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Ternary aqueous systems
Chemical Engineering Science, 1967, Vol. 22, pp. 627-631. Pergamon Press Ltd., Oxford.
Prmted in Great Britain.
Ternary aqueous systems ALFRED W. FRANCIS t Mobil Oil Corporation,
Paulsboro,
New Jersey
(Received 8 August 1966; in revised form 6 October 1966) Abstract-Forty-five ternary systems involving water are presented, including five in which there is a solid phase but only one liquid phase. Five of the graphs show two separate binodal curves, and three of them three liquid phases each. Also observed are three systems with solutropes, three with isopycnics, and two with twin index lines. Uses of cuprous chloride and silver nitrate in novel solvent combinations for extracting olefins were studied. Loss of affinity of silver nitrate for olefins caused by the presence of cupric nitrate was noted.
NEARLY three-fourths of published ternary systems having two or more liquid phases in equilibrium have water as a major component. However, systems containing water constitute only about oneeighth of systems in publications by the present author, since aqueous systems are relatively less pertinent to solvent extraction of hydrocarbons, among which his chief interest lies. Some aqueous systems have been illustrated in each of the papers of the current series [5-141; and this paper presents 45 additional ones of the investigation. EXPERIMENTAL
As in the earlier papers, known mixtures of two miscible components were titrated at a fixed temperature with the third component until the appearance of another liquid phase, using the best grade of chemicals available. Alternatively, two not miscible components were titrated to a single phase. Then more of an appropriate component was added, and the titration was repeated. Fourteen systems involving liquefied gases; graphs 11, 15 to 18, 20 to 25, 30, 34, 38, required the titration in a sealed tube, as in the papers on systems of sulfur dioxide [5] and ammonia [8], using a separate seal with each tentative observation. The ethylene system (graph 32) was observed in a visual autoclave [ 151. DISCUSSION
Presentation of the graphs is explained in the legend. The high concentration of acetaldehyde t Present address:
required in graph 1 shows that it is inefficient in making a homogeneous phase of water with benzene. Its isomer, ethylene oxide, (graph 15) is better in that respect. Graphs 4 and 5 show two of the systems of PEAKE and THOMPNIN [22] but with the addition of isopycnics in each, and the solutrope, at 3-6 % butylamine, in graph 4. Similarly, graph 3 shows the same two features in one of about 60 systems as presented by LEIKOLA [21]. Graph 19 was added to show the position of the isopycnic in the system of CONWAY and PHILLIP [l]. Very likely these and other features have been overlooked in some of the graphs of the present series. This applies especially to iso-optics and twin index lines [3], which were unknown during a large portion of this research, and would be expected to be about as plentiful as isopycnics. Graphs 6 and 7 show a substantial enhancement in solubility of cuprous chloride in ethanolamine in presence of small amounts of water or especially ammonium hydroxide or nitrate. Dioxane is distributed to paraffin hydrocarbons in preference to water; but with an olefin, distribution is almost symmetrical (graphs 8 and 9). The temperature in graphs 12 and 39 was adjusted to 22”, the critical solution temperature of water with isobutyric acid, the only aqueous CST near room temperature [2]. This results in a side line tangent to the binodal curve at its plait point. In spite of the high melting point of ethylene carbonate, 36”, no solid phase equilibrium is shown in graph 14, because it is readily subcooled.
Mobil Chemical Company, Metuchen, New Jersey.
627
.
Y-
Water
‘-.-Jo
-9 acetate
Ethylene oxide
/
\
14
Ethylene oxide /
Furfuml 17
2L 26% NaCl
Benzene
R
IA
2L
/
Octane
Water
Bromine
Water
&=+
?t /
/’
19
we
&i&Tmi&
20
L
6O%HPSO4
pentanone
628
\ a2
Ternary aqueous systems
Hydrogen bromide
Hydrogen bromide
Hydmgen bomide
Hl A
Water
Isopropyl
_alc&ol
/
629
Ether
\
ALFRED W. FRANCIS As usual [ 161aqueous systems of hydrogen halides show two separate binodal curves, graphs 11, IS,21 to 23, and 25. The dioxane system (graph 22) was studied in the area of the island by GRUBB and OSTHOFF[20]. The upper binodal curve was added as a result of the present work. Systems of hydrogen halides with ethyl ether, (graphs 23 and 25) show pronounced undercutting of the binodal curve (higher solubility of water in ether alone than in ether containing a little hydrogen halide). A similar curve with urea (graph 24) is more conspicuous, but should not be confused. It surrounds a homogeneous composition. Graph 40 is unusual in that the consolute component, trichloracetic acid, for the binodal curve, is miscible with neither of the other components. The systems of silver nitrate (graphs 30 to 34) supplement those shown for propylene and lbutene [4, 6 graph 9 1, 171which form liquid phases with anhydrous silver nitrate. The other olefins require a solvent [4, 18, 191. Cupric nitrate was tried (graph 31) in the vain hope of replacing a portion of the silver nitrate for absorption of olefins. Any substantial amount of cupric nitrate destroyed the affinity of silver nitrate for olefins.
