.0° C. were obtained from a graphical extrapolation of log D vs T of the data of Akerlof at 20, 25, 30, 40 and 50° C. The values of dielectric constant used are given in Table XIII* TABLE XIII DIELECTRIC CONSTANT OF DIOXANE-WATER, ETHYL ALCOHOL-WATER and ACETONE-WATER MIXTURES AT 1 6 . 0 ° A N D 8 6 .0° C. 4 0 ^ssaranaaBH saM SM saBESSBassBssaiK tcssBBBBaona O r g a n i c Dloxane-Water Ethyl Alooho 1-Water Aoetone-Water S o l v e n t , wt* % 15*0° 2 5 . 0 ° 16.0° 26.0° 15.0° 2 5 . 0 ° 0 82*22 7 8 . 6 4 8 2 . 2 2 7 8 . 5 4 8 2 . 2 2 7 8 . 6 4 10 73.2 69.7 76.4 72.8 7 6 . 6 7 3 . 0 20 64.0 60.8 70.4 67.0 7 0 . 2 6 7 . 0 30 54*7 5 1 . 9 6 4 . 3 61 . 1 64*2 6 1 . 0 40 4 5 . 4 4 3 . 0 68*0 55 . 0 57.4 54.6 50 36 .3 3 4 . 3 6 1 . 8 4 9 . 0 5 0 . 9 4 8 . 2 60 2 7 . 4 2 6 . 8 46.0 43.4 44,1 41.8 70 18*7 17. 7 40*3 3 8 . 0 3 7 . 6 36. 7 BO 11*3 10.7 35 . 0 3 2 . 8 31.1 2 9 . 6 90 8*62 6 . 6 0 29.9 2 8 . 1 2 5 . 2 2 4 . 0 95 3. 7 8 3*69 ... ------... 100 2 * 1 0 2 . 1 0 2 5 . 8 2 4 . 3 20.0 19.1 TABLE XXV SOLUBILITY OF CROCEO FICRATE IN DIOXANE-WATER AS SOLVENT AT 25. C. Sample Dioxane, Dioxane, Tine in Bath Titration, Acid lor- Solubility ml. wt, a hretnin. ml. malltT M . / l . 1 40.00 fteft 29 s 06 74.86 •01018 •0076 e 40.00 0.8 0 f t * 8 9 110 73.10 a .0074 3 39.70 0.30 0 * 54180 77.27 a — 4 40.00 0.40 1 * 0 33ll3 66.45 « •0068 5 39.55 0.65 UT 55 >80 54.30 a •006ft 6 39.00 1.00 8 . 6 48 >55 50.16 a •0061 7 39.00 1.00 8.6 23(35 43.42 a .0044 8 38.00 8.00 5.1 23 s 45 43.97 a .0045 9 37.00 3.00 7.7 25:50 43.08 a •0044 10 35.00 5.00 18.8 85:55 44.05 a •0045 11 38.00 8.00 80.5 26:35 50.66 a •0068 1 8 88.00 18.00 30.6 26:40 66.80 a • 0067 13 85.00 15.00 38.8 27.85 83.90 a •0066 14 88.00 18.00 45.7 27:30 81.93 •05046 •0111 15 19.00 81.00 53.2 28 >80 87.35 a •0136 16 17.50 88.30 57.0 28125 89.15 a •0147 17 16.00 84.00 60.7 89:10 29.58 a •0149 18 14.50 85.50 64.4 89:80 30.05 a .0168 19 13.00 27.00 68.1 38:15 87.35 a •0138 80 10.00 30.00 75.5 38:85 80.92 a •01X>6 81 7.00 33.00 88.9 33:10 57.08 •01018 •0066 88 4.00 36.00 90.3 33:15 15.93 a •0016 83 8.00 38.00 95.1 34:30 8.10 •00486 •00039 84 1.00 39.00 97.6 34:35 1.88 a .00009 85 — 60.00 —— — 27:25 0.84* a •00008 • 50 ml. sample ca 01 54 Samples # 7-84 rotated 22t30, liquid volumes measured at 26° C. 7-12, 2 1 - 2 4 0 . 2 g. aolid 1 2 - 2 0 0 . 4 g. solid. Residues saved* Sample # 22 0*1 g. solid rotated 24i00, liquid volumes measured at 25° C* Samples # 1, 2, 4 0*2 g* solid rotated 28 s 00 hours, liquid volumes measured at 26° C* Samples # 3, 6 , 6 0*2 g» solid rotated 48x00 hours hut up to tenq>* only last 26s00« Liquid volumes measured at 26° C. SOLUBILITY OP FLAVO PICBATE IN DIOXANE-WATER AS SOLVENT AT 25. C. Sampla DIoxana, Diozana. Tine in Bath Titration Solubility # K- Ml. wt. % hr a sain. 0.01022 H HCL, M./l. 1 40*00 1.00 M 3 8 105 18.21 *0019 2 39.00 2.00 5.0 3 8 115 19.85 •0020 3 38.00 5.00 ▼•a 38t55 21.58 .0022 4 37.00 5.00 12.2 59 s 05 25.32 .8026 5 36.00 5.00 12.8 32120 25.62 •0026 6 35.00 6.00 15.0 32 s 25 28.01 .0028 7 34.00 7.00 17.5 33S 30 30.75 •0031 8 35.00 8.00 19.0 72t25 23.46 .0024 0 35.00 8.00 19.1 59 s 40 23.37 •0024 10 34.50 8.00 19.3 56 s 00 23.48 •0024 11 32.00 8.00 20.5 72s55 23.80 •0024 12 32.00 10.00 24.4 39 s 50 24.48 •0026 13 30.00 13.00 30.9 40 s 35 28.72 .0029 14 27.00 13.00 33.2 40s 40 29.15 •0030 15 25.00 15.00 38.2 33 s 20 39.95 •0041 16 21.00 19.00 48.3 43x25 46.20 •0047 17 18.00 22.00 55.8 48x35 58.20 . 0068 IB 16.00 25.00 63.2 44 s 15 57.97 •0059 19 13.00 27.00 68.2 44 s 25 56.50 .0058 20 10.00 30.00 75.6 45 s 20 48.03 .0049 21 8.00 32.00 80.5 45x30 38.55 •0039 22 6.00 34.00 85.4 46x15 31.52 •0032 23 4.00 36.00 90.3 46x25 17.00 •0017 24 1.00 39.00 97.6 47x10 3.65 .00037 25 —— 40.00 100 47x25 0.49 .00006 26 60.00 100 27x45 2.72* •00007 * 50 ml. aaspla, 0 . 0 0 4 8 6 H acid* Ssnplss # 1-4, 9, 12-14, 16-25 0.56 g. solid / 40 ml. solrsnt. Rotstsd 56t45 hr*. Liquid volunss nssiursd st 26° C. Solid rsslduos ssvsd. Ssnplss # 5-7, 15, 24 0 . 1 g. solid / 40 ml. solTsnt. Rotstsd 24t00. Liquid TOlunss msssursd st 26# C. Ssnplss # 0, 10, 11 0.1 g. solid / 40 nl. solvsnt. Rotstsd 40100, lsst 26i00 hours st 2 5 . 0 ° C. All in unpslntsd ssnpls tubss. TABLE XVI SOLUBILITY OF CROCKO PICRATS IV DIOXAHB-IATER AS 80LVEVT AT 1 5 . 5 ° C. Sample Dioxane, Dioxane. Titration Varaality Solubility # K- al. wt. * al. a./l. 1 40.00 0 . 0 48.70 •01018 •0050 2 40.00 — 0.0 48.80 * •0050 3 40.00 0.0 49.11 9 •0060 4 39.50 0.5 0 1.3 3 4.91 9 .0036 5 39.00 1.00 2.6 29.27 9 .0030 6 55.00 5.00 12.8 26.56 9 •0027 7 32.50 7.50 19.2 28.89 9 •0029 8 30.00 10.00 25.6 34.06 9 •0005 9 22.50 17.50 44.5 65.81 9 .0067 10 20.00 20.00 50.7 82.36 9 •0064 11 18.00 22.00 55.7 79.38 9 .0081 12 15.00 25.00 63.2 83.51 9 •0065 13 12.00 28.00 7 0.6 74.95 9 •0076 14 7.50 32.50 81.7 38.50 • •0039 15 2.00 3 8.00 95.1 2.11 • •00081 16 1.00 39.00 97.6 1.38 .00486 •00M88 17 *** 60.00 100 0 .32 •01018 •000016 * 5 0 al. staple. All in unpainted Maple tubes. Staples § 1, 5, 6, 8, 9, 12, 14, 17 0*55 g. solid / 40 al. solvent. Rotate 11s00 hours but only lest 6 hours et 15.5° C. In bath 6s00-9s00 at 15.5° C. Liquid volutes aeasured at 26° C. Saaples # 2-4, 7, 10, 11, 15, 15, 16 0.35 g. in all but 15. end 16. #iioh bed 0.1 g. rotated 29s50. In bath 30t00-32s30 but only the lest 25s30-26s00 et 15.5° 0. TABLE XVII SOLUBILITT OF FLAVO PICRATE IV DIOXAHE-1ATER AS SOLVEVT AT 15.5° C. Sample Dioxane, Dloxana Titration Solubility # " t 0 : ml. wt. % 0.01018 V a./l. HCL, nl. 1 40*00 0 .0 10*60 •0011 2 40*00 — 0.0 10.68 •0011 3 38*00 2.00 5.1 12.38 •0013 4 36*00 4*00 10.3 14.54 .0018 5 34.00 6.00 15.4 17.83 .0018 6 33.00 7.00 17.9 13.11 •0013 7 32.00 8.00 20.5 13.25 .0013 8 31.00 9.00 23.0 13.86 •0014 9 30*00 10.00 25.6 14.52 •0015 10 22*50 17.50 44.5 23.40 •0024 11 20.00 20.00 50.7 31.19 .0032 12 18.00 22.00 55.7 34.48 •0035 13 15*00 25.00 63.2 36.91 .0038 14 12.00 28.00 70.6 36.18 •0037 15 7.50 32.50 81.7 13.3$* •0023 16 2.00 38.00 95.1 8.60 •00088 17 1.00 39.00 97.6 2 . 7 2 „ •00028 18 •— 60.00 100 2.10** .00005 * 15 al. samp la. *# 50 al. sample, 0*00486 I aeid. 8 Sanplsa # 1, 3-5, 6, 9, 13, 15, IB 0.35 g. solid / 40 ml. solvsnt. Rot a tod lltOO but only tho last 6 s 00 hours of sxaotly 1 5 . 5 ° 0* (Bsfors ths tsnp. Tsrisd 14.7 - 16.6° 0.) Liquid volunss asasurad 86° c. Solid rssiduss vsrs sar s d . Ssnplss # 8, 6, 7, 10-18, 14, 16, 17 0.35 g. solid in ill but 16 and 17 whldh had 0*1 g. solid. Rotstsd 89s30 hours. In bath 30s00-38s30 hours last 83s30-86sOO hours at 1 5 . 5 ° C. Liquid Toluaas vsrs nsasursd at 27° C. TABLE XVIII SOLUBILITY OF CROCSO PICRATE IN ACETOIE-VATER AS SOLVER AT 8 5 . 1 ° C. Saapl* HgO, Acetone, Acetone, Tims in Bath Titration, Vomallty Solubility # al. al. wt. i hrsiain. al. a./l. < 1 58*00 2.00 4.0 mm — 16*90 •05046 •0085 2 35.00 5*00 10*0 — 19.52 s •0099 4 34*00 6.00 12.1 47:20 17.62 s •0089 5 30.00 10.00 90.7 48:06 17.77 ■ .0089 6 29.00 11.00 22*9 — 18.86 • •0095 7 23*00 17.00 36.6 — 26.05 w .0131 8 17*00 23*00 51.4 m w 38*40 m .0194 9 11.00 29.00 67.4 — - 45.82 w .0231 10 8.00 32*00 75.8 48156 43.08 9 .0217 11 5.00 35.00 84.6 32.10 9 .0162 12 2.00 38.00 93.7 — - 13.52 9 .0068 IS 2.00 3 8.00 93.7 46*15 13.84 9 •0070 14 --- 40 100 4 5:20 14*95 9 •0015 15 40 100 43:25 15.76 9 •0016 Staples # 1, 2, 12, 14 0.25 g. solid 6, 7, 11 0.5 g. solid 8, 9, 0*7 g. solid* Rotstsd 48*50 hours hut only last 26*00 at 25.lt C. Liquid volumes asasurad 30° C. Solid residues saved* Staples # 4, 5, 15 0*25 g. solid; 10 0.6 g. solid; 15, 16 0*2 g. solid* Rotated 37:20* Liquid volumes measured 30° C* § TABLE XIX SOLUBILITY OF FLAVO PI CRATE IV ACETONE-WATER AS SOLVENT AT 26.1°. C* Sample Bao, Acetone, Acetone, Time in Bath Titration, Normality Solubility # ml* ml. at* % hrstmin* ml* m./l* 1 38*00 2.00 4*0 — ■ 19*55 *00991 •0019 2 35*00 5*00 10*0 — 23*22 * •0023 3 29*00 11.00 22.9 38*40 ■ •0038 4 23*00 17.00 36.6 — 73.85 « •0073 5 17*00 23.00 51*4 — 26*80 •05046 •0136 6 11.00 29*00 67.4 48:00 38.96 « •0196 7 5*00 3 5*00 84*6 48:50 33*60 e •0170 8 2*00 38*00 93.7 — — 16.46 s •0083 9 2.00 38.00 93.7 47:15 16.54 ■ •0083 10 40 100 24.31 •00991 .0024 11 —. 40 100 46:20 24.30 e *0084 12 40 100 45:25 23*97 ■ •0084 Samples # 1-5, 8, 10 0 .3 g. solid / 40 M l . solvent* Rotated 48:30 but at temper-* atare 26.1° C* only the last 21s00 hours* Samples in hath 48s30-50t30. Liquid volumes measured at 30° C* Solid residues saved* Samples # 6, 7, 9, 11, 12 rotated 37t20* Liquid volumes measured at 30° C* 6, 7 0*5 g. solid, 9, 11, 12 0*3 g* solid* 01 M TABLE XX SOLUBILITY OP CROCBO SULFATE IX DIOXAIB-WATER AS SOLVKW AT 15 AXD 25° C. SMBpl* Dioxana, Dloxana, Time in Bath Titration # % Ml* wt. % hr a* Min* 0 .01 aold Ml. 1 80 0.0 10s 40 48.20 2 80 — • 0 . 0 1 0 140 48.06 3 8 0 — 0 . 0 15 sOO 48.00 4 8 0 0 . 0 15t00 48.03 5 45.00 65.00 59.8 67x30 2 . 6 7 * 6 36.00 74.00 67.9 68x40 0 . 7 5 * 7 40.00 — 0 . 0 33.39 8 3 9 . 0 0 1.00 2.6 — 29.84 9 37.00 3.00 7.7 22.88 10 30.00 10.00 25.6 7.96 11 24.00 16.00 40.7 — 4.66 18 19.00 21.00 53.3 1.40 • 100 ml* aaapla* « TABLE XX (PART II) SOLUBILITY OF CROCBO SUIFATB IX DIOXANE-WATBR AS SOLVENT AT 15 AND 25° C. temple A d d Sdlpbility -log s D log D 1/D # Normality M./l. 1 .01018 .00245 2.6114 78.5 1.8949 .0187 2 ■ •00245 B BBB 5 ■ .00244 B B BB 4 • •00244 B BB B 5 .00486 •000017 4.7696 25.8 1.4116 •0388^ 6 « •000005 5.5010 19.4 1.2878 •0515^ 7 .01018 .00171 2.7670 82.2 1.915 .0122 8 ■ •00152 2.8182 79.8 1.902 •0125 9 « .00116 2.9355 76.0 1.875 •0155 10 ■ •000406 3.3915 58.5 1.767 .0171 11 .00486 •ooous MM 44.6 1 MB .088ft 12 b •000054 4*4685 33.0 1.519 •0501 1-4# 10 gr. solid, 25.0° C. 5, 6 0#1 g* solid, rotated 48 hours at 25.0° C# 7-12 0*1 g. solid, rotated 25(15 hours at 15#0° C# In contact with solid 26(00-28(00 hours# Liquid volumes Measured at o o 25 c# Samples at 25 C# in unpainted sample tubes# TABLE XXI SOLUBILITY 0? FLAVO SULFATE II DIOXANE-WATER AS SOLVENT AT 15 AND 26° C. Sanpla H^O, Dioxana, Dioxana Tine in Bath Titration # nl. Ml. wt • % hr a tain. Ml. 1 80 —— lit 30 71.60 2 8 0 — — lltSO 71.68 5 80 —- — 19:15 71.00 4 80 — 19:15 70.55 5 39*50 70*50 64*7 59s 10 4 .20f 6 32*00 78*00 71.5 60s 10 1.45* 7 80 — •— 12120 70.70 8 80 —- 12 s 20 70.75 9 80 ——- 20s30 71.98 10 80 ...... 20 s 30 71.82 11 40*00 — 0*0 — 46.82 12 39.00 1*00 ... 42.60 13 37.00 3.00 7.7 — 34.41 14 34.00 6*00 15*4 24.18 15 28.00 12.00 30*6 —- 10.26 15 16*00 24.00 60.7 -- 1.58 • 100 ml. aanpla 2 TABLE XXI (FART II) SOLUBILITY OP FLAVO SULFATE IX DIOXAXB-1ATER AS SOLVENT AT 15 AND 25° C. Sanple lomallty Solubility -log s D log D 1/D # n./l. 1 *01018 •00364 2.4413 78.5 1.8949 .0127 2 ■ •00365 a a a a S a •00361 a a a a 4 S •00359 a a a a 5 .00486 •000025 4.6021 21.9 1.3404 •0456 6 .00486 •000009 5.0458 16.7 1.2227 •0599 7 .01022 •00360 2*4413 78.5 1.8949 .0127 8 s •00360 a a a a 9 ■ •00366 a a a a 10 a •00365 a a a a 11 •01018 •00241 2.6180 82.2 1.915 •0122 12 a •00217 2.6635 79.8 1.902 •0125 13 a •00175 2.7570 75.0 1.875 .0133 14 a •00123 2.9101 68.1 1.833 •0147 15 a •000522 3.2823 54.0 1.732 .0185 16 •00486 •000038 4.4202 26.7 1.427 •0975 # 5, 6 0*1 gr. solid, e*. 110 nl* solvent, rotated 48 hours, at 25*0° C* # 1-4, 7-10 10 gr. solid* rotated at 25.0° C* # 11-16 0.1 gr. solid, rotated 43t45 hrs, liquid volunes neasured at 26° C*, rotated at 15^0° G* Sanples at 25.0 C. In unpainted sanple tubes. TABLE XXII SOLUBILITY OF CROCSO SULFATE III ETHYL ALCOHOL-WATSR AS SOLVENT AT 15 AND 25° C. Samp la HgO. EtOH, EtOH, Tim* In Bath Titration Moxmallty # ml* ml. «t. % hr* * Min. ml. 1 39*00 1.00 2.0 36:40 41.48 .01018 2 38*00 2.00 4.0 36s45 35.36 * 5 37.00 3.00 6.0 37t30 29.91 « 4 34.00 6.00 12.2 37(35 18.10 « 5 31.00 9.00 18.6 39(45 10.91 * 5 28*00 12.00 25.2 39(55 6.28 » 7 25.00 15.00 52.1 40(35 7 .40 .00486 8 22*00 18.00 39.2 40(45 4.24 • 9 19.00 21.00 4 6.5 41(35 2.36 « 10 16.00 24.00 54.1 41(40 1.18 « 11 13.00 27.00 62.0 42(25 0.22 * 12 10.00 30.00 70.2 42(30 0.33 * 13 40.00 —- 0.0 --- 33.65 •01018 14 39.00 1.00 2.0 — ~ 27.57 « 15 37.00 3.00 6.0 --- 20.08 * 16 30.00 10.00 20.8 — 5.62 « 17 25.00 15.00 32.1 —- 4.70 .00486 18 22.00 18.00 39.2 2.56 * o» 0> TABLE XXII (PAST II) SOLUBILITY OP CROCEO SULFATE IS ETHYL ALCOHOL-WATER AS SOLVSST AT 15 AND 25° C. Sample Solubility -log s D log D 1/D # m./l. 1 •00211 2.6757 77.4 1*889 •0129 2 •00180 2.7447 76.2 1.882 .0131 3 •00152 2.8182 75.2 1.876 .0133 4 •000921 3.0357 71.6 1.855 .0140 5 •000555 3.2557 65.8 1.818 *0152 6 •000320 3.4949 63.9 1*806 *0156 7 •000180 3.7447 59.7 1.776 .0167 8 •000082 4.0862 55.5 1.744 .0180 9 .000057 4.2441 51.0 1.708 .0196 10 •000029 4.5376 46.7 1.669 .0214 11 •000005 5.3010 42.3 1.6263 .0236 12 •000008 5.0969 38.00 1.5798 •0264 13 — — - 82.2 1*915 •0122 14 .00140 2.8539 81.0 1*090 •0123 15 •00102 2.9914 78.6 1.895 .0127 16 •000266 3.5751 69.8 1.844 *0143 17 .000114 3.9431 63.0 1.799 •0159 18 •000062 4.2076 58.6 1.768 .0171 # 1*12 O.l g. solid, rotated 55:35 hra* at 25*0° C. Liquid volumes measured at 27° C. # 13-18 0.1 g. solid, rotated 25:15 at 15.0° C* In bath 26:00-28:00 hours* Liquid volumes measured at 25° C. Samples at 25.0 C in unpainted sample tube**-* TABLE XXIII SOLUBILITY IN FLAVO SULFATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. Sample HjjO, EtOH, EtOH, Time in Beth Titration Normality # ml* ml. wt. % hra rnin. ml. 1 39*00 1.00 2.0 35(25 61.10 •01018 2 38.00 2.00 4.0 35(30 52.31 a 3 37.00 3.00 6.0 37(35 44.35 • 4 34.00 6.00 12.2 37(40 27.05 it 5 31.00 9.00 18.6 38(30 16.26 a 6 28.00 12.00 25.2 38(35 9.82 a 7 2 5.00 15.00 32.1 39(15 5.68 a 8 22.00 18.00 39.2 39(30 7.88 •00486 9 19.00 21.00 46.5 45(40 3.70 a 10 16.00 24.00 54.1 43(45 1.45 a 11 26.00 54.00 62.0 44:55 0 . 5 8 * a 12 20.00 60.00 70.2 45(15 0 . 1 2 * a 13 40.00 —- 0.0 ... 47.50 •01018 14 3 9 .0 0 1.00 2.0 ... 40.22 a 15 37.00 3 .00 6.0 ... 28.50 a 16 34.00 6.00 12.2 —- 16.73 a 17 28.00 12.00 25.2 ... 12.72 •00486 18 19.00 21.00 46.5 2.66 a * 50 ml* sample* Ok CD TABLE XXIII (PART II) SOLUBILITY IN FLAVO SULFATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. Sample Solubility -log s D log D 1/D # m./l. 1 •00311 2.5072 77,4 1.889 •0129 2 •00266 2*5751 76.2 1.882 •0131 3 •00226 2.6459 75.2 1.876 •0133 4 •00138 2*8601 71.6 1.855 •0140 5 .000827 3.0825 65.8 1.818 •0152 6 •000500 3.3011 63*9 1.806 •0156 7 •000289 3.5391 59.7 1.776 .0167 8 •000191 3.7190 55.5 1.744 •0180 9 •000090 4*0458 51.0 1.708 •0196 10 .000035 4.4559 46.7 1.669 •0214 11 .000007 5.1549 42.3 1.626 • 0236 12 •000001 6.0000 38.0 1.580 .0264 13 •00242 2.6162 82.2 1.915 •0122 14 •00205 2.6882 81.0 1.090 •0123 15 •00145 2.8386 78.6 1.895 .0127 16 •000847 3*0721 74.9 1.875 •0134 17 •000309 3.5100 67.0 1.826 •0149 18 •000065 4.1871 54.0 1.732 .0185 # 1-12 0.1 g. solid, rotated 34:00 at 25.0° C. Liquid volumes measured 26° C. # 13-18 0.1 g. solid, rotated 43:45 at 15*0° C. Liquid volumes at 26° C. Samples at 25*0 C*in unpainted *apple tubes,* TABLE XXIV SOLUBILITY OF CBOCEO SULFATE IN ACETONE-WATEB AS SOLVENT AT 15 AND 25° C. Sanple h 2 °, Acetone, Acetone. Tine In Bath Titration # ffll. ml. wt. % hrssmin. ml. 1 39.00 1.00 2.0 37 *30 42.55 2 3 8.00 2.00 4.0 38*25 3 7.00 5 37.00 3.00 6.0 39*15 31.87 4 34.00 6.00 12.2 40*05 21.28 5 31.00 9 .00 18.6 40*55 13.33 6 2 8.00 12.00 25.2 45*00 8.48 7 25.00 15.00 32.0 45*45 5.42 8 22.00 18.00 39.1 46*30 5.70 9 19.00 21.00 46.5 47*20 2.97 10 40.00 0.0 33.48 11 39.00 1.00 2.0 28.86 12 3 7.00 3.00 6.0 ... 