ionic behavior of nacl and kcl in the vicinity of solution / organic … liquid-liquid interface...

International Journal of Physical Sciences Vol. 1(2), pp. 027-038, June 2013 Available online at http://academeresearchjournals.org/journal/ijps

ISSN 2331-1827 ©2013 Academe Research Journals

Full Length Research Paper

Ionic behavior of NaCl and KCl in the vicinity of solution / organic solvent interface in crystallization

Kazunori Kadota1,2*, Yoshiyuki Shirakawa1, Ikumi Matsumoto1, Hikari Tamura1, Atsuko Shimosaka1 and Jusuke Hidaka1

1Department of Chemical Engineering and Material Science, Doshisha University, 1-3 Miyakodani, Tatara, Kyotanabe,

Kyoto 610-0321, Japan. 2Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan.

Accepted 27 May, 2013

The mutual diffusion behavior phenomena in the vicinity of the interface in some systems, NaCl solution / 1-butanol, / 2-butanol and / 2-butanone or KCl solution / 1-butanol, / 2-butanol and / 2-butanone were investigated to clarify the crystallization mechanism near liquid-liquid interface by measuring electric conductance. The model of mutual diffusion behavior was proposed by predicting the dehydration process near the liquid-liquid interface using FT-IR. As a result, the electric conductance near water was much larger than that of organic solvent in both solute substances such as NaCl and KCl. These results indicate that water transported into organic solvent side. It turned out that the electric conductance also increased in organic solvent side as time passes. Furthermore, it proved that sodium ion made the hydrated structure and potassium ion broke hydrated structure even in organic solution from ion dynamics consideration by FT-IR analysis. Key words: Liquid-liquid interface, crystallization, mutual diffusion, hydration, dehydration.

INTRODUCTION Powder is commonly prepared for productions in industrial applications of fine particles such as foods, medicines and cosmetics (Gotoh et al., 1997; Kawashima et al., 1994). Physical and chemical properties of powder have much influence on products composed of powder manufacturing processes. It is therefore important to control the particle size distribution, shape and morphology in industrial applications (Hosokawa et al., 2007; Welham and Setoudeh, 2005). Crystallization processes can be carried out a separation and particle generation to control physical and chemical properties (Allan, 1999; Allan, 2001; Kubota and Ooshima, 2001; Mullin, 2001; Nyvlt and Ulrich, 1994), and there have been some studies on controlling the particle morphology because of being able to produce the particles with various shapes by changing the crystallization conditions (Shan et al., 2002; Takiyama, 2004). Crystallization has traditionally been conducted using cooling, evaporative and anti-solvent crystallization operations (Choong and Smith, 2004; Hyung et al., 2008; Minamisono and Takiyama, 2013; Takiyama, 2004). However, there are

some problems concerning thermal energy, concentration gradients and temperature gradients in the supersaturated solutions (Hojjati and Rohani, 2005; Kim and Ulrich, 2001).

To solve these problems, a liquid-liquid interfacial crystallization was proposed as an advanced method in our previous studies (Kadota et al., 2007a; Kadota et al., 2007b). The liquid-liquid interfacial crystallization is a production technique to precipitate solute particles on a liquid-liquid interface which is partially miscible. Interdiffusion between aqueous solutions and organic solvents occurs near the liquid-liquid interface according to the mutual solubility curve. In previous our paper, the different types of asymmetric particles were obtained at liquid-liquid interface (Kadota et al., 2007a; Kadota et al., 2007b; Kadota et al., 2007c). Furthermore, our group

*Corresponding author. E-mail: [email protected]. Tel: +81-72-690-1217. Fax: +81-72-690-1217.

Kadota et al. 028 could successfully produce the glycine porous particles by using this liquid-liquid interfacial crystallization (Tanaka et al., 2011). From these previous works, it was found that the particle growth rate depended on the mutual diffusion between water and organic liquids. Thus, the structural change near liquid-liquid interface due to the mutual diffusion significantly affects the performance of crystallization. Several investigations have been conducted on the nucleation and crystal growth of NaCl and KCl (Okada et al., 2005; Radenović et al., 2003; Sunagawa and Tsukamoto, 1972; Zaldo et al., 1982). However, there have been few studies on the nucleation and crystal growth near liquid-liquid interface generating the phase separation between aqueous solutions and organic solvent.

