Henry's law constants of 1-butene, 2-methylpropene, trans-2-butene, and 1,3-butadiene in methanol at 374–490 K
Introduction
The study of gas solubilities is useful in providing design data for absorption processes, as well as, indirectly, in aiding the analysis of molecular interactions in solutions. For practical use, much attention has been given to the thermodynamic properties near the critical point of mixtures. High temperature data are rarely available and are difficult to measure. Hayduk and Buckley [1] observed that all gas solubilities in a solvent tend towards a common value as the solvent critical temperature is approached. Beutier and Renon [2] and Schotte [3] showed that this is due to the thermodynamic relationship for the solute (g) at the solvent (s) critical pointwhere Hg is the Henry's law constant of the solute, the fugacity coefficients of the solute in the vapor phase, Pc,s the critical pressure of the solvent and Tc,s the critical temperature of the solvent, and T is the absolute temperature.
Oxygenates such as ethers and alcohols have been used widely as fuel additives to increase the octane number, improve the combustion process, and reduce emissions, and solubility data of gases in alcohols are needed in the design of these production facilities.
To develop a molecular theory, on the other hand, an accurate intermolecular potential is necessary. Henry's law constant is directly related to the residual chemical potential of the solute at infinite dilution that is evaluated from the intermolecular potential between a solute molecule and a solvent molecule. Therefore Henry's law constant is a suitable macroscopic property for correlating the intermolecular potential between different kinds of molecules.
The gas stripping method that was originally proposed by Leroi et al. [4] is usually used to measure the activity coefficients at infinite dilution of solutes in nonvolatile solvents, when the total pressures are negligibly small.
In the previous paper [5], [6], Henry's law constants of carbon dioxide, propane, propene, butane, and 2-methylpropane in methanol at temperatures up to the critical temperature of methanol were measured by the similar method to the gas stripping method. An interesting phenomenon was observed that the plot of the infinite dilution activity coefficients of the solutes versus temperature tended towards a common value as the solvent critical temperature was approached. In this work, to support this interesting phenomenon and to compare the difference between alkanes and alkenes in the solubility phenomena, the Henry's law constants of 1-butene, 2-methylpropene, trans-2-butene, and 1,3-butadiene in methanol at high temperatures and high pressures are measured by the same method and the activity coefficients and the fugacity coefficients of the solute at infinite dilution are evaluated from these experimental data.
In the literatures, we have found the following experimental data of the mixtures studied in this work. The Henry's law constants in methanol were measured for trans-2-butene and 1,3-butadiene at 255–320 K by Miyano and Fukuchi [7], and for 1-butene and 2-methylpropene at 255–320 K by Miyano et al. [8]. The gas solubilities in methanol at 298.15 K and pressures less than 102 kPa were measured for 2-methylpropene by Miyano and Nakanishi [9], and for 1-butene by Miyano and Nakanishi [10]. The vapor–liquid equilibria were measured for 1,3-butadiene + methanol system at 323.15 K by Churkin et al. [11], 1-butene + methanol system at 326 K by Laakkonen et al. [12], trans-2-butene + methanol system at 332 K by Zaytseva et al. [13], and 2-methylpropene + methanol system at 323.15 by Ouni et al. [14]. At higher temperatures than 340 K, no data are available in the literature.
Section snippets
Experimental
The gas stripping method originally proposed by Leroi et al. [4] is based on the variation of vapor phase composition when the highly diluted solute in a liquid mixture in an equilibrium cell is stripped from the solution by a flow of inert gas (helium). The composition of the gas leaving the cell is periodically sampled and analyzed by means of gas chromatography. The peak area, S, of the solute decreases exponentially with the volume of inert gas flowing out of the cell. This rigorous
Results and discussion
As indicated in Eq. (3), can be obtained directly from this experiment. Fig. 1 shows the temperature dependencies of of 1-butene, 2-methylpropene, trans-2-butene, and 1,3-butadiene in methanol in the temperature range of 250–490 K. As shown in this figure, the values of obtained in this work are smoothly combined with those obtained by using the gas stripping method at lower temperatures [7], [8]. The smoothed lines are the calculated results from the Soave equation of state
Conclusion
Henry's law constants for 1-butene, 2-methylpropene, trans-2-butene, and 1,3-butadiene in the methanol divided by the fugacity coefficient, , have been directly measured by the similar experimental apparatus to the gas stripping method in a very wide temperature range of 374–490 K. The value of increases with the temperature, goes through a maximum around at 470 K, and approaches the critical point of the solvent with a slope of −∞. The Henry's law constants of gases in methanol
Acknowledgements
This paper reports part of the work supported by Grant-in-Aid for Scientific Research from Japan Society for the Promotion of Science (16560663), which is gratefully acknowledged.
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