IC-NRLF EXCHANGE The Solubility of Liquids in Liquids* The Partition of the Lower Acids between Water and Cottonseed OiL Also the Partition of Formic Acid between Water and Various Organic Compounds A DISSERTATION SUBMITTED TO THE BOARD OF UNIVERSITY ^ THE JOHNS HOPKINS UNIVERSITY IN PARTIAL ETO- FILLMENT OF THE REQUIREMENTS FOR THE^ 34 DEGREE OF DOCTOR OF PHILOSOPHY BY PV NEIL E. GORDON Baltimore, Maryland June, 1917 EASTON, PA.: ESCHENBACH PRINTING Co. 1922 The Solubility of Liquids in Liquids. The Partition of the Lower Acids between Water and Cottonseed Oil* Also the Partition of Formic Acid between Water and Various Organic Compounds A DISSERTATION SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE JOHNS HOPKINS UNIVERSITY IN PARTIAL FUL- FILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY toMtA] BY NEIL E. GORDON Baltimore, Maryland June, 1917 EASTON, PA.: ESCHENBACH PRINTING Co. 1922 CONTENTS Page Acknowledgment 3 Introduction 5 Material 11 Results 11 Procedure ' 13 Tables 13-31 Discussion of Results '. 32 Graphs 35 Summary ' 41 Biography 43 543933 ACKNOWLEDGMENT This investigation, having been carried out under the advice and kind assistance of Doctor Reid, I take this oppor- tunity to express my deep appreciation for the help he has given me. I also feel under obligation to Drs. Frazer, Remsen, Lovelace, and Gilpin, for instruction and encouragement received. I shall long remember the enthusiastic personality of the late Doctor Jones, who inspired me to take up graduate work at the Johns Hopkins University. THE SOLUBILITY OF LIQUIDS IN LIQUIDS. THE PARTITION OF THE LOWER ACIDS, PARTICULARLY FORMIC, BETWEEN WATER AND VARIOUS ORGANIC SOLVENTS 1 That some substances dissolve when brought into contact with various liquids must have been one of the first observations that can be classed as chemical. In the last three decades the study of solutions has been the chief occupation of chemists. Yet our knowledge of solutions is still far from adequate and some of our conceptions are still not clear. If we shake a portion of water with oxygen, another por- tion with ether, and a third with sugar, assuming constant temperature, equilibria are reached and we call the three solu- tions saturated, speaking of the concentrations of the three solutes in the water as their solubilities. The words "saturated and solubility" are used for all, but actually have quite differ- ent meanings in the three cases. The solubility of the sugar is definite, since in that case the solid phase is pure sugar, unchanged in composition and concentration by its contact with the water. In the case of the oxygen and water, the only thing that we can determine is the ratio of the concentrations of oxygen in the two phases. Since the water vapor does not affect the partial pressure of the oxygen, this ratio is definite and independent of the water vapor present in the gas phase. As previously pointed out 2 while the solubility of the ether is definite, yet the solubility that we find is not the true solubility, i. e., the amount of ether taken up by water in contact with anhydrous ether. We can no more determine the solubility of ether in water than we can 1 Contribution from the Chemical Laboratory of the Johns Hopkins University. 2 Wroth and Reid: Jour. Am. Chem. Soc., 38, 2316 (1916). 