In our previous works, the possibility of predicting mutual diffusion was indicated by measuring the solution resistance near interface between solution and organic solvent (Kadota et al., 2007c). Also the microscopic behavior of NaCl and KCl near solution / organic solvent interface might be predicted by measuring Fourier transform infrared spectroscopy (FT-IR). Early works used by FT-IR to study on hydration or dehydration process in the water, for example, hydrated structure was predicted (Cheng and Lin, 2006; Yoda and Ootawa, 2009). Furthermore, some researchers have studied on the nucleation or crystal growth in solution using FT-IR. Kaneko et al. studied polymorphic crystallization processes of fatty acids with FT-IR spectroscopy (Kaneko et al., 1999). Mehta et al. (2010) also has performed the synthesis of silver nanoparticles in homogeneous aqueous solutions of the precursor’s silver nitrate and three saccharides using FT-IR (Mehta et al., 2010). FT-IR might provide a useful tool for investigation and modeling the structure and dynamics for the liquid-liquid interface from microscopic level by experiments.

In this paper, we have researched about the crystallization mechanism in the vicinity of liquid-liquid interface by experiment. The mutual diffusion behavior in the vicinity of the interface in some systems, NaCl solution / 1-butanol, / 2-butanol and / 2-butanone or KCl solution / 1-butanol, / 2-butanol and / 2-butanone was investigated to clarify the crystallization mechanism near liquid-liquid interface by measuring electric conductance. Furthermore, we have researched the mutual diffusion behavior by predicting the dehydration process near the liquid-liquid interface using FT-IR. We showed the results of electric conductance and FT-IR spectrums for discussion of the solvent and ionic diffusion processes at liquid–liquid interfaces. EXPERIMENTAL PROCEDURES Materials Sodium chloride (99.8%) was purchased from Manac Co. and potassium chloride (99.999%) was purchased from

Merck Co and used as solute substances without further purification. Three kinds of organic solvent such as 1-butanol (99.0%), 2-butanol (99%) and 2-butanone (99%) were purchased from Nacalai Tesque Inc., Japan for organic phase. Preparation of solution Sodium chloride (NaCl) solution and potassium chloride (KCl) solution were dissolved in distilled water, and 6.099 mol/L of NaCl aqueous solution and 4.546 mol/L of KCl aqueous solution were prepared by stirring for 24 h at 300 K. Procedures for liquid-liquid interfacial crystallization An experimental apparatus is illustrated in Figure 1. First 5 × 10

-3 L of A-liquid (NaCl or KCl) aqueous solution

sufficiently stirred for 24 h at 300 K was set in the glass funnel with 0.1 μm PTFE membrane filter (ADVANTEC, H010A047A) on the bottom. Then 5 × 10

-3 L of B-liquid

for organic solvent such as 1-butanol, 2-butabol and 2-butanone was gently added to A-liquid solution with a pipette to form a liquid-liquid interface. The crystallization of solute substances (NaCl and KCl) was performed with changing the contact time of two liquids. The filtration was carried out for separation of crystallization particles from the solution under vacuum when the particles grow as required size. All NaCl and KCl crystals were gathered on the membrane filter. All precipitated crystals were dried in desiccators with blue silica gel under reduced pressure for 24 h before testing their physicochemical properties. Physicochemical properties of NaCl and KCl crystals The crystal morphology and particle size distribution was observed by scanning electron microscopy (KEYENCE, Real Surface View VE-7800). Prior to examination, all samples were mounted onto metal stubs and sputtered with a thin layer of gold under vacuum. The mass of crystals were measured and the growth rate was calculated (Kadota et al., 2007a). Electric conductance The electrochemical experiments were conducted using a Solartron 1260 frequency response analyzer and a Solartron 1278 potentiostat. The movement of the water into organic solvent was investigated by measuring the electric conductance at 1.5mm distance from the interface (Davies and Rideal, 1961; Deleersnyder et al., 2009; Kakiuchi, 2002; Shodai et al., 2006; Tsukahara, 2006). Aqueous solution concentration of A-liquid was controlled 1.0 mol/L to avoid crystallization on the electrode. B-liquid of organic solvent was placed gravely on the A-liquid of aqueous solution. A-liquid and B-liquid were prepared by stirring more than 1 h in thermostatic

