'{'UK SOLUBILITY OF PHENOL IN AQUEOUS 
 SOIAITIONS OF GLUCOSE, GLYCEROL, 
 ACETONE, ANJ) UREA 
 
 liY 
 
 IRNTNG n. MORGAN 
 
 THESIS 
 
 FOR Till-: 
 
 J)EGREE OF BACHELOR OF SCIENCE 
 
 IN 
 
 CHEMICAL ENGINEERING 
 
 COLLEGE OE LIBERAL ARTS AND SGIP^NCES 
 UNIVERSITY OF ILLINOIS 
 
 1922 
 
I 
 
 
 Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/detaiis/soiubiiityofphenOOmorg 
 
UNIVERSITY OF ILLINOIS 
 
 March. .1,5 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 .1 rv i.n.g.. . B anc.r.o ft. , , ,Mo r gan 
 
 ENTITLED Th.e...So.l.uMIlty...M..Ph.eh.Ql..l,h..Aaue.Qus....So.l.u.tiQTi§. 
 
 of Glucose, Glycerol, Acetone and Urea. 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 DEGREE OF Pach.elgr....o.f ....S.o.i.e.n.c.e,...in...C.h.e. 
 
 Approved ; 
 
 Instructor in Charge 
 
 
 HEAD OF DEPARTMENT OF 
 
 5002135 
 
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ACKNOIinjEDGLIENT 
 
 I wish to express my appreciation 
 to Dr. J. H. Reedy, for his cooperation 
 and to thank him most sincerely for the 
 many valuable suggestions offered during 
 the preparation of this thesis. 
 

 Tabls of Contents 
 
 1 
 
 j 
 
 I. 
 
 INTRODUCTION 
 
 Page ! 
 
 1 
 
 II. 
 
 HISTORICAL 
 
 2 
 
 III. 
 
 EXPERIMENTAL 
 
 
 
 1. Materials 
 
 4 
 
 
 S. Procedure 
 
 4 
 
 IV. 
 
 RESULTS 
 
 
 
 1. Glucose Solutions 
 
 8 
 
 
 2. Glycerol Solutions 
 
 9 
 
 
 3, Acetone Solutions 
 
 10 
 
 
 4. Urea Solutions 
 
 10 
 
 V. 
 
 DISCUSSION 
 
 
 
 1. Solvent Action of Organic Compounds 
 on Phenol 
 
 17 
 
 
 3. Formation of Addition Product in 
 Acetone Solutions 
 
 30 
 
 
 3. Group Influences 
 
 31 
 
 VI. 
 
 SUMiaRY 
 
 33 
 
 VII. 
 
 BIBLIOGRAPHY 
 
 24 
 
Table of Plates 
 
 Page 
 
 I. Arrangement of apparatus in Thermostat 7 
 
 II. Specific gravity Curve for Glucose Solutions 10 
 
 III, Solubility of Phenol in Glucose Solutions 11 
 
 IV, Specific Gravity Curve for Glycerol Solutions 13 
 
 V, Solubility of Phenol in Glycerol Solutions 14 
 
 VI. Specific Gravity Curve for Acetone Solutions 15 
 
 VII. Solubility of Phenol in Acetone Solutions 16 
 
 VIII, Specific Gravity Curve for Urea Solutions 18 
 
 IX. Solubility of Phenol in Solutions of Urea 19 
 

 
 
 
 
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PART I 
 INTRODUCTION. 
 
 Very little has been done in determining whether 
 mixed solutions of high concentration follow a definite 
 solubility law. Some solutes repress the solvent power 
 of water but being solvents in themselves, the total 
 solubility of the solution is increased. Other solutes., 
 simply diminish the solubility of their own, the total 
 solubility of the solution is decreased. The purpose 
 of this problem is twofold. First to ascertain the 
 solubility behavior of phenol in aqueous solutions of 
 glucose, glycerol, acetone, and urea, and second, to 
 determine if there is a similar relation between this 
 and the solubility of benzoic and salicylic acids in 
 like solutions. 
 
