Henry’s law constants and infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol, and 3-pentanol
Introduction
A systematic study of gas solubilities including the Henry’s law 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 in developing prediction methods. Especially for group contribution methods, it may be necessary to take into account the differences between isomers.
To estimate the gas solubility from a molecular theory or molecular simulation, on the other hand, an accurate intermolecular potential is necessary. The Henry’s law 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 law 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 liquid solutes in nonvolatile solvents. In previous work [2], [3], [4], [5], [6], the Henry’s law constants for propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in methanol, propanols and butanols were measured with this method. For these highly volatile solutes and solvents, a rigorous expression had been derived for data reduction [2].
In this work, the Henry’s law constants for propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol, and 3-pentanol are measured by the gas stripping method, and the infinite dilution activity coefficients of solutes are evaluated.
Section snippets
Theory
The gas stripping method, originally proposed by Leroi et al. [1], is based on the variation of the vapor-phase composition when the highly diluted solute in a liquid mixture in an equilibrium cell is stripped from the solution by the flow of inert gas (helium). The composition of the gas leaving the cell is periodically sampled and analyzed by gas chromatography (g.c.). The g.c. signal area, S, of the solute decreases exponentially with the volume of inert gas flowing out of the cell by the
Experimental
Details of the experimental apparatus were presented in our earlier paper [2], [5]. About 36 cm3 of the solvent (pentanols) was introduced into the equilibrium cell (volume ≈ 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 to within ±0.02 K and measured with a quartz thermometer (Hewlett–Packard Co., Model 2804A)
Results and discussion
The Henry’s law constants and the infinite dilution activity coefficients measured in this work are numerically indicated in TABLE 1, TABLE 2, TABLE 3 for the 1-pentanol, 2-pentanol, and 3-pentanol systems, respectively. Because all experiments were conducted under atmospheric pressure, the estimated fugacity coefficients of the solute in the vapor phase and the compressibility factors of the vapor were around unity (, Z = 1) for all systems. However, for the evaluation of the infinite
Conclusions
Henry’s law constants and the infinite dilution activity coefficients of eight gases in 1-pentanol, 2-pentanol in the temperature range of (250 to 330) K and 3-pentanol in the temperature range of (260 to 330) K have been obtained from gas stripping measurements. The Henry’s law constant did not depend on the nonideality of the vapor for the systems studied in this work. On the other hand, the nonideality of the solute at the reference state should be considered in order to obtain infinite
Acknowledgement
This paper reports part of the work supported by a Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (16560663), which is gratefully acknowledged.
References (8)
- et al.
Fluid Phase Equilibr.
(2003) J. Chem. Thermodyn.
(2004)J. Chem. Thermodyn.
(2004)- et al.
Ind. Eng. Chem., Process Des. Dev.
(1977)
Cited by (13)
Below the room temperature measurements of solubilities in ester absorbents for CO<inf>2</inf> capture
2018, Journal of Chemical ThermodynamicsPrediction of limiting activity coefficients for binary vapor-liquid equilibrium using neural networks
2017, Fluid Phase EquilibriaCitation Excerpt :5). These data include experimental published data on the IDAC of binary systems from different literature [1,28,31–50]. The data set used in the development of the neural model contains aqueous systems and both hydrocarbon and non-hydrocarbon compounds of various types including alcohols, amines, ketones, carboxylic acids, aldehydes, esters, ethers, nitriles and halogenated hydrocarbons in solute and solvent categories as well.
Accurate pre-calculation of limiting activity coefficients by COSMO-RS with molecular-class based parameterization
2013, Fluid Phase EquilibriaCitation Excerpt :The present work is, therefore, concerned with molecular-class based parameterization of COSMO-RS for a small industrially relevant selection of molecules. The molecular class selected is a subset of the data set investigated in earlier work for calculation of Henry coefficients [8], which represents a compilation from experimental studies [9–12]. It covers the limiting activity coefficients for typically six different temperatures of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene and 1,3-butadiene in, respectively, 2-propen-1-ol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol and 2-methyl-2-butanol, as well as propane, propene and trans-2-butene in methanol, and dimethyl ether in 2-propen-1-ol.
Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol
2006, Journal of Chemical ThermodynamicsGeneralized molecular solvation in non-aqueous solutions by a single parameter implicit solvation scheme
2019, Journal of Chemical PhysicsAbraham model enthalpy of solvation correlations for solutes dissolved in 1-alkanol solvents (C<inf>4</inf>–C<inf>6</inf>)
2015, Physics and Chemistry of Liquids