6 that of formic acid, since we cannot have a solution of either ether or formic acid in contact with the anhydrous liquid. We may hope that sometime a method, or formula, may be devised for finding the true, or ideal, solubility of ether in water, perhaps from the observed equilibrium of the solution of ether in water with one of water in ether, perhaps from some other data. In the case of solid iodine, where the solubilities are true solubilities, Jakowkin 1 found the ratio of the solubilities in two solvents, S a /S b , remarkably near to the partition ratio, C a /C b , or r, measured with the same two solvents. He further found that r changes progressively, approaching more and more nearly the value S a /S b as the concentrations of iodine in the two solvents increase, i. e., as C a /C b approaches S a /S b as C a and C b aproach S a and S b . As is well known, the partition ratio, r, remains constant with changing concentrations, only when the substance par- titioned dissolves in both solvents in the same form. Further- more, it is stipulated that the two solvents must be absolutely insoluble in each other, even when both contain large amounts of the common solute. This condition is, of course, never more than approximately fulfilled, the disturbing influences becoming greater, the higher the concentrations of the solute. In the present investigation formic acid has been parti- tioned between water and the following solvents: cottonseed oil, kerosene, benzene, toluene, xylene, carbon tetrachloride, carbon disulphide and bromoform. The so-called solubilities of formic acid in these eight solvents and the solubilities of these liquids in formic acid have been determined. If the solubility figure found for formic acid in benzene, say, were the ideal solubility and the partition ratio found were correct, then the product of these two should give the ideal solubility of formic acid in water which we cannot find directly. The ideal solubility from the data obtained from these eight solvents should be the same, or, since the several * Zeit. phys. Chem., 18, 590 (1895). partition ratios vary with the concentrations, the values found should tend to approach some one limit, as the concen- trations of formic acid in the non-aqueous solvents approach the solubilities of formic acid in these solvents. In the case of carbon disulphide and water, and in that only, the partition ratio remained practically constant with changing concentration, being 1606 when the acid in the water layer was 8.4% and 1616 when this had increased to 54.8%. When carbon disulphide and formic acid are shaken together there is 1.28 g of the acid to 100 g carbon disulphide in the one layer and 4.66 g carbon disulphide to 100 g formic acid in the other. Even in this case 1.28 is not the ideal solu- bility of formic acid since the solution was in contact with a mixture of 95.55% formic acid- and 4.45% carbon disulphide and not with the pure acid, but as in this case the mutual "solubilities" are the lowest and the partition ratio is the most nearly constant, this appears to be, by far, the most favorable case. Multiplying 1.28, the "solubility" of formic acid in carbon disulphide, by the partition ratio, 1616, we have 2068 as the ideal solubility of formic acid in water, i. e., 2068 g of the acid should be taken up by 100 g of water in contact with anhydrous formic acid, a condition which can, of course, never be realized. With the other seven solvents the products of the several solubilities by the respective partition ratios should approach 2068 as the concentrations increase. That is the figures in the last columns of Tables 1 and 7-12 should approach 2068 as we read down. The results are represented graphically in Fig. 1 in which these hypothetical ideal solu- bilities are plotted against the percentage of saturation of the non-aqueous layer. The curves as drawn extend only to 8%, not far enough to include all the points on the kerosene, cottonseed oil and bromoform curves. For very dilute solu- tions the figures obtained are more or less erratic on account of the difficulties involved in determining the small amounts of acid present in even large amounts of the oil layers, e. g., in the most dilute solution with carbon tetrachloride the amount of formic acid per 100 g of oil was only 0.0038 g. 8 Most of the series were terminated at 55% to 60% of formic acid in the water layer as it was thought that results with greater concentrations could not be trusted on account of mutual solubilities of the two solvents in presence of so much of the solute. But with cottonseed oil the concentra- tion was carried up to 87.2% of formic acid in the water layer when there was 5.026 g of acid per 100 g of the oil layer while the solubility of the anhydrous acid in the oil is 8.68 g per 100 g. This gives us a point in the cottonseed oil curve at 58% for which the ordinate is 1179 which is well on the way to the figure indicated by the carbon disulphide curve. PERCENT OF POSS/k. 'LE Fig. 1 JD IN THE OIL. It is interesting to note that cottonseed oil takes up only 58% as much formic acid from an 87% acid as from the 100% acid. On a molecular basis 73% of the molecules are formic acid, so it appears that the water in the acid is more than a diluent: it restrains the formic acid molecules from passing into the oil layer. A similar inference may be drawn from other experiments. In most cases where the water layer con- 9 tains over 50% of formic acid the oil layer takes up only 5% to 7% as much acid as from 100% formic acid. The results with kerosene are regarded as unreliable as the oil layer was much colored at the higher concentrations indicating some sort of reaction. Looking at the figure, there appears to be a tendency for the various curves to converge on the carbon disulphide line indicating an ideal solubility around 2000, though the bromo- form curve is very low down and the one for cottonseed oil has a considerable distance to go. The xylene curve appears to cross the 2000 line. It is certainly hazardous to extrapolate from 6 or 8% to 100%. / CAR RON TETRACHLORjnE 2 BENZENE 3 TOLUENE 4- XYLENE 5 CARBON D1SULPH/DE 6 KEROSENE Z 5 4 OF POSSIBLE FORMIC Fig. 2 0/L In Fig. 2 the same data are presented on a different basis; the ordinates are the same but the abscissae are the percentage of formic acid in water layer at equilibrium. On this basis the curves are steeper and do not show as much tendency to converge though we have the advantage of having to extra- polate over a much shorter distance, as all of the curves go as far as 55% and one even to 87%. 10 The results obtained do not settle the question but it is hoped they do open it. One method of approach has been tried : better ones may be found. Even by this method more measurements are desirable at higher concentrations, with other solvents, and with other solutes. The results so far obtained have value as partition and solubility measurements. The degrees of association of formic acid in the various solvents can be calculated from the variation of the partition ratios. 120 WO 1 60 PTiOPJONIC -/BUTYRIC t PERCENT OF ACID IN WATER LAYER Fig. 3 As formic acid is a strong acid, its dissociation in the water layer influences the partition ratios, but as its lowest concen- tration was 0.24 N, at which it is only moderately dissociated and, as it turned out, the high concentrations are the ones which are of most interest from the present point of view, the dissociation may be disregarded. It is interesting to note that formic acid shows a real partition ratio in all cases even in dilute solution, which is in marked contrast to the behavior of silver perchlorate as found by Hill. 1 1 Jour. Am. Chem. Soc., 43, 254 (1921). 11 Georgievics 1 partitioned formic acid between benzene and water. Calculating his results according to our method we obtain the following partition ratios : %Acid 4.4 5.8 6.7 7.8 8.6 8.7 13.3 13.3 18.9 23.9 Ratio 370 261 400 302 264 562 304 347 269 298 Disregarding the sixth, the average of these is 316 which is not far from 292 the average of our results over the same range. In addition to the experiments with formic acid, acetic, propionic and butyric were partitioned between cottonseed oil and water and acetic acid between kerosene and water. The partition ratios are plotted in Fig. 3. The proportion of the organic acid taken by the water layer increases rapidly as we go from formic to butyric. The formic acid curve bends sharply upward at about 70% of acid in the water layer. Acetic acid has a definite solubility in the oil but propionic and butyric have not. Formic is the only one of these that shows limited solubility in the other solvents. Materials Cottonseed Oil: The Wesson oil used was found to have an acid reaction. In order to eliminate this the oil was shaken with a dilute solution of barium hydroxide for an hour. It was then centrifuged and filtered, when it gave a perfectly neutral reaction. Formic Acid: This was distilled under reduced pressure over anhydrous copper sulphate as suggested by Garner, Saxton and Parker. The pressure used was 120 mm, when the acid distilled over at 50. This method was found to be a very satisfactory one. Beginning with an acid 89.2 percent pure, the first distillation resulted in an acid 96.5 percent, the second 98.2 percent, and the third distillation gave an acid 99.99 percent pure. This acid melted at 8.35 and had density 1.2170|. 2 This anhydrous acid was used for the solubility work only. For the partition work, commercial acid was used 1 Zeit. phys. Chem., 84, 359 (1913). 2 Am. Chem. Jour., 46, 236 (1911); J., 1886, 216. 12 since it was found to contain only water. The water it con- tained was calculated and added to the weight of wate,r taken. Acetic Acid: Like formic acid the commercial acid was used for the partition work. For the solubility the acid was purified by freezing. It was found that the number of freez- ings necessary to render it anhydrous could be cut down by introducing a crystal of the acid to prevent too great undercool- ing. It melted at 16.7, and titrated 99.9 percent pure. Its density was 1.0445||. Propionic and Butyric Acids: These acids mixed in all proportions with both oil and water and thus it was not nec- essary to make them anhydrous. As their densities and titrations showed they contained only water as an impurity, they were used without further purification. Organic Solvents: First class commercial grades of ben- zene, toluene, xylene, carbon tetrachloride, carbon disulphide, and bromoform were used. To insure purity, the boiling points and densities were taken and found to agree well with those given in the literature. Waddell 1 found in his investigation that the same partition coefficient was given with purified benzene as with commercial benzene. Standard Solutions: Standard solutions of approximately N/10 were prepared, and frequently standardized. The solu- tions were kept in large stock bottles from which they were siphoned into the burettes. The barium hydroxide bottle and burettes were protected from the air by tubes con- taining soda lime. Water: Freshly distilled water was used. Kerosene Oil: Commercial kerosene oil was distilled and the portion obtained between 180 and 260 was used in the partition work. It had a density of 0.798ff. 1 Jour. Phys. Chem., 2, 233 (1895). 