Solubility Modelling and Mixing Thermodynamics of Thiamphenicol in Water and Twelve Neat Organic Solvents from T = ( to 318.

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1 Supporting Information Solubility Modelling and Mixing Thermodynamics of Thiamphenicol in Water and Twelve Neat Organic Solvents from T = ( to ) K Xinbao Li a, Mengqian Wu a, Yang Cong b, Cunbin Du b, Hongkun Zhao b,* a School of Environmental & Municipal Engineering, North China University of Water Resources and Electric Power, ZhengZhou, He nan , People s Republic of China b College of Chemistry & Chemical Engineering, YangZhou University, YangZhou, Jiangsu , People s Republic of China

2 Figure S1. Schematic diagram of experimental apparatus: I, smart thermostatic water bath; II, mercury-in-glass thermometer; III, magnetic stirrer; IV, stirrer controller; V, jacketed glass vessel; VI, sampling port; VII, condenser.

3 4x10 7 3x10 7 Peak rea 2x10 7 1x c / mg ml -1 Figure S2. Relationship between peak area and concentration of thiamphenicol.

4 Intensity(A.U.) (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) Theta( O ) Figure S3. XPRD patterns of thiamphenicol crystallized in different solvents: (a) raw material thiamphenicol; (b) methanol; (c) ethanol; (d) n-propanol; (e) isopropanol; (f) n-butanol; (g) acetone; (h) acetonitrile; (i) ethyl acetate; (j) 2-butanone; (k) toluene; (l) water; (m) DMF; (n) 1,4-dioxane.

5 -4-6 ln(x) /T/K -1 Figure S4. The van t Hoff plots of ln(x) versus 1/T in different solvents:, DMF;, methanol;, ethanol;, 1,4-dioxane;, n-propanol;, water;, n-butanol;, acetone;, 2-butanone;, acetonitrile;, ethyl acetate;, isopropanol;, toluene.

6 mix G(J mol -1 ) (a) mix G(J mol -1 ) (b) T/K T/K Figure S5. Calculated the change of mixing Gibbs energy at measured solubility points: (a), DMF; (b), methanol;, ethanol;, 1,4-dioxane;, n-propanol;, water;, n-butanol;, acetone;, 2-butanone;, acetonitrile;, ethyl acetate;, isopropanol;, toluene.

7 Table S1 Source and purity of the materials used in the work. Chemicals Molar mass g mol 1 thiamphenicol Melting point K a b c,d e Melting enthalpy kj mol -1 molar volume ml mol -1 (295 K) 2-butanone g Source a f Beijing HWRK Chemical Co., Ltd Initial mass Purification fraction purity method Final mass fraction purity Analysis method Crystallization HPLC h None GC i n-propanol g None GC n-butanol g None GC isopropanol g None GC ethanol g Sinopharm Chemical None GC methanol g Reagent Co., Ltd., None GC toluene g China None GC ethyl acetate g None GC acetonitrile g None GC 1,4-dioxane g None GC DMF g None GC acetone g None GC water Our lab Distillation Conductivity < 2 µs cm -1 Conductivity meter a This work. Determined at kpa. The standard uncertainties u are u(t) = 0.5 K, u(p) = 0.45 kpa and u( fus H) = 0.40 kj mol -1. b,c,d,e,f,g Take from Refs. (S1,S2,S3,S4 and S5), respectively. h High-performance liquid phase chromatograph. i Gas chromatography.

8 Table S2 Parameters of the equations and RMSD values for thiamphenicol in different solvents. Solvent Modified Apelblat equation λh equation Wilson model NRTL model A B C 10 4 RMSD λ h 10 4 RMSD g 12 g RMSD λ 12 λ 21 α 10 4 RMSD ethanol n-propanol ,4-dioxane n-butanol acetonitrile ethyl acetate isopropanol DMF toluene methanol butanone water acetone

9 Table S3 Experimental mole fraction solubility (x) of thiamphenicol in different solvents at the temperature range from T= ( To ) K under kpa. a T / K Acetonitrile 100 x 100 RD Modified Apelblat equation λh equation Wilson model NRTL model RAD Ethyl acetate RAD Ethanol RAD

10 n-propanol RAD Isopropanol RAD ,4-Dioxane RAD Toluene

11 RAD DMF RAD Methanol RAD Butanone RAD n-butanol 11

12 RAD Acetone RAD Water RAD a Standard uncertainties u are u(t) = 0.05 K, u(p) = 0.45 kpa; Relative standard uncertainty u r is u r (x) = RD denotes the relative deviation; and RAD, relative average deviation. 12

13 Table S4 Activity coefficients (γ) of thiamphenicol in different neat solvents at the temperature range from T= ( To ) K. T / K γ Acetonitrile Ethyl acetate Ethanol n-propanol Isopropanol 1,4-Dioxane Toluene DMF Methanol 2-Butanone n-butanol Acetone Water

14 Table S5 The calculated values for mix G, mix H, mix S, lnγ E,, and 1 H : mix G, mix S and mix S denote the 1 mixing Gibbs energy, mixing enthalpy, and mixing entropy, respectively; γ denotes the infinitesimal 1 E, concentration activity coefficient, and H denotes infinitesimal concentration reduced excess enthalpy. a 1 T / K mix G J mol -1 mix H J mol -1 mix S lnγ J K -1 mol -1 1 E, H 1 kj mol -1 Acetonitrile Ethyl acetate Ethanol 14

15 n-propanol Isopropanol

16 DMF Toluene ,4-Dioxane

17 Methanol Butanone n-butanol

18 Water Acetone a Expanded uncertainties U are U ( mix Gº) = J mol -1 ; U ( mix Sº) = J K -1 mol -1 ; U ( mix Hº) =0.003 J mol -1 (0.95 level of confidence). 18

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