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Journal of Colloid and Interface Science 269 (2004) 466471 www.elsevier.

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Cloud point of aqueous solutions containing oxyethylated methyl dodecanoates: effects of surfactant hydrophilicity, nature of added electrolyte, and water activity
Katarzyna Materna,a, Gerard Cote,b and Jan Szymanowski a
a Poznan University of Technology, Institute of Chemical Technology and Engineering, Pl. Sklodowskiej-Curie 2, 60-965 Poznan, Poland b Ecole Nationale Superieure de Chimie de Paris, Laboratoire dElectrochimie et de Chimie Analytique (UMR CNRS No. 7575),

11, rue Pierre et Marie Curie, 75005, Paris, France Received 30 April 2003; accepted 5 August 2003

Abstract The aim of this work was to determine the cloud points of new oxyethylated methyl dodecanoates of various hydrophilicity (OMD-n, where n refers to the average degree of oxyethylation) and to correlate them with surfactant hydrophilicity and, for a given electrolyte, with water activity. Thus, it is shown that the cloud point in the absence of electrolyte (CP0 ) can be simulated by the following equation: CP0 = 165.5 log n 112.0 (with R 2 = 0.987). The effects of NaCl, NaHCO3 , and KSCN on the cloud point are also reported and discussed. The salting-out effect arising from the presence of NaCl or NaHCO3 is explained by the existence of a hydration shell with enhanced water structure as well as a zone with decreased salt concentration around the (OCH2 CH2 )n chain, as compared with the bulk. On the other hand, the salting-in effect is explained by depletion of water around the (OCH2 CH2 )n chain. Thus, it is estimated that the number b of water molecules forced back into the bulk solution from the salt-decient regions when the hydration shells of two OCH2 CH2 monomer units overlap ranges between 2 and 3 and 3 and 4 for NaCl and NaHCO3 , respectively, depending on the average degree of oxyethylation n of OMD-n. It is also shown that the water activity is a useful parameter to simulate the variation of cloud point in the presence of an electrolyte (CP) at low and moderate concentration (e.g., <1 M NaCl), CP0 /CP 1 (bR/) ln aw , where R is the gas constant and 15 J K1 mol1 . At high electrolyte concentration, the relationship between CP0 /CP and ln aw signicantly deviates from linearity. In the particular case of KSCN, an inversion of the salt effect can be observed. The salting-in effect of KSCN increases up to about 2 M, but decreases at higher KSCN concentrations, so that KSCN can even act as a salting-out salt at high concentration (typically above 3.3 M for OMD-14). 2003 Elsevier Inc. All rights reserved.
Keywords: Cloud point; Oxyethylated methyl dodecanoates; Water activity; Electrolytes

1. Introduction Cloud point separation is an innovative technique used to recover various substances from aqueous samples [14]. The technique is now often used as a preliminary preconcentration step prior to liquid chromatography [57]. Triton-type surfactants are usually used, as they can be easily monitored by a UV detector at 220 nm. The use of alkylphenol derivatives should be eliminated, however, due to environmental problems. In the past few years a direct oxyethylation of fatty acid methyl esters was
* Corresponding author.

discovered, RCOOCH3 + nH2 C CH2 (1)

O RCO(OCH2 CH2 )n OCH3 ,

E-mail address: katarzyna.materna@put.poznan.pl (K. Materna). 0021-9797/$ see front matter 2003 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2003.08.002

and new nonionic surfactants were synthesized and described [810]. These new surfactants may nd broad application in the future as they are synthesized directly from intermediate fatty acid methyl esters. The rst step in the design of cloud point separations is the determination of the cloud point (i.e., the phaseseparation temperature, denoted hereafter CP). We recall that the cloud point is an important property of nonionic surfactants. Below this temperature a single phase of mole-

