Liquid-Liquid Equilibrium Data, Viscosities, Densities, Conductivities, and Refractive Indexes of Poly (vinyl pyrrolidone)+ tri-sodium Citrate + Urea Aqueous Two-Phase Systems at Different pH

Pirdashti, Mohsen; Movagharnejad, Kamyar; Rostami, Abbas Ali

doi:10.1590/0104-6632.20170343s20150619

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Brazilian Journal of Chemical Engineering

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Thermodynamics • Braz. J. Chem. Eng. 34 (3) • July 2017 • https://doi.org/10.1590/0104-6632.20170343s20150619 copy

Liquid-Liquid Equilibrium Data, Viscosities, Densities, Conductivities, and Refractive Indexes of Poly (vinyl pyrrolidone)+ tri-sodium Citrate + Urea Aqueous Two-Phase Systems at Different pH

Authorship SCIMAGO INSTITUTIONS RANKINGS

Abstract

The present study investigated liquid-liquid equilibria of polyvinylpyrrolidone (PVP) K30 + tri-sodium citrate + urea (5% and 10% mass) aqueous two-phase systems at 25°C and pH values of 6.2, 7.4, and 10.0. Results showed that the binodal was displaced toward higher concentrations as the urea concentration increased. The effect of pH, polymer/salt (w/w) ratio, urea concentration, tie line length, and slope of tie line on the partition behavior of urea was examined. The viscosity, density, electrical conductivity, and refractive index of PVP (K30) + tri-sodium citrate + urea + water two-phase systems were measured versus pH value. The relation between tie line length and the density and viscosity of the aqueous two-phase systems was also examined.

Keywords:
Aqueous two-phase systems; Phase diagram; Urea; Viscosity; Polyvinylpyrrolidone

PVP (Mw)	Salt/Polymer	Effective parameter(s)	Reference
PVPK15 (10000)	Sodium di-hydrogen phosphate	Temperature	Zafarani-Moattar and Sadeghi (2002)Zafarani-Moattar, M.T and Sadeghi, R., Measurement and Correlation of Liquid-Liquid Equilibria of the Aqueous Two-Phase System Polyvinylpyrrolidone-Sodium Dihydrogen Phosphate, Fluid Phase Equilib, 203, No 1, 177 (2002).
PVPK15 (10000)	Di-sodium hydrogen phosphate	Temperature; type of salt	Zafarani-Moattar and Sadeghi (2005)Zafarani-Moattar, M.T and Sadeghi, R., Effect of Temperature on the Phase Equilibrium of Aqueous Two-Phase Systems Containing Polyvinylpyrrolidone and Disodium Hydrogen Phosphate or Trisodium Phosphate, Fluid Phase Equilib, 238, No 1, 129 (2005).
PVPK15 (10000)	Tri-sodium phosphate	Temperature; type of salt
PVP K15 (10000)	Magnesium sulfate	Temperature	Salabat et al. (2006)Salabat, A., Moghadasi, M.A., Zalaghi, P and Sadeghi, R., (Liquid + liquid) Equilibria for Ternary Mixtures of (Polyvinylpyrrolidone + MgSO4 + Water) at Different Temperatures, J. Chem. Thermodynamics,38, No 2, 1479 (2006).
PVPK15 (10000)	Potassium citrate	Temperature	Sadeghi (2006Sadeghi, R., Measurement and Correlation of Vapor-Liquid Equilibria of the Poly(vinylpyrrolidone)+ NaH2PO4 + H2O System at Different Temperatures, CALPHAD, 30, No 1, 53 (2006).)
PVPK15 (10000)	Sodium citrate	Temperature	Sadeghi et al. (2006Sadeghi, R, Rafiei,H.R and Motamedi, M., Phase Equilibrium in Aqueous Two-Phase Systems Containing Poly(vinylpyrrolidone) and Sodium Citrate at Different Temperatures-Experimental and Modeling, Thermochimica Acta, 451, No 1, 163 (2006).)
PVP K12 (3500)	Tri-potassium phosphate	Temperature	Zafarani-Moattar and Seifi- Aghjekohal (2007)Zafarani-Moattar, M.T and Seifi-Aghjekohal, P., Liquid-Liquid Equilibria of Aqueous Two-Phase Systems Containing Polyvinylpyrrolidone and Tripotassium Phosphate or Dipotassium Hydrogen Phosphate: Experiment and Correlation, CALPHAD, 31, No 4, 253 (2007).
PVP K12 (3500)	Di-potassium hydrogen phosphate	Temperature
PVPK17 (3882)	>Sodium sulfate	Molecular mass of PVP	Fedicheva et al. (2007Fedicheva, N., Ninni, L and Maurer, G., Aqueous Two-Phase Systems of Poly(vinyl pyrrolidone) and Sodium Sulfate: Experimental Results and Correlation/Prediction, J. Chem. Eng. Data, 52, No.2, 1858(2007).)
PVPK30 (17750)
PVPK90 (138600)
PVP (24000)	Di-ammonium hydrogen phosphate/ammonium	Temperature; pH	Foroutan and Zarrabi (2008Foroutan, M and Zarrabi, M. Activities of Water, Polymer and Salt in Liquid-Liquid Equilibria of Polyvinylpyrrolidone and (NH4)2HPO4/(NH4)H2PO4 Buffer Using the Flory-Huggins Model with Debye-Huckel and Pitzer-Debye-Huckel Equations and the Osmotic Virial Model: Effects of pH and Temperature, Fluid Phase Equilib, 266, No1, 164 (2008).)
PVP (24000)	di-hydrogen phosphate buffer	Temperature; pH
PVPK12 (3500)	Di-potassium oxalate or di-potassium tartrate	Temperature	Zafarani-Moattar and Zaferanloo (2009)
PVPK30 (60000)	Ammonium phosphate	Type of ammonium salt; temperature	Wang et al. (2012)
	Ammonium sulfate
	Di-ammonium carbonate
	Ammonium tartrate
	Ammonium citrate