13 Procedure The filling, shaking and centrifuging of the bottles con- taining cottonseed oil, water and the respective acids was carried out approximately as the former work where the alco- hols were used instead of the acids. It seemed necessary to shake the acids longer than the alcohols to obtain concordant results. The centrifuge was used only with the cottonseed oil and water. Estimation of Acids in Non-aqueous Solvent Layers. The oil layer containing the acid was drawn off by means of a spe- cial pipet, shaped similar to the Ostwald pycnometer. An amount of oil was taken out with the pipet sufficient to re- quire about 10 cc of the barium hydroxide for neutralization. The oil was put into a 180-cc beaker containing about 80 cc of distilled water for titration. The oil, with ordinary stirring failed to give up its acid promptly, making the titration slow and uncertain. A mechanical stirrer was used and this ac- celerated the speed with which the acid passed from the oil into the water. Even under these conditions the end-point was not as accurate as it was in the water. In spite of all efforts the acid seemed to have a slight tendency to cling to the oil. The other organic solvents were handled similarly. Estimation of Acid in Water Layer. A small thin-walled glass bulb was weighed, partly filled from the water layer, sealed and reweighed. The bulb was then broken under water to avoid evaporation, and the amount of acid, which it con- tained was determined by titration. The absolute solubilities of formic and acetic acids in cottonseed oil were found by shaking the oil and anhydrous acids in the constant temperature bath for four hours, and then estimating the amount of acid in the oil layer and the amount of oil in the acid layer by the titration method as just de- scribed. The absolute solubility of formic acid in the other organic solvents used and the solubility of the solvents in the formic acid were carried out in a similar manner. 14 Solubilities at 25 Formic Acid in Cottonseed Oil Cottonseed Oil in Formic Acid Sample Found In 100 g Sample Found In 100 g 0.3154 0.1656 0.4437 0.5019 0.0251 0.0416 0.0360 0.0393 8.65 8.72 8.84 8.50 0.1656 0.1141 0.1086 0.1142 0.0013 0.0009 0.0008 0.0009 0.78 0.79 0.74 0.79 Av. 8.68 Av. 0.77 Acetic Acid in Cottonseed Oil Cottonseed Oil in Acetic Acid 0.1421 0.0858 0.0831 0.0684 0.1008 0.0508 0.0309 0.0299 0.0245 0.0345 55.4 56.3 56.3 55.96 54.3 0.1016 0.0996 0.0616 0.1373 0.0894 0.0058 0.0055 0.0036 0.0073 0.0050 5.8 5.5 5.7 5.6 5.6 Av. 55.7 Av. 5.6 Formic Acid in Benzene Benzene in Formic Acid Sample Found In 100 g Sample Found In 100 g 0.2718 0.3300 0.3950 0.4277 0.4197 0.0341 0.0416 0.0502 0.0537 0.0527 14.3 14.4 ' 14.5 14.3 14.40 0.1825 0.0992 0.1455 0.0030 0.0238 0.01312 0.0189 0.0122 15.0 15.2 14.9 15.4 Av. 14.40 Av. 15.14 Formic Acid in Toluene Toluene in Formic Acid 0.2815 0.3795 0.2986 0.3565 0.0284 0.0376 0.0295 0.0358 11.20 10.98 10.96 11.17 0.1793 0.1323 0.0851 0.0149 0.0110 0.0071 9.08 9.06 9.10 Av. 11.08 Av. 9.08 Formic Acid in Xylene Xylene in Formic Acid 0.5440 0.3535 0.4480 0.0442 0.0251 0.0357 1 8.83 8.70 8.70 0.1009 0.0790 0.0063 0.0057 ^ 