22.25 13 3 0.00 10.00 20.7 —- 7.46 14 24.00 16.00 34.3 — 5.68 15 19.00 21.00 46.4 ——- 2.04 o TABLE XXIV (PART II) SOLUBILITY OF CBOCEO SULFATE IH ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Sample Normality Solubility -log a D log D 1/D # m./l. 1 .01018 •00217 2*6635 77.6 1.8899 •0129 2 * •00188 2.7258 76.5 1.8837 •0131 3 ■ •00162 2.7905 75.3 1.8768 •0133 4 « .00108 2.9666 71*7 1.8555 •0141 5 • •000679 3.1681 68.0 1.8325 .0147 6 » •000432 3.3645 64.0 1.8062 .0156 7 ■ •000276 3.5591 59*7 1.7760 •0168 8 •00486 •000138 3.8601 55.2 1.7419 •0182 9 « .000072 4.1427 50*4 1.7024 .0196 10 •01018 .00171 2*7670 82.2 1.915 •0122 11 • •00147 2.8327 81.2 1.910 •0123 12 « •00113 2.9469 78 »9 1.896 •0127 13 n •000380 3.4202 69.8 1.844 .0143 14 ,00486 •000138 3.8601 61.0 1.785 .0164 15 •00686 •000050 4*3010 5 3 a 1.725 •0189 # 1-9 O.l g. solid, rotated 35*35 hrs. at 25.0° C. Liquid volun 26° C. #10-15 0.1 g. solid, rotated 25:15 hra. at 15*0° C. Total time In bath 26*00- 28:00 hours* Liquid volumes measured at 25° C. Samples at 25*0° C. in unpalnted aaaq>le tubes. TABUS XXV SOLUBILITY OF FLAVO SUIFATE IN ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Staple Acetone, Acetone Time In Bath Titration # ml* al. wt • % ■1. 1 39.00 1.00 2.0 37*35 64.40 2 37.00 3.00 6.0 38*30 50.96 3 34.00 6.00 12.3 39s 20 35.85 4 31.00 9 .00 18.6 40s 15 25.42 5 28.00 12.00 25.2 41* 00 16.91 6 25.00 15.00 32.0 45*05 11.48 7 22.00 18.00 39.1 45*50 6.78 8 19.00 21.00 46.5 46*35 8.46 9 16.00 24.00 54.1 47*25 5.03 10 40.00 --- 0.0 --- 47.42 11 39.00 1.00 2.0 42.55 12 37.00 3.00 6.0 ... 33.79 13 34.00 6.00 12.2 —- 23.18 14 28.00 12.00 25.2 ... 11.18 15 16.00 24.00 54.1 3.38 co TABLE XXV (PART II) SOLUBILITY OF FLAVO SULFATE1 IN ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Sample normality Solubility -lOg 8 D log D 1/D # m./l. 1 •01018 •00328 2.4841 77.6 1 .890 •0129 2 a •00255 2.5935 75.3 1.877 •0133 3 a •00183 2.7375 71.7 1*856 •0141 4 a •00129 2*8894 68.0 1.833 •0147 5 a •000861 3.0650 64.0 1*806 •0156 6 a •000584 3.2336 59.7 1.776 •0168 7 a •000345 3.4622 55.2 1.742 •0182 8 •00486 .000206 3.6861 50.4 1.702 •0196 9 a •000122 3.9136 45.6 1.659 •0219 10 .01018 •00241 2.6180 82.2 1.915 •0122 11 a •00217 2.6635 81.2 1.910 •0123 12 a .00172 2.7645 78.9 1.896 •0127 13 a .00118 2.9281 75.3 1.877 •0133 14 a .000569 3.2449 66.9 1.825 •0150 15 •00486 .000082 4.0862 48.3 1.684 .0207 # 1-9 o.l g. solid rotated 35:35 hours. Liquid volines measured at 26° C. 4 10*15 0.1 g. solid rotated 15.00 C. 43:45 hours. Liquid volumes measured at 26° C. # . Samples at 25.0° C. in unpalnted sample tubes* TABLE XXVI SOLUBILITY OF CROCBO IODATE IN DIOXANE-WATER AS SOLVENT AT 15 AND 25° C. Sample Dloxane, Dloxane. Time In Bath Titration # X: ml* vt. % hrsimlxu ml. 1 20.00 ... 0.0 34s 10 22.68* 2 38.00 2.00 5.1 29 s 55 46.98 3 32.00 8.00 20.5 29S50 25.70 4 23.00 17.00 43.2 29:00 38.15 5 17.00 23.00 46*2 26:30 10.88 6 11.00 29.00 7 3 a 24:05 1.41 7 6.00 34.00 85*4 22:50 0.04 8 20 ... 0. 0 ... 16.03* 9 20 ... 0.0 ... 16.01* 10 20 ... 0.0 ... 16.06* 11 19*50 0 . 5 0 2*6 ... 14.96* 12 19*00 1.00 5.2 ... 13.60* 13 18.50 1.50 7.7 18.36* 14 17.00 3.00 15.4 ... 9.87* 15 31.00 9.00 23.0 —- 16*81 16 28*00 12.00 30*6 ... 99V73 17 23.00 17.00 43.2 — 29.28 18 18.00 22.00 55.7 ... 10.90 19 14.00 26.00 65.7 3.64 20 10.00 30.00 75.5 ... 0.56 21 10*50 49.50 82.9 34:15 0.47** * 10 ml* sample ** 50 si* sample* -a TABLE XXVI (PART II) SOLUBILITY OF CROCSO IODATE IB DIOXANS-WATER AS SOLVENT AT 15 AND 25° C. Samp la Normality Solubility -log a D log D 1/D # m«/l« 1 •05046 •0286 1.5436 78.5 1.895 .0127 2 a - *0237 1.6251 74*0 1.869 .0135 3 a •0130 1 *8870 60.3 1.780 •0166 4 •00991 •00378 2.4225 40.1 1.603 .0250 5 a •00108 2.9666 27.0 1.431 .0371 6 a •000140 3.8539 15.6 1.193 •0641 7 a •000004 5.3979 7.8 0.892 •128 8 •05046 •0202 1.6940 82 .2 1.915 •0122 9 a •0202 a a a a 10 a •0203 a a a a 11 a •0189 1.7235 79.8 1.902 •0125 12 a .0172 1*7645 77,3 1.888 •0129 13 a •0152 1.8182 75.0 1.875 .0133 14 a .0117 1.9318 68.1 1.833 .0147 15 a .008487 2.0713 60.9 1.785 .0164 16 •00991 •005919 2.2278 53.9 1.732 •0186 17 a .002902 2.5373 42.3 1.626 .0236 18 a •001080 2.9666 31.2 1.494 •0320 19 a •000361 3.4425 22.4 1.350 .0446 20 a •000055 4.2596 14.5 1.161 •0690 21 •00486 .000011 4.9586 9.6 0.962 •104 <* 76 # 1 - 1*0 g* •olid, rotated 34t00 hows; 8 - 0*8 g.j 3 - 0*6 g.; 4, 5 0,3 g.J 6, 7 0*8 g. rotstsd 22s30 hours •t 25.0° C* Liquid volumes measured at 27° C. 8-10 0*3 g« •olid, rotated 24s20 liquid volumes measured at 26° C«; 11-19 0*3 g. solid, rotated 35s30 at 15*5° C* or less, at 15*0° C. the last 7s00 hours* Liquid volumes measured at 25° C* 20, 0*2 g* solid rotated 24s20* Liquid volumes measured at 26° C. 21 0*16 g. solid rotated 31s00 at temp* 13*4 or less at 15*0 last 7s80 hours. Liquid volume measured 29° C« TABLE XXVII SOLUBILITY OF FLAVO IODATE IN DIOXANE-WATER AS SOLVENT AT 15 AND 25° C. Samp la h 2o , Dloxane, Dloxana. Tlae In Bath Titration # ml. ml. wt. % hra: nln. ml* 1 20*00 0.0 34:05 47.30* 2 3 6.00 2.00 5.1 30:30 40.99* 3 32.00 8.00 20.5 29:45 61.00 4 22.00 18.00 45.7 29:40 91.22 5 16.00 24.00 60.7 25:55 27.36 6 10.00 30.00 75.5 23:25 4.48 7 4.00 36.00 90.2 22:45 0.18 8 20 •» 0.0 — 31.62* 9 20 0. 0 ... 31.68* 10 2 0 ... 0.0 — 31.48* 11 19*50 0.5 0 2.6 — 29.63* 12 19.00 1.00 5.2 — - 27.18* 13 18.50 1.50 7.7 26.02* 14 17.00 3.00 15.4 ... 19.70* 15 31.00 9.00 23.0 37.81 16 27.00 13.00 33.1 ... 24.82 17 22.00 18.00 45.7 ... 66.01 18 16.00 24.00 60.7 21.41 19 10.00 30.00 75.5 ... 2.98 20 7.00 33.00 82.9 0.62 21 8.00 52.00 86.9 0.78** • 10 ml* Staples ** 50 ml* samp la TABLE XXVII (PART II) SOLUBILITY OF FLAVO IODATE IB DIOXANE-WATER AS SOLVENT AT 15 AND 25° C. Suplo lomuillty Solubility -log 9 D log D l/D # M./l. 1 •05046 .0597 1.2240 78.5 1.895 .0127 2 « .0517 1.2864 74.0 1.869 •0135 3 9 •0308 1.5114 60.3 1.780 •0166 4 •00991 •00904 2.0438 37.9 1.579 .0264 5 * •00271 2.5670 25.1 1.400 •0399 6 9 •000444 3.3526 13.9 1.143 .0719 7 9 •000018 4.7447 5.5 0 . 7 4 0 .182 8 •05046 •0399 1.3993 82.2 1.915 •0122 9 * •0400 * ■ ■ ■ 10 9 .0397 9 it 9 v 11 9 •0374 1*4271 79.8 1.902 .0125 12 ■ • 0343 1.4648 77.3 1.888 •0129 13 ■ •0316 1.5003 75.0 1.875 •0133 ■ 14 .0249 1*6038 68.1 1.833 .0147 15 9 •0191 1.7190 60.9 1.785 .0164 16 9 •0125 1.9031 51.7 1.714 •0193 17 •00991 •00654 2.1844 40.2 1.604 •0248 « 18 •00212 2.6737 26.8 1.428 •0374 19 ■ •000295 3.5302 14.5 1.161 •0690 20 •000061 4.2147 9.6 21 •00486 •000019 4.7214 7.3 8M © 1 - 1*0 gr. rotated M i 00 hours 85.00 C. 8 - 1.0 gr.; 3 - 0.8 g.; 4, 6 - 0.4 g.; 6, 7 - 0.8 gr. solid rotstsd 22s30 hours at 25.00 C., liquid voluaas msssursd st 8 7 ° C. 8-10 - 0.5 g. solid, 19 - 0.35 g. solid rotstsd 84(20 hours 1 5 . 0 ° C. liquid volumes messured st 8 6 ° C. 11-18, 20-21 0 . 5 g. solid rotstsd 35s30, (15.0-15.5 lsst 38s15 st 1 5 . 0 ° last 6I00 hours) Totsl tins In bath 35s45-37t45. Liquid volumes messured st 26° C. TABLE. XXVIII « SOLUBILITY OP CROC BO IODATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. Sajg> !• Ho°, EtOH, EtOH, Tims In Bath Titration # Si. ■1. wt. % hr stain. ml. 1 19.00 1.00 4.0 85.58# 2 17.00 3.00 12.1 48.32* 3 27.00 13.00 27.4 44.78 4 22.00 18.00 40.2 21.45 5 14.00 26.00 59.3 5.56 6 5.00 35.00 84.6 0.28 7 19.50 0 . 5 0 2.0 14.08* 8 19.00 1.00 4.0 11.95 9 18.50 1.50 6.0 10.28* 10 17.00 3.00 12.2 33.10* 11 31.00 9.00 18.6 51.92 12 27.00 13.00 27.4 28.60 13 22.00 18.00 39.1 13.87 14 18.00 22.50 49.5 6.79 15 14.00 26.00 59.3 3 .58 16 11.00 29.00 67.5 1.98 17 9.00 31.00 73.1 1.09 18 7 . 0 0 33.00 78.8 0.42 • 10 ml. swnpl*. OD o TABLE XXVIII (PART II) Saapla Hornallty Solubility -log a D log D # 1 .05046 .0212 1.6737 76.3 1.883 •0131 2 ■ •0120 1.9208 71.6 1.855 •0140 3 •00991 •00444 2.3526 62 .5 1.796 •0160 4 a •00213 2.6716 54.8 1.739 •0182 5 a •000551 3.2568 43.8 1.642 •0228 6 a •000028 4.5528 30.6 1.486 .0327 7 •05046 •00178 1.7496 81.0 1.209 .0124 8 a •00151 1.8210 79.8 1.902 •0125 9 a •0130 1.8861 78.5 1.895 •0127 10 •00991 .00822 2•0862 75.0 1.875 •0133 11 a •00515 2.2882 71.1 1.852 •0141 12 a •00283 2.5482 65.6 1.817 •0152 13 a •00138 2.8601 58*6 1.768 .0171 14 a .000673 3.1720 52.2 1.718 •0192 15 a •000355 3.4496 46.3 1.666 •0221 16 a •000196 3.7077 41.7 1.620 •0240 17 a •000108 3.9666 38«5 1.586 •0260 18 a •000042 4.3767 35.5 1.550 •0282 82 1, 2 0*5 g. solid; 3, 4 0*3 g. solid; 5, 6 0*1 g. solid, rotstsd 24*30 hours at 25*0° C* Total tlao In bath 24*46 - 26:45. Liquid volumes moasurod at 30° C* 7-13 0.3 g. solid; 14, 15 0*15 g. solid; rotated 35*00 hours (temp, as high as 21, but at 15.0° C* The last 2 4 4 3 0 hours) Total time In bath 36*30-38*30* Liquid volumes measured 29° C. 17, 18 0.1 g. solid, rotated 35*30 hours (15*0-15*3 last 26*00 hours, at 15*0° C. last 6*30 hours) Total tlao in bath 36*00-38*00 hours* Liquid volumes measured at 25° C* TABLE XXIX SOLUBILITY OP FLAVO IODATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT IS AND 25° C. Samp la EtOH, EtOH, Time In Bath Titration Normality # X: ml. vt. % hratmln. ml. 1 19*00 1.00 4.0 29:15 35.60* .05046 2 3 1*00 9 . 0 0 18.6 29:10 38.05 a 3 87.00 13.00 27.4 88:00 18.18 a 4 18.00 28.00 49.0 26:55 25.10 •00991 5 11.00 89.00 67.4 25:55 5.86 a 6 3.0 0 37.00 90.6 85505 0.75 .00486 7 19.50 0. 5 0 8.0 27.18* •05046 8 19.00 1.00 4.0 22.88* a 0 18.50 1.50 6.0 ... 19.80* a 10 17.10 3.00 12.1 12.30* a 11 3 1 . 0 0 9.00 18.6 ... 19.48 a 18 27.00 13.00 27.4 — 55.80 •00991 13 82.00 18.00 39.1 —- 27.78 a 14 18.00 88.00 49.0 — 15.56 a 15 14.00 26.00 59.3 ... 7.48 a 16 11.00 89.00 67.5 ... 3.76 a 17 8.00 38.00 75.9 ... 1.52 a 18 5 .00 35.00 84.6 ... 0.33 a • 10 ml* sample* a> 01 TABLE XXIX (PART II) SOLUBILITY OP FLAVO IODATE II ETHYL*ALCOHOL* WATER AS SOLVENT AT 15 AND 25° C. Saapl* Solubility -log 1 D log D 1/D # B./l. 1 •0449 1.3478 76.3 1.883 •0131 2 •0162 1.7905 67.8 1.831 •0147 3 .00917 2.0376 62.5 1.796 .0160 4 •00249 2.6038 49.5 1.695 •0202 5 •000581 3.2358 39.3 1.594 •0954 * 6 •000036 4.4437 27.9 1.446 •0358 7 •0343 1.4647 81.0 1.909 •0124 8 •0289 1*5391 79.8 1.902 •0125 9 •0250 1.6021 78.5 1.895 •0127 10 •0156 1.8069 75.0 1.875 •0133 11 •00983 2.0074 71.1 1.852 •0141 12 •00547 2.2620 65.6 1.817 •0152 15 •00275 2.5607 58.6 1.768 .0171 14 •00154 2.8125 52.5 1.720 •0191 15 •000741 3.1302 4 6.3 1.666 •0221 16 •000372 3.4296 41.7 1.620 •0240 17 •000151 3.8210 37.0 1.568 •0271 18 •000032 4.4948 32.6 1.513 *0307 s 86 1# 8 0.7 g. •olid; 3, 4 0.4 g. solid; 6, 6 0.8 g. solid; rotated 84tl6 hours at 8 5 . 0 ° C. Liquid volumes measured at 29° C* 7-13 0.5 g. solid, 14, 16 0.86 g. solid; rotated 36t00 (16.0 last 24i30 hours; had been 81° before that). Total time in bath 36i30 - 38s30 hours* Liquid volumes measured at 29° C. 16-18 0.2 g. solid, rotated 35t30 hours (15.0-16*3 last 26tOO, at 1 5 . 0 last 6 130 hours) Total time in bath 36s00 - 38i00 hours. Liquid volumes measured at 86° C. TABLE XXX SOLUBILITY OF CROCEO IODATE IN ACETONE-WATER A3 SOLVENT AT 15 AND 25° C. Sample HoO, Acetone, Acetone, Time in Bath Titration # ml. ml. wt. % hretmln. ml. 1 19.50 0.50 2.0 30s40 20 . 1 8 * 2 17.00 3.00 12.1 30 s 35 11.30* 5 31.00 9.0 0 18.5 28 s 50 19.62 4 2 2.00 18.00 39.1 27 s 55 27.57 5 14.00 29.00 61.9 26s 25 4.7 8 6 5.00 35.00 84.6 25 s 50 0.54 7 19.55 0.55 2.2 ... 14.26* 8 19.00 1.00 4 * 0 12.86* 9 18.50 1.50 6.0 ... 11.32* 10 17.00 3.00 12.1 ... 7 . 9 2 * 11 31.00 9.00 16.8 13.41 12 27.00 13.00 27.4 ... 39.62 13 22.00 18.00 39.0 ... 18.75 14 16.00 24.00 54.0 ... 7.56 15 13.00 27.00 62.0 ... 6 .70 16 10.00 30.00 70.7 ... 1.80 17 7.00 33.00 78 .8 ... 0.56 • 10 ml* sample. TABLE XXX (PART II) 30HJBILITY OF CROCEO IODATE IE ACETOEK-WATSR AS SOLVENT AT 15 AND 25° C. Saaplo Haraallty Solubility -log • D log D 1/D # m./l. 1 •05046 •0255 1.5935 77.5 1*889 .0129 2 « .0143 1.8447 71.8 1.856 •0139 3 M •00990 2.0044 68.1 1.833 .0147 4 •00991 •00273 2.5636 55.2 1.742 •0181 5 •000474 3,3242 40.6 1.609 •0246 6 •00486 •000026 4*5850 26.7 1.427 .0375 7 •05046 •0180 1*7447 81.0 1.909 .0123 8 « •0162 1.7905 80.1 1.904 •0125 9 • •0143 1.8447 79.0 1.898 .0127 10 * •00999 2.0004 75.4 1.877 •0133 11 « •00677 2*1694 72.4 1.860 •0138 12 •00991 •00393 2.4056 65.8 1.818 •0152 13 it •00186 2.7305 58.7 1.769 •0170 14 « •000749 3.1255 49.5 1.695 •0202 15 • •000664 * . 1 7 7 8 43.1 1.635 •0222 16 ■ .000178 3*7496 37.5 1.574 •0267 17 * •000055 4.2596 31*9 1.504 •0314 3 68 1 , 2 0 . 5 g .j 4 0 . 3 g. solid; 6 , 6 0 . 8 g. solid, rotated 24*15 hours at 2 5 . 0 ° C. Liquid volumes measured at 29° C. 7-13 0.3 g. solid; 14 0 . 1 5 g. solid; rotated 31s00 hours (between 15.0 to 15.4, at 15.0° C. last 7 hours). Total time In bath 21:16 - 3 4 : 1 5 hours. Liquid volumes measured at 29° C. 15-17 0.1 g. solid; rotated 3 5:30 hours (temp, varied 15.0-15.3, at 15.0 last 7 hours) Total time in bath 3 6 : 0 0 - o 58:00 hours. Liquid volumes measured at 25 C. TABLE XXXI SOLtJEILITY OP FLAVO IODATE IM ACETONE-WATER A3 SOLVENT OP 15 AND 25° C. Sample HgO, Acetone# Acetone, Time In Bath Titration # ml* ml. vt. % Hrstmln. ml. 1 19.00 1.00 4.0 30 <00 30.45* 2 31*00 9.00 18.5 29(55 46.22 3 22.00 18.00 39.1 28(45 15.20 4 16.00 24.00 54.0 27(00 27.98 5 10.00 30.00 70.1 26(15 14.97 6 6.00 34.00 81.6 42(35 1.62 7 3.00 37.00 90.6 25(10 3.62 8 2*50 37.50 92.1 42(30 0.24 9 19.50 0.50 2.0 ... 28.52* 10 19.00 1.00 4.0 ... 25.68* 11 18.50 1.50 6.0 23.09* 12 17.00 3.00 12.1 ... 16.68* 13 31.00 9.00 16.8 — 30.11 14 27.00 13.00 27.4 ... 18.92 15 22.00 18.00 39.0 ... 50.56 16 16.00 24.00 54.0 ... 18.81 17 14.00 29.00 62.0 ... 10.00 18 10.00 30.00 70.3 ... 4.18 19 7.00 33.00 78.8 ... 1.57 20 5.00 35.00 84.6 ... 0.52 * 10 ml. sample* CD TABLE XXXI (PART II) SOLUBILITY OF FLAVO IODATE IN ACETONE-WATER AS SOLVENT IT 15 AND 25° C. Susple Nornallty Solubility -log s D log D i/i> # ■•/I. 1 •05046 •0498 1*3028 76.4 1.883 •0131 2 r •0233 1.6326 68.1 1.833 .0147 3 R .00767 2.1152 55.2 1.742 •0181 4 •00991 .00277 2.5575 45.6 1.659 •0219 5 R •00148 2.8297 35.3 1.548 •0283 6 R •000160 3*7954 28.5 1.454 •0350 7 •00486 .000176 3.7545 23.6 1.373 •0424 8 •00991 •000024 4*6198 22.8 1.358 •0439 9 •05046 •0360 1.4437 81.1 1.909 •0123 10 R •0324 1*4895 80.1 1.904 •0125 11 R .0291 1.5361 79.0 1.898 •0127 12 R .0210 1.6778 75.4 1.877 •0133 13 R •0152 1.8182 72.4 1.860 •0138 14 R •00955 2.0200 65*8 1.818 .0152 15 •00991 •00501 2.3002 58.7 1.769 .0170 16 R .00186 2*7305 49.5 1.695 . 0 2 0 2 17 R •000991 3.0039 43.1 1.635 • 0 2 2 2 18 R •000414 3.3830 37.5 1.574 .0267 19 R •000156 3.8069 31.9 1.504 •0314 20 R •000051 4*2924 28.4 1.453 •0351 8 91 1, 2 0.7 g* solid; 3,4 0*4 g* solid; 5, 6 0.2 g* solid; rotated 24|15 hours 25*0° C.; liquid voIuhs measured 29° C* 7, 8 0.1 g* solid, rotated 25i20 hours 25*0° C.; liquid volumes measured at 30° C* 9*15 0*5 g. solid; 16 0*25 g. solid; rotated 31s00 hours (temp* 15*0-15*4°, at 15*0° C* last 7^ hours*) Total time in bath 31sl5-34sl5 hours* Liquid volumes measured at 29° C* 17-20 0*2 g* solid; rotated 35s30 hours (15*0-15*3° C*, at 15*0° C* last 7s00 hours) Total time In bath 36s00- 38s00 hours; liquid volumes measured at 25° C* TABLE XXXII SOLUBILITY OF CROCBO DIHITROOXALATODIAMMINE COBALTATE IH DIOXAME-WATER AS SOLVH1T AT 15 AM) 26° C. Sampla h 2o , Dloxana, Dioxin*, Tim* In Bath Titration # ml* ml. wt. % hrasmln. Ml. 1 50 ... 