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- 3 - 
 
 PART II 
 
 HISTORICAL, 
 
 ( 1 ) ( 3 ) 
 
 Nernst and A. A. No^es both agreed that the concen- 
 tration of molecules of a solute remains unchanged by the 
 
 ( 5 ) 
 
 presence of other substances, Arrhenius took exception to 
 
 this and by using Noyes' ovm data on the solubility of thallium 
 
 chloride, showed that the solvent power of a given medium was 
 
 diminished by the presence of dissolved substances. This is 
 
 shown conclusiiKely in the well known commercial process of 
 
 salting out, A more or less accepted theory expounded by Jones 
 
 and his collaborators suggested that the molecules and ions of 
 
 a solute in a water solution of the solute formed hydrates and 
 
 thus used up some of the water solvent, which caused a relative 
 
 decrease in the solubility of the water content of the solution. 
 
 ( 5 ) 
 
 Smits and Maarse found that a hydrate of phenol existed and 
 
 ( 4 ) 
 
 (6) 
 
 that it had a considerable range of metastable equilibrium. 
 
 This not only bears out the theory of hydrate formation, but 
 carries considerable weight in the present problem, Washburn 
 dismisses the subject briefly by stating that in working with 
 concentrated solutions where the "thermo dynamic environment" is 
 not constant, each solution must be treated as a problem by it- 
 self and the quantitative relations connecting its properties 
 with composition must be derived by direct experiment. Lovell 
 in working on the solubilities of benzoic and salicylic acids in 
 aqueous solutions of glucose, glycerol, acetone, and urea, found 
 that the organic solutes exerted a solvent action on the acids. 
 
 ( 7 ) 
 
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- 3 - 
 
 Also that the total solubility in all cases was found to be 
 lees than the combined solubilities of the components of the 
 solutions acting separately. He developed an expression for 
 the solubility in a binary medium as follows: Let A and B 
 
 be two solvents where a and b represent the number of moles of 
 each present and S the solubility. The expression then be- 
 comes S - aSA - bSg abk. 
 

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 PART III 
 EXPERIMENTAL 
 
 Materials - In carrying out an experiment of this nature 
 it is necessary to have a substance of comparatively low 
 solubility and negligible ionization in aqueous solutions. 
 
 Also there must be a reasonably accurate method of determining 
 the substance quantitatively from water solutions. Phenol 
 satisfied all three of these conditions although the quanti- 
 tative determination of it proved to be somewhat difficult. 
 
 The phenol used was the crystallized product sold by the 
 J. T. Baker Chemical Company, and had a melting point of 40.5® 
 and a solubility of thirteen grams in one hundred grams of 
 water. The glucose, glycerol, acetone, and urea were all of 
 the highest grade available. Solutions of the latter were 
 prepared of concentrations varying from 1^ to 35^ by weight. 
 These solutions were only prepared as needed, as it was found 
 that the stock solutions of glucose and glycerol could not be 
 kept any length of time without a noticeable change due to 
 enzyme action. The specific gravity curves were drawn from 
 data taken from Landolt and Bornstein Tabellen, 
 
 Procedure - 200 cc, of the mixed solvent solution, i.e. 
 ifo glucose in water, was placed in a 500 cc. Erlenmeyer flask 
 with an excess of solid phenol. The flask was equipped with 
 a centrifugal stirrer and placed in a thermostat carefully 
 regulated at 25® C. Eight of these separate solutions, four 
 
- 5 - 
 
 solutions in duplicate, were placed in the thermostat at one 
 time as shown in Plate I, and stirred simultaneously for about 
 twenty hours. The excess phenol was then allowed to separate 
 out by standing and two 10 cc. portions of the aqueous layer 
 removed for analysis. Tlie quantitative procedure for deter- 
 mining the amount of phenol dissolved by the mixed solvent 
 solution caused some difficulty at first. The method of adding 
 an excess of liquid bromine to the solution was attempted, thus 
 forming the insoluble tribromphenol. The excess bromine was 
 determined by adding potassium iodide and titrating the iodine 
 thus liberated with tenth normal sodium thiosulphate solution. 
 