pH	Total System(%mass)		Top phase (%mass)				Bottom phase (%mass)				Urea	TLL(%)	STL (%)
	100wp	100ws	100wp	100ws	ρ	η	100wp	100ws	ρ	η	Urea	TLL(%)	STL (%)
	100wp	100ws	100wp	100ws	kg.m^-3	mPa.s	100wp	100ws	kg.m^-3	mPa.s	100 w_u
											100 w_u
*6.2*	13.60	16.00	23.40	9.04	1.1254	181.0	2.20	24.08	1.1678	3.589	5	25.99	1.41
	13.00	16.00	22.52	9.47	1.1256	161.4	2.45	23.29	1.1636	3.585	5	24.37	1.45
	12.30	15.20	20.79	9.75	1.1232	124.4	2.88	21.26	1.1515	3.497	5	21.29	1.56
	12.00	15.10	19.78	10.18	1.1232	106.7	3.02	20.62	1.1481	3.483	5	19.75	1.61
	11.00	14.50	17.65	10.65	1.1202	72.73	3.37	19.01	1.1391	3.450	5	16.55	1.71
	10.50	14.10	16.76	10.73	1.1187	61.16	4.10	17.53	1.1312	3.486	5	14.37	1.86
	13.60	16.00	21.11	10.41	1.1296	139.6	5.20	22.10	1.1614	3.944	10	19.74	1.36
	13.00	16.00	20.11	10.72	1.1292	120.3	5.30	21.00	1.1543	3.874	10	18.03	1.44
	12.30	15.20	19.16	10.96	1.1282	102.6	5.50	19.80	1.1473	3.823	10	16.27	1.55
	12.00	15.10	18.01	11.15	1.1265	83.42	5.70	19.00	1.1427	3.799	10	14.60	1.57
	11.00	14.50	17.48	11.31	1.1264	75.95	6.50	18.00	1.1380	3.836	10	12.85	1.64
	10.50	14.10	16.56	11.60	1.1257	63.68	7.20	17.00	1.1334	3.861	10	10.81	1.73
*7.4*	15.00	11.50	24.51	6.79	1.1131	180.9	1.17	18.41	1.1285	2.660	5	26.08	2.01
	14.00	11.50	23.44	7.05	1.1115	155.3	1.30	17.33	1.1224	2.643	5	24.41	2.16
	13.00	11.10	21.28	7.47	1.1091	114.9	1.81	15.96	1.1146	2.728	5	21.24	2.29
	12.50	11.00	19.22	8.01	1.1072	83.16	2.33	15.48	1.1131	2.877	5	18.46	2.26
	12.00	10.80	17.73	8.36	1.1052	63.57	3.09	14.61	1.1100	3.057	5	15.92	2.34
	11.50	10.70	15.64	8.96	1.1039	42.74	4.39	13.69	1.1073	3.293	5	12.20	2.38
	12.00	13.60	23.57	7.62	1.1170	170.8	3.50	17.93	1.1304	3.338	10	22.56	1.95
	11.50	13.45	22.02	7.97	1.1155	138.0	3.91	17.22	1.1267	3.377	10	20.33	1.96
	10.65	13.00	20.17	8.29	1.1129	103.8	4.62	15.90	1.1200	3.428	10	17.31	2.04
	10.00	13.00	19.00	8.63	1.1121	86.06	4.96	15.36	1.1173	3.455	10	15.57	2.09
	9.00	13.00	17.46	9.06	1.1112	65.93	5.45	14.56	1.1134	3.490	10	13.20	2.18
	8.00	13.00	15.26	9.64	1.1094	42.74	6.38	13.75	1.1105	3.582	10	9.78	2.16
*10.0*	15.00	9.30	27.19	4.13	1.1019	204.1	1.07	15.21	1.1076	2.375	5	28.38	2.36
	14.00	9.25	24.89	4.72	1.0995	156.0	1.23	14.54	1.1044	2.413	5	25.62	2.41
	13.00	9.20	23.17	5.09	1.0972	123.9	1.48	13.75	1.1003	2.471	5	23.35	2.51
	13.00	8.90	21.53	5.59	1.0967	100.8	2.71	12.98	1.0982	2.836	5	20.22	2.54
	12.50	8.90	19.80	6.08	1.0949	77.26	3.78	12.27	1.0968	3.080	5	17.17	2.59
	12.00	8.80	16.76	6.95	1.0927	45.99	5.01	11.57	1.0958	3.297	5	12.63	2.54
	14.00	10.00	24.40	5.27	1.1031	158.3	2.63	15.09	1.1102	2.922	10	23.88	2.22
	13.50	9.80	22.84	5.59	1.1013	129.2	3.37	14.39	1.1075	3.073	10	21.37	2.21
	13.20	9.70	21.69	5.98	1.1007	110.3	3.94	13.70	1.1049	3.170	10	19.35	2.3
	12.50	9.75	20.29	6.43	1.1001	90.61	5.01	12.86	1.1020	3.330	10	16.58	2.38
	12.45	9.70	18.90	6.90	1.0998	73.39	6.90	12.07	1.1014	3.572	10	13.06	2.32
	12.40	9.60	17.50	7.34	1.0991	57.97	7.89	11.52	1.1004	3.665	10	10.48	2.30

