(21)Ginnings, D. C., Corruccini, R. L . , Ind. Eng. Chem. 40, 1990 (1948). (22)Haltenberger, W., Jr., Ibid., 31, 783 (1939). (23) HedstFGm, B. 0. A , , T j u s , E., Chem.-Ing.-Tech. 24, 22 (1952). (24)Hougen, 0. A., Watson, K. M., “Chemical P r o c e s s P r i n c i p l e s , ” p. 495, Wiley, New York, 1947. (25) Hougen, 0.A., Watson, K. M., Ragatz, R. A., “Chemical P r o c e s s Principles,” p. 324, Wiley, New York, 1954. (26)Ibid., p. 325. (27)I b i d . , p. 326. (28) Ibid., p. 327. (29) Ibid., p. 390. (30) International C r i t i c a l T a b l e s , vol. 4, p. 262, McGraw-Hill, New York, 1928. (31)Ibid., vol. 5, p. 102. (32)Ibid., p. 114 (33) Ibid., p. 132. (34) Ibid., p. 137. (35)Ibid., p. 138. (36) I b i d . , p. 159. (37) Keenan, J. H . , Keyes, F. G., “Thermodynamic P r o p e r t i e s of Steam,” Wiley, New York, 1936. (38)Kendall, J., Booge, J. E., Andrews, J. C . , J. Am. Chem. SOC. 39, 2303 (1917). (39) Kobe, K. A , , Couch, E. J . , Jr., Ind. Eng. Chem. 46, 377 (1954). (40) Kobe, K. A., Harrison, R. H., and Pennington, R. E., Petroleum Refiner 30, No. 8, 119 (1951). (41) Lange, N. A,, “Handbook of Chemistry,” 7th ed., Handbook P u b l i s h e r s , Sandusky, Ohio, 1949. (42) Levy, B., Davis, T. W., J . Am. Chem. SOC. 76, 3268 (1954).
(43) McKinley, C., Brown, G. G., Chem. Met. Eng. 49, No. 5, 142 (1942). (44) Merkel, F., Arch. Warmewirtsch. u. Dampfkesselw. 10, 13 (1929). (45)Merkel, F.,Z.Ver. deut. Ing. 72, 109 (1928). (46) Newmann, M. B.,2. physik. Chem. A158, 285 (1932). (47) Othmer, D. F., Silvis, S. J., Spiel, A., I n d . Eng. Chem. 44, 1864 (1952). (48) P a r k s , G. S., Kelley, K. K., J . A m . Chem. SOC. 47, 2089 (1925). (49)P a r k s , G. S., Nelson, W. K., J . P h y s . Chem. 32, 61 (1928). (50) Perry, J. H., “Chemical Engineers’ Handbook,” 3rd ed., p. 1052, McGraw-Hill, New York, 1950. (51)Ibid., p. 1701. (52) P l e w e s , A. C.,others, Can. J. Technol. 32, 133 (1954). (53) R o s s , W. D., Chem. Eng. Progr. 48, 314 (1952). (54) Schiebl, K., “WZrmewirtschaft i n d e r Zuckerindustrie,” p. 166 and appended chart, Steinkopf, Dresden, 1939. (55) Senter, G . , P r o c . Chem. SOC.(London) 25, 292 (1909). (56) Standiford, F. C., Badger, W. L., Ind. Eng. Chem. 46, 2400 (1954). (57) Tyner, M., A.1.Ch.E. Ioumaf 1, 87 (1955). (58) Tyner, M., Chem. Eng. Progr. 45, 49 (1950). (59) Van Nuys, C. C., Trans. Am. Inst. Chem. Engrs. 39, 663 (1943) (60) Vogt, E. G., Ibid., 43, 39 (1947). (61)Wilson, A , Simons, E. L,Ind. Eng. Chem. 44, 2214 (1952). (62) Wilson, H. R ,McCabe, W. L., Ibid., 34, 558 (1942). Received for review February 3, 1956. Accepted June 13, 1956. Division o f Industrial and Engineering Chemistry, 130th Meeting ACS, Atlantic C i t y , N. J . , September 1956.
Liquid-Liquid Equilibria for Alcohol -Sodium
Hyd roxide -Wa ter Sys tem s A. L. MILLS AND FRED HUGHES Manchester
Oil
Refinery
Ltd., Traffard Park, Manchester, England
s o l u b i l i t y d a t a h a v e been published for sodium hydroxide in aqueous ethyl alcohol (2) and i n aqueous isobutyl alcohol ( I ) , but no data were a v a i l a b l e for aqueous isopropyl alcohol (I.P.A.). Information o n t h e solubility of strong c a u s t i c soda s o l u t i o n s in isopropyl alcohol arid in industrial methylated spirit (1.lT.S.) w a s required for pilot plant neutralization experiments. Industrial methylated spirit i s t h e commercial f o r m of ethyl alcohol available i n t h e United Kingdom. On refining petroleum, particularly o n processing for highly refined white o i l s by sulfonation, it i s n e c e s s a r y to extract oil-soluble sulfonic a c i d s from t h e sulfonated o i l and to neutralize t o t h e corresponding sodium s a l t s . T h e quality and e s p e c i a l l y t h e color of t h e by-product sodium petroleum s u l f o n a t e s a r e influenced b y t h e r e s i d e n c e time of t h e sulfonic acid-oil reaction product, particularly if t h e equipment i s mild s t e e l . For t h e two s y s t e m s of processing which may b e applied-centrifuge o r batch-it i s e s s e n t i a l that, for t h e centrifuge process, neutralization and extraction proceed simultaneously, whereas for batch 1957
processing i t i s preferred that t h e two s t a g e s should t a k e p l a c e concurrently. For either processing system, i t i s a distinct advantage if a homogeneous neutralizing-extracting solution i s used. Prelininary experiments indicated that industrial methyla t e d spirit and ethyl alcohol b e h a v e differently and it w a s decided therefore t o i n v e s t i g a t e t h e s y s t e m s for industrial methylated spirit and isopropyl alcohol a t 25 and 60 O C .
MATERIALS A s i t w a s e x p e c t e d t h a t information resulting from t h i s project might b e applied t o plant s c a l e processing, no attempt w a s made to purify materials which were of technical quality a n d had t h e following properties.
Aqueous c a u s t i c soda I.M.S. I.P.A.
Specific Gravity at 2o°C.
Strength, Weight %
1.4590 0.8064 0.7852
43.0 94.2 100.0
CHEMICAL AND ENGINEERING DATA SERIES
35
ALCOHOL
T a b l e 1. Solubility D a t a for Isopropyl AlcoholSodium Hydroxide-Water System ( P e r Cent by Weight at 25' and 60°C. F i g u r e s 1 and 4 )
1.P.A.
I.P.A.
NaOH
H,O
97.2 87.1 75.1 63.1 51.5 41.1
1.2 0.4 0.4 1.0 2.0 2.7
1.6 12.5 24.5 35.9 46.5 56.2
NaOH
&
H,O
Data a t 25OC. 4.3 5.8 7.8 11.7 18.2 50.0
30.9 21.8 13.4 5.8
2.3 0.0
T i e L i n e s , Water Layer
64.8 72.4 78.8 82.5 79.5 50.0(2)
T i e L i n e s , Solvent Layer
0.6 1.5
31.5 23.7
67.9 74.8
96.3 74.3 62.5 51.7 40.9 36.0
1.6 0.6 1.0 1.4 2.4 2.8
2.1 25.1 36.5 46.9 56.7 61.2
0.6 0.6
97.4 97.2
2.0 2.2
Data a t 6OOC. 31.2 21.9 13.5 5.9 1.5 0.0
Tie L i n e s , Water Layer 0.7 1.3
30.5 23.4
Table
3.2 4.8 6.7 10.6 16.6 63.5
65.6 73.3 79.8 83.5 81.9 36.5 (3)
T i e L i n e s , Solvent Layer
68.8 75.3
98.8 97.0
0.2 0.6
1.0 2.4
Figure
II. Solubility D a t a for Industrial Methylated SpiritSodium Hydroxide-Water System ( P e r C e n t by Weight ot 25' and 60'C. F i g u r e s 1 and 3)
I.M.S.
