[Anteateay Joursat oF Scurser, Vor, 263 May 1965, P. 445-454] THE SOLUBILITY OF CARBON DIOXIDE IN NaCl SOLUTIONS AT HIGH TEMPERATURES AND PRESSURES* SUKUNE TAKENOUCHI and GEORGE C. KENNEDY Institute of Geophysies and Planetary Physics, University of California. Los Angeles ABSTRACT. The solubility of carbon dioxide in 6 and 20 weight percent NaCl soluti hhas heen measured up to pressures of 1400 bars and up to temperatures of 450°C. The solubility of earbon dioxide in NaCI solution is much lower than in pure H:O; however, the general form and trend of the solubility curves is approximately the same. Both pressures and temperatures in the system NaCl-H.0-COs are raised sharply above critical pressures and temperatures in the binary system Hz0-CO:. Evidence from vacuoles in minerals suggests that some hydrothermal solutions are highly saline. Under appropriate pressure such solutions may exist as liquids in the crust to temperatures of 500 to 600°C. INTRODUCTION Three of the geochemically important binary systems with water as one of the constituent components have recently been investigated in this laboratory. These binary systems are: H,0-Si0:, HsO-NaCl, and H,0-CO:. Natural hy- drothermal solutions will probably. as a close approximation. be quaternary with water, silica, “salt”, and CO; as the prineipal components. Studies of the composition of fluid inclusions in minerals show that chlorides and carbon dioxides are however the major components in addition to water. Many fluid inclusions are even saturated with salt at room tempera- ture. Waters from many hot springs are rich in brine. For these reasons we have examined a portion of the system H,Q-NaCI-CO,. Our major concern has been that of the effect of sodium chloride on the solubility of carbon dioxide in water. PREVIOUS WORK, Only a very few measurements over a limited pressure and temperature region have been made on the solubility of carbon dioxide in salt solutions. Prutton and Savage (1945) investigated the solubility of carbon dioxide in CaCl, solutions at temperatures of 75°, 100°, and 120°C and up to pressures of 700 atmospheres, The concentration of salt in their solution was approxi- mately 10, 20, and 30 percent. Malinin (1959) has also published results on solubility of carbon dioxide in 10 percent CaCl, solutions at temperatures of 200 to 350°C and at pressures up to 400 bars. He found that the presence of 10 percent CaCl. lowered the solubility of carbon dioxide by 1.5 to 2.5 fold but that the general shape of the isotherms of the system remained the same as those in the system water-catbon, dioxide. Ellis and Golding (1963) studied the solubility of carbon dioxide in NaCl solutions over the temperature range 170° to 300°C and up to pressures of approximately 200 bars, The concentration of their NaCl solutions was 0.5, 1, and 2 molal. * Publication No, 4 fornia, Los: Angeles Institute of Geophysics and Planetary Physics, University of Cali- Tifornia 90024,446 Sukune Takenouchi and George C. Kennedy—Phe Solubility of The results from the work of Prutton and Savage and from Malinin re- calculated in weight percent CO, are shown in figure 1, The solid lines show Malinin’s data for 10 weight percent CaCl, solution at three different tempera- tures, and the broken lines show the data of Prutton and Savage for various concentrations of CaCl; at 121°C. EXP! IMENTAL WORK, ‘Phe experimental apparatus used in this work was the same as that pre- viously described and used in determining the solubility of CO, in pure water (Takenouchi and Kennedy, 1964). ‘The temperature of the system was regu- lated to within + 0.8°C, and pressure was determined hy readings from Heise 7004 600} 4 PRESSURE (BARS) 200} 4 —Data of Malinin ——Data of Prutton ‘ond Savoge © 3 16 5 Og wh % Fig. 1. Solubility of carbon dioxide in CaCl solutions (after Malinin, 1959, and Prutton’ and Savage, 1945).Carbon Dioxide in NaCl Solutions at High Temperatures and Pressures 447 Bourdon Tube gauge of 15” face, calibrated against a dead weight tester, with a range of 0 to 2000 bars and an interval of 2 bars. The general experimental procedure and the method of determination of CO: in the samples were the same as reported in the system H,0-CO;. Samples were taken at time intervals of from 24 to 48 hours. Our samples of the liquid phase ranged in weight from 0.3 to 1.0 grams, and the NaCl and CO, content of these samples was determined by analysis. Pressure dropped during the sampling approximately 10 to 60 bars, All results were plotted against the initial pressure of the system before sampling. Little or no change in chemical equilibria took place during the short time of sampling owing to the pressure drop attendant with the sampling, Our measurements of CO, solu- bility in NaCl solutions