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cular or micellar solution exists; above it, the surfactant loses sufcient water solubility and a cloudy dispersion results. In some situations the solution phase separates into a surfactant-rich phase and a surfactant-poor phase. As a result, various solutes including organic substances and metal species can be transferred into the surfactant-rich phase and signicantly enriched, as the volume of the latter is typically one order lower than the volume of the aqueous phase. The separation can be carried out 2030 C above the cloud point, which should be rather low, especially in the preconcentration of temperature-sensitive substances. Several trends in cloud point with surfactant molecular structure are commonly known: cloud point increases with relative polyoxyethylene chain content and decreases with increasing alkyl carbon chain length. It is worth noting that the cloud point of aqueous surfactant solutions can be strongly inuenced by the presence of other materials. For example, cloud point can be decreased by the introduction of polar compounds, anions that are water structure formers 3 (hard bases, F , OH , SO2 4 , Cl , and PO4 ), and cer+ tain cations (NH4 , alkali metal ions except for Li+ ). Cloud point can be increased by addition of long-chain nonpolar material, anions that are water structure breakers (large, polarizable anions, soft bases, SCN , I ), and certain cations (polyvalent cations, H+ , Li+ ) [11]. Several empirical relationships between surfactant structure and cloud point can be found in the literature. Gu and Sjblom [12] have demonstrated a linear relationship between the cloud point and the logarithm of the oxyethylene group number for alkyl oxyethylates, alkylphenyl oxyethylates, and methyl-capped alkyl oxyethylate esters, as well as a linear relationship between the cloud point and alkyl carbon number for linear alkyl oxyethylates. More recently, Huibers et al. [13] have proposed a general empirical relationship using the logarithm of the number of oxyethylene groups and three topological descriptors that account for hydrophobic domain variation for estimating the cloud point of pure nonionic surfactants of the alkyl oxyethylate class. The cloud point of polydispersive surfactants solutions can be also correlated with the hydrophile lipophile balance [14]. A thermodynamic analysis of the cloud point phenomenon has been proposed on the basis of the FloryHuggins theory [15,16]. Kjellander and co-workers [17,18] have discussed the water structure and cloud point of polyoxyethylene glycols in water in the absence and presence of electrolytes. Theoretical models have been proposed. The aqueous solution has been divided into the hydration shell, surrounding the polymer chain, with enhanced water structure and the bulk, where the water is not inuenced by the presence of polyglycol. When the temperature is increased, water molecules are forced back into the bulk solution from the salt-decient regions, which allows the overlap of the latter and nally the splitting of the solution. Rupert [19] has pointed out that spherical micelles of nonionic surfactants resemble polymer coils in a solution. As a result, the clouding of water/nonionic surfactant systems can be analyzed

using a FloryHuggins approach. The proposed model predicts correctly that the micelles start to attract each other at 30 to 40 C below the CP, but the phase separation is prevented by the ideal mixing entropy. At CP the Gibbs free energy of interaction compensates for the ideal entropy of interaction, and phase separation occurs. The model has been further developed by Inoue et al. [20] for the binary surfactant mixture system, and the expression describing CP as a function of the composition has been derived, assuming a regular solution model for mixed micelles. The aim of this work was to determine the cloud points of oxyethylated methyl dodecanoates of various hydrophilicity and to correlate them with surfactant hydrophilicity and, for a given electrolyte, with water activity. The aim of this work was to present the effects of electrolytes upon the clouding of solutions containing new type surfactants, but not the formulation of the thermodynamic model. The effect of saltingin electrolytes seemed the most interesting and completely new.

2. Materials and methods The various oxyethylated methyl dodecanoates [C11 H23 CO(OCH2 CH2 )n OCH3 ] used were kindly provided by the Institute of Heavy Organic Synthesis, Kedzierzyn-Kozle (Poland), and are denoted hereafter as OMD-n, where n refers to the average degree of oxyethylation. The surfactants effectively tested exhibited average degrees of oxyethylation n ranging from 6 to 14 and their compositions determined by GC and HPLC were reported in previous papers [2123]. Simulsol OX 1006L [C10 H21 (OCH2 CH2 )6 OH] was kindly provided by Seppic (France) and used as delivered. Analytical grade sodium chloride, sodium hydrogenocarbonate, and potassium thiocyanate were from POCh Gliwice (Poland) and used as delivered. Finally, deionized water was used for the preparation of all the aqueous solutions. The cloud points were determined in a classical way by heating the micellar solutions above their CP and then by leaving their temperature to slowly decrease under intensive mixing, until the instant of complete disappearance of the turbidity (the temperatures at which the solutions became transparent were assumed to be the cloud points). The determination was repeated at least three times for each solution and the error in the average values of CP did not exceed 1 C.