6.81 7.77 Lv. 7~29 ^v. 8.74 15 Solubilities at 25 Formic Acid in Carbon Tetrachloride Carbon Tetrachloride in Formic Acid 0.1910 0.3434 0.3623 0.3158 0.0069 0.0115 0.0119 0.0105 (3.76) 3.45 3.40 3.44 0.0484 0.0934 0.0918 0.0030 0.0062 0.0063 6.60 6.95 7.31 Av. 3.43 Av. 6.95 Formic Acid in Carbon Bisulphide Carbon Bisulphide in Formic Acid 2.4628 1.9878 2.6070 4.7033 4.9431 7.461 0.0313 0.0240 0.0311 0.0549 0.0569 0.0959 1.29 1.28 (1.21) (1.18) (1.16) 1.29 0.0631 0.1429 0.0604 0.1398 4.47 4.85 Av. 1.28 Av. 4.66 Formic Acid in Bromoform Bromoform in Formic Acid 1.9684 1.2830 3.2351 0.0475 0.0310 0.0767 2.47 2.47 2.42 0.1301 0.1085 0.0362 0.0220 25.2 25.4 Av. 2.45 Av. 25.3 Formic Acid in Kerosene Kerosene in Formic Acid Sample Found In 100 g Sample Found In 100 g 3.3003 2.9977 0.0294 0.0267 0.899 0.905 0.1003 0.0681 0.0015 0.0011 1.52 1.60 0.897 1.56 Acetic Acid in Kerosene Kerosene in Acetic Acid 1.0690 0.7638 0.1909 0.1367 21.74 21.80 0.0735 0.0802 0.0082 0.0088 12.6 12.3 Av. 21.77 Av. 12.4 16 Partition Experiments The results are given in the tables below, no completed determination being omitted, the first column showing the final percentage of acid in the water layer, the next three the amounts of water, oil and acid weighed in, while the fifth and sixth give the amounts of acid found in the two layers, the sum of these should equal the weight of acid in column four. In the sev- enth is found the molecular partition ratio or the acid dissolved by 1 mol. of water divided by that dissolved by 1 mol. of the oil. The m. wt. of cottonseed oil was assumed to be 885. In the case of kerosene this ratio is omitted. The next column gives the partition ratio for equal weights of water and oil and the last gives this weight ratio multiplied by the solubility of the acid in the oil when this is known. TABUS 1 Partition of Formic Acid between Cottonseed Oil and Water % Acid Water Oil Acid Weight acid in Partition ratios Weight ratio X 8.68 Water Oil Molec- ular Weight 1.1 15.42 66.85 0.183 0.169 0.0115 1.29 63.6 552 2.3 16.94 70.53 0.423 0.399 0.0253 1.33 65.7 570 3.7 14.57 75.37 0.595 0.556 0.0430 1.36 66.8 580 4.2 22.54 72.63 1.036 0.990 0.0471 1.38 67.8 588 5.5 22.66 67.69 1.385 1.326 0.0592 1.36 66.9 581 8.1 12.05 81.52 1.163 1.064 0.1064 1.38 67.7 588 12.7 27.00 63.19 4.077 3.945 0.1224 1.54 75.4 654 14.4 6.84 5.91 1.166 1.152 0.0130 1.56 76.5 664 20.9 13.11 20.47 3.556 3.470 0.0680 1.62 79.7 692 30.3 5.57 6.576 2.500 2.429 0.0323 1.87 91.9 798 32.4 12.62 22.87 6.168 6.045 0.1192 1.81 88.8 771 51.1 4.54 5.051 4.827 4.747 0.0563 1.91 93.9 815 62.5 3.65 5.857 6.258 6.087 0.0997 1.99 97.9 850 71.3 3.16 4.981 8.043 7.854 0.1241 2.03 99.5 864 80.7 1.79 6.102 7.720 7.463 0.2222 2.34 114.8 996 86.3 0.799 7.728 5.493 5.023 0.3705 2.67 131.1 1138 87.2 0.72S 8.589 5.894 4.972 0.4317 2.76 135.8 1179 17 TABLE 2 Partition of Acetic Acid between Cottonseed Oil and Water % Acid Water Oil Acid Weight acid in Partition ratios Weight ratio X55.7 Water Oil Molec- ular Weight 1.9 25.84 68.32 0.544 0.5105 0.0363 0.757 37.2 2071 2.1 24.32 66.23 0.550 0.5130 0.0364 0.781 38.4 2137 2.4 26.70 65.86 0.696 0.6504 0.0463 0.705 34.6 1930 7.5 27.51 71.33 2.408 2.238 0.1711 0.690 33.9 1888 8. '2 26.31 64.31 2.513 2.346 0.1718 0.671 33.4 1859 12.7 26.68 68.80 4.185 3.877 0.3006 0.677 33.3 1853 14.1 28.28 69.97 4.9751 4.636 0.3471 0.672 33.0 1840 16.2 24.75 67.27 5.195 4.791 0.3940 0.673 33.1 1841 28.9 13.13 25.64 5.673 5.345 0.3177 0.667 32.9 1830 31.8 11.13 25.35 5.534 5.178 0.3453 0.695 34.2 1903 46.9 4.38 5.950 4.044 3.875 0.1424 0.752 36.9 2059 