Henry’s constants and infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in isobutanol and tert-butanol

doi:10.1016/j.jct.2004.05.010

The Journal of Chemical Thermodynamics

Volume 36, Issue 10, October 2004, Pages 865-869

https://doi.org/10.1016/j.jct.2004.05.010 Get rights and content

Abstract

The Henry’s constants and the infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene and 1,3-butadiene in isobutanol at T = (250 to 330) K and tert-butanol at T = (300 to 330) K are measured by a gas stripping method. The rigorous formula for evaluating the Henry’s constants from the gas stripping measurements is used for data reduction of these highly volatile mixtures. The accuracy of the measurements is about 2% for Henry’s constants and 3% for the estimated infinite dilution activity coefficients. In the evaluations for the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and the Pointing correction is not negligible, especially at higher temperatures, and the estimation uncertainty in the infinite dilution activity coefficients includes 1% for nonideality.

Introduction

A systematic study of gas solubilities such as the Henry’s constant, is useful in providing design data for absorption processes as well as, indirectly, in aiding the analysis of molecular interactions in solutions.

Although a large number of {alkane + alcohol} and {alkene + alcohol} solubility data have been published, few data are available for C4-gases such as butane, 1-butene and their isomers. The solubility data will be useful to develop prediction methods. Especially for group contribution methods, it may be necessary to take into account the differences between isomers. To develop molecular theory, on the other hand, an accurate intermolecular potential is necessary. The Henry’s constant is directly related to the residual chemical potential of the solute at infinite dilution, which is evaluated from the intermolecular potential between a solute molecule and a solvent molecule. Therefore, the Henry’s constant is a suitable macroscopic property for testing the intermolecular potential between different kinds of molecules.

The gas stripping method, proposed by Leroi et al. [1], has been used to measure the activity coefficients at infinite dilution of solutes in nonvolatile solvents, when the vapor pressures of solutes were negligibly small. In previous work [2], [3], [4], [5], the Henry’s constants of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in methanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol were measured with this method. For these highly volatile solutes and solvents, rigorous expression was derived for data reduction.

In this work, Henry’s constants of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in isobutanol and tert-butanol are measured by the gas stripping method.

Section snippets

Theory

The gas stripping method, originally proposed by Leroi et al. [1], is based on the variation of vapor phase composition when the highly diluted solute of the 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 gas chromatography. The peak area, S, of the solute decreases exponentially with the volume of inert gas flowing out from the cell, and this relationship

Experimental

Details of the experimental apparatus were presented in our earlier paper [2], [5]. About 36 cm³ of the solvent (isobutanol or tert-butanol) was introduced into the equilibrium cell, of volume about 40 cm³, and the accurate quantity was determined by mass. Then the equilibrium cell was immersed in a constant-temperature bath (filled with ethylene glycol + water) and connected to a supply of helium. The temperature was controlled within ±0.02 K, and measured with a quartz thermometer

Results and discussion

The Henry’s constants and the infinite dilution activity coefficients measured in this work are numerically indicated in TABLE 1, TABLE 2 for isobutanol and tert-butanol (normal freezing point = 298.8 K) systems, respectively. As all experiments were obtained under atmospheric pressure, the estimated fugacity coefficients of the solute in the vapor phase and the compressibility factors of the vapor were around to be unity ( $ϕ_{g}^{V} = 1$ , Z = 1) for all systems. On the other hand, for evaluation of the

Conclusion

The Henry’s constants and the infinite dilution activity coefficients of eight gases in isobutanol at T = (250 to 330) K and tert-butanol at T = (300 to 330) K have been obtained from gas stripping measurements. The Henry’s constant did not depend on the nonideality of the solute and the solvent for the systems studied in this work. The activity coefficients, on the other hand, strongly depended on the nonideality of the solute at the reference state.

The accuracy of the Henry’s constants measured

Acknowledgement

This paper reports part of the work supported by a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (16560663), which is gratefully acknowledged.

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