3. Results and discussion The cloud points of oxyethylated methyl dodecanoates [4] increase in a typical way with an increase of surfactant hydrophilicity, i.e., the length of the polyoxyethylene chain. The effect of surfactant concentration is small and disappears at concentrations above 1%. Each successive oxyethylene group affects the cloud point less. As a result, a linear relationship CP vs log n can

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Fig. 1. Relationship between the cloud point and the average degree of oxyethylation (log n), for COMD-n = 1% in pure water.

Fig. 3. Effect of NaHCO3 concentration on the cloud point of various oxyethylated methyl dodecanoates OMD-n, for COMD-n = 1%.

Fig. 2. Effect of NaCl concentration on the cloud points of various oxyethylated methyl dodecanoates OMD-n, for COMD-n = 1%.

Fig. 4. Effect of KSCN concentration on cloud points of various oxyethylated methyl dodecanoates OMD-n, for COMDn = 1%.

be derived (Fig. 1), CP0 = 165.5 log n 112.0 (with CP0 in C) R2 (2) = 0.987), for COMD-n = 1% wt (regression coefcient where log refers to decimal logarithm, superscript indicates that the solution is free from any electrolyte, and n designates to the average degree of oxyethylation. The shape of Eq. (2) is in a good agreement with the empirical equations previously reported by Gu and Sjblom [12] for the cloud points of various nonionic surfactants. It appears that the value of the coefcient of log n in Eq. (2) is in the same range as the value reported by Huibers et al. [13] (in Eq. (2) in Ref. [13], log should be interpreted as natural logarithm). However, a signicantly weaker effect of the polyoxyethylene chain has been reported for triblock copolymers [24], in which the hydrophilic polyoxyethylene chain present in the molecule center was screened by two hydrophobic polyoxyalkylene (polyoxypropylene or polyoxybutylene) chains. An addition of salting-out electrolytes (NaCl and NaHCO3 ) causes a sharp decrease of CP (Figs. 2 and 3), while an increase of CP is observed in the presence of a salting-in electrolyte such as KSCN (Fig. 4). To better understand the effects of salting-out and saltingin electrolytes on the cloud points of the oxyethylated methyl

dodecanoates, it is of interest to examine the basic physicochemistry of the clouding process further. For such a purpose, the model developed by Florin and co-workers from the FloryHuggins theory in the case of high-molecularweight poly(ethylene oxide), PEO, in water and aqueous salt solutions is considered below [17,18]. It is recalled that the self-association of water arising from hydrogen bonding is of outstanding importance in regard to many properties peculiar to aqueous systems, and that it is reasonable to describe the structure of liquid water as a tetrahedral water network. When high-molecular-weight poly(ethylene oxide) is added at low temperature, its oxyethylene group hydrates, which allows its solubilization. The structure of water in the hydration shells formed around the PEO chains is enhanced compared with the bulk. At high temperatures, such enhanced structure is unfavorable for entropic reasons, its extent decreases, and nally the system phase-separates. Introduction of a salt into an aqueous solution of PEO changes the phase-separation temperature. This alteration varies considerably in magnitude depending on the kind of electrolyte introduced and on its concentration. According to Florin and co-workers [17,18], in the presence of many salts, the above-mentioned hydration shell around the PEO chain with enhanced water structure also corresponds to a zone with decreased salt concentration (i.e., with an excess of water molecules), as compared with the bulk. When the

