Theoretical Foundations of Chemical Engineering, Vol. 37, No. 1, 2003, pp. 5153.

Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 37, No. 1, 2003, pp. 5457. Original Russian Text Copyright 2003 by Sabirzyanov, Shagiakhmetov, Gabitov, Tarzimanov, Gumerov.

Water Solubility of Carbon Dioxide under Supercritical and Subcritical Conditions

A. N. Sabirzyanov, R. A. Shagiakhmetov, F. R. Gabitov, A. A. Tarzimanov, and F. M. Gumerov
Kazan State Technical University, ul. Karla Marksa 68, Kazan, 420015 Tatarstan, Russia
Received March 27, 2002

AbstractThe solubility of carbon dioxide in water at t = 25, 50, 100, and 150C and p = 1080 MPa is studied experimentally by a static method in a constant-volume cell. The results are described by the entropy method of similarity theory. The calculated and experimental data are in satisfactory agreement.

Up to now, the solubility of low-volatile substances in compressed uids has been described and predicted without regard for the dissolution of the uids in the low-volatile phase [1, 2]. We believe that the experimental determination of the solubility of supercritical uids in raw and waste liquids is of importance in designing large-scale supercritical processes and in rening computational methods for predicting the solubility. There are many experimental works devoted to the solubility of compressed gases in liquids; by contrast, the solubility of supercritical uids in liquids is poorly studied. The methods used to calculate the binary solubility of supercritical uids in liquids are thermodynamically nonrigorous and are based on extrapolating the saturation vapor pressure of the dissolved gas to the supercritical region [3].
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EXPERIMENTAL Our experimental setup for measuring the solubilities of gases in liquids is schematized in Fig. 1. The pressure control system consists of an MP-2500 deadweight gage 1, a high-pressure mercury seal 2, a cylinder 3 containing the gas to be examined, highpressure valves 46 and 10, a Bourdon pressure gage 8, and connecting pipelines. The desired pressure was produced using a hydraulic press and the hydraulic amplier of the MP-2500 pressure gage. Seal 2 consists of two communicating high-pressure vessels half full of mercury. The space above the mercury in the righthand vessel is lled with castor oil and communicates with the deadweight gage. After the system was pumped using vacuum pump 12 to a residual pressure

1 10 7 5 9 10 11 3 12 6 4 2 8

Fig. 1. Schematic of the experimental setup: (1) MP-2500 deadweight gage, (2) mercury seal, (3) gas cylinder, (46, 10) high-pressure valves, (7) tee, (8) standard pressure gage, (9) heat-insulated high-pressure autoclave, (11) ball, and (12) vacuum pump. 0040-5795/03/3701-0051$25.00 2003 MAIK Nauka /Interperiodica

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SABIRZYANOV et al.

Solubility 102 (in mole fractions) of carbon dioxide in water t, C 25 50 100 150 p, MPa 10 2.33 1.85 1.30 1.07 20 2.62 2.13 1.89 1.94 40 2.86 2.46 2.33 2.82 60 2.65 2.70 3.99 80