0.0 8x10 8.18 2 5 0 — 0.0 13x30 8.01 5 50 ... 0.0 8x30 8.14 4 5 0 •— 0. 0 13x45 8.20 6 39*00 1.00 2.6 40x35 8.20 6 3 8.00 2.00 5.1 40x00 8.08 7 36.00 4.00 10.3 39x55 7.72 8 34.00 6.00 15.4 39x20 7.19 9 30.00 10.00 25.5 39x15 6.51 10 26.00 14.00 35.6 37x50 5.36 11 22.00 18.00 45.7 37x45 3.97 12 18.00 22.00 55.7 37x00 2.63 15 14.00 26.00 65.6 36x55 1.22 14 11.00 29.00 73.0 41x35 0.45 15 40.00 0 . 0 ... 5.29 16 40.00 — 0.0 — 5.20 17 40.00 ... 0.0 — 10.70 18 39.00 1.00 2.6 — 4.73 19 38.00 1.00 2.6 ... 4.90 20 38.00 2.00 5.1 ... 5.10 21 38.00 2.00 5.1 ... 4.76 22 37.00 3.00 7.7 —- 4.72 23 37.00 3 .00 7.7 ... 4.80 24 35.00 5.00 12.8 ... 4.59 25 35.00 5.00 12.8 ---- 4.38 TABLE XXXII (PART I CONT.) 3aspla Dloxana, Dloxane. Tima in Bath Titration # X: si. «t. % hrsssln. si. 26 35*00 7.00 18.0 US 27 30.00 10.00 25.6 3«tt 28 28.00 12.00 30.7 —- 3 . 7 0 29 26.00 14.00 35.7 3.54 <0 01 TABLE XXXII (FART II) 80UJBILITY OF CROCEO DINITROOXALATODIAMMINE COBALTATE IN DIOXANE-WATER AS SOLVENT AT 15 AND 25° C. lamp la Nornalltj Solubility -log 8 D log D 1/D # ■•/l# 1 •01018 •000555 3.2557 70.5 1.895 •0127 2 a •000544 ■ it ■ a 3 ■ •000554 a a a a 4 a •000556 * a a a 5 •00991 •000542 3*2660 76.2 1.882 •0131 6 ■ •000534 3*2725 74.0 1*869 •0135 7 a •000510 3.2924 69.3 1*841 .0144 8 ■ •000475 3.3233 64.8 1.812 •0154 9 * •000430 3.3665 55.8 1.747 •0179 10 ■ •000354 3.4510 46.8 1*670 •0224 11 a •000262 3.5817 37.9 1.579 •0264 12 a •000174 3 .7595 29.1 1.464 •0342 13 * •000081 4 .0915 21.0 1.322 •0476 14 a *.000030 4.5229 15.6 1.193 •0641 15 •00991 •000349 3.4609 82*2 1.915 •0122 16 a •000344 ■ a a a 17 •00486 •000346 a a a a 18 •00991 •000313 3.4962 79.8 1.902 •0125 19 a •000324 N a a a 20 it •000336 3.4881 77,3 1.888 •0129 21 a •000314 ii a a a 22 M •000312 3.5114 75. 0 1.875 •0135 23 • •000518 ii a a a 24 N •000304 3.5287 70.2 1*846 .0143 25 « •000290 a a a a TABLE XXXII (PART II CONT.) Sample Normality Solubility -log s D log D 1/D # m./l. 26 *00991 .000279 3*5544 65.5 1.816 •0153 27 « •000252 3*5986 58.6 1.768 .0171 28 ■ .000244 3*6126 53.8 1.731 •0186 29 a *000234 3*3300 49*0 1*692 •0 0 0 3 1-4 0.5 g. solid* 5-9 0.2 g. solid; 10-15 0.1 g* solid, rotated 35*45 hours at 25.0° C. Liquid volumes measured at 28° C. 14 0.1 g* solid, rotated 25*20, liquid volume measured at 30° C. 15-17 0*5 g* solid* 18, 20, 22, 24 0*05 g* solid, rotated 25*40 hours at 15*0° C* Liquid volumes measured at 27° C. 19, 21, 23, 25-29 0*05 g* solid, rotated 24*00 hours at 15*0° C* Liquid volumes measured at 25° C* to o» TABLE XXXIII SOLUBILITY OF FLAVO DINITROOXALATODIAMMINE COBALTATS IE DIOXANE-WATER AS SOLVENT AT 15 AND 25° C' Staple HgO, Dioxane, Dloxane, Tine In Bath Titration # Ml. ml* wt. % Hraimln* ml* 1 50 — 0.0 8:00 31.20 2 50 0.0 8:45 31.30 3 50 --- 0.0 12:40 31.21 4 38.00 2.00 5.1 43:15 31.77 5 34.00 6.00 15.4 43:10 30.70 6 30*00 10.00 25.5 42:40 28.95 7 24.00 16.20 41.0 42:30 23.85 8 20.00 20.00 50.7 42:00 17.76 9 16.00 24.00 60.7 41:55 10.76 10 12.00 28.00 70.6 41:20 4.61 11 8 .00 32.00 80.4 41:15 0.91 12 5.00 35.00 87.8 40:40 0.18 13 40 ... 0.0 «• 18.94 14 40 ••• 0.0 18.86 15 4 0 —- 0.0 18.81 16 39.00 1.00 2.6 18.53 17 37.00 3.00 7.7 — 18.51 18 34.00 6.00 15.4 19.20 19 30.00 10.00 25.6 18.38 20 24.00 16.00 40.7 16.00 21 18.00 22.00 55.8 — 10.78 22 15.00 25.00 63.2 — 6.81 23 12.00 28.00 70.6 —- 3.49 24 10.00 30.00 75.6 1.62 25 8.00 32.00 80.5 —— 0.44 TABLE XXXIII (PART II) SOLUBILITY OF FLAVO DINITROOXALATODIAMMIHB COBALT ATS Hi DIOXANE-WATER AS SOLVEHT AT IS AHD 25° C. SaaplA Norullty Solubility -log 8 D log D 1/D # »./l. 1 •01018 •00212 2.6737 78*5 1.895 .0127 2 * •00212 9 9 * a 3 9 .00212 9 9 9 9 4 •00991 •00210 2.6778 74.0 1.869 .0135 5 a •00203 2.6925 64.8 1.812 .0154 6 9 •00191 2.7190 55.8 1.747 •0179 7 9 •00158 2.8013 42.1 1.624 •0232 a 9 •00117 2.9318 33.6 1.526 •0298 9 9 .000711 3.1481 25.1 1.400 •0398 10 ■ •000305 3.5157 17.4 1.241 •0574 11 9 .000060 4«2218 10.5 1.021 •0953 12 9 •000018 4.7447 6.6 0.820 • 151 13 •00991 •00125 2.9048 82.2 1.915 •0122 14 9 •00125 9 9 * 9 15 9 •00124 9 9 9 9 16 9 •00122 2.9136 79.8 1.902 .0125 17 9 •00122 2.9136 75.0 1.875 •0133 18 9 .00127 2.8962 68.1 1.833 .0147 19 9 •00121 2.9172 58.5 1.767 .0171 20 9 •00106 2.9748 44.5 1.648 • 0224 21 9 •000712 3.1475 31.3 1.496 .0319 22 9 •000450 3.3468 24.7 1.393 •0405 23 9 •000231 3.6364 18.2 1.260 •0550 24 9 •000107 3.9706 14.3 1.155 .0699 25 9 •000029 4.5376 11.0 1.041 •0909 98 1-3 0*6 gr. solid. Rotated at 86.0° C. 4-8 0.2 g. solid, rotated 35t4fi at 25.0° C. 9-12 0.1 solid, rotated 35*46 at 2 6 . 0 ° C. Liquid volumes measured at 28° C. 13-15 0.1 g. solid, rotated 25i40 at 15 . 0 ° C. Total time In bath 26t00-28t00 hours. 16-21 0 . 0 6 g. solid, rotated 25s40 at 1 5 . 0 ° C. Total time in bath 26140-29140 hours. Liquid volumes measured at 25° C. 2 2 - 2 5 0 . 0 6 g. solid, rotated 2 4 | 0 0 hours at 1 5 . 0 ° C. Total time In bath 2510 0 - 2 7 130 hours. Liquid volumes measured at 25° G. TABU XXXIV SOLUBILITY OF CROCEO DINITROOXALATODIAMMINE COBALTATE IH ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 85° C. EtOH, KtOH, Time In Beth Titration Sample V* # Si. Kl. wt. % hretmln. ml. 1 35.00 5.00 10.1 4.40 2 31.00 9.00 18.6 ... 2.68 3 28.00 12.00 25.2 ... 2.03 4 28.00 12.00 25.2 41*30 2.12 5 BA.00 16.00 34.3 40*55 1.20 6 39.00 1.00 2.0 —- 4.32 7 36.00 2.00 4.0 ... 3.69 8 37.00 3.00 6.0 ... 3.22 9 35.00 5.00 10.1 ... 2.40 10 33.00 7.00 14.0 .« 1.81 11 30.10 10.00 20.7 ... 0,65 to to TAB LB XXXIV (FART II) SOLUBILITY OF CROCBO DINITROOXAIATODIAMHINB COBALTATE IX ETHYL ALCOHOL-WATKR AS SOLVENT AT 15 AND 25° C. S«Mpl# Normality Solubility -log a D log D 1/D # a./l. 1 •00991 •000291 3.5361 72.7 1.862 .0137 2 • .000177 3.7520 67.8 1.831 •0148 5 a •000134 3.8729 63,9 1.806 .0157 4 « •000140 3.8539 63.9 1.806 .0157 5 ■ •000079 4.1024 58.3 1.765 .0172 6 •00991 •000285 3.5452 8 1.0 1.909 .0124 7 M •0002443.6126 79.8 1.902 •0125 8 ft .000113 3.6716 78.6 1.895 .0127 9 ■ •000159 3.7986 76.2 1.882 •0131 10 « •000120 3.9208 73.8 1.868 •0136 11 It •000043 4.3665 69«8 1.844 •0143 101 1-3 0.1 g. solid, rotated 24*30 hours at 2 5 . 0 ° C. Liquid volumes measured at 30° C* 4-5 0*1 g. solid, rotated 25t20 hours at 2 5 , 0 ° c« Liquid volumes measured at 30° C« 6-9 0*05 g. solid, rotated 25s40 hours at 1 5 . 0 ° C. Total time in bath 26*00—28t00 hours* Liquid volumes measured at 27° C. 10-11 0*05 g* solid, rotated 24*00 hours at 15*0° C* Total time in bath 25*00—27*30 hours* Liquid volumes measured at 25° C. TABLE XXXV SOLUBILITY OP FLAVO DINITROOXA1ATODIAKKINE COBALTATE IH ETHYL ALCOHOL-WATER AS SOLVEMT AT 15 AND 25° C. EtOH, 3«Mpl« V' EtOH, Tima In Bath Titration # ml. ml. wt. % hrstmln. ml. 1 39*00 1.00 2.0 _ . 28.80 2 34*00 6.00 12.2 16.38 3 28.00 12.05 25.2 —- 8.46 4 22.00 18.00 39.1 ... 4.61 5 15.00 25.00 56.7 ... 1.82 6 10.00 30.00 7 0.2 40i50 0.48 7 39.00 1.00 2.0 — 16.45 8 37.00 3.00 6.0 --- 12.82 9 34.00 6.00 12.2 —- 8.70 10 30.00 10.00 20.8 —- 5.86 11 25.00 15.00 32.1 3.39 12 20.00 20.00 44.1 2.58 TABLE XXXV (PART II) SOLUBILITY OP FLAVO DINITROOXALATODIAMMINE COBALTATE IN ETHYL ALCOHOL-WATER AS SOLVENT AT 15 AND 25° C. Sample Normality Solubility log a D log D 1A> # m./l. 1 .00991 •00190 2.7212 77.4 1.889 •0129 2 * •00108 2.9666 71.5 1.854 .0140 3 V •000559 3*2526 63.9 1.806 .0157 4 m •000305 3.5157 55.5 1.744 •0180 5 9 •000120 3.9208 45.1 1.654 •0222 6 9 •000052 4.4949 37.8 1.577 •0265 7 .00991 .00109 2.9626 81.0 1.909 •0124 8 9 •000847 3.0721 78.6 1.895 .0127 9 9 • 000575 3.2403 74.9 1.875 .0134 10 9 .000387 3.4123 69.8 1.844 .0143 11 9 •000224 3.6497 63.0 1.799 •0159 12 •00486 •000084 4.0757 55.5 1.744 •0180 104 1*6 0.15 g. solid, rotated 24s30 hours at 25*0° C. Total time in bath 24s45*26s45* Liquid volumes measured at 30° C. 6 0*1 g. solid, rotated 25s20 at 2 5 . 0 ° C. Liquid volume measured at 26° C. 7-12 0 . 0 6 g* solid rotated 25t40 hours at 15*0° C. Total time In bath 26s40-29s40 hours* Liquid volumes measured at 25° C« TABLE XXXVI SOLUBILITY OF CROCEO DINITROOXALATODIAMMINE COBALTATE IK ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Sample H o°. Acetone, Acetone, Time In Bath Titration, # il. ml. wt. % hra:min. ml. 1 38.00 2.00 4.0 ... 7.18 2 32.00 8.00 16.4 --- 5.05 3 24.00 16.00 34.3 ... 2.96 4 16.00 22.00 48.9 ... 1.78 5 10.00 30.00 70.1 ... 0.80 6 39.00 1.00 2.0 —- 4.71 7 38.00 2.00 4.0 ... 4*41 8 37.00 3.00 6.0 ... 3.98 9 35.00 5.00 10.1 ... 3.47 10 32.00 8.00 16.4 ... 2.80 11 28.00 12.00 25*2 ... 1.98 12 24.00 16.00 34.4 ... 1.70 13 20.00 2 0 . 0 0 .... 44.0 ... 1.38 TABLE XXXVI (PART II) SOI UBILITY OF CROCEO DIN ITROOXALATODIANKINE COBALTATE IN ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Snplo Xanuillty Solubility -log s D log D 1/D # M./l. 1 •00991 •000475 3.3233 76.4 1.883 •0131 2 ■ .000334 3.4763 69.3 1.841 •0144 3 ■ •000199 3.7011 58.3 1.766 .01X2 4 •000117 3*9318 48.8 1.688 •0205 5 « •000052 4.2840 35.4 1.548 .0282 6 •00991 •000311 3.5072 81.2 1.910 •0123 7 « •000285 3.5452 80.1 1.904 •0125 8 • •000263 3.5800 78.5 1.895 .0127 9 • •000229 3.6402 76.7 1.885 •0130 10 h •000185 3.7328 72.6 1.861 •0138 11 « •000131 3.8827 66.9 1.825 •0150 12 n .000112 n 3*9508 60.9 1.785 .0164 13 •000091 4.0410 54.7 . i - m . . .0183 107 1-4 0*1 g. solid, rotatad 24*30 hours at 2 5 . 0 ° C* Total time In bath 24*46-26*45 hours* Liquid volumes measured at 30° C* 5 0*1 g. solid, rotatsd 26*30 at 8 6 * 0 ° C* Total time In bath 26*00. Liquid volume aisasurod at 30° C. 6-9 0*05 g. solid, rotatsd 25*40 at 15*0° G. Total tine In bath 26t00-28t00 hours* Liquid volumes Measured at 27° C* 10-11 0*06 g* solid, rotated 24i00 hours at 1 6*0° C* Total time in bath 25t00-27i30 hours* Liquid volumes measured at 25° C* 15-17 0,1 g. solid rotated 36*30 hours, (15,0-15.3 last 26*00 hours, at 16.0 the last 6*30 hours.) Liquid volumes measured at 25° C. TABLE XXXVII SOLUBILITY OF FLAVO DINITROXALATODIAJIk INE COBALTATE IN' ACETONE-WATER AS SOLVENT AT 15 AND 25° C. Sample H„0, Acetone, Acetone, Time In Bath Titration # fil. ml. vt. % hratmin. ml. 1 38.00 2.00 4.0 27*55 29.66 2 31.00 9.00 18.6 27:20 21.98 3 24.00 16.00 34.3 27*15 15.86 4 17.00 23.00 51.5 26*35 8.85 5 10.00 30.00 70.2 24*10 3.12 6 5.00 35.00 84.6 23*20 0.36 7 39.00 1.00 2.0 -— 17.87 8 37.00 3.00 6.0 --- 16.38 9 34.00 6.00 12.2 14.71 10 3 0.00 10.00 20.8 --- 12.67 11 25.00 15.00 32.0 --- 12.86 12 20.00 20.00 44.0 --- 7.80 13 18.00 22.00 49.0 --- 7.95 14 15.00 25.00 56.7 —- 4.38 15 12.00 28.20 64.7 3.01 16 9.00 31.00 73.1 ... 1.68 17 7.00 33.00 78.8 0.94 106 TABLE XXXVII (PART II) SOLUBILITY OF FLAVO DINITROOXALATODXAKMINE COBALTATE IN ACETONE-TfATSR AS SOLVENT AT 15 AND 25° C. Sample Normality Solubility -log a D log D 1/D # m./l. 1 0 . 0 0 9 9 1 .00196 2.7077 76.4 1.883 .0131 2 it .00145 2.8386 68.1 1.833 •0147 3 tt .00105 2.9788 58.3 1.766 .0172 4 N .000585 3.2328 47.3 1.675 .0212 5 « .000206 3.6861 35.3 1.548 •0284 6 tt .000024 4.6198 26.7 1.427 .0375 7 0.00 9 9 1 .00118 2.9281 81.2 1.910 •0123 8 ■t .00108 2.9666 78.9 1.897 .0127 9 it .000972 3.0123 7 5.3 1.877 •0133 10 it .000837 3.0773 69.8 1.844 •0143 11 it .000717 3.1445 62.4 1.795 .0160 12 * .000515 3.2882 54.7 1.738 .0183 13 it .000525 3.2798 51.5 1.712 .0194 14 it .000239 3.5391 46.5 1.668 •0215 15 it •000199 3.7011 41.3 1.616 .0243 16 « .000111 3.9547 35.6 1.551 .0291 17 H .000062 4.2076 31.9 1.504 •0314 110 1 - 6 0*15 g* solid, rotated 22s30 hours at 25*0° C* Measured liquid volumes at 27° C# 7-12 0*06 g« solid, rotated 25t40 hours at 15*0° C* Total time In hath 26s40 — 29s40* Liquid volumes measured at 25° C. 13—14 0*06 g* solid, rotated 24s00 hours at 15*0° C* Total time In hath 25s00 - 27s30 hours* Liquid volumes measured at 25° C. TABLE XXXVIII A SOLUBILITY OP CHOCEO Alt!) PLAVO PERMANGANATE IN WATER AT 15 AND 25° C. Solid Rotated Titration Normality Solubility V* fil. hours ml. j u / ju Flaro 25° 0,75 20 54:55 22.01* 0.05046 0 .0278 Croceo 25° 0,5 20 35:00 9.20* ■ 0.0116 Flavo 15° 0,4 40 24:20 31.00 0.05046 0.0156 ■ N it 33.30 « 0.0168 ■ II 9 33.41 m 0.0169 Croceo 15° 0,25 40 9 13.71 0.05046 0.00692 it it 9 13.71 « 0.00692 it it It 13.63 H 0.00688 e 10 ml* sample* TABLE XXXVIII B EFFECT OF ADDED POTASSIUM CHLORIDE OH SOLUBILITY OF CROCEO SULFATE Sunple KCJ KC1 Tine in Titration Solubility -log a Ionic # gr. per m./l* bath 0*00991 M m./l. Strength 40*00 hrssatln* acid* ml* tt ______ml.soIn. 6 rotated 34 hours In water 0*15 g. solid, rotated 25:50 hours* 25*0° C* 7 rotated 55i hours 1 0.0 ... •00245 2.6108 •00734 .0857 2 ... •00259 26(50 50,97 •00255 2.5969 .01017 •1008 5 — .00517 26:45 52,47 •00260 2.5850 •01297 .1139 4 ... .00776 26:00 53,38 •00264 2.5784 .01569 .1252 5 ... .01034 25:55 54,72 .00271 2.5670 •01847 .1359 6 ... •02513 42:25 59.85 .00297 2.5272 •03403 •1845 7 ... *05040 63:20 67.55 •00335 2.4750 •06044 •2458 In 20*7£ dloxane 0*10 g. solid rotated 47:30 hours 25.0° C. 1 ... 0.0 ...... 000820 3.0862 •00246 •0496 2 .0806 •01026 50:55 20,11 •000996 3.0017 •01325 .1151 3 •0608 .02039 51:00 22.12 ,00110 2.9586 •02368 •1575 4 • 1031 .03457 51:50 24.92 •00124 2.9066 •03828 .1957 5 .1365 •04544 51:55 26.37 .00131 2.8827 •04936 •2222 In 20*4£ EtOH , 0.1 g. solid, rotated 24:00 hours at 25.0° C. 1 0.0 •000495 3.3054 •00149 •0385 2 .0317 .01063 27:20 12.01 .000595 3.2254 •01242 .1115 3 •0612 •02053 27:25 13.04 •000646 3.1898 •02247 .1499 4 *1011 * .03390 28:00 13.90 .000689 3.1618 •03597 •1897 5 .1396 .04681 28:05 15.54 .000770 3.1135 •04912 •2216 TABLE XXXVIII B (CONT.) EFFECT OF ADDED POTASSIUM CHLORIDE OH SOLUBILITY OF CROCEO SULFATE Suq>l« KC1 KOI Time In Titration Solubility -log s Zonle # gr. per m./l. bath 0.00991 N m./l. Strength 40.00 hra:mln. acid, ml. n ysr m l .soIn. In 22.4JC Acetone 0,1 g. aolld rotated 47 s 30 hours 25.0° C. 1 0.0 —• .000530 3.2757 .00159 •0399 2 .0525 .01090 49 s 15 13.40 .000664 3.1778 .01289 .1135 3 .0616 .02066 49S 20 14.52 .000719 3.1433 •02282 •1511 4 • 1002 •03360 50s30 16.05 .000796 3.0991 .03569 •1894 5 .1442 .04636 50s 35 17.53 .000669 3.0610 .05097 •2257 TABLE XXXIX EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO SULFATE Sample KC1 KC 1 Tine in Titration Solubility -log 8 Ionlo # gr.per m./l. bath 0.00 9 9 1 N m./l* Strength 40*00 hrstnln. acid, ml. u 7* ml.soln. In water, 0.15 g. solid, rotated 25:50 hours 25.0° C. # 6 rotated 34 hours # 7 rotated 55:30 hours 1 0.0 ... —- .00363 2.4401 •00363 •0602 2 —- •00259 28:20 74.86 .00371 2.4307 .01578 •ixn 3 ... .00517 28:15 76.96 .00381 2.4191 .01661 • 1289 4 ... .00776 27:35 78.58 .00389 2.4101 •01944 .1394 5 — .01034 27:30 80.20 .00397 2.4012 •02226 • 1492 6 ... •02513 42:30 87.62 •00434 2.3625 •03816 •1909 7 -- .05087 63:15 98.70 .00469 2.3106 •06554 .2560 In 20.7 wt. i dioxane p 0 . 