were made along isotherms ranging from 150° to 400°C at intervals of 50°C for the 6 weight percent NaCI solution and from 150° to 450°C at intervals of 100°C for the 20 weight percent NaCl solution. The composition of the coexisting gas phase was not determined, Samples were taken along isotherms at various pressures. The initial sample pulled was at low pressures, and each successive sample was taken at a higher pressure. Pressures were adjusted by introduction of CO; into the system. The CO, composition of our samples was determined by titration against standard HCl solution. CO, was absorbed in sodium hydroxide and estimated by back titration with HCl (Kolthoff and Sandell, 1952). The NaCl concentra tion of the solution was determined by the Mohr method using standardized AgNO, solution and a potassium chromate solution as an indicator (Kolthoff and Sandell 1952). At high temperatures the amount of water present in the gas phase was substantial so that the concentration of the salt in the liquid phase increased sharply over that of the initial solution as made up. Therefore small amounts of distilled water were introduced in order to maintain the NaCl concentration of the liquid phase essentially constant. RESULTS Results from the present experimental program are shown in table 1 and figures 2 and 3, Smoothed values are shown in table 1, and the experimental values are plotted in figures 2 and 3. For comparison the solubility of COs in pure water is shown in figure 4. The solubility of CO, in the liquid phase is expressed as weight percent of the total weight of sample and is shown for NaCl concentrations of approximately 6 and 20 weight percent. ‘The NaCl concentrations however are shown in weight percent of the weight of H.O + NaCl, not H,O + NaCl + COs. Therefore, throughout our runs there was a change in the NaCI concentration as the CO, solubility changed. This method of determining and presenting our results was dictated by experimental con- venience, Throughout the runs, the concentration of salt was 6 + 0.5 and 20 = 1.2 weight percent NaCl of H,O + NaCl. The variation in concentra- tion of NaCl from experiment to experiment was owing to the ranging volume and composition of the gas phase present in our bomb, We found it difficult to keep the NaCl concentration of the liquid phase within narrower limits than these,148 Sukune Takenouchi and George C. Kennedy—The Solubility of Tame 1 Solubility data Weight percent CO, in H.O, in NaCl coneentration of 6 wt perce and in NaCl concentration of 20 wt percent ‘Temperature Nacl NaCl Pressure HO ow % ww % 450°C 500 bars wt % —wt% 22 0 % 600 = 42 700 = 60 800. = 76 900, 92 400° 300 4400 500, 350° 200 rat 300 26 400 Po= 225 bars 39 500, Xe= 223 wt % 5 600 62 800 79 1000 95, 1200 108, 1400 120 300° 100 200 300 400 500 600 Pe 800 Xe 1000 1200 1400 250° 100 28 10 200 60 20 300 96 28 400 121 34 500 M3 41 00, 16a 4 800, 204 Ba 1000 242 66 1200 3 7 6 1400 288 0 a2 200° 100 32 5 200 61 44 300 79 56 400, 95 65 500 108 72 00 18 79 300 Bz 89 1000 M42 96 1200 150 102 1400 156 107 150° 100 31 25 09 200, Ba 40 16 300 Gl 47 22 400 69 52 25 500, 75 56 28 00 80 60 32 800 90 66 38 1000 O7 72 43 1200 103, 17 48 1400 108 80 53Carbon Dioxide in NaCl Solutions at High Temperatures and Pressures 449 The salting out effect of COs in water is clearly shown in both figures. The general shapes of the CO; solubility curves in the system NaCl-CO;-H.0 are similar to those in the system H,0-CO, at low temperatures, but the CO, solu- bility in solutions with high NaCl concentration is markedly less than in pure water. The presence of salt also sharply suppresses the onset of critical phe- nomena (see fig. 5). DISCUSSION Many recent studies of liquid inclusions in minerals show that these liquid inclusions characteristically range in composition from dilute salt solu- tion to almost saturated salt solution and that sodium or calcium chloride and carbon dioxide are the prominent components in addition to water (Newhouse, 1932; Skropyshev, 1957; Roedder, 1958; Ames, 1958; Kalyuzhnyy, 1958; Lisitin and Malinko, 1961; Maslova, 1961; Takenouchi, 1962; Roedder, Ingram, and Hall, 1963; Hall and Friedman, 1963; and Roeder, 1963). 