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Heterogeneous phase behavior of solid carbon dioxide in light hydrocarbons at cryogenic temperatures
Author(s) -
Jensen Robert H.,
Kurata Fred
Publication year - 1971
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690170223
Subject(s) - methane , solubility , eutectic system , carbon dioxide , chemistry , propane , butane , ternary operation , hydrocarbon , thermodynamics , mole fraction , ternary numeral system , phase (matter) , inorganic chemistry , organic chemistry , catalysis , physics , alloy , computer science , programming language
Solubilities of solid carbon dioxide in liquid ethane, propane, and n‐butane were measured from the hydrocarbon triple point or mixture eutectic point to the triple point of carbon dioxide, and an experimental uncertainty was determined for each data point. A eutectic point was discovered in the carbon dioxide– n ‐butane system at approximately 134°K., with a eutectic composition of approximately 0.25 mole % carbon dioxide. A nonlinear least squares analysis was used to fit the binary solubility data and carbon dioxide‐methane data from the literature to the Wilson equation for the liquid‐phase carbon dioxide activity coefficient. Better agreement with experimental data was obtained by adding two empirical constants to the Wilson equation. This study shows that the Wilson equation is an excellent model for solid carbon dioxide solubility in liquid methane, ethane, propane, and n ‐butane, over the entire composition range, and that the Wilson equation provides a better model than do corrections based on regular solution theory. The ternary system carbon dioxide‐methane‐ethane was also studied, and liquid and vapor compositions were measured for each of ten ternary mixtures in solid‐liquid‐vapor equilibrium. Ternary phase diagrams were constructed, and an empirical correlation was derived for solid carbon dioxide solubility in methane‐ethane mixtures above 166°K. An important finding was that solid carbon dioxide is more soluble in some mixtures of methane and ethane than in either of the pure components.