1 5 g« solid rotated 47:30 hoursi 25.0° C. 1 0.0 .... .00144 2.8416 •00432 .0657 2 ,0298 .00999 48:05 34.21 .00170 2.7696 .01507 .1228 3 .0593 •01989 48:10 38.18 .00189 2.7235 .02557 •1599 4 .1027 •03444 48:55 43.12 .00214 2.6696 .04085 •2021 5 .1384 .04641 49:00 47.02 .00233 2.6326 •05340 .2311 In 20.2 wt. % EtOH, 0 •15 g. solid, rotated 24:00 hours 25,0° C. 1 ... 0.0 ...... 000740 3.1300 •00222 •0471 2 .0317 •01063 25:05 17.93 .000888 3.0114 •01329 •1153 3 .0613 .02056 25:10 20.20 .00100 3.0000 •02356 •1535 4 .1011 .03390 26:10 23.08 .00114 2.9431 .03733 .1932 5 .1373 •04604 26:15 25.29 .00125 2.9031 •04980 •2238 TABLE XXXIX (PART II) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO SULFATE Sample KC1 KC1 Time in Titration Solubility -log s Ionic # gr. per m./l# bath 0.00991 N m./l# Strength 40.00 hrs:mln. acid. ml. u ml. eoln. In 22.4 vt. % Acetone , 0.1 5 g. solid rotated 24(00 hours. 25.0° C. 1 -- 0 . 0 — .00103 2.9872 .00309 .0556 2 .0317 .01063 30(40 24.34 •00121 2.9172 .01992 .1411 3 .0592 .01985 30*45 26.50 .00131 2.8827 •02379 • 1542 4 .0982 .03293 31*30 30.78 •00153 2.8153 .03751 .1957 5 .1386 .04648 31(35 33.70 .00167 2.7773 •05149 .2269 TABLE XL EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO DINITROOXALATODIAMMINE COSALTATE Sample KC1 KCl Time in Titration Solubility -log 8 Ionic # gr. per m./l. bath 0.00991 N m./l. Strength 40.00 hrssmin. acid, ml. u ml. In water, 0.05 g. solid1, rotated 55s30 hours 25.0° C. 1 0.0 —- ... .000555 3.2557 .00056 .024 2 .0308 .01033 62 s 40 9.20 .000608 3.2161 .01094 • 1046 3 .0601 .02015 62S35 9.70 •000641 3.1931 .02079 .1442 4 .1060 .03555 62S 05 9.99 .000660 3.1805 •03621 .1903 5 .1518 .05091 62 s 00 10.60 .000700 3.1549 .05161 .2272 In 14.9 wt. % dioxane, 0.05 g., rotated 55:30 hours 25.0° c. 1 0.0 .000480 3.3188 .00048 .022 2 .0304 .01019 61s 20 8.37 .000553 3.2573 .01074 .1037 3 .0602 .02019 61:15 8.80 •000582 3.2351 .02077 •1441 4 .1054 .03535 60:35 9.11 .000602 3.2204 .03595 •1896 5 .1510 .05063 60:30 9.57 .000633 3.1986 .06126 •2264 In 5.2 wt. % iEtOH, 0.05 g. solid, rotated 55:30 hours 25.0° C. 1 0.0 — ... .000378 3.4225 •00038 •019 2 .0304 .01019 58:50 6.97 .000461 3.3363 .01065 •1032 3 .0604 .02025 58:45 7.29 .000482 3.3170 .02073 .1440 4 .1064 .03561 58:10 7.57 .000500 3.3010 •03611 •1900 6 1 1 5 .1494 .05010 58:05 8.04 .000531 3.2749 •05063 •2262 i TABLE XL (FART II) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCBO DINITROOXALATODIAMKINE COBALTATS Sample KC1 KC1 Time In Titration Solubility -log a Ionic # gr. per m./l. bath 0.00991 N m./l. Strength 40.00 hrssmin. acid, ml. u ml. F In 5.0 wt. % Acetone, 0.05 g. solid, rotated 55t30 hours 25.0° C. 1 0.0 ...___ •000465 3.3326 •00047 .022 2 .0340 .01140 57:20 7.82 .000517 3.2865 •01192 •1092 3 .0606 .02032 57:15 8.21 •000543 3.2652 •02086 .1444 4 .1083 •03632 56:30 8.58 .000567 3.2464 •03689 .1921 5 .1508 .05057 56:25 8.80 .000581 3.2358 .05115 .2262 7 1 1 TABLE XLI EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO DINITROOXAIATODIAMHINE COBALTATE Sample KC1 KC1 Time In Titration Solubility -log 8 Ionic # gr.per m./l. bath 0.00991 B m./l* Strength 40*00 hrssmln. acid, ml. u ml* F o o o In HgO, 0*1 g* solid, rotated 34:00 hours 25. . 1 0.0 ... .00212 2.6737 •00212 .0460 2 *0296 .00993 41:40 35.09 •00232 2.6345 •01225 .1107 3 *0596 .01999 41:35 36.80 •00243 2.6144 •02242 •1498 4 *1064 .03568 40:45 38.55 .00255 2.5935 .03823 • 1955 5 .1523 .05107 40:40 40.16 .00265 2.5768 .05372 .2318 In 19*9 wt* % dloxane,, 0.1 g. solid, rotated 34:00 hours 25.0° C. 1 ... 0.0 .00196 2.7077 .00196 •0443 2 .0322 .01080 40:00 34.20 .00226 2.6459 .01306 • 1143 3 .0601 .02015 39:55 36.18 .00239 2.6216 .02254 •1501 4 .1196 .04011 38:25 39.19 .00259 2.5867 .04270 • 2066 5 .1545 .05181 38:20 41.02 .00271 2.5670 •05452 .2335 '.n 20.4 wt. % EtOH, 0.1 g. solid, rotated 34:00 hours 25.0° C. 1 ... 0.0 ...... 000705 3.1518 .00071 .027 2 .0302 .01013 37:45 12.78 •000844 3.0737 .01097 •1047 3 .0604 .02025 37:40 13.51 .000893 3.0492 •02114 .1452 4 .1158 .03883 37:00 14.77 .000976 3.0106 • 03981 • 1995 5 .1553 .05208 36:55 15.35 .00101 2.9957 .05309 •2304 TABLE X U (PART II) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO DINITROOXALATODIAMMINE COBALTATE Sample KC1 KCI Tine In Titration Solubility -log 8 Ionic # gr. per m./l* bath 0 .00991 M m./l. Strength 40.00 hrstmln. acid, ml. u ml. In 21*»4 wt. % acetone # 0.1 g# solid, rotated 34(00 hours 25.0° C. 1 — 0.0 .00143 2.8447 •00143 .0378 2 .0307 .01030 36120 24.20 .00161 2.7932 •01191 .1091 3 •0635 .02129 36(15 25.98 .00172 2.7645 •02301 .1517 4 .1158 .03883 35(40 27.62 .00183 2.7375 •04066 •2016 5 • 1564 .05245 35(35 29.00 .00192 2.7167 .05437 .2332 TABLE XLII EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO IODATE S a m p l e S C I KC1 Titration Normality S o l u b i l i t y -log 8 Xonlo # g r . p e r m./l. ml. . m . / l . S t r e n g t h 4 0 . 0 0 u m l . F In water, 0.3 g. solid / 20.00 ml. HgO, rotates 18 hours 1 4 . 9 - 1 5 . 5° C. at 15 . 0 ° C . The last 3-4 hours, 10 ml. samples. 1 -- 0 . 0 • 0 2 0 2 1 . 6 9 4 6 • 0 2 0 2 3 • 1 4 2 2 2 • 0 0 6 2 8 16.51 .05046 . 0 2 0 8 1 . 6 8 1 9 . 0 2 7 6 1 . 1 6 6 2 3 . 0 1 3 8 2 1 6 . 8 6 " • 0 2 1 3 1 . 6 7 1 6 • 0 3 5 0 9 . 1 8 7 3 4 . 0 1 7 5 9 1 7 . 1 0 " . 0 2 1 6 1 . 6 6 5 5 • 0 3 9 1 6 . 1 9 7 9 5 . 0 2 5 1 7 1 7 . 4 1 " . 0 2 2 0 1 . 6 5 7 6 . 0 4 7 0 9 . 2 1 7 0 In 22.3 wt. % dloxane, 0.3 g. solid, rotated 18 hours 14 .9-15.5° C. at 15.0° C . l a s t 3 - 4 h o u r s . 1 0 . 0 . 0 0 8 8 0 2 . 0 5 5 5 • 0 0 8 8 0 . 0 9 3 8 2 . 0 3 1 1 . 0 1 0 4 3 18.61 .05046 . 0 0 9 4 9 2 . 0 2 2 6 . 0 1 9 9 2 • 1 4 1 1 3 . 0 6 2 0 . 0 2 0 7 9 1 9 . 4 2 " • 0 0 9 8 0 2 . 0 0 8 8 . 0 3 0 5 9 • 1 7 4 9 4 . 0 9 4 8 . 0 3 1 7 9 2 0 . 2 0 " . 0 1 0 2 1 . 9 9 1 4 • 0 4 1 9 8 • 2 0 4 9 5 . 1 1 8 7 . 0 3 9 8 1 2 0 . 8 2 " . 0 1 0 5 1 . 9 7 8 8 • 0 5 0 3 2 . 2 2 4 3 In 40.8 wt. % d l o x a n e , 0.2 g. solid, rotated 24:15 hours a t 1 5 . 0 ° C . l a s t 4 h o u r s . 1 0 . 0 • 0 0 3 6 0 2 . 4 4 3 7 . 0 0 3 6 0 . 0 6 0 0 2 . 0 3 0 9 . 0 1 0 3 6 40.85 .00991 . 0 0 4 0 5 2 . 3 9 2 5 • 0 1 4 4 1 . 1 2 0 1 3 . 0 7 6 9 . 0 2 5 7 9 4 4 . 7 5 ■ • 0 0 4 4 4 2 . 3 5 2 6 • 0 3 0 2 3 . 1 7 4 0 4 . 1 1 9 4 . 0 4 0 0 4 4 7 . 8 5 " . 0 0 4 7 4 2 . 3 2 4 0 . 0 4 4 7 8 . 2 1 1 6 i -H 8 i'ABLK XLII (PART II) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO IODATE Sample KC1 KC1 Titration Normality Solubility -log 8 Ionic # gr. per m./l* ■ 1 * • m./l. Strength 40*00 u /u* ml* In 20*2 wt* EtOH, rotated 20:30 hours, at 15.0° C. last 6:15 hours • 1 0.0 ___ .00470 2.3279 .00470 •0685 2 •0298 .00999 51.53 .00991 •00511 2.2916 .01510 • 1229 3 *0594 *01991 53.90 n .00534 2.2724 •02525 •1589 4 .0*093 •02995 55.98 n ,00555 2.2557 .03550 • 1884 5 • 1215 •04074 63.75 t» .00632 2.1994 .04706 • 2169 In 39*8 wt* % EtOH, 0*2 g. solid, rotated 24:15 hours, at 15.0° C. last 4:30 hours. 1 0*0 ___ .00120 2.9208 .00120 •0346 2 •0321 .01076 15.62 .00991 .00155 2.8097 •01231 .1110 3 .0800 *02683 17.20 n .00171 2.7670 .02854 • 1689 In 45*0 wt* % EtOH, 0.1 g. solid, rotated 39:40 at 25.5° C. last 10 hours. 1 0.0 0.0 ... .00165 2.7825 .00165 .0406 2 .0315 •01056 18.22 .00991 .00181 2.7433 .01237 .1112 3 .1006 •03374 21.84 it .00216 2.6647 •03590 • 1895 121 TABLE XLII (PART III) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF CROCEO IODATE Sample XC1 K C 1 Titration Normality Solubility -log s Ionic # gr.per m./l* ■ 1 . m./l. Strength 40.00 u ml* In 23.1 wt. % acetone, 0.2 g. solid , rotated 16:30 hours at 15.0° C. the last 6:15 hours. 1 0.0 0.0 •00480 2.3188 .00480 .0693 2 .0303 .01016 11.36 .05046 .00573 2.2418 .01589 .1261 3 .0613 .02056 11.95 i .00603 2.2197 .02659 •1631 4 .0911 .03055 12.28 R .00620 2.2076 .03675 .1917 5 .1199 •04021 12.67 it .00639 2.1946 •04660 .2159 In 40.0 wt. i acetone , 0.2 g. solid, rotated 24:15 hours , at 15.0° C. the last 4:30 hours. 1 0.0 .00170 2.7696 .0170 •04 2 .0306 .01026 20.48 .00991 .00203 2.6925 .01229 • 1109 3 .0787 .02639 22.78 n .00226 2.6459 •02865 •1693 4 .1205 .04041 24.40 w .00242 2.6162 •04284 • 2068 TABLE XL!II EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO IODATE Sample SCI KC1 Titration Normality Solubility -log s Ionic # gr.per m./l. ■1* . m./l. Strength 40.00 u / r ml. In water, 0.5 gr. solid / 20.00 ml. solvent. rotated 18:00 hours, at 15.0° C. the last 3-4 hours1. 1 _—_ 0.0 ... .0399 1.3990 .03987 .1997 2 ... .00628 32.30 .05046 •0408 1.3893 .04703 •2168 3 ... .01382 32.72 it .0413 1.3840 .05510 .2347 4 ... .01750 33.40 n .0421 1.3757 •05963 •2442 5 .02513 33.83 n .0427 1.3696 .06781 • 2604 In 22 •3 wt. % dloxane, 0.5 g. solid , rotated 18:00 hours at 15.0° C. the last 3-4 hours • 1 0.0 ...... 0198 1.7033 .01975 .1407 2 .0306 .01026 41.30 .05046 .0208 1.6819 .03110 .1763 3 .0692 •02321 43.94 it .0222 1.6536 •04538 • 2130 4 .0921 .03089 45.18 n .0228 1.6421 .05369 .2317 5 ♦ 1196 .04011 47.08 « .0238 1.6234 .06387 •2548 In 40 .8 wt. % dloxane, 0.3 g. solid , rotated 24:15 hours but at 15.Oc* C. only the last 4:30 hours. 1 0.0 __ ... .00840 2.0757 .00840 .0917 2 .0315 .01056 19.78 .05046 .00998 2.0008 •02054 • 1433 it 3 .0774 .02596 22.51 .0114 1.9431 .03736 .1933 3 2 1 4 .1209 •04054 24.87 it .0126 1.8996 .05309 • 2304 EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO 10DATE Sample KC1 KC1 Titration Normality Solubility -log a Ionic # gr.per m./l. ml* m./l* Strength 40*00 u / ? ml* In 20.2 wt. % EtOH, 0*2 g. solid, rotated 20*30, at 15.0° C • last 6:15 hours • 1 0*0 -- •00890 2.0506 .00890 •0943 2 •0300 •01006 18*88 *05046 .00953 2.0210 •01959 •1400 5 •0602 .02019 21.00 * .0106 1.9747 .03079 .1755 4 .0897 .03008 21.30 *» .0108 1.9666 .04083 *2021 5 • 1183 .03967 21.72 " .0110 1.9586 .05065 •2251 In 39*0 wt* % EtOH, 0.2 g. solid, rotated 24*15 hours, at 15.0° C • last 4*30 hours. 1 -- 0.0 ------.00245 2.6108 •00245 •0495 2 .0300 .01006 31.09 .00991 .00308 2.5114 •01314 • 1146 3 .0765 .02565 35.72 It .00354 2.4510 .02919 .1708 4 .1210 .04058 40.05 It .00397 2.4012 .04457 .2111 In 45.0 wt. % BtOH, 0 •1 g. solid. rotated 39:40 hours last 10:00 hours 25.5° C. 1 0.0 0.0 33.58 .00991 .00333 2.4776 .00333 n .0577 2 .0156 .00523 37.70 .00374 2.4271 .00897 •0939 n 3 .0596 .01999 43.97 .00436 2.3605 .02435 .1560 4 .1391 .04665 53.18 it .00527 2.2782 .05192 .2279 TAELS XLIII (PART III) EFFECT OF ADDED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO IODATB Sample KC1 KC1 Titration Normality Solubility -log s Ionic # gr. per m./l* ml*. m./l. Strength 40*00 u & ml* Id 23 • 1 wt * * acetone, 0.3 g. solid, rotated 16t30, at 15*0° C. last 6tl5 hours* 1 0.0 .0106 1.9747 *0106 • 103 2 *0316 •01060 26*24 .05046 .0132 1*8794 *02384 • 1544 3 .0607 *02036 27 *81 N .0137 1.8633 •03409 .1846 4 .0204 ,03032 28*50 II •0144 1*8416 .04470 •2114 5 .1213 *04068 29*62 11 .0150 1.8239 .05563 .2359 In 40.0 wt* % acetone, 0.2 g* solid, rotated 24tl5 hours, at 15*0° only last 4s30 hours* 1 0.0 ___ •00490 2*3098 *00490 .0700 2 .0307 .01030 54*80 .00991 *00543 2*2652 .01573 .1254 3 .0770 .02582 62*09 n .00615 2.2111 *03195 .1787 4 .1222 .04098 67.56 it .00670 2.1739 .04768 .2184 TABLE XLIV EFFECT OF ADDED POTASSIUM CHLORIDE OH THE SOLUBILITY OF CROCEO PICRATE Sample KC1 EC1 Time In Titration Acld- Solubility -log s Ionic # gr.per m./l* bath ml. Normal- m./l. Strength _ 40.00 hrsxmln. Ity u y r ml. In H«0, 0.25 g. solid, 2, 3 rotated 28*00 hours 25*0° 4, 5 rotated 35x40 hours the last 10x00 hours at 25*5° C. 1 0.0 — — —- .0076 2.1192 .00762 .0873 2 •00259 31x40 15.40 •05046 .0078 2.1079 .01036 .1017 3 .00517 31x45 15.82 tt .0080 2.0969 .01315 .1147 4 .0588 .01971 46x25 16.80 tt .0085 2.0706 •02819 •1681 5 •0984 •03300 47x05 17.52 if .0088 2.0555 .04184 • 2046 In 10.0 wt. % dloxane , 0*2 g. solid, rotated 23x45 hours at 25.0° c. 1 0.0 0.0 30x50 37.78 .00991 .0037 2.4318 .00374 •0612 2 .0165 .00553 30x55 41.16 it .0041 2.3872 •00961 •0980 3 •0328 .01100 31x35 44.76 tt • 0044 2.3565 ,01544 • 1243 4 .0615 .02062 31x40 43.05 n .0048 2.3188 .02538 •1593 5 .1006 .03374 32x30 52.97 n .0052 2.2830 .03899 .1974 6 .1382 .04634 32x35 55.15 tf .0055 2.2596 .05181 .2276 In 39.9 wt. % dloxane , 0.3 g. solid, rotated 23x45' hours at 25.0° c. 1 0.0 0.0 28x10 17.78 .05046 .0090 2.0458 .00897 •0947 2 .0158 .00530 28x15 18.58 it • 0094 2.0269 •01468 •1212 3 .0324 .01087 28:45 19.64 it .0099 2.0044 .02078 •1441 4 .0613 .02056 29x00 20.66 it •0104 1,9830 .03099 .1761 5 .1015 .03404 29x50 21.97 tt .0111 1.9547 •04513 •2125 TABLE XLV EFFECT OF ADJED POTASSIUM CHLORIDE ON THE SOLUBILITY OF FLAVO PIC RATE Sample EC1 EC1 Time In Titration Solubility -log a Ionic # per m./l. bath 0*00991 N m./l* Strength 40.00 hrasmln* acid, ml* u Vu1 ml* In water* 0.1 g. solid* 2-5 rotated 28s30 hours 25*0° C.* 6-8 rotated 35:40 hours* the last 10s00 hours at 25*5 C* 1 —- 0*0 — ... .0017 2.7696 .00171 .0414 2 .00259 30:50 16.40 .0016 2.7959 .00422 •0650 3 .00517 30s45 17.44 .0017 2.7696 .00690 •0831 4 — .00776 29:10 17.84 .0018 2.7447 .00953 .0976 5 ... .01034 29:05 18.82 .0019 2.7212 •01221 .1105 6 .0626 *02099 45:35 20.01 .0020 2.6990 .02297 • 1516 7 .1016 .03407 45:40 21.08 .0021 2.6778 .03616 .1904 8 .1395 .04678 46:20 21.30 .0021 2.6778 •04889 •2211 In 15.4 wt. % dloxane* 0 •15 g. solid* rotated 47:30 hours at 25.0° C. 1 •-— 0.0 ... .0029 2.5376 •00285 •0534 2 .0144 .00483 52:05 24.09 .0024 2.6198 .00722 •0850 3 .0290 .00973 57:15 25.25 • C025 2.6021 .01223 • 1106 4 .0607 .02036 57:20 26.01 .0026 2.5850 •02294 • 1515 5 .1013 .03397 57:55 28.20 .0028 2.5528 .03677 • 1917 6 .1372 .04601 58:00 36.55 .0036 2.4439 .04963 •2228 In 15.4 wt. % dloxane, 0 •15 g. solid, rotated 35:40 hours * the last 10:00 hoursi at 25.5° C • 1 0.0 0.0 39:55 29.71 .0029 2.5376 .00294 •0542 2 .0169 .00567 40:00 30.75 .0030 2.5229 .00872 •0934 3 .0329 .01103 40:45 26.55 .0026 2.5850 .01366 • 1168 4 .1013 .03397 41:30 36*38 .0036 2.4437 .03758 •1938 5 .1401 .04698 41:35 37.81 .0037 2.4318 .05073 .2252 TABLE XLV (PART II) EFFECT OF ADDED POTASSIUM CHLORIDE OK THE SOLUBILITY OF FLAVO PICRATE Sample KC1 KC1 Tine in Titration Solubility -log 8 Ionic # gr.per m./l. bath 0.00991 N m./l. Strength 40.00 hrstmln. acid, ml. u ml. In 20,.7 wt. % dloxane, 0 .15 g • solid, rotated 47:30 hours at 25.0° C. 1 0.0 __ - •0024 2.6198 •00243 •0493 2 •0149 .00500 52:00 25.49 .0025 2.6021 .00753 •0868 3 .0299 .01003 52:45 27.02 .0027 2.5686 .01271 • 1128 4 .0614 .02059 52:50 28.25 .0028 2.5528 .02339 .1529 5 .1015 .03404 56:35 29.60 .0029 2.5376 .03697 .1923 6 .1388 .04655 56:40 30.47 .0030 2.5229 .04907 •2215 In 39 . 9 vt, ^ dloxane, 0 . g. solid rotated 23:45 hours 25.0° C. 1 0.0 0.0 24:00 44.02 .0044 2.3565 .00436 .0660 2 .0143 .00480 24:05 45.4e .0045 2.3468 .00931 •0965 3 .0320 JD1073 24:55 47.12 .0047 2.3279 •01540 • 1241 4 .0627 .02103 25:00 48.74 .0048 2.3188 .02586 .1605 5 .0995 .03337 25:45 51.04 .0051 2.2924 .03843 • 1960 6 . • 1431 .04798 25:50 49.80 .0049 2.3098 .05292 •2301 CALCULATIONS AND DISCUSSION Cl8 and Trans Tetrammlnedlnltro Cobalt III Plcrate The solubility of the plcrate salts show no regular change with dielectric constant In either water-dloxane or water-acetone mixed solvent. (See Figures 3 to 5) In water-dloxane the oroceo (trans) plcrate solu bility decreases to a minimum at 10 wt. % dloxane, In creases to a maximum at 61 wt. % dloxane then drops off to a very low solubility in pure dloxane. The flavo (cis) plcrate solubility Is only one-fifth that of the trans salt in water. Its solubility increases until at 17 wt. % dloxane there is a sharp break In the solubility curve. Beyond 17 wt. £ dloxane the solubility again Increases to a maximum at 64 wt. % dloxane. then decreases In solubil ity. At about 90 wt. % dloxane the cis salt becomes more soluble than the trans salt. There Is no simple relation ship between the solubility of orooeo and flavo plcrate i.e. a plot of the solubility of croceo plcrate vs the sol ubility of flavo plcrate at the same composition does not give a straight line as It does In the case of water-ethyl 12 alcohol solvent. 129 ISO In water-acetone the solubilities of both orooeo flavo picrate increase with increase in amount of acetone* The croceo picrate reaching a maximum at 67 wt* % acetone, the flavo plcrate at 73 wt# ^ acetone* At about 85 wt* jh acetone the flavo plcrate solubility becomes greater than that of croceo plcrate* The solubility in pure acetone is about the same as the solubility of the flavo plcrate in pure water* A maximum in solubility in the water-acetone solvent at about 65 wt• % acetone was observed by Fischer4* for potassium picrate and sodium dlnltro phenolate* Fischer thought the unusual shape of the curves was due to shifts in equilibrium between two forms of the plcrate ion eaoh of which had a different solubility* Bronsted and Petersen2^ report the solubility of a p form of croceo picrate but give no other information* Both croceo and flavo plcrate seem to come out of solution during their preparation in one crystalline form which on standing a short time goes into another crystalline form* It might be that a crys talline form unstable in water is stable in the mixed sol vent* X-ray powder photographs of the solid residues should be of interest* The saturated solution at the maximum in water-acetone solvent had a reddish color* Whether this was a concentra tion effect (the flavo plcrate is 15 times more soluble at the maximum than it is in water), or an indication of a 13 1 shift In the absorption spectra was not checked* Kortum^ found a shift in the absorption spec trust of picrate ion toward the red in the middle range of solvent composition of water-ethyl alcohol solvent but the absorption spectra were identical In pure water and pure ethyl alcohol* The possibility of different crystalline forms is fur ther born out by the physical appearance of the solid resi dues* (See Table XLVI) The differences in color might be due only to the particle size but they might be an indication of different crystalline form or to some addition compound with the solvent* Solid residues of flavo plcrate were filtered, dried overnight between filter paper and analyzed for water by Fischer Reagent, for ammonia and for cobalt* Results were Dloxane , Water NH, ^ Co .. wt* % wt. % wt. %* 0 0*6 14*8 13.3, 13.5 20*6 0 . 3 12.7 11.3, 11.2 55*9 0 * 0 12.7 11.6, 11.3 Theory, flavo picrate 15*2 13.2 flavo plcrate • dloxane 12.7 11.0 * Corrected to dry weight* Another batch of flavo plcrate residues were analyzed for NH3 . 198 TABLE XLVI APPEARANCE OF CROCEO AND FLAVO PICRATE RESIDUES FROM SOLUBILITY DETERMINATION IN WATER-DIOXANB Dloxane. Appetrimoe »nd flolor wt, %______croceo (trans) plcrate Flavo (ole) plcrate 0 Fine orange cryetale Fine yellow-orange crystal* 7*8 Fine yellow-orange crystals Fine yellow-orange crystals 12*9 " w ■ " Coarse orange-brown crystals 20#6 * ** n " Coarse orange-brown crystals 3 3 . 9 * * B " Orange-yellow crystals 48*4 Fine orange crystals h tt 55.9 tt tt tt 63*4 Fine yellow-orange crystals tt n it 80.6 Fine yellow crystals 87.9 Fine orange crystals « « « 97.6 n n n very 100 Pale yellow crystals • • « volu minous Dloxane NH. wt. % wt. % 12*9 12.5 20*6 12*6 87*9 12*9 100 13*2 Several samples of both croceo and flavo plcrate from both water-dloxane and water-acetone solvent were filtered, dried In air between filter papers 2 4 - 4 8 hours and stored in cork stoppered one dram bottles for several months before sending to Galbraith Mloroanalytlcal Laboratories* for C and H analysis* The results of the C and H analysis are given In Table XLVI1, # Galbraith Mloroanalytlcal Laboratories, P.O. Box 32, Knoxville, Tenn* The results of these analyses Indicate one mol of dloxane la associated with eaoh mol of flavo picrate f r o m at least 12% to \00% dloxane In the mixed solvent* The low result of C and H at : > W dloxane may be due to loss of dloxane on the long standing before analysis• There are not so many results on croceo plcrate but there appears to be some dloxane associated with It, at least at 50*7 a n d 97.5 wt* % dloxane* No trace of aoetone was found associ ated with either croceo or flavo plcrate but this might not be significant since the solid residue might have lost acetone in standing several months before analysis* The compound fonnatlon between dloxane and flavo plcrate Is no explanation of the maximum or minimum In the solubility curve since the solid In equilibrium with the saturated so lution seems to have a mol of dloxane associated with it over the entire solubility range where there is dloxane in the mixed solvent. X-ray powder photographs of the solid residues and absorption spectra of the solutions should be taken for further Information* Hart and Bordeaux^ give kinetic evidence of an associ ation In solution between dloxane and phenol* lhere la no evidence that picrate ion might be in the form of picric acid in the mixed solvent and a similar association take place but It Is a possibility* Fieser51 says that phenolic substances when crystal- 134 TABLE XLVII CARBON AND HYDROGEN ANALYSIS OF CROCEO AND FLAVO PICRATE RESIDUES FROM VARIOUS MIXED SOLVENTS Compound Solvent Organic Sample Cl • Ho° t o % H wt* % mg* mg* Flavo pi- H^O 0 10.006 5*940 3.012 16.10 3.36 crate * tt " Dloxane 50.7 4.850 2*919 1.510 16.42 3.49 n it it it 7.835 4.695 2*381 16*36 3.40 tt tt tt 95*1 4.100 3*219 1.400 21.42 3.82 it N H it 6.098 4.740 2.029 21.21 3.72 tt ” Acetone 93.7 9.014 5.341 2.715 16.17 3.36 Croceo pi- Ho0 0 8.553 4.912 2*453 15.67 3.20 crate * tt * Dloxane 50.7 12.107 8*696 4.078 19.60 3.76 it tt tt tt 7.106 5.111 2.481 19.67 3.91 it tt it 97.5 5*930 4.475 2.103 20.59 3.97 tt tt n tt 4.955 3.791 1.835 20.88 4.14 tt tt Acetone 67.4 14.188 8.060 4.167 15.50 3.29 Theory % ■C % H Flavo plorate 16 .1 3.16 Flavo plorate * U s e d from dloxane frequently are found to separate In the form of more or less stable solvated complexes* Flatt and Jordan® find that picric acid is 10 times more soluble In 69 wt* % ethyl alcohol than In water* Fischer*^ finds barium plcrate Is 2*5 times as soluble in 69 wt* % ethyl alcohol, potassium picrate is 0*65 times as soluble in 69 wt* % ethyl alaohol and sodium plcrate is 0*60 times as soluble In 69 wt* % ethyl alcohol as In wa ter* Blosser!® find3 both croceo and flavo plcrate to be 136 about the seme solubility in 69 wt. jt ethyl alcohol as in water* The much greater Increase In solubility of the pic ric acid than any of Its salts nay be an Indication that some of the picrate Ion hydrolyses to plcrlo acid which in turn Is much more soluble because of interaction with the alcohol* Solubility and Solvent Composition The decrease In solubility of the sulfate, lodate and dl-dlnltrooxalatodlammlne cobaltate of both the croceo (trans) and flavo (ols) cation with addition of organic solvent to water is shown graphically in figures 6 to 17* In all cases addition of ethyl alcohol decreases the solubility more rapidly than either dloxane or acetone, and dloxane decreases the solubility least rapidly* The solubility of the lodate and sulfate of both the croceo and flavo cation decrease in a smooth exponential like curve as the weight per cent organic portion of the solvent is increased* The dl~dlnltrooxalatodlammlne solu bility decreases more slowly, the flavo salt solubility decreases almost linearly to 30 wt* per cent dloxane and the croceo salt solubility in water-dloxane Is almost linear to 75 wt* per cent dloxane* 43 Hansen and Williams have determined the solubility of croceo 30^ in water-ethyl alcohol at two points* These are the points marked x on figure 6 j 19, io 4 si. 136 Solubility and Dielectric Constant The decrease In solubility of the lodate, sulfate and dl-dlnitrooxalatodiammlne oobaltate of both the crooeo (trans) and flavo (els) oation with decrease In dleleotrlo constant of the solvent is shown graphically In figures 18 to 29. The decrease In solubility with decrease in dielectric constant Is definitely partially dependent on the specific solvent mixture as well as the dielectric constant. For the salts studied the decrease In solubility with dielec tric constant Is slowest In water-dloxane solvent and Is fastest In water-ethyl alcohol solvent. Ihe decrease In solubility with dielectric constant of oroceo sulfate and lodate (figures 18, 19, 22, 23) In water-ethyl alcohol and water-acetone lie almost on the same curve. The solubility of flavo sulfate and lodate (figures 2 0 , 2 1 , 24, 25) Is definitely greater in water-acetone than in water-ethyl alcohol at the same dielectric constant. The solubility in water-dloxane Is always much greater than In either water-acetone and .water-ethyl alcohol at the same dielectric constant. For example, at 15° C. the solu bility of flavo IOg at D • 55 Is about 4 to 6 times as great In water-dloxane as water-ethyl aloohol or water-acetone. The oroceo and flavo dl-dlnitrooxalatodlammlne cobal- tate show no consistent relation between solubility and 137 dielectric constant for the three solvent mixtures tested (see figures 26-29)* Comparison of Crooeo and Flavo Solubilities In Water The solubility of each oroceo and flavo salt In water and the ratio of flavo/orooeo solubility Is given In Table XLVIII* TABLE XLVIII Anion Oroceo. m*/l* Plavo. m./l. Flavo £rooeo 15 25 15 25 15 25 Plorate 0.0050 0*0076 0.0017 0.0011 0*220 0.224 Sulfate 0.00171 0.00245 0.00241 0.00363 1*41 1*48 lodate 0.0202 0*02B6 0.0398 0.0597 1.97 2.09 Permanganate 0.00690 0.0116 0.0167 0.0278 2.42 2.40 dl-dinitro- 0.000346 0.000555 oxalatod iammlne 0.00125 0.00212 3.62 3.82 The variation In the ratio of flavo (cis) to crooeo (trans) solubility from 0*224 for the piorate to 3*7 for the dl-dinitrooxalatodlammine cobaltate shows the influence of the anion on the isomeric oations to be greatly differ ent • Mayper11 assumed spherloal ions and calculated the radius of the sulfate and din I trotetr aianine cobalt III ion from crystallographlc data* Similar calculations were made for the permanganate* lodate* and picrate ion* see Tables XLIX and L* 138 TABLE XLZX CHYSTALLOGRAPHIC RADII Ion Radius, A.V. Dlnltrotetrannine cobalt III 3*0 Picrate 3*0 Sulfate 2.0 lodate 2*0 Permanganate 2*1 dl-dlnltrooxalatodiammine oobaltate 3*0 (7) (aaaumed same as dlnltrotetrannine cobalt III) There is apparently no relation of anion size to the ratio of flavo to crooeo solubility* TABLE L CALCULATION OP ANION RADII PROM CRY3TALL0GRAPHIC DATA* ASSUMING SPHERICAL ANIONS Compound KMnO*a* « ym Picric Acid Crystal form rhOm.Vn19 rhemi.v'l6 rham.Coy Lattice Constants 5.75 9.10 9.25 6.37 5.69 19.08 A.V. 4.05 7.40 9.68 No. molec. 2 4 8 Vol. unit cell. 148 384 1705 Vol. per molec. 74 96 213 cation ** 0.98 1.33 --- cation 8 20 -- 66 76 213 *nl0n vl/3 anion * 2 2.0 2.1 3.0 ® Crystal data from Rubber Handbook of Chemistry and Physics pp. 2015 to 2068. ** Cation radii from Pauling. Nature of the Chemical Rand. 130 The flavo (cis) cation la unsymmetr leal and as a result has a dipola moment. The flavo salta would gen erally be expected to have a higher solubility than the symmetrical oroceo (trans) ealts. Thla Is not true In lene I* sulfonate, chrornate, d lehr ornate and the hexaflap^ silicate were also less soluble than the corresponding croceo salts* The flavo chloride, bromide, nitrate, Iodide, perchlorate, chlorate, and sulfate were more soluble than the corresponding crooeo salts. There seems to be no obvious explanation for this reversal in solubil ity of the Isomeric salts. Heats of Solution Williamson45 derives the equation for the reaction pure solvent / pure solute saturated solution where AH s0ln * heat absorbed per mol of solute dissolved In the nearly saturated solution. V - vy / V_ • total number of Ions per molecule M = molality, and f * activity coefficient of the solute. * 0 the equation would ■ ¥ X r l ( ^ r ) St4, ( m ) r . *> • ~i J <«> Although^^is not equal to soro it is small e.g. -0.0415 for sodium earbonat# (45.). and equation (4) was used to obtain an approximate value of the heat of solution in the various mixed solvents. For a hydrated solute Williamson derives the equation -p z h -dL y> for the reaction HgO / solute * XHgO saturated solution The term involving the activity of water is obtained In terms of the activity of the solute from the Gribbs- Duhem relation and the final equation is W " j » ) f£ J L *01 ~ J ^ Crooeo picrate is the only hydrated salt used. For it ( f - -£!EL \ ^ o.ttt* v 4/•// / The term was Ignored in water* In the water-dloxane mixed solvents both crooeo and flavo plcrates are associated with a mol of dloxane. This is a three oomponet system of water, dloxane. and solute. The heat of solution expression includes a ( - £ r ~ - K term. It was assumed the term Is negligible and the heats of solution of the crooeo and flavo plcrates were calculated 141 from the equation for an unsolvated electrolyte* The equation used was 4 # * * * - [/., C r - /*, c r 7 i) t ‘ m tii Z O C The croceo and flavo S04 heats of solution were calculated from the equation 6/Cij. = //7- >°° ■ Af c« J** and the crooeo and flavo IOg and dlnltrooxalatodlammlne cobaltate from the equation A K„ ti « >*,•<*[*!*•* ~ /%t C'*]4H Results are summarised in Tables LI and LII* TABLE LI HEAT OF SOLUTION OF CROCEO AND FLAVO PICRATE IN DIOXANE-WATER Dioxane, wt, % Heat of Solution ______Flavo picrate 6roceo piorate 0 16,600 15,200 5 --- 17,800 10 17,600 17,800 15 16,400 ... 20 21,200 19,600 30 20,400 17,600 40 20,400 16,000 50 16,600 18,200 60 16,400 21,000 65 16,400 20,400 70 15,200 19,600 80 17,800 20,200 90 ...... 95 • 24,000 100 8,800 8,200 142 TABLE LII HEATS OF SOLUTION Organic Dioxane Ethyl Alcohol Aoetone wt * % Flavo Crooeo Flavo Croceo Flavo 090010 The Sulfate 0 21,000 18,300 21,000 18,300 21,000 18,300 10 25,000 17,000 23,100 20,400 20,700 19,500 20 23,000 18,300 24,000 27,600 22,500 22,500 •30 25,000 31,800 14,400 24,600 20,700 27,600 40 25,000 26,100 14,400 24,000 15,900 18,600 50 31,000 49,500 —- 21,900 25,800 60 28,000 --- -- ... -- The lodate 0 13,800 11,600 13,800 11,600 13,800 11,600 10 13,600 12,200 15,600 13,200 15,400 13,600 20 13,200 10,600 16,000 13,000 17,400 13,800 30 13,200 9,200 18,800 19,400 17,000 14,400 40 12,200 6,800 19,800 20,600 14,400 15,800 50 7,000 6,800 20,800 23,600 14,400 19,000 60 8,600 8,600 6,200 23,600 22,000 13,800 70 8,600 -- —- —- 39,600 -- The dl-dinitrooxalatodiammlne cobaltate 0 18,000 16,000 18,000 16,000 18,000 16,000 10 17,200 17,000 21,600 22,600 18,600 18,800 20 16,200 16,200 19,600 35,400 17,800 19,200 30 14,800 21,800 20,000 ... 