cent water so as to make it liquid at room temperature. The double listings in graphs 1, 6, and 29 are not mixtures, but are alternative single components. A total of 45 systems are presented. All involve two or three liquid phases except those in graphs 2, 6, 7, 27, and 31. Temperatures are 25” except when shown otherwise above the right side line in graphs 1, 12, 16,21, 32, and 39. Small circles on the binodal curves are plait points. Dashed lines in graphs 3, 4, and 5 indicate isopycnics [3], or tie lines connecting compositions of equal densities in equilibrium. The line marked “blue”, graph 16, and those marked “yellow” and “blue”, graph 20, are twin index lines [3], not really tie lines, and not rigorously straight (because the systems are quaternary), passing through compositions with equal refractive indices, and giving colored emulsions. The solutropes, graphs 3, 4, and 17, are tie lines parallel to a side line. In lieu of other tie lines certain areas are marked 2L, S +L, or 3L to show the numbers of liquid or solid phases (U instead of S for urea in graphs 24, 27, and 35). Three liquid layers are shown in graphs 13,36, and 37. Graphs
Name
Abbreviation LEGEND czH4co3
Gasoline HCl HI
All triangular graphs except 6, 16,20,34 to 38 are ternary as marked at their corners. Water is plotted at the lower left corner except in graph 38. In graph 34 the hydrocarbon “component” is 70 per cent propylene and 30 per cent of either propane or n-hexane (two different systems). In graph 35 the aqueous “component” is 50 per cent formamide, and the hydrocarbon is either octane or cetane (two different systems). In graphs 36 and 37 the top component is a mixture of phenol and cresols; and in graph 38 the trichloroacetic acid contains 11 per
KSCN Lube oil Methymaph 4-Methyl2-pentanone 26% NaCl Solutrope U W
REFERENCES J. B. and PHILIP J. B., Ind. Engng Chem. 1953 45 1083. FRANCIS A. W., Adv. Chem. Ser. 1961 31 184. FRANCIS A. W., Znd.Engng Chem. 1953 45 2789. FRANCIS A. W., J. Am. Chem. Sot. 1951 73 3709. FRANCISA. W., J. Chem. Engng Data 1965 10 45. FRANCIS A. W., J. Chem. Engng Data 1965 10 145. FRANCIS A. W., J. Chem. Engng Data 1965 10 260. FRANCIS A. W., J. Chem: Engng Data 1965 10 327. FRANCIS A. W., J. Chem. Engng Data 1966 1196. FRANCIS A. W., J. Chem. Engng Data 1966 11234. CONWAY
630
Ethylene carbonate Straight run, 30” Aniline pt. Anh. hydrogen chloride Anh. hydrogen iodide Isopycnics Potassium sulfocyanate Lubricating oil (see Ref. [5 or 61 Table 1) I-Methylnaphthalene
14 36, 37 11, 24 25 3, 4, 5 2 13, 29
Methyl isobutyl ketone Aqueous solution
19 16 3, 4. 17 24, 27, 35 35
Urea Water
1
Ternary aqueous systems [ll] [12]
[13] [14] [15] [16] [17] [18] [19] I201 i21] [22]
FRANCISA. W., .I. Chem. Engng Data 1966 11 557. FRANCISA. W., .I. Chem. Engng Data to be published FRANCISA. W., J. Chem. Engng Data to be published FRANCISA. W., Chem. Engng Ski. to be published FRANCIS A. W., J. Phys. Chem. 1954 58 1099. FRANCISA. W., J. Phys. Chem. 1958 62 579. FRANCISA. W., (to &cony-Vacuum Oil Co.) U.S. Patent 2,498,204, February 21, 1950. FRANCISA. W., (to Socony-Vacuum Oil Co.) U.S. Patent 2,673,225, March 23, 1954. FRANCIS A. W. and REID E. E., (to Socony-Vacuum Oil Co.) U.S. Patent 2,377,211, May 29, 1945. GRUBBW. T. and OSTHOFFR. C.. J. Am. Chem. Sot. 1952 74 2108. LEIKOLAE., Acta. Chem. Fenn. 1940 13B 13. PEAKEJ. S. and THOMPSONK. E. JR., Ind. Engng. Chem. 1952 44 2439. R&rrn~On presente quarante-cinq systemes temaires contenant de I’eau, parmi lesquels cinq comprennent une phase solide mais seulement une phase liquide. Cinq dcs graphiques montrent deux courbcs &par& binodales, et trois d’entre elles representent trois phases liquidea chacune. On a aussi observe trois systemes avec solutropes, trois avec isopycniques et deux avec lignes jumelQs de reference. On a etudie l’emploi de chlorure cuivreux et de nitrate d’argent dans dea combinaisons nouvelles de solvant pour l’extraction d’oldfines. On a note la perte d’affinitt du nitrate d’argent pour les olefines causee par la presence de nitrate cuivrique. Zusammenfassung45 Ternarsysteme, die Wasser enthalten, werden behandelt, einschliesslich von f&f Systemen, bei denen es eine feste Phase, aber mu eine fliissige Phase. gibt. Ftinf der Diagramme enthalten zwei getrennte Binodalkurven, und drei von ihnen je drei fltissige Phasen. Es werden such drei Systeme mit Solutropen festgestellt, drei mit Isopyknen und zwei mit doppelten Indexlinien. Es wurde der Gebrauch von kuprochlorid und Silbemitrat in neuartigen Liisungskombinationen zur Extraktion von Olefinen untersucht. Es wurde festgestellt, dass die Gegenwart von Kupfernitrat zu einem Verlust der Affinitat von Silbernitrat ftir Olefine ftlhrt.
