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Filipe Hobi Bordon Sosa, Fabiane Oliveira Farias, Marcos Rogério Mafra
Filipe Hobi Bordon Sosa, Fabiane Oliveira Farias, Marcos Rogério Mafra
ABSTRACT
Liquid–liquid equilibrium (LLE) data used in this work were previously obtained by our group research. The quaternary systems were composed to cholinium chloride: glucose +
poly(propylene)glycol (400 gmol-1) + H2O at 298.15 K. The Non-Random Two-Liquid (NRTL) model have been used to fit the DES-based aqueous two-phase systems. The interaction
parameters of the models were estimated. The liquid−liquid equilibrium (LLE) experimental data were well correlated to the activity coefficients of the NRTL model, and the mean
deviations was less than 1,1%.
FIGURE 1 –Three-dimensional phase diagram and respective experimental and correlated tie-lines
1. INTRODUCTION
Deep eutectic solvents (DES) are a kind of green solvents formed by the association of a
hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD), which have been
used as phase forming components of aqueous two phase systems (ATPS) with the main
purpose of extract biomolecules. Passos et al. [1] and Farias et al. [2] evaluated the DES
stability in ATPS and both works proved that the DES complex (between the HBA and
HBD) are disrupted due to the high-water content present at the ATPSs, and
consequently these systems are actually quaternary systems.
Considering the lack of results about thermodynamics modeling in the quaternary
systems, or DES-based ATPS, in this work, the experimental data published in a
previous study [3], were correlated with the NRTL model for the activity coefficient,
with estimation of new interaction parameters of quaternary systems.
2. Materials and Methods TABLE 1 - NRTL FITTED PARAMETERS OF QUATERNARY SYSTEM COMPOSED BY CHOLINIUM CHLORIDE (HBA)
2.1 Experimental + GLUCOSE (HBD) + PPG + WATER AT 298.15 K AND ATMOSPHERIC PRESSURE.
The experimental data used in this work were previously obtained by the group and HBA:HBD molar ratio Parameters (i – j) A(0)ij A(0)ji Alfa(0)ij or ji RMSD %
have already been published by Farias et al. [3]. The systems evaluated were composed Cholinium Chloride – Glucose -8927.6 7949.8 0.2000
Cholinium Chloride – PPG 7154.1 575.5 0.2003
to cholinium chloride: glucose + poly(propylene)glycol (400 gmol-1) + H2O at 298 K. Cholinium Chloride – Water -1011.1 -9000.0 0.3425
2:1 1.1
Glucose – PPG 1735.6 -2805.3 0.2517
Three different molar ration cholinium chloride: glucose, 2:1, 1:1 and 1:2, were
Glucose – Water -64.1 -5146.7 0.2429
evaluated. PPG - Water -856.9 2002.7 0.2000
2.2 Parameter estimation Cholinium Chloride – Glucose -9000.0 7511.2 0.2122
Cholinium Chloride – PPG 8730.8 567.2 0.2260
The estimation of the model parameters followed the procedure described by Cholinium Chloride – Water -1100.5 -8973.5 0.4378
1:1 Glucose – PPG 1983.3 -2582.8 0.2000
0.9
Stragevitch and d’Ávila (1997) [4]. The procedure consists of the minimization of an
Glucose – Water -63.5 -5083.7 0.2947
objective function using the simplex method [5] and several direct calculations of the PPG - Water -858.3 1947.1 0.2123
Cholinium Chloride – Glucose -8192.2 509.0 0.2122
equilibrium curve. Cholinium Chloride – PPG 3491.9 1456.3 0.2260
2 2
𝐷 𝑀 𝑁−1 𝐼.𝑒𝑥𝑝 𝐼.𝑐𝑎𝑙𝑐 𝐼𝐼.𝑒𝑥𝑝 𝐼𝐼.𝑐𝑎𝑙𝑐
OF= σ𝑘 σ𝑗 σ𝑖 𝑥𝑖𝑗𝑘 − 𝑥𝑖𝑗𝑘 + 𝑥𝑖𝑗𝑘 − 𝑥𝑖𝑗𝑘 Cholinium Chloride - Water 97.3 -558.9 0.4035
1:2 Glucose – PPG 1171.8 -6178.5 0.2000
1.1
Glucose – Water -1705.8 -2911.4 0.2947
With the set parameters, comparisons between the compositions calculated and PPG - Water -874.3 1896.7 0.2121
experimental of the two phases system were made through the deviation (RMSD – root
4.CONCLUSION
mean square deviation), given by equation: The NRTL model was used to correlate the equilibrium results for the quaternary system
2 2
𝑀 𝑁 𝐼.𝑒𝑥𝑝 𝐼.𝑐𝑎𝑙𝑐 𝐼𝐼.𝑒𝑥𝑝 𝐼𝐼.𝑐𝑎𝑙𝑐 to determine the activity coefficient. A good correlation between the models and the
σ𝑖 σ𝑗 𝑥𝑖𝑗 − 𝑥𝑖𝑗 + 𝑥𝑖𝑗 − 𝑥𝑖𝑗
𝛿𝑥 = 100.
2𝑀𝑁 experimental data was observed. The binary interaction parameters obtained in this
work can be used in project, simulation and operation of aqueous two-phase extraction
3. RESULTS AND DISCUSSION
processes biochemical industry.
One can see in Table 1 a satisfactory representation of liquid–liquid equilibrium of 5. REFERENCES
[1] Passos, H., Tavares, D. J. P., Ferreira, A. M., Freire, M. G, Coutinho, J. A. P. ACS Sustainable Chemistry &
quaternary system composed by Cholinium chloride (HBA) + Glucose (HBD) + PPG + H2O Engineering 4 (2016) 2881–2886.
[2] Farias, F. O.,, S.G., Sosa, F. H. B., Igarashi-Mafra, L., Coutinho, J. A. P., Mafra, M. R. Fluid Phase Equilibria 448 (2017) 143-151.
was obtained by all molar ratios of HBA: HDB. The NRTL models were able to represent [3] Farias, F. O., Passos, H., Lima, A. S., Mafra, M. R., Coutinho, J. A. P. ACS Sustainable Chemistry & Engineering 5 (2017) 9402-9411.
[4] Stragevitch, L., D’ÁvilaBrazil4ian J. Chem. Eng. 14 (1997).
the phase split over the entire range of compositions analyzed. The mean deviations [5]Nelder, J.A., Mead, R. Comput. J. 7 (1965) 308–313.