17,400 22,000 40 13,400 —- 28,400 -- 16,200 13,800 50 10,200 --- 16,200 --- 60 9,800 -- --- 12,200 -- 70 13,400 ------11,400 --- 80 19,000 ——— »«■ ••• • The total heat of solution of an eleotrolyte may be expressed as total heat of solution ■ crystal lattice energy - (heat of hydration of cation / heat of hydration of anion) 143 The crystal lattice energy is positive, hence a large er positive total heat of solution would indicate a loi^heat of hydration (solvation)* There is some tendency for the heats of solution in water-ethyl alcohol to he more posi tive than the heats of solution in water-dloxane of the same per cent water for the same salt* The force required to separate the ions of an electrolyte is related to the dielectric constant of the dissolving medium and hence the heat of solution may be partially dependent on the dielectric constant* When the heat of solution is plotted versus the dielectric constant of the mixed solvents at 20° C* (figures 81 to 8 6 ) the tendenoy for the heat of solution in water-ethyl alcohol to be greater than in water-dloxane at the same dielectric constant is more pro nounced than in case of solvents of the same per cent wa ter (flavo sulfate is an exception)* In water-ethyl alcohol mixed solvents the heat of solution increases as the di electric constant deoreases* In water-dioxane mixed sol vents the heat of solution inoreases for the flavo sul fate, croceo sulfate and croceo dl-dlnltrooxalatodlammine cobaltate and deoreases for the flavo lodate, croceo lodate and croceo dl-dlnltrooxalatodlammine oobaltate as the di electric constant decreases* In water-acetone the heat of solution Is between that in water-ethyl alcohol and In water-dioxane* The heat of solution in water-acetone in creases as the dielectric constant decreases except for 144 the flavo dl-dlnltrooxalatodlommlne cobaltate. The high heat of solution would Indloate a lower heat of solratlon and probably a lower lonlo radius In the water-ethyl alcohol mixed solvents. The lonlo radii cal culated from the simple B o m equation are smaller In the water-ethyl alcohol solvent. (See Table U V ) 'The Increase In heat of solution with a decrease In dielectric constant would Indicate decreasing solvation as the organic port of the solvent was Increased. Solva tion in the water-dloxane solvents might decrease less rapidly because the dioxane Is not as effective In keeping water molecules from the Ions as either the ethyl alcohol or acetone. The flavo salt heats of solution In water are always higher than those of the crooeo salts. This Indicates the crystal lattice energy effect of the flavo (els) salt out weighs the Increased solvation effect that might be ex pected because of the dipole moment of the unsyrnnetrical ion. Test of the Born Equation A form of the Born equation for the activity coef ficient of an ion at zero ionic strength and standard state at D 5 ® ^ 2 *r T6 r 146 For a slightly soluble eleotrolyte going into solution " V+ M ^ & The thermodynamic solubility product constant la J* c* ** c4 U (9.) where CA - o&tion concentration m*/l« Cg - anion concentration m*/l* If 3 - solubility in m*/l. « Then CA - 3 °B s V- 3 and (8 ) becomes * - * V * s * - * £ V / w Taking the logarithm of both sides of (9) and solving for JnS gives * * r- ♦ v- (*++*) L -» * <4af/, — JJTkT [** ^ Substituting for the activity coefficients the Born equation (7) above gives i0 S . • « * / — Assuming an average radius f * f* * rm the equation becomes , _ c » fK»l* ♦ *. 7 /„ . /* J -* * * * * - — - [ — £ ~ 7 T -— J ° ° 146 Slnoe * -» K Then W 2*% * - « “* fc, i* I- 2 ~ K. /.* Substituting in the brackets of equation (11) *- «.* - _ rv***. l . - a ■' ■ ■— t • iTTTZr I * ~ *+i- k* ♦ 4ft. *♦ *K. L i and equation (1 1 ) becomes , ^ 9*1-4' . /iti-J** v... in s * comtf* y* * ■■■ ■ ■ c (4«//< - (**•) 24CT&r 2+TCr At constant temperature and constant average Ionic radius the logarithm of the solubility at zero ionic strength should be a linear function of the inverse of the dielectric constant of the dissolving medium* The Born equation was checked by plotting log s vs l/D for the lodate, sulfate and dl-dlnltrooxalatotiiammlne cobaltate In the three solvent mixtures. See figures 42- 62. The solubilities of croceo and flavo lodate* at 15° G. were corrected to zero ionic strength by two methods. (1) The experimentally determined activity coefficients (Table LVIII) were used. /j • — ~ #«« * <#/ a V. A 4 ' , The activity coefficients used were 147 water-dloxane water-ethyl alcohol water-acetone Flavo 0.80 entire range 0.80 0-10# EtOH 0.80 0 to 30# 0.86 10-30# " 0.86 30# 0.90 30 Oroceo 0.86 0-10# dioxane 0.86 0-10# EtOH 0.86 0 to 10# 0.88 10-30# " 0.92 10-30# 10-30# " " 0.97 10-30# 0.90 30 " 0.93 30 it " 0.93 30 (2) The Debye-Huckel limiting law was used In figures 42 to 47 log s vs l/D for flavo and croceo IO^ at 15° C. Is plotted! 1 . with uncorrected solubilities 2 . solubilities corrected to zero ionic strength by the experimentally determined activity coefficients 3. solubilities corrected to zero ionic strength by the Debye-Huckel limiting law. The correction of solubilities to zero ionic strength does little to make the log s vs l/D plott more linear. The other plots of log s vs l/D use the uncorrected solu bilities. In Table LIII are given the dielectric constants at which deviations from a straight line of the log s vs l/D plot become noticeable* 148 TABLE LIII d i e l e c t r i c c o n s t a n t w h e r e d e v i a t i o n f r o m b o r n e q u a t i o n s t a r t s Water-dloxane Water-ethyl Water-aoetone ______aloohol______Croceo lodate 40 74 74 Flavo lodate 57 73 74 Croceo sulfate 60 63 68 Flavo sulfate 59 . 74 72 Croceo fCo(NH3 )2 (N0 p)2 (G2 °4 ^J * linear linear 72 Flavo £Co(NH3 )2 (NG2 )(G2^4^ 2 linear 74 linear The lodate and sulfate plots of log s vs l/D (figures 42-58) all show a definite curvature except flavo sulfate at 25° C. In water-ethyl alcohol* (figure 55) The 3orn equation does not hold below about D = 58 in water-dioxane or below about D - 72 in either water- ethyl alcohol or water-acetone. The dl-dlnltrooxalatodiammine cobaltate appears to obey the Born equation in some solvents, (figures 59- BO) The experimental data were used to calculate the solvated lonlo radii from the Born equation. The calculation was carried out as follows /» * <*04* - *•/ * * 1 " — ( * ' *'f — Z X T 0mim r <•/«. Subtracting the two -ifeiii* equations ♦ J tiiil ***■• •* * r 4 % . r * r r *Li r *0,0 ~ /0f *m0 7 • {~T"' ^ * ‘ f — - _ i 7 **T r L 0 ^ Of J „ t i m . 0 * - £ . . 7 where — a A io/rrc'* i { * < . J * T /. wfa #«•« #/ // •< The calculation was made using water as the reference dielectric constant and calculating the radii from each ex* perlmental solubility in the mixed solvent• Thus the radii were calculated from slopes of straight lines drawn from log In water to log s in the mixed solvent* The results of the above calculation for croceo and flavo lodate, sulfate, and dl-dlnltrooxalatodlammine in the various solvent mixtures are sunsnarized in Table LIV* The 3orn solvation mean Ionic radii Increase as the dielectric constant decreases (Table LIV) indicating again the Born equation does not hold* The Born solvation mean ionic radii in water-ethyl al cohol and water-acetone at a given dielectric constant Is nearly the same for a given electrolyte e*g« oroceo sulfate, flavo sulfate, croceo lodate, flavo lodate and croceo dinitro oxalatodlammlne cobaltate* The corresponding radius in i'APLE LIV BORN ELATION IONIC KADI I EtOH Acetone - Dioxane - V - V V 15° 260 15° 25° 15° 25° D r , A D r , A _ D r , A D r , A D r, A D r , A Flavo lodate 79.8 1.3 81.0 0.38 81.1 0.3 77.3 1.3 79.8 0.27 80.1 0.41 75.0 1.2 74.0 1.6 78.5 0.31 79.0 0.45 68.1 1.5 75.0 0.33 76.3 0.38 75.4 0.49 76.4 0.61 60.9 1.6 60.3 1.7 71.1 0.39 72.4 0.47 51.7 1.8 65.6 0.43 67.8 0.42 65.8 0.60 68.1 0.59 40.2 2.0 37.9 2.0 58.6 0.52 62.5 0.49 58.7 0.66 55.2 0.73 26.8 2.5 25.1 2.4 52.5 0.60 49.5 0.74 14.5 3.3 13.9 3.4 46.3 0.71 49.5 0.65 43.1 0.77 45.6 0.83 9.6 4.1 41.7 0.72 39.3 0.76 37.5 0.91 35.3 1.2 7.3 4.7 5.5 8.0 37.0 0.76 31.9 0.99 32.6 0.74 27.9 0.86 28.4 0.96 23.6 1.4 Croceo lodate 1.2 81.0 0.44 81.0 0.24 77.3 1.2 79.8 0.29 80.1 0.39 75.0 1.1 74.0 1.2 78.5 0.32 79.0 0.41 77.5 0.47 68.1 1.3 75.0 0.35 76.3 0.37 75.4 0.45 60.9 1.4 60.3 1.4 71.1 0.40 71.6 0.45 72.4 0.42 71.8 0.48 53.9 1.5 65.6 0.44 62.5 0.49 65.8 0.52 68.1 0.52 42.3 1.7 40.1 1.7 58.6 0.52 58.7 0.58 55.2 0.64 31.2 1.9 27.0 2.0 52.2 0.59 54.8 0.49 49.5 0.69 22.4 2.3 46.3 0 .70 43.1 0.83 40.6 0.80 14.5 2.6 15.6 2.7 41.7 0 . 7 3 43.8 0.71 37.5 0.87 9.6 3.5 7.8 3.6 38.5 0.75 31.9 0.93 26.7 0.98 35.5 0.74 30.6 0.80 TA-^LK LIY (PAftT II) BORN R A T I O N IONIC RADII Dioxane - HgO EtOH - H20 Acetone - HgO ~ ' 15° ' '' 2l°------1'5<>----- 55p - -...... 1ST------25* ~ D p. A D p » V ^ r■ ^ D r. A ______D r. A______D _____ r, A Flavodl-dlnlfcrooxalatodlajmnlne cobalt ate *9.8 5.0 &1 .B 0.42 7 5 . 0 17. 74.0 22. 78.6 0.37 77.4 0.51 68.1 neg. 64.8 18. 74.9 0.44 58.5 9.6 55.8 14. 69.8 0.51 71.5 0.53 44.5 18. 42.1 9.8 63.0 0.62 63.9 0.62 31.3 1 0 . 33.6 8.0 55.5 0.61 55.5 0.68 24.7 7.9 25.1 6.9 45.1 0.92 18.2 5.6 17.4 5.7 14.3 6.7 81.2 0.5 * 11.0 6.0 10.5 6.4 78.9 1.0 6.6 8.0 75.3 1.3 76.4 1.4 69.8 1.5 68.1 1.5 62.4 2.0 54.7 2.0 58.3 1.8 51.5 2.4 46.5 1.8 47.3 1.8 41.3 1.9 35.6 2.0 35.3 1.9 31.9 1.8 26.7 1.5 Croceo dl-dinitrooxalatodlaiamlne cobaltate 79.8 1.1 81.0 0.29 81.2 0.3 77.3 3.2 76.2 4.7 79.8 0.25 80.1 0.44 75.0 2.7 74.0 5.7 78.6 0.30 78.5 0.52 70.2 3.8 69.3 5.6 76.2 0.33 76.7 0.55 76.4 0.71 65.5 4.1 64.8 4.8 73.8 0.38 72.7 0.43 72.6 0.73 58.6 4.4 69.8 0.29 67.3 0.51 66.9 0.82 69.3 0.92 151 53.8 5.3 55.8 5.6 63.9 0.58 60.9 1.1 58.3 1.2 rABLE LIV (PART III) BORN i.QUA'i'IOH IONIC RADII Dioxane - h 2o EtOH “ HgO Acetone - V IS® 25° 15° 25° 15° 25° D P. AD P . A_ _ D r. A D rf_ A D P i A D r . A Croceo dl-dinitrooxalatodiammlne cobaltate (cont.5 49.2 5*9 46.8 6.0 54.7 1.3 37.9 5.0 48.8 1.4 29.1 5.1 21.0 5.0 Flavo Sulfate 79,6 lJt 70.6 2.2 81.0 0.4 81.20.55 75.0 2.0 63.6 2.3 78.6 0.56 77.4 0.68 78.9 0.85 77.6 1.0 68.1 2.1 61.2 2.2 76.2 0.69 75.3 0.88 75.3 0.91 54.0 2.5 56.3 2.5 74.9 0.66 75.2 0.69 71.7 1.1 46 .0 2.8 71.6 0.74 66.9 1.1 68.0 1.1 36.8 3.2 67.0 0.75 65.8 0.93 64.0 1.1 26.7 3.5 28.2 3.8 63.9 0.81 59.7 1.2 21.9 3.7 59.7 0.87 55.2 1.3 16.7 2.8 54.0 1.0 55.5 0.99 43.3 1.5 50.4 1.4 51.0 1.03 45.6 1.5 46.7 1.03 42.3 0.96 38.0 0.92 Croceo Sulfate 79.6 t ;5 • • 81.0 0.4 81.2 0.6 75.0 1.7 71.3 1.7 78.9 0.85 77.6 1.1 68.3 1.7 78.6 0.56 77.4 0.75 76.5 0.84 60.3 2.1 76.2 0.77 75.3 0.88 75.3 0.81 58.5 2.0 57.6 2.0 74.9 0.66 75.2 0.70 71.7 0.95 47.6 2.5 71.6 0.74 66.9 1.1 68.0 0.86 152 45.6 2.2 67.0 0.75 65.8 0.93 64.0 0.92 | x'AiLE LIV (FART IV) BOuli i^A l'IO N IOMC RADII Dioxane - h 2o St OH - h2o Acetone - H20 '"IB*” “53*7 15v 25° - 15^ 25° D p . A D p. A D r. A D r.*_ A _ D rj A D r * A Croceo Sulfate (cont.) 44\T" 2.5" 4?.4 2.3 63.9 0.79 59.7 1.0 36.7 2.6 59.7 0.85 55.2 1.1 33.0 2.6 33.3 2.9 54.0 1.0 55.5 0.86 48.3 1.4 50.4 1.1 25.8 2.9 51.0 1.0 46.7 1.1 42.3 1.0 38.0 1.3 154 water-dloxane la 3 to 4 times larger* This la a reflec tion of the closeness of the two curves In plots of s 73 D. (See figures 18 to 29*) £ 1 K o i z u m i 7 finds (1) the radius of lead sulfate in water-acetone, water-glycine, water-ethanol, and water- :nethanol to be oonstant at Isodelectrlo constants of 74*1 and 76 *4 at 25° C. but the radius in water-dloxane is different. ( 2 ) The solubility Is different at isodielec- trlc constant (See Table LV) for each solvent mixture in dicating other solvent effects than dielectric constant* T A B L E L V DATA OP KOIZUMI ON SOLUBILITY OF PbS0 4 A T 2 5 ° C . Solubility, m./l. x 10u D D i o x a n e Acetone Glycerine E t O H U e O H (H«0) 78.54 148.1 148.1 148.1 1 4 8 . 1 1 4 8 . 1 76.35 121.0 9 2 . 0 1 0 9 , 5 100.2 9 6 . 0 74.10 109.2 5 0 . 8 6 9 . 2 6 0 . 2 6 1 . 8 El Koizumi attritubes the high solubility in water-dloxane to the much lower dipole moment and dielectric constant oi the dioxane as compared to the other organic solvents (See Table LVI). Thus the water molecules ure more easily 3orted out by the ions in solution and the water-dioxane solvent behaves more "water-like" than the other mixed solvents of comparable composition. The 3orn solvation mean radii (Table LIV) at high dielectric constant are generally only 1/5 to l/4 t h e m e a n 155 TABLE LVI DIFOLE MOMENT AND DIELECTRIC CONSTANT OP THE PURE SOLVENTS USED IN PREPARING THE MIXED SOLVENTS Solvent Dipole Moment* Dlelectrlo Constant** 2 5 * C . W a t e r 1 . 8 7 7 8 . 5 D i o x a n e 0 . 4 2 . 1 Ethyl Alcohol 1 . 7 0 2 4 . 3 Acetone 1 . 3 2 1 9 . 1 # LeFevre Dipole Momenta, Methven and Co., 194B 2 n d E d . 4 6 ** Akerlof 39f 40 ionic radii estimated from cryatallographic data. Even in solvents of low dielectric constant where the Born solvation mean radii are largest they barely approach the mean cryatallographic radii of 2.5 to 3.0 A.V. (Table XLIX). An exception is the oroceo and flavo dl-dinitrooxalato- diammine cobaltate in water-dioxane solvent whose radii are 2 to 7 times the cryatallographic radii. Actually the ?orn aolvation mean radii may be of no more significance than the Debye-Huckel distances of closest approach which are sometimes negative and for practical purposes mean ingless as physical constants* Salt Effects I Debye-Huckel Limiting Slopes and Activity Soefflclenta. The Rlcol-Davla Empirical Relation* The Debye-Huckel limiting law47 for the mean activity 156 coefficient of a strong electrolyte la - /> . / . * * r k s o * " " V f * ‘ (D t ) 4'1 * ’ *' ore the standard state Is the activity coefficient is o n l t i t y as the mol fraction of the solute approaches zero* The Debye-Huckel limiting law is related to the solubility a s f o l l o w s - * * * / ■ - c r c S - g In a saturated solution c * » IV t c . * • (**)*&-*)(* f/ Designating the solubility at the ionic strength of the saturated solution as S^g^and the hypothetical solubility at zero ionic strength as Su - 0 S ¥ ft" ^ = i . . . >r»o /j * / Jm * 'ter* • /i » 7 --- -/•* -fj * - A* Jzz. - tur*** t,i./rr 1 ~ “ t- & T) " • 157 Tho solubility of both the flavo and crooeo salts was determined In the presence of adddd potassium chloride (see Tables XXXVIII to XLV) in water and at one point in water-dioxane, water-ethyl alcohol, and water-acetone (2 points for the lodates), The log s vs IF curves were plotted (see figures 63-30), and the best straight line drawn through the points and extrapolated to u » o, The Debye-Huokel limiting law slope calculated and drawn from log a at u s o for comparison. The dotted line of the figures is the Debye-Huckel limit ing law slope. The effect of added electrolyte on the solubility was studied to determine (1) whether or not the salts behaved as ideal electrolytes in the concentration range and sol vents used and (2) to check the main assumption of the Ricci Davis empirical relation which is that a given electrolyte in its saturated