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Supporting Information: Salt Eect on -Based Aqueous Biphasic Systems Applied to Alkaloids Partition: An Experimental and Theoretical Approach

Mateus Oltramari Toledo1, Fabiane Oliveira Farias1, Luciana Igarashi Mafra1, Marcos R. Mafra1∗

1Department of Chemical Engineering, Federal University of Paraná (UFPR), Polytechnic Center, 81531-990, Curitiba-PR, Brazil.

∗Corresponding Author: Marcos R. Mafra, Dr. Federal University of Paraná Jardim das Américas, 81531-990 Curitiba, PR, Brazil Telephone: +55-41-3361-3586 E-mail: [email protected] (institutional) 2

Table S1: Experimental binodal weight fraction data for the systems composed † of ethanol (we) + NaH2PO4 (ws) + water at 298.15 K and 91 kPa .

100ws 100we 100ws 100we 1.8 48.5 13.8 22.5 2.3 45.9 14.9 21.4 3.0 43.4 15.8 20.7 3.4 40.8 17.0 19.1 4.2 38.7 18.0 18.5 5.1 36.6 19.4 17.3 5.9 34.5 20.9 15.9 6.4 33.3 22.4 14.8 7.2 31.9 24.5 13.0 7.8 30.7 26.6 11.7 8.8 29.2 29.6 9.6 9.8 27.9 32.5 7.8 10.7 26.7 35.7 6.3 11.4 25.8 39.8 4.6 12.0 24.6 43.9 3.6 13.1 23.1 † Standard uncertainties u are u(w) = 0.001, u(T ) = 0.2 K, and u(P ) = 10 kPa. 3

Table S2: Experimental binodal weight fraction data for the systems composed † of ethanol (we) + K2HPO4 (ws) + water at 298.15 K and 91 kPa .

100ws 100we 100ws 100we 4.2 36.7 15.8 16.3 4.8 35.4 16.5 15.4 4.9 34.3 17.2 14.7 5.5 33.1 17.8 14.0 6.0 31.6 18.5 13.3 6.1 31.4 19.5 12.5 6.5 30.4 20.6 11.6 6.9 28.4 21.6 10.8 7.0 29.5 22.3 10.1 7.5 27.5 24.0 9.3 7.7 26.6 25.5 8.9 8.4 25.8 26.6 8.2 9.1 24.8 29.6 7.0 10.0 23.5 31.2 6.2 10.3 22.7 32.8 5.7 11.5 21.3 34.9 5.1 12.3 20.2 36.7 4.5 12.9 19.5 38.5 3.9 13.4 19.0 40.5 3.4 13.9 18.1 44.0 2.9 14.9 17.1 46.5 2.8 † Standard uncertainties u are u(w) = 0.001, u(T ) = 0.2 K, and u(P ) = 10 kPa. 4

Table S3: Experimental binodal weight fraction data for the systems composed † of ethanol (we) + K3PO4 (ws) + water at 298.15 K and 91 kPa .

100ws 100we 100ws 100we 0.7 58.6 20.3 13.9 1.5 53.9 21.5 12.9 2.2 46.4 22.8 11.7 3.8 40.6 24.2 10.5 5.8 35.3 25.6 9.6 7.8 30.5 27.6 8.2 9.5 27.6 29.7 7.0 11.2 25.0 32.6 5.5 13.0 22.6 35.3 4.3 14.4 20.7 38.6 3.3 16.3 18.5 40.1 3.0 18.0 16.5 43.2 2.0 19.2 15.2 48.9 1.5 † Standard uncertainties u are u(w) = 0.001, u(T ) = 0.2 K, and u(P ) = 10 kPa. 5

Table S4: Experimental binodal weight fraction (wt%) data for the systems com- † posed of ethanol (we) + K2CO3 (ws) + water at 298.15 K and 91 kPa .

100ws 100we 100ws 100we 2.3 56.9 19.6 13.4 4.2 43.7 20.8 12.1 5.2 40.1 21.9 10.9 6.1 36.9 23.2 9.8 7.1 34.4 24.5 8.5 8.7 31.1 25.9 7.3 9.6 28.9 27.1 6.6 11.0 26.4 28.6 5.7 12.0 24.4 29.8 5.0 13.1 22.7 30.6 5.0 14.0 21.0 31.1 4.4 14.7 19.8 32.4 3.9 15.4 18.7 33.0 4.0 16.0 17.7 34.0 3.4 16.8 16.6 36.9 2.6 17.6 15.4 39.0 2.1 18.3 14.3 40.4 1.9 18.6 14.1 † Standard uncertainties u are u(w) = 0.001, u(T ) = 0.2 K, and u(P ) = 10 kPa. 6

Table S5: Experimental binodal weight fraction data for the systems composed † of ethanol (we) + K3C6H5O7 (ws) + water at 298.15 K and 91 kPa .