631
Prmted in Great Britain.
Ternary aqueous systems ALFRED W. FRANCIS t Mobil Oil Corporation,
Paulsboro,
New Jersey
(Received 8 August 1966; in revised form 6 October 1966) Abstract-Forty-five ternary systems involving water are presented, including five in which there is a solid phase but only one liquid phase. Five of the graphs show two separate binodal curves, and three of them three liquid phases each. Also observed are three systems with solutropes, three with isopycnics, and two with twin index lines. Uses of cuprous chloride and silver nitrate in novel solvent combinations for extracting olefins were studied. Loss of affinity of silver nitrate for olefins caused by the presence of cupric nitrate was noted.
NEARLY three-fourths of published ternary systems having two or more liquid phases in equilibrium have water as a major component. However, systems containing water constitute only about oneeighth of systems in publications by the present author, since aqueous systems are relatively less pertinent to solvent extraction of hydrocarbons, among which his chief interest lies. Some aqueous systems have been illustrated in each of the papers of the current series [5-141; and this paper presents 45 additional ones of the investigation. EXPERIMENTAL
As in the earlier papers, known mixtures of two miscible components were titrated at a fixed temperature with the third component until the appearance of another liquid phase, using the best grade of chemicals available. Alternatively, two not miscible components were titrated to a single phase. Then more of an appropriate component was added, and the titration was repeated. Fourteen systems involving liquefied gases; graphs 11, 15 to 18, 20 to 25, 30, 34, 38, required the titration in a sealed tube, as in the papers on systems of sulfur dioxide [5] and ammonia [8], using a separate seal with each tentative observation. The ethylene system (graph 32) was observed in a visual autoclave [ 151. DISCUSSION
Presentation of the graphs is explained in the legend. The high concentration of acetaldehyde t Present address:
required in graph 1 shows that it is inefficient in making a homogeneous phase of water with benzene. Its isomer, ethylene oxide, (graph 15) is better in that respect. Graphs 4 and 5 show two of the systems of PEAKE and THOMPNIN [22] but with the addition of isopycnics in each, and the solutrope, at 3-6 % butylamine, in graph 4. Similarly, graph 3 shows the same two features in one of about 60 systems as presented by LEIKOLA [21]. Graph 19 was added to show the position of the isopycnic in the system of CONWAY and PHILLIP [l]. Very likely these and other features have been overlooked in some of the graphs of the present series. This applies especially to iso-optics and twin index lines [3], which were unknown during a large portion of this research, and would be expected to be about as plentiful as isopycnics. Graphs 6 and 7 show a substantial enhancement in solubility of cuprous chloride in ethanolamine in presence of small amounts of water or especially ammonium hydroxide or nitrate. Dioxane is distributed to paraffin hydrocarbons in preference to water; but with an olefin, distribution is almost symmetrical (graphs 8 and 9). The temperature in graphs 12 and 39 was adjusted to 22”, the critical solution temperature of water with isobutyric acid, the only aqueous CST near room temperature [2]. This results in a side line tangent to the binodal curve at its plait point. In spite of the high melting point of ethylene carbonate, 36”, no solid phase equilibrium is shown in graph 14, because it is readily subcooled.
Mobil Chemical Company, Metuchen, New Jersey.
627
.
Y-
Water
‘-.-Jo
-9 acetate
Ethylene oxide
/
\
14
Ethylene oxide /
Furfuml 17
2L 26% NaCl
Benzene
R
IA
2L
/
Octane
Water
Bromine
Water
&=+
?t /
/’
19
we
&i&Tmi&
20
L
6O%HPSO4
pentanone
628
\ a2
Ternary aqueous systems
Hydrogen bromide
Hydrogen bromide
Hydmgen bomide
Hl A
Water
Isopropyl
_alc&ol
/
629
Ether
\
ALFRED W. FRANCIS As usual [ 161aqueous systems of hydrogen halides show two separate binodal curves, graphs 11, IS,21 to 23, and 25. The dioxane system (graph 22) was studied in the area of the island by GRUBB and OSTHOFF[20]. The upper binodal curve was added as a result of the present work. Systems of hydrogen halides with ethyl ether, (graphs 23 and 25) show pronounced undercutting of the binodal curve (higher solubility of water in ether alone than in ether containing a little hydrogen halide). A similar curve with urea (graph 24) is more conspicuous, but should not be confused. It surrounds a homogeneous composition. Graph 40 is unusual in that the consolute component, trichloracetic acid, for the binodal curve, is miscible with neither of the other components. The systems of silver nitrate (graphs 30 to 34) supplement those shown for propylene and lbutene [4, 6 graph 9 1, 171which form liquid phases with anhydrous silver nitrate. The other olefins require a solvent [4, 18, 191. Cupric nitrate was tried (graph 31) in the vain hope of replacing a portion of the silver nitrate for absorption of olefins. Any substantial amount of cupric nitrate destroyed the affinity of silver nitrate for olefins.
cent water so as to make it liquid at room temperature. The double listings in graphs 1, 6, and 29 are not mixtures, but are alternative single components. A total of 45 systems are presented. All involve two or three liquid phases except those in graphs 2, 6, 7, 27, and 31. Temperatures are 25” except when shown otherwise above the right side line in graphs 1, 12, 16,21, 32, and 39. Small circles on the binodal curves are plait points. Dashed lines in graphs 3, 4, and 5 indicate isopycnics [3], or tie lines connecting compositions of equal densities in equilibrium. The line marked “blue”, graph 16, and those marked “yellow” and “blue”, graph 20, are twin index lines [3], not really tie lines, and not rigorously straight (because the systems are quaternary), passing through compositions with equal refractive indices, and giving colored emulsions. The solutropes, graphs 3, 4, and 17, are tie lines parallel to a side line. In lieu of other tie lines certain areas are marked 2L, S +L, or 3L to show the numbers of liquid or solid phases (U instead of S for urea in graphs 24, 27, and 35). Three liquid layers are shown in graphs 13,36, and 37. Graphs
Name
Abbreviation LEGEND czH4co3
Gasoline HCl HI
All triangular graphs except 6, 16,20,34 to 38 are ternary as marked at their corners. Water is plotted at the lower left corner except in graph 38. In graph 34 the hydrocarbon “component” is 70 per cent propylene and 30 per cent of either propane or n-hexane (two different systems). In graph 35 the aqueous “component” is 50 per cent formamide, and the hydrocarbon is either octane or cetane (two different systems). In graphs 36 and 37 the top component is a mixture of phenol and cresols; and in graph 38 the trichloroacetic acid contains 11 per
KSCN Lube oil Methymaph 4-Methyl2-pentanone 26% NaCl Solutrope U W
REFERENCES J. B. and PHILIP J. B., Ind. Engng Chem. 1953 45 1083. FRANCIS A. W., Adv. Chem. Ser. 1961 31 184. FRANCIS A. W., Znd.Engng Chem. 1953 45 2789. FRANCIS A. W., J. Am. Chem. Sot. 1951 73 3709. FRANCISA. W., J. Chem. Engng Data 1965 10 45. FRANCIS A. W., J. Chem. Engng Data 1965 10 145. FRANCIS A. W., J. Chem. Engng Data 1965 10 260. FRANCIS A. W., J. Chem: Engng Data 1965 10 327. FRANCIS A. W., J. Chem. Engng Data 1966 1196. FRANCIS A. W., J. Chem. Engng Data 1966 11234. CONWAY
630
Ethylene carbonate Straight run, 30” Aniline pt. Anh. hydrogen chloride Anh. hydrogen iodide Isopycnics Potassium sulfocyanate Lubricating oil (see Ref. [5 or 61 Table 1) I-Methylnaphthalene
14 36, 37 11, 24 25 3, 4, 5 2 13, 29
Methyl isobutyl ketone Aqueous solution
19 16 3, 4. 17 24, 27, 35 35
Urea Water
1
Ternary aqueous systems [ll] [12]
[13] [14] [15] [16] [17] [18] [19] I201 i21] [22]
FRANCISA. W., .I. Chem. Engng Data 1966 11 557. FRANCISA. W., .I. Chem. Engng Data to be published FRANCISA. W., J. Chem. Engng Data to be published FRANCISA. W., Chem. Engng Ski. to be published FRANCIS A. W., J. Phys. Chem. 1954 58 1099. FRANCISA. W., J. Phys. Chem. 1958 62 579. FRANCISA. W., (to &cony-Vacuum Oil Co.) U.S. Patent 2,498,204, February 21, 1950. FRANCISA. W., (to Socony-Vacuum Oil Co.) U.S. Patent 2,673,225, March 23, 1954. FRANCIS A. W. and REID E. E., (to Socony-Vacuum Oil Co.) U.S. Patent 2,377,211, May 29, 1945. GRUBBW. T. and OSTHOFFR. C.. J. Am. Chem. Sot. 1952 74 2108. LEIKOLAE., Acta. Chem. Fenn. 1940 13B 13. PEAKEJ. S. and THOMPSONK. E. JR., Ind. Engng. Chem. 1952 44 2439. R&rrn~On presente quarante-cinq systemes temaires contenant de I’eau, parmi lesquels cinq comprennent une phase solide mais seulement une phase liquide. Cinq dcs graphiques montrent deux courbcs &par& binodales, et trois d’entre elles representent trois phases liquidea chacune. On a aussi observe trois systemes avec solutropes, trois avec isopycniques et deux avec lignes jumelQs de reference. On a etudie l’emploi de chlorure cuivreux et de nitrate d’argent dans dea combinaisons nouvelles de solvant pour l’extraction d’oldfines. On a note la perte d’affinitt du nitrate d’argent pour les olefines causee par la presence de nitrate cuivrique. Zusammenfassung45 Ternarsysteme, die Wasser enthalten, werden behandelt, einschliesslich von f&f Systemen, bei denen es eine feste Phase, aber mu eine fliissige Phase. gibt. Ftinf der Diagramme enthalten zwei getrennte Binodalkurven, und drei von ihnen je drei fltissige Phasen. Es werden such drei Systeme mit Solutropen festgestellt, drei mit Isopyknen und zwei mit doppelten Indexlinien. Es wurde der Gebrauch von kuprochlorid und Silbemitrat in neuartigen Liisungskombinationen zur Extraktion von Olefinen untersucht. Es wurde festgestellt, dass die Gegenwart von Kupfernitrat zu einem Verlust der Affinitat von Silbernitrat ftir Olefine ftlhrt.
631