I
W. M. JACKSON and J. S. DRURY Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tenn.
Miscibility of Organic Solvent Pairs In these 1600 observations of miscibility may lie the key to a multitude of industrial problems, particularly in solvent extraction the miscibility of many organic solvents can be predicted from well-known solubility generalizations, there are frequent exceptions to these rules. Because these exceptions may be of particular interest in solvent extraction systems, a large number of qualitative miscibility observations have been made in this laboratory. Some of these data have been reported ( I ) . Results of more than 1600 additional observations are recorded in Tables I and 11. Analytical reagent grade solvents were used except in the few instances when these were not commercially available. Sulfuric acid, ALTHOUGH
while not a n organic solvent, was included because of general interest. The classifications were made a t 20' C. in the following manner. One-milliliter portions of each solvent comprising a pair were shaken together for approximately a minute. If no interfacial meniscus was observed after the contents of the tube were allowed to settle, the solvent pair wds considered to be miscible. M. If a meniscus was observed without apparent change in the volume of either solvent, the pair was regarded as immiscible, I. This classification is a qualitative one. since solvent pairs may exhibit various
degrees of partial miscibility while existing as separate phases. If a n obvious change occurred in the volume of each solvent, but a meniscus was present, the pair was classified as partially miscible, S. The designation R indicates that the two solvents reacted. literature Cited (1) Drury, J. S., IND.ENG.CHEM.44,2744 (1952). RECEIVED for review March 6, 1959 ACCEPTEDJ u n e 24, 1959 Based on work performed for the U. S. Atomic Energy Commission by Union Carbide Corp.
Source of Chemicals Used in Miscibility Studies 1. Eastman, white label 2; Eastman, yellow label 3. Union Carbide Chemical Corp., research sample 4. Matheson, Coleman a n d Bell, laboratory grade
Name Tetradecanol Heptadecanol 3-Heptanol n-Hexyl ether Benzyl ether 2,6,8-Trimethyl 4-nonanone Diisobutyl ketone Ethyl cinnamate Ethyl phenyl acetate n-Heptyl acetate Isoamyl acetate Ethyl benzoate Methyl isopropyl ketone Ethyl chloroacetate Tri-n-butyl phosphate Cinnamaldehyde +Phenetidine Di-n-amylamine 2-Bromoethyl acetate 4-Methyl-n-valeric acid Diethylacetic acid Di-n-butyl carbonate Ethyl ether Ethyl alcohol
Source 3 3 3 3 1 3 3 1 1 1 1 1 4 1 12
1 1
1 1 1 1 1 5 6
5. 6. 7. 8. 9. 10.
Mallinckrodt, reagent grade U. S. Industrial Chemicals, U.S.P. Baker & Adamson, reagent grade Baker, reagent grade Matheson, technical grade Celanese, research sample
Name Acetone Chloroform Benzene Sulfuric acid (concd.) Diethyl formamide Diethylenetriamine Triethylene glycol Triethylenetetramine Diisopropylamine Di-%-butylamine Di-(2-ethylhexyl)amine Di-n-propylaniline
a-Methylbenzylethanolamine a-Methylbenzyldiethanolamine a-Methylbenzylamine a-Methylbenzyldimethylamine 2-Phenylethylamine Isopropanolamine 2-Methyl-5-ethylpyridine Ethyl chloroacetate Ethylene glycol Glycerol 1,3-Butylene glycol 2,3-Butylene glycol
11. Fisher Scientific, purified grade 12. Technical grade 13. Virginia Carolina Chemicals Corp., research sample 14. Eastman, research sample 15. Unknown
Source 7 8 7
7 1 3 1 9 1 3 3 1 3 3 3 3
1 2 3 1
1 8 10 10
Name
Source
Dipropylene glycol 1,2-Propanediol 1,3-Propanediol 3-Chloro-1,2-propanediol Ethylene glycol monomethyl ether Ethylene glycol monoethyl ether Ethylene glycol monobutyl ether Diethylene glycol monomethyl ether Diethylene glycol monoethyl ether Diethylene glycol monobutyl ether Diethylene glycol diethyl ether Diethylene glycol dibutyl ether Ethylene glycol ethyl butyl ether Ethylene diacetate Triethyl phosphate Dibutyl hydrogen phosphite Trimethylene chlorohydrin 2-Chloroethanol Ethylene glycol monophenyl ether ,n-Amyl cyanide Salicylaldehyde Anisaldehyde +Cresol Pyridine
3 1 2 2 11 11 11 11 11 11 1 12
VOL. 51, NO. 12
DECEMBER 1959
15 11
14 13 1 1 3 1 1
4 2 1
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INDUSTRIAL AND ENGINEERING CHEMISTRY
