Wednesday, April 3, 2019
Liquid Liquid Equilibrium of Pold (Ethylene Glycol)
suave fluidness Equilibrium of Pold (Ethylene Glycol)LiquidLiquid Equilibrium of Poly (ethylene glycol) 1500 + di-Potassium Tartrate +Water at different pH (6.41, 7.74 and 9.05)Alireza BaraniChemical Engineering Department,Faculty of Engineering, Shomal University, Amol, PO Box 731, IranMohsen Pirdashti1Chemical Engineering Department,Faculty of Engineering, Shomal University, Amol, PO Box 731, IranAbbas Ali RostamiChemical Engineering Department,Faculty of Engineering, Shomal University, Amol, PO Box 731, IranAbstractLiquid liquid proportionality (LLE) entropy have been determined for sedimentary deuce- manikin formations (ATPSs) containing (ATPS) poly (ethylene glycol) ( thole) 1500 +di potassium tartrate + piddle at 298.15 K and in various pH set (6.41, 7.74 and 9.05). Two material proper weds ( denseness and deflective index number) were used to obtain the compositions of var. and the ends of the tie- epithelial ducts. The proceeds of pH on the binodal skid, tie-li ne length and slope of tie line be discussed. The binodal curves of these systems have been correlated by Bleasdales equation. Furthermore, the Othmer-Tobias and Bancroft equations was used to correlate the tie line entropy points. Finally, the effective excluded volume (EEV) of the seasoniness into the PEG aqueous base were obtained.Keywords ATPS Phase diagram pH Refractive index Poly(ethylene glycol) di potassium tartrate intromissionThe dissolving of one polymer and one salt or two aqueous polymer solutions together in weewee results in the formation of two unmixable aqueous phases systems, called Aqueous Two-Phase Systems (ATPSs). Albertson introduced these systems in 1965 for the purpose of separating the biological materials1. Several industries gutter benefit from employing ATPS including biotechnology, petroleum, paint, adhesives, and pharmaceuticals 2, 3. Moreover, the ATPS is effective in providing separation technique due to its easy scale-up viability 4-6, econo mic efficiency7, 8, ease of continuous process 9, decreased interfacial tension 10, short processing time 11, low energy consumption 12, 13, obedient resolution 14, high yield 15, coitionly high load might 16, and selective extraction 17. The data derived from phase diagram, composition and the physical properties of the phase formation atomic number 18 essential in order to optimize, design and improver the size of these processes and develop the models that predict phase partitioning18-20. Poly Ethylene Glycol (PEG) is a pissing-soluble hydrophilic and biocompatible polymer active by the studies about ATPS 21. Accordingly, Selber et al. (2004) 3 provided a useful summary of experimental liquid-liquid data and symmetricalness diagrams for systems including PEG, inorganic salts and water. Peng et al.10 (1995) investigated the phase diagram and protein partition coefficient in ATPS containing PEG and K2HPO4 + KH2PO4 and found some merits in this polymer-salt system. Further more, several studies 22-27 have focused on the Liquid-Liquid Equilibrium (LLE) data of PEG + salt ATPSs. Zafarani-Moattar et al. (2008) indicated some advantages of use tartrate such as biodegradability and effectiveness in partitioning of biological materials through organism discharged into biological profligacy water treatment plants 27. In the current study, the phase equilibrium data for PEG1500 +di-potassium tartrate (K2C4H4O6 ) +H2O were determined at 298.15K and three pH valuates (6.41 , 7.74, and 9.05). In addition, the effects of pH on the binodal curve and trace-Line Length (TLL) and Slope of Tie Line (STL) were determined. Likewise, the standardization curves were applied as an analytical technique MN1with mensuration the density and refractive index. Finally, Othmer-Tobias and Bancroft equations 28 were used to fit the tie- line data and Bleasdales equation was employed 29 to correlate the experimental LLE data from the investigated systems. experimentalMaterials To prepargon the materials, PEG HO (C2H4O) n H with average of 1500 gmol-1 and di potassium tartrate with minimum purity of 99.5% by caboodle were obtained from Merck. The polymer and salts were used without further purification with the distilled deionized water. 