Abstract
The phase equilibrium CO2(g)=CO2(aq) and the aqueous reactions CO 2−3 +H+=HCO −3 , HCO −3 +H+=CO2(aq)+H2O, and Na++CO 2−3 =NaCO −3 were studied from 225 to 325°C using a flow calorimetric technique. Heats of mixing of gaseous CO2 with liquid H2O and with aqueous NaOH solutions were measured at these temperatures. Log K, ΔH, ΔS, and ΔCp values were determined for these reactions from the heat of mixing data. Equations for these thermodynamic quantities valid at infinite dilution (I=0) and 12.4 MPa are given as a function of temperature from 225 to 325°C. The log K and ΔH values agree well with literature values at these temperatures for the first and third reactions, but not for the second reaction. No previous results have been reported for the fourth reaction at high temperatures. The isocoulombic reaction principle is tested using the log K values determined in this study. This principle is found to be valid for the reactions where each charge on one side of the equation is balanced on the other side by a charge of the same sign and magnitude, but not for the reaction where two single negative charges (HCO −3 and OH−) are balanced by one double negative charge (CO 2−3 ).
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
X. Chen, S. E. Gillespie, J. L. Oscarson, and R. M. Izatt,J. Solution Chem. (in press).
A. J. Ellis,Am. J. Sci. 257, 217 (1959).
A. J. Ellis,Am. J. Sci. 257, 287 (1959).
A. J. Ellis and R. M. Golding,Am. J. Sci. 261, 47 (1963).
I. L. Khodakovskiy, B. N. Ryzhenko, and G. B. Naumov,Geochem. Int. 5, 1200 (1968).
V. B. Naumov, A. Kh. Khakimov, and I. L. Khodakovskiy,Geochem. Int. 11, 31 (1974).
R. C. Murray, Jr. and J. W. Cobble, inProceedings of the 41 st International Water Conference (Pittsburgh, Pennsylvania, 1980).
D. M. Mason and R. Kao, inThermodynamics of Aqueous Systems with Industrial Applications, ACS Symposium Series No. 133, S. A. Newman, ed., (American Chemical Society, Washington, D.C., 1980).
H. C. Helgeson,Am. J. Sci. 267, 729 (1969).
L. N. Plummer and E. Busenberg,Geochim. Cosmochim. Acta 46, 1011 (1982).
T. J. Morrison and F. Billett,J. Chem. Soc. 3819 (1952).
R. F. Weiss,Mar. Chem. 2, 203 (1974).
G. Houghton, A. M. Mclean, and P. D. Ritchie,Chem. Eng. Sci. 6, 132 (1957).
S. D. Malinin,Geochemistry 292 (1959).
B. N. Ryzhenko,Geochemistry 463 (1963).
C. S. Patterson, R. H. Busey, and R. E. Mesmer,J. Solution Chem. 13, 647 (1984).
A. J. Read,J. Solution Chem. 4, 53 (1975).
C. S. Patterson, G. H. Slocum, R. H. Busey, and R. E. Mesmer,Geochim. Cosmochim. Acta 46, 1653 (1982).
H. C. Helgeson,J. Phys. Chem. 71, 3121 (1967).
S. Arnorsson and S. Sigurdsson,Geochim. Cosmochim. Acta 46, 1513 (1982).
J. A. Barbero, L. G. Hepler, K. G. McCurdy, and P. R. Tremaine,Can. J. Chem. 61, 2509 (1983).
R. S. Smith, C. J. Popp, and D. I. Norman,Geochim. Cosmochim. Acta 50, 137 (1986).
B. N. Ryzhenko and O. V. Bryzgalin,Geochem. Int. 24, 122 (1987).
R. M. Garrels, M. E. Thompson, and E. Siever,Am. J. Sci. 259, 24 (1961).
R. M. Garrels and M. E. Thompson,Am. J. Sci. 260, 57 (1962).
J. N. Butler and R. Huston,J. Phys. Chem. 74, 2976 (1970).
R. M. Pytkowicz and J. E. Hawley,Limnol. Oceanogr. 19, 223 (1974).
M. Whitfield,Limnol. Oceanogr. 19, 235 (1974).
C. P. Kerr, inThermodynamics of Aqueous Systems with Industrial Applications, ACS Symposium Series No. 133, S. A. Newman, ed., (American Chemical Society, Washington, D.C., 1980).
A. H. Truesdell and B. F. Jones,J. Res. U. S. Geol. Surv. 2, 233 (1974).
J. I. Bischoff and W. E. Seyfried,Am. J. Sci. 278, 838 (1978).
N. I. Khitarov, B. N. Ryzhenko, and E. B. Lebedev,Geochemistry 42 (1963).
R. M. Garrels and C. H. Crist,Solutions, Minerals, and Equilibria (Harper and Row, New York, 1965).
L. Haar, J. S. Gallagher, and G. S. Kell,NBS/NRC STEAM TABLES: Thermodynamic and Transport Properties and Computer Programs for Vapor and Liquid States of Water in SI Units (Hemisphere, Washington, 1984).
C. A. Meyer, R. B. McClintock, G. J. Silvestri, and R. C. Spencer, Jr.,ASME Steam Tables: Thermodynamic and Transport Properties of Steam, 5th edn., (The American Society of Mechanical Engineers, New York, 1983).
J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore,Steam Tables (Wiley, New York, 1969).
A. Saul and W. Wagner,J. Phys. Chem. Ref. Data 18, 1537 (1989).
P. G. Hill,J. Phys. Chem. Ref. Data 19, 1231 (1990).
W. T. Lindsay, Jr., inProceedings of the 41 st International Water Conference (Pittsburgh, Pennsylvania, 1980).
W. T. Lindsay, Jr., inThe ASME Handbook on Water Technology for Thermal Power Systems, P. Cohen, ed., (The American Society of Mechanical Engineers, New York, 1989) Chap. 7.
J. M. Simonson and R. J. Ryther,J. Chem. Eng. Data 34, 57 (1989).
J. L. Oscarson, X. Chen, S. E. Gillespie, and R. M. Izatt,Thermochim. Acta 185, 51 (1991).
X. Chen, Ph.D. Dissertation, Brigham Young University (Provo, Utah, 1991).
R. M. Izatt, J. L. Oscarson, X. Chen, and S. E. Gillespie,Determination of Thermodynamic Data for Modeling Corrosion. Volume 3: CO 2 −NaOH−H 2 O System, EPRI Report NP-5708 (Electric Power Research Institute, Palo Alto, California, 1992).
R. Nakamura, G. J. F. Breedveld, and J. M. Prausnitz,Ind. Eng. Chem. Process Des. Dev. 15, 557 (1976).
A. R. Parkinson, R. J. Balling, and J. C. Free, inProceedings ASME Int. Computers in Eng. Conf. (Las Vegas, Nevada, 1984).
J. W. Cobble, private communication.
Author information
Authors and Affiliations
Additional information
Taken in part from the Ph.D. Dissertation of X. Chen, Brigham Young University, 1991.
Rights and permissions
About this article
Cite this article
Xuemin Chen, Gillespie, S.E., Oscarson, J.L. et al. Calorimetric determination of thermodynamic quantities for chemical reactions in the system CO2−NaOH−H2O from 225 to 325°C. J Solution Chem 21, 825–848 (1992). https://doi.org/10.1007/BF00651511
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00651511