1509 3 8 8 PRESSURE (BARS) 8 "350°(H20) 6 wt % NaCl SOLUTION 0 16 20 30 40 CO wt. % Fig. 2. Solubility of carbon dioxide in 6 weight percent NaCl solution,450 Sukune Takenouchi and George C. Kennedy—The Solubility of White (1957a,b) has shown that one of the most common hot spring waters is characterized chemically by abundant sodium chloride and that other chemi- cally distinct types of hot spring waters may be derived from the sodium chloride waters, White (White, Anderson, and Grubbs, 1963) has described a very saline high temperature solution from a deep drill hole in the Imperial Valley, California, He suggests that this brine may be of pure magmatic water and that it may be an active ore-forming solution, Substantial amounts of min- erals are being deposited from this cooling brine. According to White the depth of the well is approximately 5200 feet and the temperature ranges from 270°C to 370°C in the lower portion of the hole. Analyses shows that 80 to 93 volume percent of the gas present is carbon dioxide and the solution contains 5.4 weight percent Na, 4.0 weight percent Ca, and 18.4 weight percent Cl. Total concentration of salts in the solution is 33.2 weight percent. It is, of course, incorrect to assume that naturally occurring hydrothermal systems are all represented by the system water-carbon dioxide-sodium PRESSURE (BARS) gh 350° (H20) 20 wt % NaCi SOLUTION ° 10 20 30 COp wt. % Fig. 3 Solubility of carbon dioxide in 20 weight percent NaCl solutionCarbon Dioxide in NaCl Solutions at High Temperatures and Pressures 451 chloride. However, the general behavior of this ternary system probably more nearly approximates that of the naturally occurring system than does any pure binary system with water. As seen in figures 2 and 3 the presence of NaCl greatly extends the pressure-temperature region of liquid-gas behavior. Critical phenomena are sharply suppressed. Figure 5 shows critical points in the syst m H,O-NaCl. taken from the data of Sourirajan and Kennedy (1962). and the vapor pressure curves of 5. 10. and 20 weight percent NaCl solutions. In summary, the solubility of carbon dioxide in salt solutions depe markedly on the concentration of salt, and solubility decreases rapidly as the amount of salt increases, It is unreasonable to expect a large quantity of carbon dioxide to be dissolved in a hydrothermal solution when the salt concentration high. Even with high partial pressures of carbon dioxide, liquids exist in the system H,0-NaCl at temperatures and pressures sharply above the critical point of pure water, No sharp temperature boundary. such as 374°C, can be 1500) PRESSURE (BARS) 500} CP of WATER 0 20 30 40 C02 wt% Fig. 4. Solubility of carbon dioxide in pure water (after Takenouchi and Kennedy, 961).452 Sukune Takenouchi and George C. Kennedy—The Solubility of set between the regions of pneumatolytic transport for mineral deposition and the liquid-hydrothermal region. Magmatic emanations from cooling granitic bodies may be homogeneous when they first separate from the granite body, but if they contain a consider- able amount of salt they will soon dissociate into two fluid phases: one CO.— rich and the other H,Q-NaCl rich. Results from the present study agree well with the data of Ellis and Golding (1963) over the very limited region of overlap, It is difficult to com: pare our results direetly with the data of Prutton and Savage (1945) and of Malinin (1959) because their studies involved CaClh, not NaCl, but the general trend of the two sets of solubility curves is similar. High temperature solutions in the system Hz0-NaCl-CO, were found to be extremely corrosive. Our measurements were terminated at 450° with 20 weight percent NaCI solution owing to the extremely rapid deterioration of our stainless steel equipment, The exact content of iron in our solutions was not determined; however, after a series of experiments many crystals of siderite were found on the walls of our stainless steel autoclave. ACKNOWLEDGMENTS Our experimental apparatus was constructed and maintained in excellent working condition by Mr. T. J, Thomas. Thanks are owing to Dr. D. E. White for chemical information of the Imperial Valley geothermal well. Partial finan- cial support for the investigations was from the Geophysies Branch of the Office of Navy Research. Tanue 2 NaCl content of liquid phase in the various runs ‘Temp °C Pressbars NaCl wt % Deviation 6 Wt percent NaCl solution 150 90 5.67 0.33 200 208 613 +013 200 552. on +011 250 189 5.2 0.28 250 1si8 647 +047 300 11 5.89 0.11 300 526 6.03 +003 350 1379 661 +061 400 355 626 +0.26 400 487 6.46 +0.46 400 609 621 +021 20 Wr percent NaCl soluti 150 1050 20.14 +014 250 598 20.42 +042 250 1042 20.76 +076 350 285 19.02 0.98 350 546 2081 +081 350 1100 2118 +118 450 529 18.95 =1.05 450 700 21.20 +120Carbon Dioxide in NaCl Solutions at High Temperatures and Pressures 453 1000} 800} 600} PRESSURE (BARS) 400] 200} fe) ‘200 300 400 500 600 TEMPERATURE (°C) Fig. 5. Critical yoint of the system HsO-NaCl and vapor pressure curves of 5, 10, sand 20 weight percent NaCI solutions (after Sourirajan and Rennedy, 1962). Rurewexcrs, Ames, L, Lu, Jey 1958, Chemical analyses of the fluid inclusions in a group of New Mexico minerals: Keon, Geology, v. 53, p. 473-0. Ellis, A. Joy and Golding, R. 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