2.2. Apparatus and Procedure.2.2.1. uninflected MethodsThe same method acting of calibration plots and evaluation of parameters in the literatures 30 were employed to obtain the compositions in both phases from measurements of the two physical properties (density and refractive index) at 298.15 K. in order to obtain the compositions, calibration equations were previously obtained. Homogeneous triad mixtures with compositions from 0 to 30 wt% (total solute composition) were prepared by weight, and then density and refractive index were measured at 298.15 K. the concentration of PEG and salt were obtained employ eq 1, which related the refractive index and density to the concentration of salt and PEG at 298.15 K, where represents the mass fraction of PEG, is the mass fraction of di-potassium tartrate, and is the value of the refractive index and density of pure water at 298.15 K. experimental data were fitted to polynomial expansions up to order 2 by least-squares (order 3 was proved unnecessary in all cases 23(1)Where Z is the physical property (density or refractive index) and to are fitting parameters. The refractive index was determined by refractive index measurements at 298.15 K victimization a refractometer (CETI Belgium model) with an accuracy of 0.0001. Then, densities was measured by using an Anton Paar oscillation U-tube densitometer (model DMA 500) with a precision of 10-4 g.cm-3.2.2.2. Binodal CurveThe experimental apparatus employed is akin(predicate) to the one used previously 31. A glass vessel, volume of 25 cm3 was used to carry out the equilibrium endeavor. It was provided with an external jacket containing water at constant temperature. The temperature was controlled to within +-0.05 K. The binodal curves were determined by the cloud-point method 32. The cloud-point method was investigated by titration method where step by step and exactly cognize amounts of polymer (titrant) was added to an aqueous solution salt of known concentration (or vice versa) beneath stirring until the solution becomes cloudy. 2.2.3. The TLL and STLTie lines were also determined using the equilibrium set designed by ourselves and according to previously described procedures 14. For the determination of the tie lines, we selected 4 samples for all(prenominal) pH that were prepared by blend appropriate amounts of PEG, salt, and water in the vessels. Samples were stirred for 5 min and settled for 24 h, with temperature controlling condition, to ensure that equilibrium was established. To separate the resulting phases, the tubes were centrifuged (Hermle Z206A, Germany) at 6000 revolutions per minute for 5 min. The resulted phases showed no turbidity and the cap and la ughingstock samples were easily separated. subsequently the equilibrium was achieved, phases were with- drawn using syringes. The top phase was sampled first, with care being taken to leave a layer of material at least 0.5 cm thick above the interface. The fall into place phase was remain in the glass vessel with a long needle. TLL provides an empirical measurement of the compositions of the two phases, which can be calculated by the following equationTLL=(2)Where and announce the concentration of PEG and salt in top and bottom phase, and STL is tending(p) by the ratio of the variation between the polymer and salt concentrations in the top and bottom phases as presented in Eq. 3STL=(3)Where and are the polymer and salt concentrations, uttered in mass percent, respectively, and the superscripts T and B designate the top and bottom phases, respectively.2.2.4.Binodal Curve and TLL CorrelationFor the binodal data correlation, the Bleasdales equation 27 can be fittingly used to repr oduce the binodal curves of the investigated systems(4)Where a, b, and c represent the fitting parameters and and demonstrate the polymer and salt mass fractions, respectively. The binodal data of the above expression were correlated by least-squares regression.The reliableness of the measured tie-line compositions was ascertained by Othmer-Tobias (Eq. 5) and Bancroft (Eq. 6) correlation equations(5)(6)Where is the mass fraction of polymer in the top phase, is the mass fraction of salt in the bottom phase, and are the mass fractions of water in the bottom and top phases, respectively, and , , , and are