50.9 4.360 6.064 4.729 4.516 0.1720 0.743 36.5 2035 62.1 1.387 7.574 2.586 2.270 0.3118 0.809 39.7 2212 70.2 1.001 7.572 2.794 2.361 0.4311 0.843 41.4 2308 81.8 1.958 5.975 9.574 8.827 0.6483 0.845 41.5 2314 Partition of Propionic Acid between Cottonseed Oil and Water % Acid Water Oil Acid Weight acid in Partition ratios Water Oil Molecular Weight 3.4 7.4 14.3 23.0 36.2 59.8 62.5 67.3 38.15 39.75 20.05 15.09 3.416 2.988 0.8750 0.4755 48.33 42.39 20.09 20.88 7.705 5.516 7.750 8.919 1.620 3.836 4.045 5.855 2.744 5.311 2.853 2.873 1.347 3.165 3.335 4.502 1.938 4.438 1.458 0.979 0.2819 0.6580 0.7240 1.358 0.7779 0.8959 1.366 1.874 0.123 0.104 0.094 0.093 0.114 0.186 0.192 0.199 6.05 5.13 4.62 4.59 5.60 9.14 9.45 9.79 18 TABLE 4 Partition of Butvric Acid between Cottonseed Oil and Water % Acid Water Oil Acid Weight acid in Partition ratios Water Oil Mblecular Weight 2.7 5.0 9.2 14.0 30.5 41.3 16.135 16.568 6.530 3.139 3.911 1.802 24.590 25.095 6.562 6.755 6.597 6.590 0.747 1.612 1.164 1.308 3.458 3.203 0.4526 0.8798 0.6615 0.5106 1.714 1.268 0.2764 0.7350 0.4906 0.7880 1.692 1.948 0.0508 0.0369 0.0276 0.0284 0.0348 0.0484 2.495 1.813 1.355 1.395 1.709 2.380 TABLE 5 Partition of Formic Acid between Kerosene and Water % Acid Water Oil Acid* Weight acid in Partition ratio Weight ratio Weight ratio X 0.897 Water Oil 17.9 30.9 38.9 43.2 59.8 66.3 10.634 9.801 9.778 2.547 2.725 3.153 65.717 72.723 65.189 7.422 5.645 30.950 2.324 4.452 6.283 1.945 4.160 6.400 2.316 4.388 6.224 1.936 4.060 6.200 0.00648 0.01586 0.02146 0.00308 0.00714 0.05358 2209 2052 1933 1831 1180 1136 1981 1841 1734 1642 1058 1019 TABLE 6 Partition of Acetic Acid between Kerosene and Water % Acid Water Oil Acid Weight acid in Partition ratio Weight ratio Weight ratio X 21.77 Water Oil 9.1 17.0 27.2 46.9 59.2 7.110 6.027 6.786 2.503 2.819 32.024 30.676 29.831 8.479 6.243 0.730 1.392 2.665 2.330 4.273 0.7127 1.236 2.532 2.214 4.089 0.02164 0.05796 0.1332 0.09804 0.1217 1483 1086 836 765 744 32300 23600 18200 16700 16200 19 TABLE 7 Partition of Formic Acid between Benzene and Water % Acid Water Oil Acid Weight acid in Partition ratios Weight ratio X 14.40 Water Oil Molec- ular Weight 5.3 6.4 9.9 13 . 6 18.5 29.2 41.2 58.2 20.61 11.46 19.96 21.71 28.39 10.30 12.71 3.272 74.21 89.07 82.54 65.42 51.66 28.71 32.92 40.73 1.138 0.742 2.195 3.444 6.506 4.395 9.126 5.096 1.146 0.716 2.192 3.432 6.437 4.258 8.894 4.695 0.0126 0.0175 0.0329 0.0382 0.0434 0.0449 0.1060 0.3279 75.1 73.5 63.5 62.4 62.3 61.0 50.8 41.1 327 319 275 270 270 264 220 178 4710 4590 3960 3890 3890 3810 3170 2570 TABLE 8 Partition of Formic Acid between Toluene and Water % Acid Water Oil Acid Weight acid in Partition ratios Weight ratio X 11.08 Water Oil Molec- ular Weight 5.3 7.9 16.5 31.0 41.7 59.7 21.04 20.43 10.319 9.210 5.618 3.276 79.04 64.20 88.00 84.70 30.87 32.68 1.174 1.799 2.086 4.257 4.181 5.186 1.177 1.761 2.039 4.148 4.019 4.834 0.0118 0.0158 0.0498 0.1166 0.0837 0.2391 74.0 68.5 68.5 64.0 52.8 39.5 378 350 349 327 270 202 4190 3880 3870 3620 2990 2230 RETURN TO the circulation desk of any University of California Library or to the NORTHERN REGIONAL LIBRARY FACILITY Bldg. 400, Richmond Field Station University of California Richmond, CA 94804-4698 ALL BOOKS MAY BE RECALLED AFTER 7 DAYS 2- month loans may be renewed by calling (510)642-6753 1-year loans may be recharged by bringing books to NRLF Renewals and recharges may be made 4 days prior to due date DUE AS STAMPED BELOW APR 241995 20,000 (4/94) Pamphlet Binder Gaylord Bros. 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