 The chief difficulty encountered with this method was the 
 volatility of the liquid bromine. Koppenshar' s modification of 
 this method was then tried in thich the original 10 cc. sample 
 taken was diluted a thousand times and an excess of a bromide - 
 bromate solution (3,784 grams KBrOa' and 10 grams KBr to 1 liter) 
 added together with 5 cc. HCl. The solution was allowed to 
 stand until the tribromphenol had formed and settled. The 
 excess bromine present was then determined by adding KI and 
 titrating with tenth normal thiosulphate solution. The main 
 difficulty in this method was the large experimental error caused 
 by the high dilution, but this error was much smalled than that 
 found in the first method. Because of the possible error, 
 duplicate runs were made on each of the solvent solutions and 
 check determinations were made of the phenol dissolved in each 
 of the duplicate samples. The average of the four determinations 
 

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 PART IV 
 RESULTS 
 
 Glucose - The results of the solubility of phenol in glucose 
 water solutions are tabulated in Table I and the graphical rep- 
 resentation is given in Plate III, The black line shows the 
 solubility of phenol in glucose-water solutions in grams per 
 100 grams of solution, ?;hile the red line shows the calculated 
 solubility of phenol in the water present in 100 grams of the 
 glucose-water solutions. Because of the dilution to which the 
 phenol solution is subjected during the process of determining 
 the amount of phenol which went into solution, a slight exper- 
 imental error will produce a very appreciable discrepancy in 
 the final result. For example, 0.1 cc. difference in the amount 
 of the thiosulphate solution used in titrating the excess of 
 bromine added will produce a difference of 0.4 grams in the 
 weight of phenol found to be present. The results have there- 
 fore been interpreted to mean that the black and red lines should 
 practically coincide on the graph. In other words the presence 
 of glucose lowers the solubility of the solution but does not 
 alter the solvent power of the water present. An alternate 
 explanation would be that the solubility of the phenol in the 
 glucose hydrate is the same as that of water. 
 

 
 
 
 
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- 9 - 
 
 TABLE I 
 
 The 
 
 Solubility 
 
 of Phenol in Glucose 
 
 Solutions. 
 
 Glucose 
 
 Sp. Gr. 
 
 Grams phenol /l 00 gras. 
 
 sol. 
 
 Gms. Phenol 
 dissolved in 
 water present 
 
 0 
 
 1.0000 
 
 13.001 
 
 
 in 100 gms. of 
 solution. 
 13.001 
 
 1 
 
 1.0037 
 
 13.633 
 
 
 13.871 
 
 5 
 
 1.0171 
 
 12.133 
 
 
 13.351 
 
 10 
 
 1.0379 
 
 11.770 
 
 
 11.700 
 
 15 
 
 1.0585 
 
 11.393 
 
 
 11.051 
 
 30 
 
 1.0793 
 
 10. 488 
 
 
 10.401 
 
 35 
 
 1.1000 
 
 9.448 
 
 
 9.751 
 
 Glycerol - Table II and Plate V show the solubility of 
 phenol in glycerol -water solutions. In this case as before, 
 the red line represents the solubility of phenol in the water 
 present in 100 grams of solution and is the same in the case 
 of glucose since it is a function of the percent water present 
 in the solution. However, the black curve representing the 
 solubility in grams per 100 grams of solution shows a marked 
 deviation from the similar curve for glucose. The solubility 
 increases with an increase in the percentage glycerol present. 
 This increase in the solubility is comparatively small in low 
 concentrations, but increases very rapidly above 15'^. This shows 
 that glycerol solutions are better solvents for phenol than those 
 of glucose, and leads to the belief that glycerol itself has a 
 specific solubility for phenol. This increase in solubility, 
 due to the presence of glycerol cannot be assumed to be additive 
 as the solubility curve is not a straight line. 
 

 
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- 13 
 
 Glycerol Sp. Gr. 
 
 
 from curve 
 
 0 
 
 1.0000 
 
 1 
 
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 5 
 
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 10 
 
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 15 
 
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 100 gais. solution 
 
 13.001 
 
 13,387 
 
 14.065 
 
 14.890 
 
 17.566 
 
 37.603 
 
 51.336 
 
 Gms. phenol dissolved 
 in water present in 
 100 gms, solution, 
 
 13,001 
 13.871 
 13.351 
 11.701 
 11.051 
 10, 401 
 9.751 
 
 Acetone - The results of the determinations with acetone- 
 water solutions are given in table III and Plate VII, The 
 
 solubility of phenol showed a very marked decrease in solubility 
 
 in solutions up to 5'^ acetone, but at higher concentrations the 
 
 solubility became constant. The decrease in solubility was much 
 
 greater than that in the glucose-water solutions. 
 