the correct parameters.Besides, the obtained experimental data can also adapt to the equation provided by Guan and co-workers33Ln (.WPEG/ ) + ./ = 0(7)Where and stand for the polymer and salt molecular weight, respectively. Moreover, V* is the Effective Excluded majority (EEV) of the salt in the PEG aqueous solution.Results and DiscussionFitting parameters of calibration e quationThe values of the coefficients a, b, c, d, e and f for the system studied are shown in table 1, respectively. slacken 1.The value of the coefficients observed from eq. 1.1.33410.05810.1302-0.07180.22570.3882/g.cm30.98420.67830.17610.00980.16430.1018Binodal CurveThe binodal curve data of the PEG + di-potassium tartrate + H2O system are presented in put over 2.Table 2. Binodal curve data of the PEG 1500 + di-potassium tartrate+ water system at 298.15 K and 0.1 MPa at different pH values42.719.0127.7510.4943.4310.4939.579.5045.587.2043.677.2035.5010.2142.047.8041.887.8034.4810.3239.318.3039.518.3028.5411.5835.779.0128.939.0133.7010.5523.8812.0122.0412.223.1713.0116.1814.7719.8914.7717.0715.0113.9415.7316.5315.7314.2516.2113.4216.0514.5316.0512.1117.0211.7516.9112.5516.9111.2817.527.5919.7111.1619.717.0121.016.9020.369.1920.366.1721.645.2923.198.1023.195.8522.015.0322.247.4522.245.0627.534.7424.016.7624.014.6523.504.3224.705.8024.703.1726.013.6226.014.9926.02Standard uncertainti es u(wi) = 0.002 u(P) = 5 kPa u(T) = 0.05 K.Figure 1 shows the binodal curves obtained from Bleasdales equation. The effect of pH is clear very small on the size of the heterogeneous region. This trend is in agreement with the experimental results of de Oliveira 12 and Martins 15.Figure 1. Phase diagram of the PEG (1500) + di-potassium tartrate + water (3) two-phase system at T = 298.15 K and various pH (6.41, 7.74 and 9.05) (-) experimental binodal (6.41(pink), 7.74(blue) and 9.05 (green) (-) calculated binodal using Bleasdales equation (3).TLL and STLTie line compositions are given in Table 4. Figure 2 presents the tie lines and the binodal curve together for the PEG + di-potassium tartrate + water system at 298.15 K.Figure2. Phase diagram of the PEG + di-potassim tartrate + water two-phase system at T = 298.15 K and pH 6.41 (a), 7.74 (b) and 9.05 (c) (---) experimental binodal (- --- -) calculated by using eq. 4.Table 4. Phase composition, tie-line data and physical propert ies of PEG 1500 + di-potassium tartrate+ water aqueous two-phase system at 298.15 K and 0.1 MPa Total System(%mass) net phaseBottom phase6.41172010.5533.701.12171.392223.504.651.16201.370331.802.24172110.2135.501.12261.393624.014.311.16521.370534.102.2618209.5039.571.12521.396525.013.701.17161.371039.072.3118219.0142.651.12751.398526.013.171.17821.371742.972.327.7417209.0135.771.11421.391923.155.291.16061.371033.622.1417218.3039.311.11571.393224.014.741.16601.371437.962.2018207.8042.041.11721.394724.704.321.17051.371841.332.2318217.2045.581.11951.396626.013.621.17911.372745.972.239.0517204.0139.511.08441.383125.186.761.17911.378139.001.5417213.3041.881.08361.383527.015.801.19121.379643.171.5218203.0842.661.08351.383628.015.341.19801.380644.871.4918212.8043.671.08331.383828.804.991.20341.381446.591.48The tie lines are determined by connecting each jibeing set of total, top, and bottom phase compositions. The coexisting phases are close in composition. A mass balance check was made b etween the initial mass of each component and the amounts in the bottom and top phases on the basis of equilibrium compositions. The mass of each phase was calculated from volume and density measurements. The relative error in the mass balance was less than 3 piece those of the top phases ranged from 1.08 to 1.12 g/cm3. The density difference between the phases (), change magnitude with an increase in the TLL and slightly decrease with an increase in pH. From Figures 7, it is observed that the density differences between the phases show linear relationship with TLL. A comparable stick out was likewise depicted 31, 34, 35.Figure *. Relationship between density difference () and tie line length (TLL) for the PEG 1500 + di-potassium tartrate + water at different pH values.3.4. Binodal curve and tie-line data correlationThe coefficients of equation 4, along with the correspond
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