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[1] * Corresponding author: pirdashti@yahoo.com

w_p	w_s	w_u	ρ	η	n_D	k
w_p	w_s	w_u	kg.m^-3	mPa.s	n_D	mS.cm^-1
0	0	0	0.9970	0.894	1.3327	0.125
0	0	5	1.0137	0.987	1.3391	6.43
0	0	10	1.0215	1.104	1.3450	14.10
5	0	0	1.0061	1.046	1.3401	0.125
5	0	5	1.0203	1.215	1.3456	5.82
5	0	10	1.0348	1.426	1.3552	10.9
10	0	0	1.0115	1.210	1.3450	0.240
10	0	5	1.0340	1.460	1.3521	2.12
10	0	10	1.0468	1.751	1.3640	7.73
15	0	0	1.0210	1.460	1.3517	0.321
15	0	5	1.0470	1.798	1.3600	1.04
15	0	10	1.0559	2.213	1.3719	6.30
0	5	0	1.0266	2.362	1.3406	27.1
0	5	5	1.0425	2.693	1.3463	33.5
0	5	10	1.0538	2.941	1.3538	38.5
5	5	0	1.0390	2.706	1.3475	23.1
5	5	5	1.0524	2.973	1.3565	28.3
5	5	10	1.0649	3.201	1.3631	33.7
10	5	0	1.0500	2.992	1.3551	18.9
10	5	5	1.0644	3.231	1.3653	24.7
10	5	10	1.0776	3.449	1.3728	30.1
15	5	0	1.0605	3.294	1.3634	13.5
15	5	5	1.0761	3.478	1.3738	19.4
15	5	10	1.0916	3.686	1.3821	25.2
0	10	0	1.0540	5.655	1.3480	40.6
0	10	5	1.0711	6.205	1.3557	46.1
0	10	10	1.0832	8.184	1.3602	51.1
5	10	0	1.0708	6.284	1.3573	36.3
5	10	5	1.0853	8.502	1.3656	41.3
5	10	10	1.0950	10.35	1.3716	46.9
10	10	0	1.0838	8.635	1.3687	31.8
10	10	5	1.0935	10.52	1.3755	36.9
10	10	10	1.1102	11.34	1.3817	42.1
15	10	0	1.0967	10.59	1.3767	26.9
15	10	5	1.1061	11.41	1.3855	32.3
15	10	10	1.1218	11.76	1.3913	36.6
0	15	0	1.0912	9.360	1.3563	46.8
0	15	5	1.1038	16.36	1.3623	53.3
0	15	10	1.1167	25.60	1.3679	55.4
5	15	0	1.1032	16.80	1.3669	43.1
5	15	5	1.1163	27.13	1.3731	49.1
5	15	10	1.1313	38.08	1.3798	50.1
10	15	0	1.1161	27.83	1.3775	38.6
10	15	5	1.1295	39.09	1.3837	43.8
10	15	10	1.1443	50.89	1.3897	45.7
15	15	0	1.1338	40.59	1.3862	32.8
15	15	5	1.1471	52.57	1.3937	38.2
15	15	10	1.1591	65.29	1.4017	41.1