solution has a mean activity coefficient Independent of the solvent. Agreement with the Debye-Huckel limiting law is fair. In Table LVIX the calculated Debye-Huckel limiting law slope and the observed slope is compared* In general the flavo salts show a greater slope than calculated especially in water-ethyl alcohol solvent and the croceo salts show a lower slope than calculated. The oroceo salts show a bet ter agreement with theory in most solvents than the flavo salts. This may be due to the croceo salts lower solubil- 158 ity, however a comparison of crooeo 30^ and flavo [,co(nh3 )2 (N02 )2(c204 3 which lie In about the same solu bility region show the flavo salt to have a higher slope and the croceo salt a lower slope , with the exception of v/a ter-dioxane, than theory* If the unsymmetrloal flavo Ions sort out the more rolar water molecules and are thus surrounded by solvent molecules of higher dielectric constant than the macro dlolectrlc constant of the solvent one would expect a lower salt effect slope than theoretical since the Debye- Huckel limiting law slope decreases as dielectric constant Increases* This Is not the case* By the same reasoning one would not expect the symmetrical crooeo Ions to sort out the water molecules as much as the flavo Ions and thus the flavo salt effects slopes should be less than the croceo salt effect slopes* This is not the case* Dr* Verhoek suggests that water is collected about one nltro rroup of the flavo ion and shields the other nltro group so part of its effectiveness Is lost* The nltro groups of the crooeo Ion are not adjacent and water molecules can be attracted by both nltro groups. Thus the symmetrical croceo ion may be more effective in sorting out water mole cules than the unsymmetrloal flavo Ion* The larger than theoretical slope shen treated by the ertended Debye-Huckel theory TABLE LVII COMPARISON OF DEBYE-HUCKEL LIMITING LAW OBSERVE . AND CALCULATED SLOPES Temperature. Solvent Organic, D Anion Flavo Croceo 0 C. wt. % Obs. Calo. Obs. Calc. 15.0 H2° 0 82.22 lodate 0.480 0.498 0.475 0.498 « Dioxane 22.5 60.6 N 0.695 0.786 0.600 0.786 • EtOH 20.2 70.2 II 0.705 0.631 0.585 0.631 * Acetone 23.1 68.4 tt 0.675 0.656 0.655 0.656 • Dioxane 40.8 44.4 H 1.15 1.254 0.790 1.254 w EtOH 39.8 58.1 If 1.17 0.838 0.835 0.838 ■ Acetone 40.0 57.3 ■ 0.915 0.855 0.840 0.855 25.5 EtOH 45.0 51.9 If 1.16 0*948 0.87 0.948 ~ 25.0 HgO 0 78.5 Sulfate 6.95""" TI3I3 0.59 1.015“ Dioxane 20.7 60.0 n 1.27 1.526 1.24 1.526 EtOH 20.2 66.9 N 1.32 1.289 1.08 1.289 Acetone 22.4 65.7 If 1.22 1*323 1.30 1.323 25.6 h 2° 0 78.5 dl-dinitro- 0.58 0.506 0.50 0.506 Dioxane 14.9 65.2 oxalatodiam- — «a«e 0.64 0.669 Dioxane 19.9 60.9 mine cobal- 0.78 0.741 — — Ethyl alcohol 5.2 75.6 tate —— 0.62 0.536 Ethyl alcohol 20.4 66.8 • n 0.85 0.645 -- -- Acetone 5.0 75.9 it ii « — 0.53 0.533 Acetone 21.4 66.3 ii ii 0.69 0.653 — — ” 25.0' figO 0.0 78.5 Picrate 0.55 0.606 0.55 O.506 25.0 Dioxane 10.2 69.6 ii — 0.50 0.611 25.5 it 15.4 64.8 n 0.65 0.678 — 25.0 ti 20.7 60.0 t! 0.60 0.763 - - 25.0 it 39.8 43.0 If 1.11 1.26 0.83 1.26 159 leo would give a negative distance of closest approach. The Debye-Huckel Theory as extended for symnetrloal electrolytes by Gronwall, Laller and Sandued40 and for un- symrretrloal electrolytes by Laller, Gronwall and Greiff40 will give positive distances of approach when the observed slope la greater than the Debye-Huckel limiting law slope. The salt effects were not carried out to high enough lonlo strengths to show actual curvature In the log s vs plot and thus no efforts were made to calculate Ionic dis tances of closest approach from either extended theory. The Rlccl-Davls empirical relation0 la based on the assumption that a given salt has a constant mean activity coefficient In saturated solution Independent of solvent. Thus one can equate the Debye-Huckel limiting law expres sion for the mean activity coefficient at saturation of a salt In two solvents as follows: and <1 { / o f Z>, - / o j 0 , ) / • j - /fj * 161 a n d obtalna the Rlcol-Davls empirical relation* The assumption of a constant mean activity coefficient of a saturated solution Independent of solvent was checked :-j calculating the mean activity coefficient at saturation of the various salts In water and at least one point In each of the mixed solvents from The results are tabulated In Table LVIII. The assumption of a constant mean activity coefficient a t saturation Independent of solvent appears to be only ap proximately true. The average mean activity coefficient and Its average deviation at saturation of flavo iodate Is 0.835 £ 0*038, of croceo Iodate Is 0.900 £ 0.027, of the flavo sulfate 0.Q3 £ 0.03, of the croceo sulfate 0.88 £ 0.02, o f t h e flavo piorate 0.91 £ 0.03, of the croceo plcrate 0.88 £ 0.04, of the flavo dl-dinitrooxalatodiaiwilne cobal- t a t e 0.94 £ 0.01 and the croceo dl-dlnitrooxalatodlanmlne cobaltate 0.97 £ 0.00* R i o cl and Davis^ say most available data show the as sumption of constant mean activity coefficient to be true for 1-1 electrolytes and only approximately true for 1-2 1-3 etc. electrolytes. In this study the sulfate, a 1-2 electrolyte, shows as much constancy of mean activity co efficient at saturation In the various solvents as does the 162 TABLE LVIII DEAD ACTIVITY COEFFICIENT OF SALT IN ITS 3ATURATED SOLLTTIONS Solvent Organic, Dielec Temper- Anion Mean Activity wt. % tric ature Coefficient Con Flavo Croceo stant iuO ’ ' o §275 15.0 Iodate 0.801 0,859 Dioxane 22.3 60.6 If " 0.798 0.882 Dioxane 40.8 44.4 n " 0.809 0.902 Ethyl Alcohol 20.2 70.2 " 0.862 0.917 « " 39.8 58.1 n " 0.903 (0.933)* 1.01 Acetone 23.1 68.4 n 11 0.782 (0.920)* 0.974 Acetone 40.0 57.3 ii " 0.859 0.933 Ethyl Alcohol 45.5 51.9 25.5 " 0.87 (0.91)* 0.85 Average £ average deviation 0.835 £ 0.038 0.900 £ 0.027 H p ° 0 78.5 25.0 Sulfate 0.79 0.84 Dioxane 20.7 60.0 N " 0.82 0.87 Ethyl Alcohol 20.2 66.9 fl " 0.87 0.91 Acetone 22.4 65.7 ft " 0.85 0.89 Average £ average deviation 0.83 £ 0.03 0 .88 £ 0.02 irzo o 78.5 25.0 dl-dini-0.94 ' 0.9V Dioxane 14.9 65.2 it trooxa- — 0.97 Dioxane 19.9 60.9 n latodlam-0.92 -- Ethyl Alcohol 5.2 75.6 tt mine co- -- (0.98)* baltate 1.03 if Ethyl Alcohol 20.4 66.8 " 0.95 -- Acetone 5.0 75.9 n it _ _ 0.97 tt Acetone 21.4 66.3 " 0.94 — Average £ average deviation 0.94 £ 0.01 0 .97 £ 0.00 Hp° 0 78.5 25.0 plcrate 0.95 l)."9d Dioxane 10.2 69.6 n tt 0.92 Dioxane 15.4 64.8 it " 0.92 -- Dioxane 20.7 60.0 tt " 0.90 -- tt U1oxane 39 • 8 43.0 H 0.85 0.83 Average £ average deviation 0.91 £ 0.03 0 .08 £ 0.04 * Value from straight line through saturated solution noint parallel to "beat" straight lino. (See Figures 70, 71, 74 and 77.) 163 1-1 electrolyte*• Hansen and Williams 43 have also determined the mean activity coefficient at saturation of croceo SO^ with the following results* Hansen and Williams This Study Ho0 0.802 0.84 etnyl alcohol, (20.2 wt. %) 0 . 9 1 ethyl alcohol, 20 mol % 0 * 9 2 9 (ca* 39 w t • %) ethyl alcohol, 40 mol % 0 * 9 5 2 ca. 63 wt* % The agreement in water is not particularly good. The mean activity coefficient of the salt in its satu rated solution appears to be more nearly constant for the iodate and sulfate in water and water-dioxane solvent than in either water-acetone or water-ethyl alcohol* The mean activity coefficient at saturation of the dl-dinitrooxalato- iliammine cobaltate does seem to be independent of solvent. The Ricci-Davis empirical relation was checked by plotting log s vs log D (for the iociate see figures 34-37, for the sulfate figures 30-33, and for the dl-dinitrooxalato- diammine cobaltate figures 38-41), and calculating the ex perimental slopes which are tabulated in Table LIX. The dotted line of the figures is the predicted slope of three# The Riooi-Davis empirical relationship holds fairly well for the sulfate and iodate of both the croceo and flavo ions in water-dioxane solvent* In water-ethyl alcohol and water- acetone there appears to be a linear relationship betwoen 164 lor s and log D but the observed elope la 2 to 3^ times neater than the predicted Ricci-Davis slope of 3* The dl-dlnitrooxalatodiammine cobaltate, which showed constant mean activity coefficients of saturation in the various solvents, have approximately a slope of 3 only In weter-acetone solvent* The plot of log a vs log D is linear in water-ethyl alcohol but has twice the predicted slope of 3 . The plot shows definite curvature In the high dielec tric constant range of water-dioxane solvent but becomes linear with a slope of approximately 3 in the low dielec tric constant range* Previous research In which the Ricci-Davis equation is cited as giving a better reproduction of the experimental data than the Born equation^*®#^,11 jlfta been carried out in water-dioxane mixed solvents* It would appear that the Ricci-Davis empirical equation is good for only the water- dioxane solvent. It is the water-dioxane solvent mixture that shows the best constancy of mean activity coefficient of saturation of salts dissolved in it* It Is also this solvent mixture in which the pure solvents of the mixture were most different in their dipole moments and dielectric constants* (See p* 155) Although the Ricci-Davis treatment does not consistently ive the expected slope of three there is a more nearly li near relationship between log s vs log D than between log a vs l/D as predicted by the Born equation* The significance 165 T A B L E L I X SLOPES OF THE PLOT OF LOG S VS LOG D A n i o n Solvent-Ulxture F l a v o C r o c e o 1 5 u 2 5 ° 1 5 ^ 2 5 ^ Sulfate wat er-dloxane 3 . 3 3 . 6 3 . 8 4 . 3 water-ethanol 9*3 1 0 . 4 8 . 3 9 . 0 water-acetone 6 * 4 6 . 7 8 . 0 7 . 9 I o d a t e water-dioxane 2*8 2.8 3.2 3 . 3 water-ethanol 7.6 7.0 7.6 7 . 7 water-acetone 6*2 5.8 6 . 2 6 . 6 d]-dinitro- water-dioxane n o n - linear non-linear oxalatodiam- water-ethanol 6 . 7 5 . 6 9 . 3 7 . 3 rdne cobaltate water-acetone n o n - l i n e a r 3 . 5 3 . 3 oT this, If any, Is yet to be explained* ^.lerrum Ion Association Bjerrum^®, 5 5 derives the equation ¥/r A/c PM O k ) 0 - « ) * / o e s \ 0 H T / w h e r e . V f e r Y j r w l t h J h J d l l 6 • * Ok T a n d / * * - / ' * r O k T for the Ionic association or formation of ion pairs under the influence of Coulombic forces* The derivation assumes rigid unpolarizable spheres contained in a mediiun of a fixed macro- 166 scopic dielectric constant. The probability that an 1 ion is a distance r from a J Ion la found. If the ions are of opposite sign the probability can be shown to possess a minimum at a distance ^ such that rt 4* /i* * - / . ^ 2 0*r r Ions at a distance »* < are assumed to be associated, those at a distance r > are assumed to be not associated. BJerrum55 calculated that a 1-1 electrolyte in water at 18° C. was not associated if the mean distance of ap proach of the ions, a, is greater than 3.5 A.U. Fuoss and Kraus 5 6 calculate that for a mean distance of closest approach of d.4 A.U. there will be no association in a solvent of dielectric constant of 44 or higher. The degree of association, (1 -«6), and the minimum distance, ^ » were calculatedfor the croceo and flavo salts in the same mixed solvents as those in which the Debye-Huckel salt effects were run. The results are sum marized in Table LX. For the calculation of b the mean distance of closest approach was taken as twice the calculated Born radius for each particular solvent mixture and dielectric constant (Table LIV). Values of Q (b) were obtained from a plot of b vs Q (b) using the Q (b) values tabulated by BJerrum ( / * A 4 /r ) and by Fuoss and Kraus56 (/f i 4 & ^O). 167 The use of twice the calculated mean solvated Born r a d i u s In the BJerrum Ion association calculation may be o p e n to question* The Born equation is derived on a dif f e r e n t basis than the BJerrum equation which Is derived in a m a n n e r analogous to the Debye-Huckel equations* One rcifht expect better results from the Debye-Huckel mean dis t a n c e of closest approach If i t were available* The distance of closest approach from the calculated erystallographlc radii (Table XLIX) is 5*5 to 6.0 A*D*,'V large enough for all except the sulfate to have no associ ation. The calculation of the BJerrum ion association using twice the Born solvated mean radius shows some association of all the salts except the dl-dinitrooxalatodiammine cobal tate in water-dioxane* An assumption of the Debye-Huckel theory is complete dissociation of the electrolyte in solution. In Debye- X Huckel salt effect^the added salt was completely dissoci ated and the slightly soluble salt partly associated and solubility and ionic strength was not corrected for the association the Debye-Huckel limiting law slope would be less than theory* The flavo iodate In water-ethyl alcohol is the most associated salt, however it shows a greater salt effect slope than theory. The croceo iodate in water-ethyl alcohol also shows association but Its salt effect slope is 168 TABLE LX I1JERHUM ION ASSOCIATION AND MINIMUM DISTANCE OP APPROACH — ------t w i c e Born r*aiui,A.tr« n. -"*< 1— Anion Solvent D T1 CTC'CTO FTa?<5 »,A«17^r5oeo flavo iodate Dioxane 60.6 15 2.8 3.2 4.7 0.023 0.040 tt tt 44.4 it 3.4 4.0 6 .4 0.030 0.053 ” Ethyl-aloo- hol 70.2 tt 0.80 0.80 4.0 0.100 0.178 ti tt 58.1 tt 1.04 1.04 4.9 0.031 0.064 " Acetone 68.4 tt 1.04 1.20 4.2 0.044 0.070 n tt 57.3 tt 1.20 1.32 5.0 0.037 0.063 Sulfate Dioxane 60.0 25 4.2 4.6 9.1 0.024 0.039 n Ethyl alco hol 66. 0 tt 1.86 1.86 8.2 0.048 0.067 " Acetone 65.7 it 1.80 2.2 8.3 0.066 0.066 dl-d ini-bloxane 65.2 S5 3 .6 -- 4 . i none ^ «e trooxala- 9 60.9 it 32. 