100ws 100we 100ws 100we 1.4 63.4 18.2 25.4 2.5 55.3 19.7 23.5 3.2 51.9 19.9 23.0 4.2 49.5 20.5 22.5 5.0 48.3 21.4 21.3 6.1 44.7 22.1 20.2 7.5 41.6 22.2 20.3 8.7 39.5 23.9 18.3 9.1 38.9 24.7 17.3 11.6 34.8 25.1 16.8 11.6 34.8 25.7 16.3 12.9 32.8 26.6 15.3 14.4 30.8 27.6 14.2 14.8 30.0 28.3 13.5 15.7 29.0 28.9 13.1 16.8 27.4 30.4 11.8 17.7 26.1 33.2 9.6 † Standard uncertainties u are u(w) = 0.001, u(T ) = 0.2 K, and u(P ) = 10 kPa.

Table S6: Critical point of systems composed of salt (ws) + ethanol (we) + water at 298.15 K and 91 kPa.

2 Salt Angular Intercept r 100ws 100we

NaH2PO4 1.787 -31.305 0.951 24.768 12.960 K2HPO4 1.261 -9.418 0.877 18.338 13.702 K3PO4 1.801 -19.863 0.932 19.442 15.161 K2CO3 3.164 -35.496 0.996 16.602 17.028 K3C6H5O7 2.112 -16.091 0.982 19.096 24.241 7

70 70 This work This work Katayama and Miyahara47 Katayama and Miyahara47 60 60 Liu et al.48 Gerlach and Smirnova49 50 50

40 40

30 30

20 20 Ethanol % (w/w) Ethanol % (w/w)

10 10

0 0 0 10 20 30 40 50 0 5 10 15 20 25 30 35 40

NaH2PO4 % (w/w) K2HPO4 % (w/w)

(a) (b)

70 70 This work This work Wang et al.19 Salabat and Hashemi51 60 60

50 50

40 40

30 30

20

Ethanol % (w/w) 20 Ethanol % (w/w)

10 10

0 0 0 10 20 30 40 50 0 10 20 30 40 50

K3PO4 % (w/w) K2CO3 % (w/w)

(c) (d)

70 This work Wang et al.19 60 Zafarani-Moattar et al.50

50

40

30

Ethanol % (w/w) 20

10

0 0 10 20 30 40 50

K3C6H5O7 % (w/w)

(e)

Figure S1: Comparison of binodal curves of systems composed by water, ethanol, and salt at 298.15 K and 91 kPa obtained in this work with literature ones. (a) Monosodium phosphate, (b) Dipotassium phosphate, (c) , (d) carbonate and (e) Potassium citrate. 8

Table S7: pH measurement of tie-lines for salt + ethanol + water systems at 298.15 K and 91 kPa†.

Salt TL pH top pH bottom 1 4.53 4.54 2 4.50 4.47 3 4.44 4.40 NaH PO 2 4 4 4.39 4.37 5 4.35 4.31 6 4.32 4.29 1 9.93 10.14 2 9.98 10.01 3 10.00 10.10 K HPO 2 4 4 10.06 10.16 5 10.05 10.16 6 10.04 10.13 1 13.62 13.52 2 13.64 13.43 3 13.61 13.80 K PO 3 4 4 13.60 13.76 5 13.54 13.63 6 13.61 13.97 1 13.04 13.03 2 13.02 13.05 3 13.03 13.10 K CO 2 3 4 13.05 13.12 5 13.07 13.14 6 13.12 13.21 1 8.97 9.04 2 8.98 9.02 3 9.03 8.99 K C H O 3 6 5 7 4 8.97 9.03 5 9.00 9.06 6 8.99 9.06 † Standard uncertainties u are u(w) = 0.1 %, u(T ) = 0.1 K, and u(P ) = 10 kPa. 9

Table S8: Partition coecient (K), extraction eciency (E %) and selectivity (S) for Nicotine and Caeine at dierent systems composed of salt + ethanol + water.

Nicotine Caeine Salt S KE (%) KE (%)

NaH2PO4 1.09 51.06 13.29 92.73 0.08 K2HPO4 20.21 94.98 27.56 96.31 0.73 K3PO4 128.02 98.98 30.80 95.79 4.16 K2CO3 168.58 98.64 54.18 95.89 3.11 K3C6H5O7 23.26 92.28 13.43 87.45 1.73 10

(a) (b)

Figure S2: Chemical speciation of alkaloids. (a) Caeine and (b) Nicotine. ChemSpider - Search and Share Chemistry (http://www.chemspider.com, accessed on August 2018)