Int. J. Phy. Sci. 029

Figure 1. Experimental apparatus for liquid-liquid interfacial crystallization.

Figure 2. SEM photographs of asymmetric solute substance by liquid-liquid interfacial crystallization. (1-butanol was used as organic solvent). (a) NaCl crystal, (b) KCl crystal.

tank at 300 K. 20 ml of A-liquid was set in glass vessel. The electric probe was set in the vicinity of liquid-liquid interface (Kadota et al., 2007c). Fourier transform infrared spectroscopy (FT-IR) A Fourier transform infrared spectrum (FTIR) was performed using JASCO FT-IR 6100 to observe the mutual behavior of three component solutions which consist of ion-water-organic solution. Samples were prepared using KBr pallet method and scanned in the range from 400 to 4000 cm

-1, with a resolution of 4 cm

-1.

All the spectra were processed by ATR correction

(Śmiechowski and Stangret; 2008). RESULTS AND DISCUSSION Liquid-liquid interface crystallization of NaCl and KCl Particles of NaCl and KCl were produced by a liquid-liquid interfacial crystallization method. The morphology of NaCl and KCl crystal was examined by SEM photograph (Figure 2). The hollow and asymmetric NaCl or KCl crystal has been produced as can be seen from SEM images. Compared NaCl crystals with KCl crystals, NaCl crystals were much finer shape than KCl crystals.

Figure 1 Experimental apparatus for liquid-liquid interfacial crystallization.

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Figure 2 SEM photographs of asymmetric solute substance by liquid-liquid

interfacial crystallization. (1-butanol was used as organic solvent.)

(a) NaCl crystal, (b) KCl crystal

Kadota et al. 030

Figure 3. Mutual solubility curves between water and organic solvent. (a) Water/1-butanol (b) Water/2-butanol (c) Water/2-butanone.

As mentioned in previous papers (Kadota et al., 2007a; Kadota et al., 2007b), the asymmetric crystals have not been obtained by any other crystallization although the asymmetric crystals are very effective substances for catalysis. The asymmetric crystals generated on the liquid-liquid interface because the growth rate was faster than that on the organic solvent side. Mutual solubility curves between water and organic solvent are given in Figure 3 (Barton, 1984). In case of 1-butanol and 2-butanol against water, the amount of water solving into the organic solvent was larger than that of those organic solvent into water at room temperature. On the other hand, the converse phenomenon took place in case of 2-butanone against water. The amount of 2-butanone solving into the water was larger than that of water into 2-butanone at room temperature as shown in mutual curve. Therefore, two types of mutual solubility curves were used for liquid-liquid interfacial crystallization. Crystallization mechanism of NaCl and KCl on the liquid-liquid interface Time course of crystallization mass of NaCl and KCl crystals using interfacial crystallization are provided in

Figure 4. Crystallization mass of NaCl crystals in any solvents increased proportionally as shown in Figure 4. On the other hand, KCl crystals rapidly precipitated in the early stages almost until 500 s, and then the rate of crystallization mass of KCl crystals decreased. As noted in Figure 2, NaCl crystals were finer shape than KCl crystals. This reason is that the growth rate of NaCl was constant on the liquid-liquid interface. Figures 5 and 6 provide the time course of particle size distribution of NaCl crystals and KCl crystals using each organic solvent, respectively. The particle size distribution of NaCl crystals in any organic solvents shifted into larger side with changing time. In contrast, the particle size distribution of KCl crystals did not shift into as much as that of NaCl against time. In addition, the smaller size of KCl crystals exists even though time advances. This indicates that the crystal growth dominates in case of the liquid-liquid interfacial crystallization of NaCl but the nucleation dominates in case of KCl. Actually, fine crystals of KCl were observed on liquid-liquid interface with changing time. We realized that the crystallization mechanism of NaCl crystals was different from that of KCl crystals on the liquid-liquid interface regardless of the same crystal structure. It is known that the hydrated