NaOH
H,O
51.0 49.2 43.7 37.1 29.6 23.0
21.1 18.9 18.4 18.6 19.7 20.8
27.9 31.9 37.9 44.3 50.7 56.2
I.M.S.
H,O
22.0 23.1 24.6 27.6 30.2 50.0
60.9 65.1 68.3 69.5 68.6 50.0(2)
T i e L i n e s , Water Layer
T i e L i n e s , Solvent Layer
1.9 0.8
29.0 34.4
69. I 64.8
50.5 50.7
60.7 60.3 54.3 45.3 35.6 30.0
16.9 13.4 12.2 12.9 14.7 15.8
22.4 26.3 33.5 41.8 49.7 54.2
20.4 21.0
29.1 28.3
16.4 18.2 19.8 22.5 26.2 63.5
56.5 62.0 66.6 69.7 70.7 36.5 (3)
Data a t 60°C. 27.1 19.8 13.6 7.8 3.1 0.0
Tie L i n e s , Water L a y e r
T i e L i n e s , Solvent Layer
1.2 0.5
60.1 60.8
31.1 36.1
67.7 63.4
13.5 16.6
Ternary diagrams for industrial methylated spirit (94.2% ethyl alcohol) isopropyl alcohol, and ethyl alcohol-sodium hydroxide-water systems Per cent by weight a t 60'C. T i e l i n e s tor isopropyl olcohol I.M.S., t h i s work A I.P.A., this work X E t h y l alcohol (2)
---
NaOH
Data a t 25'C. 17.1 11.8 7.1 2.9 1.2 0.0
1.
were analyzed for sodium hydroxide content by titration with standard a c i d and for alcohol content by oxidation with standard potassium dichromate and iodometric determination of t h e e x c e s s reagent with potassium iodide and sodium thiosulfate. Water contents were determined by difference. All d a t a were recalculated to solid sodium hydroxide content, s o that they would be clearer and more p r e c i s e in meaning. UCOHCL
26.4 22.6
T a b l e 111. Solubility D a t a for Isobutyl AlcoholSodium Hydroxide-Water System ( I ) ( P e r C e n t by Weight at 25'C. F i g u r e 2)
Isobutyl Alcohol 93.0 6.2 5.2 4.5 3.5
NaOH
H,O
Isobutyl Alcohol
NaOH
H,O
1.1 1.3 2.8 3.9 5.8
5.9 92.5 92.0 91.6 90.7
3.1 0.9 0.4 0.1 0.0
6.7 14.5 21.7 32.1 50.0
90.2 84.6 77.9 67.8 50.0
T i e L i n e s , Water Layer 0.1
0.4
35.0 24.8
64.9 74.8
T i e L i n e s , Solvent Layer 99.5 99.5
0.3 0.3
0.2 0.2
PROCEDURE T h e ternary diagrams for sodium hydroxide and water with industrial methylated spirit and isopropyl alcohol were constructed a t 25 and 60 O C . ; t h e cloud point method w a s used t o determine t h e boundary of t h e two-layer region. Tie l i n e s were constructed by preparing mixtures of known composition, shaking them thoroughly, and separating them after equilibrium w a s established. T h e separated l a y e r s
36
INDUSTRIAL AND ENGINEERING CHEMISTRY
Figure 2. Ternary diagrams for industrial methylated spirit, isopropyl alcohol, and isobutyl alcoholsodium hydroxide-water systems P e r cent by weight a t 2 S ° C . T i e lines for isopropyl alcohol I.M.S., this work A I . P . A . , this work X Isobutyl alcohol ( 7 )
---
VOL. 2, NO. I
1.M.S. -
T a b l e IV. Solubility Doto for E t h y l AlcoholSodium Hydroxide-Woter System (2) ( P e r C e n t by Weight at 6OoC. F i g u r e 1)
A
EtOH
NaOH
H,O
64.1
15.4
20.Sa
T i e Lines, Water Layer 0.0
1.8 5.2 10.0
44.5 34.8 26.4 23.3
55.5 63.4 68.4 66.7
EtOH 0.0
NaOH 63.5
H,O 36.5 (3)
Tie Lines, Solvent Layer 64.2 65.2 62.5 54.1
22.4 13.7 9.5 10.2
13.4 21.1 28.0 35.7
work.