 TABLE III 
 
 Gms. phenol dissolved 
 
 Glycerol 
 
 Sp. gr. 
 from curve 
 
 Gms. phenol per 
 100 gms. solution 
 
 in water present : 
 100 gms. solution 
 
 0 
 
 1.0000 
 
 13.001 
 
 13.001 
 
 1 
 
 .998 
 
 11.691 
 
 13,871 
 
 5 
 
 .993 
 
 8.333 
 
 13.351 
 
 10 
 
 .985 
 
 8.083 
 
 11.700 
 
 15 
 
 .976 
 
 8.137 
 
 11.051 
 
 30 
 
 .969 
 
 8.175 
 
 10.401 
 
 35 
 
 .962 
 
 8.375 
 
 9.751 
 
 Urea - The results obtained from the urea-water solutions 
 are tabulated in Table IV and ploted on Plate IX. The urea 
 increased the solubility of the phenol in the urea-water solu- 
 tions in a manner similar to that of glycerol. In this case 
 however, the marked increased did not occur until a 30^ conceu 
 
SpE.c/Fic Cma^JiTY Curve, For Vrhyinq Percents 
 Of Ctlycerol In Wrter. 
 
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- 17 
 
 tratration was reached, while with glycerol the greater increase 
 occurred above 15'^ concentration. 
 
 
 
 TABLE IV. 
 
 Gms. phenol dissolved 
 
 urea Sp. Gr. 
 
 Gms. phenol dissolved 
 
 in water present in 
 
 
 from curve 
 
 in 100 gms. solution 
 
 100 gms. of solution 
 
 0 
 
 1.0000 
 
 13.001 
 
 13.001 
 
 1 
 
 1.0035 
 
 13.308 
 
 13.871 
 
 5 
 
 1.0135 
 
 14. 874 
 
 13.351 
 
 10 
 
 1.0365 
 
 16.357 
 
 11.700 
 
 15 
 
 1.0380 
 
 19. 403 
 
 11.051 
 
 30 
 
 1,0535 
 
 31.047 
 
 ID. 401 
 
 35 
 
 1.0660 
 
 39.569 
 
 9.751 
 
 
 
 PART V 
 
 
 
 
 DISCUSSION.' 
 
 
 
 Solvent Action 
 
 of Organic Compounds ^ 
 
 on Phenol - From the 
 
 results of these determinations it is apparent that the solU' 
 
 bility of phenol in mixed aqueous solutions is decreased by 
 the presence of glucose and acetone and increased by the presence 
 of glycerol and urea. In the case of glucose, the decrease in 
 the solubility of the phenol was practically inversely propor- 
 tional to the concentration of the solution, showing that the 
 glucose neither repressed or aided the solvent action of the 
 ViTater. This does not exactly follow the theories of Noyes 
 and Arrhenius, that the presence of dissolved molecules reduces 
 the solvent power of water. However, it may be possible that 
 the glucose alone has a slight solvent power for phenol which 
 would overcome any decrease in the solvent power of water that 
 the presence of glucose might incur. Lovell found similar 
 
30 
 
 Specific Crt^avity ^94 
 
^or 
 
 Crram^ T^henol D/oso/ved 
 
- 20 “ 
 
 conditions existing in the solubility of benzoic and salicylic 
 acids in glucose solutions. The solubility of the two acids 
 was decreasec, but there was a slightly higher solubility in 
 the solution than in the water present in an equivalent amount 
 of solution. The glycerol and urea produced an increase in the 
 solubility of the phenol. This shov/s that glycerine and urea 
 exert a solvent influence on the phenol. These again are like 
 the results found by Lovell as to the solubility of benzoic and 
 salicylic acids in solutions of glycerol and urea. 
 