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Figure 4. Time course of crystallization mass of sodium chloride and potassium chloride crystals using interfacial crystallization. (a) 1-butanol, (b) 2-butanol, (c) 2-butanone as organic phase.

Figure 5. Time course of particle size distributions of sodium chloride crystals using, (a) 1-butanol, (b) 2-butanol, (c) 2-butanone as organic phase.

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Figure 4 Time course of crystallization mass of sodium chloride and potassium chloride crystals usinginterfacial crystallization(a)1-butanol,(b)2-butanol,(c)2-butanone as organic phase.

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Figure 6. Time course of particle size distributions of potassium chloride crystals using, (a) 1-butanol, (b) 2-butanol, (c) 2-butanone as organic phase.

Figure 7. Hydrated structure depending on ion species, (a) Sodium ion forms structure making ion in water (b) Potassium ion forms structure breaking ion in water.

structure forming in the solution is different between sodium ion and potassium ion (Marcus, 1986; Ohtaki and Randnai, 1993). Figure 7 illustrates the hydration model of each sodium or potassium ion in the solution. Sodium ion is known as the structure-making ion. On the other

hand, potassium ion is known as the structure-breaking ion. Dehydration process of sodium ion gradually occurs near the liquid-liquid interface since sodium ion which is the structure-making ion thickly forms the hydrated ion. Potassium ion which is the structure-breaking ion

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Figure 6 Time course of particle size distributions of potassium chloride crystalsusing (a)1-butanol, (b)2-butanol, (c)2-butanone as organic phase.

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Figure 7 Hydrated structure depending on ion species (a) sodium ion forms structure making ion in water (b) potassium ion forms structure breaking ion in water

(b) Potassium ion(a) Sodium ion


Figure 8. Time course of electrical conductance using sodium chloride solution. (a) 1-butanol, (b) 2-butanol, (c) 2-butanone system.

disorders the hydration structure. As a result, there are higher possibilities of dehydration of potassium ion than that of sodium ion near the liquid-liquid interface. This means that the nucleation of KCl dominantly occurs on the interface compared with NaCl. Mutual diffusion of sodium and potassium ion The electric conductance in organic solvent side measured against the contact time at six positions. Figure 8 provides plots of time variation of the conductance at six positions from the interface in each organic solvent side contacted with NaCl solution. Figure 9 shows that of KCl solution. The electric conductance near water is much larger than that of organic solvent in both solute substances. It turned out that water transported into organic solvent side because the electric conductance increased in organic solvent side as time passes. Especially, the electric conductance of 1-butanol and 2-butanol proportionally increases as time passes. The order of electric conductance variation in the vicinity of interface corresponded with that of crystallization mass in both organic solvents. The diffusion of water into organic solvent at the position of F does not occur even at the contact time of 2400 s. The diffusion of water into 2-butanone occurred immediately when the solution

contacted with 2-butanone since the electric conductance of 2-butanone initially valued high. Considering from these results, the difference of the electric conductance variation expresses the difference of concentration distribution of each solvent. Similar tendency was observed in case of KCl solution. Figure 10 shows the mutual diffusion coefficient of NaCl and KCl calculated from electric conductance at position B. Mutual diffusion coefficient was calculated by Equation 1 as shown (Matano, 1979):

(1)

Where D, t, x and are the diffusion coefficient, time, the distance from interface, concentration, respectively. The electric conductance of solution drastically increases as the measured position approaches to the interface. It was confirmed that the water at lower vessel moved to the organic solvent, and the crystallization of the NaCl or KCl solving to the water occurred. The water moves to organic solvent. The solute ions coordinated water occur dehydration in the vicinity of the liquid-liquid interface and then the crystal generates on the liquid-liquid interface.