3.26 5.42

of 102 mm Hg, gas from cylinder 3 was admitted into the left vessel of seal 2 until mercury reached the lowest level, and the cylinder was then shut off from the system using valve 5. The gas was compressed with the hydraulic press of the deadweight gage through the mercury seal. Next, valve 10 was closed and another portion of the gas was admitted into the system. These manipulations were repeated until the desired pressure was attained in the vessel 9. The accuracy rating of the MP-2500 gage was 0.02. Vessel 9 was heated to a preset temperature with three Nichrome heaters. The heater circuit voltage was controlled with RNO-250-2M laboratory autotransformers. The vessel temperature was measured with a ChromelCopel thermocouple calibrated against a PTS-10 platinum resistance thermometer. The equilibration vessel 9 is a stainless steel cylinder with a working volume of 96 cm3. It has a sealed top cover with a built-in high-pressure valve (10) for shutting off the vessel from the rest of the system during agitation and equilibration. Valve 10 built in the bottom of this vessel is designed for sampling the liquid phase. Vessel 9, along with valves 10 is heat-insulated and housed. In static measurements of gas solubility in liquid, vessel 9 was rocked about its horizontal axis through an angle of 160 for perfect mixing of the phases. It made two rocking motions per minute. This method combined the advantages of the static and dynamic methods, since rocking markedly increased the phase-contact area. Moreover, rocking caused gas bubbling through a liquid layer. Perforated ball 11 was placed into the vessel for an even more intensive phase mixing. The time necessary for the complete saturation of the liquid with the gas was determined from two series of measurements. In the rst, the carbon dioxide concentration in water at xed temperature and pressure was determined at 15-min intervals until the gas content of the liquid stopped varying. In the second, agitation was interrupted each 15 min to measure the gas pressure in the vessel. In the early stages of saturation, the pressure decreased. To maintain the pressure at a constant value, new portions of the gas were forced from the head space of the mercury seal into the vessel. The complete saturation time was found to be the same in the two series of measurements. Therefore, in further measurements, equilibration (complete saturation of the liquid

with the gas) was judged from pressure variation in the vessel. After agitation, the vessel was held upright for 11.5 h. The liquid to be analyzed was sampled through a capillary with an inner diameter of 0.5 mm so as to obviate disequilibrium in the sample or the main liquid. Sampling was carried out at a constant pressure, which was maintained by admitting gas into vessel 9 from the head space of the mercury seal. The samples were immediately collected in a series of detachable weighed ampoules. The gas that resulted from throttling the sample through the high-pressure valve was collected in graduated asks, and its volume was measured. The gas volume reduced to normal conditions (t = 20C, p = 760 mm Hg) varied between 200 and 3000 cm3 and was measured with an accuracy of 1 cm3. In this way, gas solubility can be determined from the weight of the liquid and the volume of the gas, with an overall relative error of 3%. RESULTS AND DISCUSSION Carbon dioxide solubility data at t = 25, 50, 100, and 150C and p = 1080 MPa are listed in the table. Sampling the liquid phase from the vessel bottom at t = 25C and p = 60 and 80 MPa and at t = 50C and p = 80 MPa was difficult, because the carbon dioxide was denser than water. The density of the carbon dioxide was calculated by Altunins equation of state [4]. Our solubility data agree within 7% with the solubility data reported by King et al. [5] for t = 25C and p = 10 and 20 MPa. However, we collected solubility data in much wider ranges of temperature and pressure, including the region where the solubility of gases in liquids is most difcult to predict. At a given temperature, the solubility of the uid in the liquid grows steadily with increasing pressure. At the same time, the way the solubility varies with temperature depends strongly on the pressure. This dependence can apparently be explained by the fact that, at p = 40, 60, and 80 MPa, the densities of CO2 and water are similar in the temperature range examined. In this work, we describe the binary solubility of subcritical and supercritical carbon dioxide by the entropy method of similarity theory [6], which was used earlier [7] to generalize data on the binary solubility of various liquids in supercritical carbon dioxide. Solubility is an equilibrium property by denition. Solutions of low-volatile substances in subcritical and supercritical uids, as well as solutions of supercritical uids in low-volatile solvents, are innitely dilute. Therefore, the state of such a system can be fairly exactly described using the thermodynamic parameters and functions of state of the pure solvent. Accordingly, we propose writing the right-hand side of the similarity equation (1) (see below) in terms of the entropy change for the pure solvent. The driving force of the transfer of a component from one phase to the other is the difference between the chemical potentials of the component
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THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING

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in these phases. The transferred substance dilutes the solvent and changes its chemical potential. Therefore, the driving force of substance dissolution in the liquid supercritical uid system can be estimated indirectly from the change in the chemical potential of the pure solvent upon the transition of the system from one equilibrium state to another. While the generalized force of dissolution is the chemical potential (or the difference between its current and standard values), the generalized coordinate characterizing the extent of the process is the amount of substance dissolved. As the generalized coordinate of the process in question, we consider the solute mole fraction (counted from zero). The generalized force multiplied by the change in the generalized coordinate is known to be the generalized work done in the process. In the system under consideration, work is done by the solvent, which accommodates the molecules of the solute in its free volume. The similarity equation for dissolution appears as S 1 S 2 y - , ------------------- = -------------- R y S S (1)

70

50

30 1 2 3 4 5 3 2 1 (S1 S2)/R 0

10

10 4

Fig. 2. Solubility of subcritical and supercritical carbon dioxide in water at p = (1) 10, (2) 20, (3) 40, (4) 60, and (5) 80 MPa.

where y and yS are the mean solubility values corresponding to the solvent entropy change from S1 to S2 and to the scaling entropy change S of the solvent, respectively, and and S are the chemical potential changes of the solvent for the entropy change (S2 S1) and the scaling entropy change S. The ratio y/yS is the relative change in the generalized coordinate, and the ratio /S characterizes the relative change in the generalized force. The product of these quantities denes the generalized work done in the process. This work and, accordingly, the nal form of Eq. (1), depend on the process path. Therefore, it should be specied for which process path generalization is done. Most of the available experimental solubility data refer to the isotherm, which is the most convenient process path. Figure 2 generalizes our water solubility data for subcritical and supercritical carbon dioxide in wide ranges of state parameters. Evidently, the water solubility of supercritical CO2 in wide ranges of temperature and pressure obeys the equation =

ity theory. In view of earlier data [7], the results of this study suggest that the mutual solubility of the components in a liquidsupercritical uid system can be described by a general similarity equation. REFERENCES
1. Bartle, K.D., Clifford, A.A., Jafar, S.A., and Shilstone, G.F., Solubilities of Solids and Liquids of Low Volatility in Supercritical Carbon Dioxide, J. Phys. Chem. Ref. Data, 1991, vol. 20, no. 4, p. 713. 2. Bartle, K.D., Clifford, A.A., and Shilstone, G.F., Estimation of Solubilities in Supercritical Carbon Dioxide: A Correlation for the PengRobinson Interaction Parameters, J. Supercrit. Fluids, 1992, no. 5, p. 220. 3. Walas, S.M., Phase Equilibria in Chemical Engineering, London: Butterworth, 1985. 4. Altunin, V.V., Teplozicheskie svoistva dvuokisi ugleroda (Thermal Properties of Carbon Dioxide), Moscow: Izd. Standartov, 1975. 5. King, M.B., Mubarak, A., Kim, J.D., and Bott, T.R., The Mutual Solubilities of Water with Supercritical and Liquid Carbon Dioxide, J. Supercrit. Fluids, 1992, no. 5, p. 296. 6. Usmanov, A.G., Teploperedacha i teplovoe modelirovanie (Heat Transfer and Thermal Modeling), Moscow: Akad. Nauk SSSR, 1959. 7. Sabirzyanov, A.N. and Gumerov, F.M., Generalizing Binary Solubility Data for Low-Volatile Liquids in Supercritical Fluids, Teor. Osn. Khim. Tekhnol., 2001, vol. 35, no. 2, p. 138. 8. Kestin, I. and Sengers, J.V., New International Formulation for the Thermodynamic Properties of Light and Heavy Water, J. Phys. Chem. Ref. Data, 1986, vol. 15, p. 305.
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j=0

S1 S2 j - , a j --------------R

(2)

with a0 = 0.188, a1 = 6.975, a2 = 2.478, and a3 = 2.297. The chemical potential and entropy of water are calculated by the equation of state suggested in [8]. Thus, we obtained new experimental solubility data for subcritical and supercritical carbon dioxide in water. We explored the region of state parameters in which it is most difcult to describe the dissolution of compressed gases in liquids. The experimental data were generalized using the entropy method of similar-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING