THERMODYNAMIC MODELING OF PSEUDOTERNARY AQUEOUS TWO PHASES SYSTEMS

WITH DEEP EUTECTIC SOLVENTS

Filipe Hobi Bordon Sosa1*, Fabiane Oliveira Farias2,Marcos Rogério Mafra2
1- LEF, Departamento de Desenvolvimento de Processos e Produtos – Faculdade de Engenharia Química -
Universidade Estadual de Campinas (UNICAMP), Campinas, São Paulo, Brazil
2 - Departamento de Engenharia Química – Universidade Federal do Paraná (UFPR), Curitiba, Paraná, Brazil
*Corresponding Author: filipehobi@yahoo.com.br

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.

were found to be < 1,1 %. 6. ACKNOWLEDGEMENTS

Thus, the NRTL model is well-fitted with the experimental data indicating its feasibility
for describing the behavior of other equilibrium systems.