 Formation of Addition Product in Acetone Solutions - The 
 acetone solutions gave remarkably peculiar results. The solu- 
 bility of the phenol in the acetone-water solution fell far 
 below the solubility of the phenol in the water present in the 
 same solution. The solubility finally became constant above 
 5'^ solutions. With similar solutions Lovell found that the 
 solubility of benzoic and salicylic acids increased with an 
 increase in the concentration of acetone. In the case of phenol, 
 therefore, presuming there should be a similarity for all solu- 
 tions, an addition product must have been formed between the 
 phenol and acetone, or there was a marked hydration between 
 the phenol and water. The latter does not seem reasonable, 
 
 since there is no difficulty of a like nature experienced with 
 
 ( 8 ) 
 
 any of the other organic solutes used. Schmidlin and Lang 
 found a compound of acetone and phenol which was in the form 
 of long needles melting at 15°C. There being no better name 
 
 available, they called it Phenol-acetone. This assists in 
 
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- 31 - 
 
 bearing out the assumption of an addition product being formed. 
 Another reason for assuming the formation of the so called 
 phenol acetone can be found by means of the Phase rule. The 
 solution has one degree of freedom (F), that of temperature, 
 and consists of three components (C) namely, water, acetone, 
 and phenol. By substituting in the general phase rule formula 
 F = C - 3 - P and solving for the number of phases present, 
 
 (P) it is found that there should be four phases present. 
 
 Only three of these phases can be accounted for, the vapor 
 phase, the solution phase, and the phenol phase. It can be 
 assumed therefore, that the fourth phase must be some combin- 
 ation of the phenol and acetone. Also according to the above 
 phase rule conditions the concentration of the phenol in solu- 
 tion should remain, which it does; as can be seen from the 
 fact that the curve is perfectly vertical above 5^ acetone. 
 
 Group Influences - In making a comparison of group in- 
 fluences or the effects of certain groups on organic solvents, 
 it was found that OH groups apparently reduced the solubility. 
 Phenol, benzoic acid, and salicylic acid all showed lower solu- 
 bility in glucose solutions than in glycerol and the former has 
 many more OH groups than glycerol. The CH 3 group in the acetone 
 aided the solubility of the benzoic and salicylic acids, but due 
 to the formation of the addition product between phenol and 
 acetone, the actual solubility of phenol in acetone solutions 
 was not obtained and consequently a comparison with phenol 
 
cannot be made in this case. The CO group exerted no apparent 
 influence on the solubility of any of the compounds used and 
 therefore it is concluded that this group does not have any 
 active influence on the solubility. However, the NHg groups 
 have quite a noticeable effect on the solubility. The phenol, 
 benzoic acid, and salicylic acid were all more soluble in urea- 
 water solutions than in any other of the mixed solutions. 
 
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- 33 - 
 
 PART T 
 SUJmRY 
 
 1. The solubility of phenol has been determined at 
 35® in solutions of glucose, glycerol, acetone, 
 and urea varying from 1-35^ by weight. 
 
 3. These solutes with the exception of glucose and 
 acetone have a solvent action on phenol, 
 
 3. The formation of an addition product with phenol 
 in acetone solution was shown. 
 
 4. A comparison was made of the solubility of 
 phenol with benzoic and salicylic acids in the 
 same kind of solutions. 
 
 5. A comparison was made of the group influences 
 on the solubility of phenol, benzoic acid, 
 and salicylic acid. 
 
- 24 - 
 
 PART VIII 
 BIBLIOGRAPHY 
 
 1. Nernst - Theoretical Chemistry, p. 357 (1911) 
 
 2. A. A. Noyes - Z, Physik, Chem, 243 (1890) 
 
 3. Arrhenius - Z. Physik. Chem. , 224 (1899) 
 
 4. H. C. Jones - Z. Physik. Chem. , 1^, 419 (1894) 
 
 5. Schmitts and Jiaa.rse - Proc. Acd. Wettenschappen, 
 
 14, 192 (1907) 
 
 6. Washburn - Prin. of Phys. Chem. , p. 179 (1915) 
 
 7. C. B. Lovell - Bachelor Thesis U. of I. (1921) 
 
 8. Schmidlin and Lang , Ber. 43, 2860-20. 
 
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