and 60 O C . for ‘industrial methylated spirit and isopropyl alcohol, respectively.
DISCUSSION
F i g u r e 3. Ternary diogroms for industrial methyloted spiritsodium hydroxide-water system Per cent by we$ht ot 25’0nd 60°C. T i e l i n e s a t 60 C.
---
RESULTS T h e data for the four s y s t e m s are given in T a b l e s I to IV. Data for ethyl alcohol, industrial methylated spirit, and isopropyl alcohol at 60°C. are shown on triangular coordinates in Figure 1; data for isobutyl alcohol, industrial methylated spirit, and isopropyl alcohol at 25 O C . a r e shown in Figure 2. F i g u r e s 3 and 4 compare data at 25” I PA -
Sodium hydroxide is considerably less soluble in isopropyl and isobutyl alcohols than in ethyl alcohol, t h e z o n e s of immiscibility increasing with increasing molecular weight of alcohol. It would b e interesting to compare t h e s e results with t h o s e obtained for n-propyl and n-butyl alcohols. T h e z o n e s of immiscibility increase for both industrial methylated spirit and isopropyl alcohol with increasing temperature, confirming t h e findings of P e y r o n e l (2) who observed similar behavior with ethyl alcohol, and s u g g e s t e d that rupture of the ethyl alcohol-sodium hydroxide association i s greatly affected by temperature. T h e phenomenon is not s o apparent with isopropyl alcohol and would probably b e even less so with isobutyl alcohol. T h e concavity on the water-isobutyl alcohol s i d e of the triangular graph, observed by Fritzsche and Stockton ( 2 ) w a s found with isopropyl alcohol. Sodium hydroxide i s more soluble in industrial methylated spirit than ethyl alcohol at high alcohol concentrations but at concentrations below 48% (by weight) of alcohol the solubility is reversed, probably again b e c a u s e of different molecular associations. T h e graphs and data m a y b e advantageously u s e d where neutralizing blends of sodium hydroxide in alcohol are required, particularly in t h e petroleum industry where simultaneous neutralization and extraction of sulfonic acids m a y b e effected. Blend proportions and concentrations to provide completely miscible neutralizing solutions may b e deduced and a r e particularly important in centrifugal separations.
ACKNOWLEDGMENT T h e authors wish to acknowledge the a s s i s t a n c e of J . P. Charlton in the construction of t i e l i n e s and to thank t h e directors of Manchester Oil Refinery Ltd., for permission to publish t h e s e results. T h e figures were drawn by J o y c e Lomas.
LITERATURE CITED
F i g u r e 4. Ternary diogroms for isopropyl olcoholsodium hydroxide-woter system P e r cent by weight ot 25’ and 60°C. T i e l i n e s o t 6OoC.
---
1957
(1) Fritzsche, R. H . , Stockton, D. L . , Ind. Eng. Chem. 38, 73740 (1946). (2) Peyronel, G.,Gazz. chirn. i t a f . 79, 792-9 (1949). (3) Seidell, A., “Solubilities of Inorganic and Metal Organic Compounds,” Vol. 1, p. 1284, Van Nostrand, New York, 1940. Received for review January 21, 1956. Accepted June 27, 1956.
CHEMICAL AND ENGINEERING D A T A SERIES
37