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temperature is increased, the dehydration of the PEO chains takes place. The extent of the hydration shells then decreases and water molecules are forced back into the bulk solution from the salt-decient regions, which allows the overlap of the latter and nally the splitting of the solution. In fact, the inuence of electrolytes can be separated into the effects of cations (Na+ and K+ in this case) and of an ions (Cl , HCO 3 , and SCN ) [13,14,25,26]. Due to their own hydration, which decreases the water activity, the presence of cations such as Na+ and K+ favors the dehydration of the polyoxyethylene chain and as a result causes a decrease of CP. The Cl anion mainly enhances the structure of water in the bulk of the solution. This weakens the formation of hydrogen bonds between the water molecules and the polyoxyethylene chains, which makes easier the dehydration of the latter and also results in a decrease of CP. Such explanations stand for the oxyethylated methyl dodecanoates. HCO 3 acts in the same way as Cl , but Fig. 3 shows that its effect is even stronger than the latter. On the other hand, SCN anion is known to destroy the structure of bulk water and increase the cloud point by making more water molecules available to interact with the PEO chains [11]. In reality, the situation is more complex, as it has been shown that the SCN anion largely penetrates into the hydration shells around the oxyethylene groups, resulting in a zone with increased thiocyanate concentration (i.e., with a depletion of water molecules), as compared with the bulk (as exemplied in Table III in Ref. [27]). The presence of SCN anion in the hydration shell of the oxyethylene groups may give rise to repulsive interactions between the surfactant chains and thus also contributes to the increase of CP [27]. The possible formation of complexes between the oxyethylene groups and K+ is also to be considered. Beyond the qualitative explanations given above, it should be kept in mind that the situation is certainly more complex, as ions affect in different way the various structures encountered in water, i.e., the four compounds considered by Luu et al. [28]. In their model, Florin and co-workers [17,18] have established that the observed change in the cloud points due the presence of an electrolyte arises from the difference w w0 = b 1 0 1 + , (3)

Fig. 5. Effect of water activity on the ratio of cloud points in the absence (CP0 ) and presence (CP) of NaCl in the range 0.251 M NaCl, for COMDn = 1%.

The difference w w0 varies almost linearly with absolute temperature in the case of PEO solutions [18]: w w0 = T ( = 15.5 J K1 mol1 ; = 5.7 kJ mol1 ; R 2 = 0.9994). (4) If Eqs. (3) and (4) are identied, 1 0 1 is replaced by RT ln aw , and T is equated to the cloud point, one obtains 1/CP = /[ + ] bR/[ + ] ln aw , (5)

where R and aw denote the gas constant and the water activity (at CP), respectively. In the absence of electrolyte, aw = 1 and = 0, which gives 1 CP
0

or = CP0 ,

(6)

where CP0 refers to the cloud point in the absence of electrolyte. As a result, Eq. (5) can be rewritten as 1 CP0 = CP 1+
CP0

bR 1+
CP0

ln aw .

(7)

At high water activity (i.e., at low electrolyte concentration), the salt effects whose inuence is depicted by are weak and the contribution of in Eq. (7) can be neglected, which leads to bR CP0 1 ln aw . (8) CP By using the water activity data available in the literature [29], the experimental results given in Figs. 2 and 3 for NaCl and NaHCO3 , respectively, have been replotted under the form of CP0 /CP vs ln aw , as shown in Figs. 5 and 6. Examination of these gures shows that a series of straight lines are obtained from Eq. (8) as expected. From the slopes of the straight lines and by using the value of found for polyoxyethylene glycols (i.e., = 15.5 J K1 mol1 ), the values of b plotted in Fig. 7 can be obtained (b is the average number of transferred water molecules when the hydration shells of two OCH2 CH2 monomer units overlap).

where w and w0 are the molar free energy contributions from PEO chainPEO chain interactions and overlaps of hydration shells and salt-decient zones (if any), in the presence and absence of salt, respectively, b is the average number of transferred water molecules when the hydration shells of two OCH2 CH2 monomer units overlap, 1 and 0 1 refer to the chemical potential of water in the bulk and in the standard state, respectively, and includes all the remaining salt effects. Florin et al. [18] found that b greatly varies from one salt to another. For instance, for PEO solutions at 90 C, b is close to 3 for NaCl, but only to 0.3 for KI. A negative value of b is even obtained at 96 C, which indicates a depletion of water and an excess of salt near the PEO chains.

