Liquid–liquid equilibria measurements of ternary systems (acetonitrile + a carboxylic acid + dodecane) at 303.15 K
Introduction
In the chemical industries liquid–liquid extraction plays an important and cost effective role as a separation process [1]. Liquid–liquid equilibrium (LLE) data are important for a proper understanding the properties of the multicomponent systems as well as the design of the efficient separation processes [2]. The separation of carboxylic acids from hydrocarbons is of importance in the Fischer–Tropsch process [3]. Acetonitrile, a relatively inert and inexpensive solvent has been reported in the literature [4] as a good solvent for the separation of carboxylic acids from hydrocarbons [5]. The separation or the removal of organic residues from waste streams released from industries has been important from both points of view (i) pollution control and (ii) recovery of useful materials. The disposal of waste waters containing most widely used industrial organic acids such as acetic acid, propanoic acid has been recognized as a significant expense to the industry and environment [6].
In this regard, the new LLE data for (acetonitrile + acetic or propanoic or butanoic or 2-methylpropanoic or pentanoic or 3-methylbutanoic acid + dodecane) at 303.15 K were measured. The binodal curve data have been summarized using the modified Hlavatý [7] equation, a β function and a log γ equation using methods previously described by Letcher et al. [8]. The tie-line data were correlated using the NRTL model [9] and the UNIQUAC model [10].
Liquid–liquid equilibrium (LLE) data on a number of ternary mixtures containing acetonitrile have been reported in the literature: (acetonitrile + acetic acid or propanoic acid or butanoic acid or 2-methylpropanoic acid or pentanoic acid or 3-methylbutanoic acid + cyclohexane or heptane) at 298.15 K by Letcher and Redhi [5], but to the best of our knowledge there is no data reported in open literature on the systems investigated in this work. The present work is a part of our comprehensive investigation on liquid–liquid equilibrium (LLE) data of ternary mixtures containing organic solvents which are useful in the chemical industry [5], [8].
Section snippets
Chemicals
The carboxylic acids, namely acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid as well as dodecane were obtained from Fluka Chemicals, with mole fraction purities of ≥0.99. Acetonitrile was purchased from HiperSolv, had a mole fraction purity of ≥0.99. The acids were stored under 0.4 nm molecular sieves to avoid the absorption of moisture. Pure component specifications: suppliers, specified purity and GC purity are given in Table 1. The
Results and discussion
In this work the experimental LLE data for six ternary systems of {acetonitrile (1) + acetic or propanoic or butanoic or 2-methylpropanoic or pentanoic or 3-methylbutanoic acid (2) + dodecane (3)} at 303.15 K were measured. The compositions of the mixtures on the binodal curve are given in Table 3, the tie-lines in Table 1S and these compositions are plotted in Fig. 1(a–f).
Similar liquid–liquid equilibria data of ternary systems have been reported in the literature (acetonitrile + a carboxylic acid +
LLE data correlation
For a ternary liquid mixture with only one pair of immiscible liquids, the use of Hlavatý [7] has been until recently the only successful method in fitting an equation to the binodal curve. Three equations have been fitted to the ternary data for each system following the work of Hlavatý [7]. The coefficient Ai relate to a modified Hlavatý equation:
The coefficient Bi relate to β function equation:
The coefficient Ci, relate to the log γ equation:
Conclusion
Liquid–liquid equilibrium data for the six ternary systems of {acetonitrile (1) + acetic acid (or propanoic acid or butanoic acid or 2-methylpropanoic or pentanoic acid or 3-methylbutanoic acid) (2) + dodecane (3)} were determined at 303.15 K. The separation of acetic acid, propanoic acid or butanoic acid or 2-methylpropanoic or pentanoic acid or 3-methylbutanoic acid) from dodecane is feasible by extraction with acetonitrile, as can be concluded from the selectivity values. The calculation based on
Acknowledgements
The authors acknowledge funding from Department of Science, Technology and the National Research Foundation (DST/NRF) and Durban University of Technology South Africa for financial support.
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