Liquid–liquid equilibrium of 1-propanol, 2-propanol, 2-methyl-2-propanol or 2-butanol + sodium sulfite + water aqueous two phase systems
Highlights
► Phase diagrams of alcohol + sodium sulfite + water were reported. ► Salting-out ability of different salts and alcohols was discussed. ► Wilson model was generalized to correlate the tie-line data. ► Binary interaction parameters of Wilson and e-NRTL models were reported.
Introduction
Aqueous two phase systems (ATPSs) composed of two immiscible aqueous phases which are in equilibrium. These systems introduced in 1965 by the pioneering work of Albertsson and the physicochemical properties and applications of the polymer–polymer and polymer–salt type ATPSs have been well documented previously [1], [2], [3]. Also, other types of ATPSs (i.e. slat–salt–water, alcohol–salt–water, etc.) have been introduced and the experimental and theoretical investigation of the phase equilibrium conditions in such ATPSs is extensively studied due to their applications in the recovery and purification of chemicals or biological materials.
In recent years several research groups are focused on the measurement and thermodynamic investigation of ATPSs composed of an aqueous solution of a short chain aliphatic alcohol in the presence of an electrolyte [4], [5], [6], [7], [8], [9]. In the studied systems, several types of organic and inorganic salts were used. However, there is no report on the liquid–liquid equilibrium (LLE) of aliphatic alcohols and aqueous solution of sodium sulfite salt until now and therefore it is reliable to study the LLE of alcohols + sodium sulfite + water ternary systems to understand the properties of the these systems.
On the other hand, thermodynamic investigation of the LLE data using reliable models in such ATPSs is an important sight of the studies in these systems. The local composition based models such as the NRTL [10] and electrolyte-NRTL [11] models and the group contribution based models such as UNIQUAC [12] or UNIFAC [13] models have been extensively used for the correlation of the LLE data in such mixed solvent–electrolyte systems [14], [15], [16], [17], [18]. The group contribution based models are the molecular structure dependent models and the use of them needs to calculate the volume and surface parameters. Whereas, local composition based models are nondependent to the structure of the molecules and can be used for the correlation of the LLE data without any knowledge of the structure of the studied molecules.
For first time, Wilson [19] introduced an expression for the excess free energy of mixing by applying the local composition concept to the Flory–Huggins [20] equation for free energy of mixing, and used the obtained equation to represent the vapor–liquid equilibrium (VLE) of some binary systems. Other authors were extended the Wilson model in different ways. As examples, Zhao et al. [21] was extended the Wilson model to the electrolyte solutions and Xu et al. [22] modified Wilson model for the representation of the excess Gibbs free energy of binary polymer solutions. Also, Sadeghi [23] combined the electrolyte Wilson model [21] with the polymer Wilson model [22] to represent the excess Gibbs free energy of aqueous polymer + electrolyte solutions.
After the work of Wilson, Renon and Prausnitz [10] derived the nonrandom two liquid (NRTL) model based on Scott's two-liquid model [23] and on an assumption of nonrandomness similar to that used by Wilson, and used the proposed model for the correlation and prediction of the binary and ternary VLE and LLE data. Afterward, Chen et al. [24] proposed the electrolyte NRTL model based on the NRTL model of Renon and Prausnitz [10] and successfully used it to represent thermodynamic properties of aqueous electrolyte solutions. The model has been extended to represent the multicomponent electrolyte solutions [11] and can be able to give a reasonable representation of LLE of electrolyte solutions at low salt concentrations. Recently, Chen and Song [25] generalized the electrolyte NRTL model to represent the equilibrium of mixed solvent electrolyte systems.
In this work we studied the LLE of 1-propanol, 2-propanol, 2-methyl-2-propanol or 2-butanol + sodium sulfite + water ATPSs, and the experimental binodal and tie-line data at T = 298.15 K were reported. The effect of different alcohols and different anions on the phase-formation ability of the studied systems was discussed considering the intermolecular interactions. Also, to study the effect of temperature on the phase separation ability of the studied systems the cloud point data as a function of alcohol mole fractions at T = 293.15–323.15 K with 5 K intervals was measured. Also, the use of the Setschenow-type equations to study the slating-out effect of the mentioned ATPSs along with some previously studied alcohol + salt + water systems [26], [27], [28], [29], [30], [31], [32], [33] was discussed. Moreover, the modified segment based Wilson equation [23] was generalized to represent the mixed solvent electrolyte systems and the performance of this model in the correlation of the studied ATPSs was examined. The correlation ability of the generalized Wilson model was compared with the e-NRTL model.
Section snippets
Materials
The physicochemical properties of the used chemicals were described in Table 1.
Apparatus and procedure
The cloud point titration method was performed to collect the binodal curve data. In this method, an appropriate amount of aqueous solution of sodium sulfite solution or alcohol was placed in a double-wall glass cell, and the solution was stirred using a magnetic stirrer. The water at constant temperature was circulated between the walls of the double-wall cell to control the temperature of the cell. The temperature
Phase diagrams of the studied ATPSs
The experimental binodal curves and tie-line compositions for 1-propanol, 2-propanol, 2-methyl-2-propanol or 2-butanol + sodium sulfite + water ternary systems at T = 298.15 K are reported in Table 3, Table 4, respectively. Furthermore, the phase diagrams of the mentioned systems are shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4, respectively.
Effect of different alcohols and anions on the phase diagrams
Comparison between the studied binodal curves in this work and the ones reported for some aliphatic alcohols + disodium hydrogen citrate + water ATPSs at T = 298.15 K [26]
Conclusions
The liquid–liquid equilibrium of 1-propanol, 2-propanol, 2-methyl-2-propanol or 2-butanol + sodium sulfite + water ATPSs was studied at T = 298.15 K. The obtained results show that the tow-phase formation ability of the ATPSs composed of different alcohols is in the order of: 2-butanol > 2-methyl-2-propanol > 1-propanol > 2-propanol. The phase-separation ability of the studied systems was related to the solubility and boiling-point of the relevant alcohol. On the base of the solubility data the alcohols
List of symbols
- a, b, and c
parameters of Eq. (4)
- am
constants of Eq. (1) for nonelectrolyte
- aca
constants of Eq. (1) for salt
- Aφ
Debye–Hückel parameter
- C
the parameter of Wilson model fixed at C = 10
- β
intercept of Eqs. (2), (3)
- kca
salting-out coefficient
- ca
slat
- d
density (kg m−3)
- Dev
deviation
- GE
excess Gibbs energy (J mol−1)
- Hi j
Wilson binary interaction parameter between component i and j
- Ix
Ionic strength in mole fraction bases
- k
Boltzmann constant (=1.381 × 10−23) (J K−1)
- mi
morality of component i (salt or nonelectrolyte)
- n
mole number
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