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Figure 8 Time course of electrical conductance using sodium chloride solution-(a)1-butanol, (b)2-butanol,(c)2-butanone system.

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Kadota et al. 034

Figure 9. Time course of electrical conductance using potassium chloride solution. (a) 1-butanol, (b) 2-butanol, (c) 2-butanone system.

Figure 10. Mutual diffusion coefficient calculated from electrical conductance located at position B.

Microscopic behavior of NaCl and KCl near liquid-liquid interface The microscopic behavior of NaCl and KCl near solution / organic solvent interface was predicted by measuring Fourier transform infrared spectroscopy (FT-IR). We

created the system for existence of organic, water, and solute substance to solve the structure hydrated ion in the organic solvent side. OH stretch band was separated from three components solution spectra, and compared with others different amount of solute were shown in Figures 11 and 12. Furthermore, the hydrogen band

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Figure 11. IR spectrums of sodium chloride solution separated from sodium chloride solution. (a)1-butanol,(b)2-butanol, (c)2-butanone system.

Figure 12. IR spectrums of potassium chloride solution separated from potassium chloride solution. (a) 1-butanol, (b) 2-butanol, (c) 2-butanone system.

Figure 11 IR spectrums of sodium chloride solution separated from sodium chloride solution-

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Kadota et al. 036

Table 1. Hydrogen band energy calculated by IR spectrums.

Variable NaCl ΔE[kJ] KCl ΔE[kJ]

1-butanol 0.01153 0.1268

2-butanol - 0.1153

2-butanone - 0.1268

Figure 13. Prediction of precipitation on liquid-liquid interface.

energy calculated from peak shift as shown in Figures 11 and 12 was described in Table 1. The hydrogen band energy shifted to high energy side as the electrolyte concentration increased in aqueous solution. This was caused from the existence of ion, which destroyed water-water hydrogen band. The variation of shift energy of KCl in solution became higher than that of NaCl in solution. A potassium ion behaves as structure-breaking ion in organic solution with high density. In brief, ionic species effect on the hydrated structure in case that the solution breaks into organic solution. Some researchers have studied on the nucleation or crystal growth in solution using FT-IR (Cheng and Lin, 2006; Yoda and Ootawa, 2009). However, there have been few researches about the nucleation or crystal growth in the vicinity of liquid-liquid interface. Figure 13 illustrates the change of hydration in the mixed solution. In case of NaCl solution, which sodium ion is structure-making ion, hydrated structure keeps even if ion concentration is higher. In contrast, dehydration of potassium ion occurs in case of KCl solution, which potassium ion is structure-breaking ion as the concentration of potassium ion become higher.

It proved that sodium ion made the hydrated structure and potassium ion broke hydrated structure in organic solution from dynamics consideration. CONCLUSION In the liquid-liquid interfacial crystallization, the mutual diffusion behavior in the vicinity of the interface in some systems was investigated to clarify the nucleation and crystallization mechanism near liquid-liquid interface by measuring electric conductance and FT-IR. The electric conductance near water was much larger than that of organic solvent in both solute substances. It turned out that water transported into organic solvent side because the electric conductance increased in organic solvent side as time passes. The diffusion of water into 2-butanone occurred immediately when the solution contacted with 2-butanone since the electric conductance of 2-butanone initially valued high. The hydrogen band energy shifted to high energy side as the electrolyte concentration increased in aqueous solution. This was caused from existence of ion, which destroyed water-

Contact with organic solventHydrated ion

Increase in ion concentration

Na+

Sodium chloride

Hydrated ion

K+

Dehydrated ion

① ②

③

Potassium chloride③

Figure 13 Prediction of precipitation on liquid-liquid interface

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ionic behavior of nacl and kcl in the vicinity of solution / organic … liquid-liquid interface...

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