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Fig. 6. Effect of water activity on the ratio of cloud points in the absence (CP0 ) and presence (CP) of NaHCO3 , for COMD-n = 1%.

Fig. 8. Effect of water activity on the ratio of cloud points in the absence (CP0 ) and presence (CP) of NaCl in the range 0.254 M NaCl, for COMD-n = 1%.

Fig. 7. Effect of the average degree of oxyethylation (n) on the average number b of water molecules forced back into the bulk solution (see Eq. (3)). Fig. 9. Effect of NaCl concentration on coefcient (see Eq. (3)).

The values of b thus obtained, ranging between 2 and 3 and between 3 and 4 for NaCl and NaHCO3 , respectively, clearly illustrate the process of dehydration. It appears that b slightly increases with the oxyethylation group number n both for NaCl and NaHCO3 . It is also of interest that the values of b found for NaCl with OMD-n are slightly lower than those previously reported with PEO (i.e., b 3). At lower water activity (i.e., at higher electrolyte concentration) the salt effects depicted by in Eq. (7) cannot be longer ignored. This is exemplied in Fig. 8, where a deviation from linearity clearly appears as water activity is decreased by addition of NaCl. From the deviation from linearity, it is possible to estimate the value of , = CP0 (CP0 /CP)extrapolated (CP0 /CP)experimental 1 , (9)
Fig. 10. Effect of water activity on the ratio of cloud points in the absence (CP0 ) and presence (CP) of KSCN, for COMD-n = 1%.

where (CP0 /CP)extrapolated refers to Eq. (8) extrapolated at low water activity and (CP0 /CP)experimental to the experimental data. The values of are plotted in Fig. 9. Examination of Fig. 9 shows that the salt effect depicted by becomes signicant only at high electrolyte concentration (i.e., [NaCl] > 1 M).

In the case of KSCN, the plot of CP0 /CP vs ln aw is almost linear for OMD-14 and OMD-13 up to about 0.8 M (i.e., down to ln aw = 0.02), but signicantly deviates from linearity for lower values of the oxyethylene group number n, even at low KSCN concentration (Fig. 10). From

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tify various effects of salting-out and salting-in electrolytes upon the dehydration process of polyoxyethylene chain. Acknowledgment The work was supported by the KBN donation for institute activity DS 32/044/2003. References
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Fig. 11. Effect of NaCl and KSCN concentration on the cloud point of OMD-14 and Simulsol OX 1006L, for COMD-14 = 1% and CSimulsol = 2%.

the slopes of the linear parts of the curves obtained with OMD-14 and OMD-13, one can calculate a value of b close to 1.7. Such a negative value suggests that KSCN creates a depletion of water around the polyoxyethylene chain (i.e., a zone with increased concentration of salt), as compared with the bulk, as already observed in the literature [18,27]. For lower oxyethylene group number (i.e., n 12), the early deviation from linearity suggests that the salt effects depicted by become important even at low KSCN concentration. This can be explained by the hydrophobic hydration of the alkyl chain, which becomes important for more hydrophobic surfactants, i.e., with lower length of the hydrophilic polyoxyethylene chain. In fact, a series of experiments performed at high KSCN concentration shows an inversion of the effect of KSCN, as an additional increase of KSCN concentration leads to a maximum of CP and then causes its decrease, so that KSCN can even act as a salting-out salt at high concentration (typically above 3.3 M for OMD-14) (Fig. 11). The phenomenon is not specic to oxyethylated methyl dodecanoate, as a similar change of CP is observed for typical oxyethylated alcohol (Simulsol OX 1006L [C10 H21 (OCH2 CH2 )6 OH]). This phenomenon may arise from various effects, including (a) the saturation of the hydration shells around the oxyethylene groups by the SCN anion, inhibiting any further increase of salt excess in this zone, and (b) the dehydration effect of K+ discussed previously, which could then become prevalent.

4. Summary The cloud point of nonionic surfactants such as oxyethylated methyl dodecanoates depends upon surfactant hydrophobicity and type and concentration of electrolyte. Theoretical equations in which water activity is used as an independent parameter are useful to understand and quan-