4.5 -- none todlammine Ethyl cobal- alcohol 75.6 tt 0.96 - - 3*6 0.002 tate 9 66.8 n -- 1.20 4 .1 — 0.004 " Acetone 76.9 n 1.42 -- 3.6 0.001 -- tt it 66.3 it —— 3.0 4.1 —— 0.002 very near to the Debye-Huckel limiting law slope. The dl- dinitrooxalatodiaiwnine cobaltate shows little Ion association yet It shows little better agreement with the Debye-Huckel limiting law slope than the other salts. It appears that ion association calculated in this manner offers no expla nation of deviations of the croceo and flavo salts from the Debye-Huckel limiting law. The calculated correction for ion association is in the r i jht direction to explain the departure of log s vs l/D of the Born equation from linearity, but the calculated ion association Is not enough to make the results linear. For 169 example flavo iodate In water-dioxane at D * 25, should have a solubility of 0,000083 m./l. rather than 0,0017 m*/l. If the Born equation slope at high dielectric con stant was followed to low dielectric constant. The BJerrum ion association is 0,113, not nearly enough to make this rorreotion. Likewise the solubility In water-ethyl alcohol at D : 58,1 should be 0.00040 m,/l« rather than 0*0038 m ./l, and ( 1 - •** ) Is 0,064; in water-acetone at D - 57,3 uhe solubility should be 0,00040 m./l, instead of 0,0023 m ./l. and (1 - 4t) is 0.063. Hence, at best, the BJerrum ion association Is only a partial explanation of deviation I'rora the Born relationship at low dielectric constant. SUMMARY 1. The Born equation and Ricci-Davis empirical equa tion for change of solubility of electrolytes with dielec tric constant of the solvent were tested by determining the solubility of the iodate and dl-dinltrooxalatodiaiianine co- L-altate of both the croceo (trana dlnitrotetrammine cobalt III) and flavo (cis dinitrotetranwine cobalt III) univalent cations in the solvents water-dioxane, water-ethyl alcohol, ami water-acetone at both 15 and 25° C*; the solubility of coth croceo and flavo sulfate in water-dioxane at 15° and in water-ethyl alcohol and water-acetone at both 15 and 25° C.; the solubility of both croceo and flavo picrate in water-dioxane at 15*5 and 25° C* and in water-acetone at or.0 n 2. The effect of potassium chloride as added electro lyte was determined in water and at least one solvent mix ture In each of the mixed so]vents for every salt studied* 5. There was no apparent relationship between solu- b'llty and dielectric constant for the picrates In either oi‘ the solvents tested* In water-dioxane solvent as the proportion of dioxane in the solvent increased the solubil ity of croceo picrate decreased to a minimum of about £ the 170 171 solubility in water at 10# dioxane, Increased to a m a x i m u m of about 2 ti ies the solubility in water at 61 % d i o x a n e then decreased to about 1 the solubility in water at looo irare dioxane* Flavo picrate was only 1/5 as soluble as the croceo picrate in pure water* The solubility of flavo pi crate increased as dioxane was added to about twice its solubility in water at 17# dioxane, then there was a sharp iccrease in solubility and then an increase to a maximum of a:out 4 times the solubility in water at 64# dioxane, then a decrease in solubility to pure dioxane* At about 90# dioxane the solubility of the flavo salt became greater than that of the croceo salt* In water-acetone solvent the croceo picrate solubility Increased to a maximum of three times the solubility In water at 67# acetone then decreased to a solubility of out 1/5 that in water In the pure acetone* The flavo picrate solubility increased as the proportion of acetone in the solvent was Increased to a maximum of 15 times the solubility in water at 73# acetone then decreased to about lii tines its solubility in water In pure acetone* At about H5# acetone the flavo picrate became more soluble than the croceo picrate# Evidence that one mol of dioxane was associated with each mol of both the croceo and flavo picrate solid residue w a s f o u n d # 172 Differences in the physical appearance and color of the solid residues from water-dioxane wore noted* ho evidence of an addition compound between acetone and either of the picrates was found however the saturated solution of the picrate at the maximum showed a reddish oolor* 4. The iodate and sulfate of both cations showed a dependence of solubility on dielectric constant, however a plot of solubility versus cJTelectrie constant gave a sepa rate curve for each mixed solvent* The dl-dlnltrooxalatodiaironine cobaltate solubility showed little dependence on dielectric constant in water- dioxane solvent but showed dependence on dielectric con stant in water-ethyl alcohol and water-acetone solvents* 5. lleats of solution of the various salts in the rulxed solvents were calculated from solubility measurements at the two temperatures* 6. Debye-Huckel salt effects showed the salts to ehave fairly ideally in the concentration range and solvent oaed. Calculation of mean activity coefficients of the salts in their saturated solution showed the assumption of hicci and Davis of a constant mean activity coefficient of n salt in its saturated solution Independent of solvent to be only approximately true* 173 7, The Iodate, sulfate, and dl-dinitrooxalatodiammine cobaltate solubilities deviated from the Born relationship at dielectric constants of 72-74 In water-ethyl alcohol and water-acetone and of 60 in water-dioxane* Correction of 3OK0 oi' the solubilities to zero ionic strength gave negli gible improvement* Calculated values of the Born equation mean solvated radii of the sulfate and iodate in the various mixed solvents were about J to J the radii estimated from crystallographic lata. The radii in water dioxane are always greater than the radii in water-ethyl alcohol and water-acetone* The Born radii of dl-dinitrooxalatodiammine cobaltate in water-dioxane are 2 to 4 times greater than the estimated crystallographic radii* In water-ethyl alcohol and water- acetono they are approximately the equal but only £ to | the crystallographic radius* 8 * The Ricci-Davis empirical relation slope of 3 in the log a vs log D plot was approached only in water-dioxane solvent by the iodate and sulfate and in water-acetone sol vent by the dl-dlnltrooxalatodlammine cobaltate* Most of the salts showed a linear relationship between log s and lo;; D but the slope was 2 to 3^ times greater than the ex pected slope of three* The flavo dl-dinitrooxalatodiammine cobaltate shows a linear relationship only in the lower dielectric constant 174 range of water-dioxane solvent* 9* The degree of Ion association was calculated from the Rjerrum Ion association theory using twloe the calcu lated Born mean ionic radius as the distance of closest a proach* All the salts except the dl-dlnltrooxalatodlammlne cobaltates in water-dioxane showed some association* The calculated correction for ion association is in the right direction to explain departure of the Born equation from linearity but it is not nearly enough to make the results linear* It offers no explanation of the deviations from the Debye-Huckel limiting law salt effects* FIGURES 176 Tube to Waah Down Spray Trap Oondeneer inch Pyrex Oondeneer " Boiler 8p«olal Receiver > fvade from a lOOal. r.b. Plaek and a 500 Srlenaeyer flaek) Figure 1 Ammonia Analyeie Apparatue 177 rigur« 2 Ifethod of Taking Staple PI pat i*o Oorepreeeedv *1 r Lina - > Rubber Tubing ~ Pyre* U Sintered Olaaa niter Rubber Stopper 2U/M-0 Standard Taper Joint Sample Tube (To Soale) 3 on* \ : e ; 6 8 fc8 C 6 C : i t 4 t l i q w i - *ur# t> (trAn*) Sulfete 2 5 C ' ' p . " "j eolubilltyt*. $llireat Coaioelti e. vatfr^BloxAntj • 4 *AtAT-ffeyl Atoohoi I & wttjt^AOAtoh*:• ;•'' ! • Qp H&m o ti Apd AtXItA®* t)Atk See Tuplea tT,rXtT 0 i*Q - m 9 tMQ - * * •- , I* : nteture 7 Croo«o (t|*nB) ; 2.10 -1 Sofcipiiity vs. flolvppt pjppop^tion Watar-Dioxahfe WBter^Wtlirl Alooh >1 Water-Apetonp l v* 0 - S«e itablad , X t l V 1 . ^ 1.20 - f>. o.-fio - Pv^O - S o.o orgfchic.wt. i Solubility w b » Solvent Cb*po«J.tion W*te*-Dio*ane VkValr-mfl' Al*»6i:: iPt^^Aoetone ee Taslee m fXrtII^TV. ▼a. 3ol*reht lt>n ® water- )lo*mne £ Water-Ethyl A £ Wptt er- loetope Ornate ft. i % H Figure 10 Crocpo (tranw) Todate 2rV c 0 h x cr** Sol^bi.lijty re. Soljrent pompoiltlon & Water-Dloxanb jo ti Water-Cthyl {tloobol P water-Aoetone ' ' • ' See fable* XTVt ,TTVttt ,***. '{ * ZM. \ ■o.tr Origanlc, wt. % : Figurt li Crooeo (trane) I ©data 15 a *T Solubility ▼«. Solvent Composition 0 Watexl-Dloiana ; * ■ WateX-tthyl Aloohol I * Watax-Aoetone ! 3ea Tablea XXVI.XlfVIII.XXX. Q.50 - \ 0.29 - Id ^ 0,0 I 3P 9 0 prga.nl 0 wtL % ' ritare 12 Flavo (cl*) IOdate C Solubility vfe Solvent Oompo*itio* wit ter-n i ozone ti fater-tthyl Alcohol fi. t$,ter-^cetoi»? ! * I 5*20-9 Or some QfUVSjQ «• • O O O Solubility,n,/l,*10^ (\j l E M f j. Pigorv Orooep runitroojalfttodlamminf Cobaltate ^.00 — 'j*5 - '1 Solubility t *. Solvent Co4po»ltDb <*> w«t«rOD Login* & wa-t«x-i(thyl >1 A'" : H * i £ - t * - Jd- W-O M . • H e ♦» rigtafre ig Orooeo (trftn*) nlnitrooxalatodlammine Cofcfr.lta.t* 15 G Im ljubl U ty *>. golyat & WHt«r-Di wean* a Wa,tsp-Et aylr Atoofeo|l a ▼at«r-Ac|eton4 ■5-**00 1.00 o.o o ) ; - * a t 6 7 Jrgwtio wt li . i . . , . t) 1 ■ ■ ■ 'Zftvo 7oi* Dlnltrooxalatod ianamine 061*1 tata SoluMlit fattx«>ioxan« fatai-ftlitl Alpahol 8«> Tablaa *txiii>x*fcv,mvti. 1.^0 - te*anlo Figure 1 Flay© (© •) rtinitrooxalatodiammlne OdbAUtaii- jT folubll ty vi. So ▼ant -**hyl llooh^l l.*Q- «Aoaton# ■■ *. blait m t i . m v , K x m i * 4 € Crganio. wt _r jpirtlof Orooe >(trafit) lfat# 25 0 i . 6 w r •r~vthyl ileoh^l ■A Vr Action* ® B«|i>««n « n d 4*111 taia* D4ta ble* ▼TMXTI.XXIV. 4 WlW' — •' 0,1*0 -£ . . 8b 65 * f 35 s| IsotrljQ Cois.tant 1194 .cjoo«olftraji? falfat*...... _ foluW _1| ty o«* l?;09nitMit o W*t«r-Dlox*** 2 watfr*ftl*yX Alotflol **tar-Aottoa« 3e«f«bl«^ XX,fcXII,bCXIV. — - * p -4-*-— 0.0 i©otno c>iwt*fct . o 6 ^>i + , o o0* 9olubl)lty, a*/lj x 10^ 196 e.*o ; ai F l M o (ol») SUXffttt 15J3 ©ojltiWliAy i«y Dt«X«atjrio ojaast^nt © *©tv-irthjl Alcjohoi A ©at«r -Acetone l.rtfv -- 9 * Tab: M It* i xr :xI f m . lit* t V £ 0,0 *!> o no 09 x 10 OV ^JT 40 n> VJI *4 to *o X H 198 euro 23 (tran§) ::odatt- 1 5 0 ...... Solubility ▼»• D ifleotti0 C 0 AUobol * Wb * ~ A b b ;6Ab ; ... * ... j 9<« t*UlM i:X71f TtXTtiyfXXX 0.0 $!► leottio Oi^stAbt 199 Flgur# *1 - 1 avo (ol«)llodata ■6 M - ?i ~ 7 “ Solttbt.lty ira. DUlactrtcfcoaatint • water-DJ OVUki O fattr-11 looh>l **atar-n 8#a tableii TTVtlfXX :x,XXjcj. •o.#o Dieleotrio C o m U n f U,(K“ f t w r t *5 rflavo (ola) Iodata Solubility vs. DieleoUrlo donatant — e r w a w - m aatev-fthyl Alaohol HataxUAoatona 368 Table a XTTI1 .XXIX, XXXI. i V 4 *-• S5 *<> V 7 I ♦ Dleliotrlo Coaitant * ' t ' ' ' ' 1 . * . , • 1 ] T t • 201 ----j _ - - , , . ____ Oroofeo (fana) Dinitrooxalatodlaramine CObaltat* 5510 Boltiblll 5jr Diatactxlc Qaiataafc 4 ■ Lloohbl A Wifrar-ififtton k> 1 f .00" 8*f ;'!**!•* TTri,niiT,r:xn. SCfr “ XJT X t - - 4 3Q3 H i w t (Oin) Dialtrooxalatorflammine -H- 0 t - ®> v44tr«t)ld«4M ■ ■ ; ' ' .ejfiur-EttiHLuftjeikAl iwiiai^Aeataia T mm.ttirc.jtmi \ 35 eatUtlQ J3G 09 204 t : • i ::: ^lavo (eli Di nl t r ooxalat od 1 ammi he "Col foXtWUtTyr** $ Vat «tar tioohot 1 X*at*r-»A#+t*ft* !raiii#xxt?*nim. j I 10 Conetaxvt n &i x * ( 0 Mttr s? itttor-tfthyl loohxL £» ifiUr-Aa* and ^illliJM irmi: XJII« I • i 1 ! 206 2,6© - • 34 ■ O*oi#d r*n«) ©ul £> ' D j o*in#-»w4* Cl *»t«ii-tthyl AlciQhol J A ;tnt©zj^Ae«tod« * ■ TmpijBP xx#n n *».70 “ 5.00 - 1.9 FU to (Oil) auifatc ~T~r ■ :: -tog a II* Log D © Wat«r-I loxant 9 gatar-itkyi Aloctool. ■'■ 8«#t*ablei ;rri,mn,i'rr. . 8DB 0 . m wprrftbri; Ueoiip?. jr« b iit» jtt'swajii. <■ i * t It a n • 1 TT . i * i : i: m m 4 I t * ♦ 4 * i •» t I Y U! IS : & 4 1 :: ; 4 ! £ H s 3 f t 1 i: OJ 8 i ■ t ! 3 I .. 3 ■ i i mn i t r ooxalat m od i asm ijnjel 1* : m i I ftrfclfcltDinitrooxalatodiammih n h M t t t ii ittti ' ‘ r. : d » 11 44* n f H i Dinitrooxalatodiamm it: 8? 4 TO *11 n f t H I — ::: iifi- t H 4-4 .♦> * * t 1 4 * • t + T uw>; ( Dlnltrooxalatortlammirid !t1 L - :: I* m S Coefficient 1 I *>p ■ :: r ri nn Coefficient t ! ; : i . J * n ' - I it 1!! . :: i A 1 1 i li d 1 i l 4111-1 n r Coefficient m 2 ttf I Li airTIE $ f? : k U - 4 t r f t )U9X9i;idO0 f l r - :t: ti U t i O o e f r l c i e n y W 41 I 55 If5 u t r. H I: ! 01 1 * t * -*■ I ■ ♦ I kU ’.rtt m ; 1 ft :! : :! A) : iJ T ♦ t . ; i ] 1 j . , . + -J • J 4-4— i---- L V - f - t ■t m z r 1' - 1* + - t * ; 4- n i L flfir boio ft S a r * l i m ySL ft* W b U ♦ ♦ * f * + f t + 1 - * + « * , , 1 . * < I * t * + : ' l ::: I :■ — f e w r ■ I H W* f X] M f*U » m 11 m 1' 1 T'TI:ri j ■■ u k ! r 5r n u 3 ■ t ! a t; n I? s : :t 3 m Dlni trooxalatodlammlna .11! U U I ti-*'t ft * U f- u 1 tl 1 I: 1 ■ n r-+ M HU X IDlnl ooxalatodlansmlziQ t * t t ■m -m 11 I l» V - r u n u f J :4 H T t iw trooxalatodiammiftf • :: h f ’ I p U. IF"? 3 Dini trooxalatodlamaiire ' X, y . y I / y o n lo s ts•Ugtrb : Cii-to. Oi... o H 4 V ? O' /*- W cu ! l* :!*;! li: f U H m * ) : WUAtif M l * u*-i' ss* T«5i» mir-' / 9 / y > : A $ % Y i m m I i r n n r u m Hi I w i m* i • mM : t ; A Tr20 x / *9K aoti I::; ■♦-r—r t T * S c m t t . : moiftno Aoeton® 1*. TO; 1 - i- : I /ipnlD[ Btreigtb ^ . -4 i . + 4 * 2.20 S^lthyl A oofabL T**l« . ' * *;0tr s & /toilte: Btreti^; : h I ; l ! t P I! ' s 5 t w ? /i*5jri533;is ! a I t ? i Li rrt n o A :: i ; t ■! risiifcW ft : j:'; : m a x Cro-cfco ftrtnp). Ttodirti i.. o • ■ • • r.., ? I | t t * I ■ ■ ■ 4 I i ! ! I . , t . iT" ::: f«i*) * t>inltrooxalafodlammi K r e S J S I $ E 515 I \ I. A PC & «: & % \ S * & & & i f ! ; ‘ t H -1 I • ::: / rigt^b A lortUe :: “WJ; ■ 5r 5b>9: < plox^ne B®e T SbTe XLV. u : m t t r a t o s t. 10.2 loiAn* 5, -hi* io:*na 9*4 W * i * $ 5 * +• * IMS f M t Sill 1 ! 1 1 I . i i f - .. ■ - - 4 i • 4 4 ] t * * • ! t ) i 1 ! • 1 t 1 * « : * t » * 1 ' * 1 1 * ! * * T * ; i ; -4-4- 1 - M * * 1 • J iii: 1 i . 1 2k ! tI 20 — 4 - -4-j ! i 4----4 t: rrtr> ■ * i V ♦' iI •■1 r ) * * * tt<* tt4u>« dli 4] 4 4 4 4 SdiutidamiiMttecd a ' 1 ttvn (otO, i : ! 4 T* . 4 ) . I ' 1 * t > + * ( ■ f-M t 1 * * *-• . ♦ i t: * * 4 t i :iizt I t fTT 4-4-- -t-t-» t »■ f* f > t • * * i,i * i I * }} 1 1 ' i 1 t 4 4 m ,:r !~4i;| * * * 4 I? r> m m I I- i . U ? l ) i t i i muHifi ! •>**+ & ¥ figux* *2 Htittn Qcnctiuif 3? « W 1 I SE arisn< I TMb eqttljo - - ; n 1 it- ft J t! ■ ' ^| 1: **■ ♦■ * i ^ * tm ; * : m h i• ’ ‘ i I ’ : 1 r . ’ i i -* :* i • i ■ • + i • L J n !: i +4 ts 8 I lioxane * Dial««triat Oonstant * : i ^2 Haat of itlOB nlelootrio ;Oqn»t, .8 flat ja) fDi rii trqoxala todiaittlna -i r :con*xt*i# *atar-pia**ne . i Matiair- itfay% Aloohol | I j 49 . "^StSr- K8 6 1 dHtf * & 4aa jjTablfl W LI 1.1 I * i . * * ’ u % 4 f * ■ - t ' $ 1 4 /:! t • t *1**1 ■ I ■ * t * * * t |: ■ •;* f * 1 : ; i 1 1 ' ! 1 i ■ ■ ----- ■fm: t • • i - i10 70 46 fc> t : ; t * ■t t • * * : i 1 ' * * t 1 ‘ t t • * I . . t * 1 r T + *■ t * \\u\4 4 * * i, *IJJ-l U Ltii n i l -j-1- t i—L- M; * Hart jorf floltrt 9 BIBLIOGRAPHY 1. M. Born, Z. Phyaik., 1, 45 (1920). 2. J. E. Rlool and T* W. Davia, J. An, Cham, Soo., 62. 407(1940). 3. J. N. Bronated, A, Delbanoo and K. Volquarta, Z, phyaik, Chem., 162 A. 128 (1932). 4. J, N» Bronated and J, W» Williams, J. An. Chan. 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Chem., 224. 1 (1935). 55. N. BJerrum, Kgl. Danske Vldensk. Selskab., 7, No. 9 (1926). 56. R. M. i1 U038 and C. A. Kraus, J. Am. Chem. Soc., 56. 1019 (1933). AUTOBIOGRAPHY I, H. (Henry) Lawrence Clever, was b o m in Mansfield, Ohio, June 14, 1923, I received my secondary school educa tion in the Springfield Township Rural Consolidated School at Ontario, Ohio* My undergraduate training was obtained at The Ohio State University, from which I received the degree Bachelor of Science in 1945, I worked in the Or- ganlo Section of the Analytical Department of Shell Develop ment Co,, Smeryvllle, California as a Junior Chemist from September, 1945 to March, 1947, I entered the Graduate School of The Ohio State University March, 1947, where I specialized in the Department of Chemistry, I received the degree Master of science in 1949, I held the position of a Research Fellow on The Ohio State University Research Foundation Project 270 1947-1949, while completing the requirements for the degree Master of Science, I held the position of Research Assistant on the Ohio State University Research Foundation Project 270 1949-1950 and the position of a Research Foundation Fellow of the Chemistry Department 1950-1951 while completing the requirements for the degree Doctor of Philosophy* 266