Article pubs.acs.org/jced
Effect of Solvent on Reactive Extraction of 2‑Methylidenebutanedioic Acid by Using N‑Methyl‑N,N‑dioctyloctan-1-ammonium Chloride Seyhan Günyeli,† Hasan Uslu,*,‡ and Ş. Iṡ mail Kırbaşlar†
Chemical Engineering Department, Iṡ tanbul University, 34320, Avcılar, Iṡ tanbul, Turkey Chemical Engineering Department, Beykent University, Ayazağa, Iṡ tanbul, Turkey
† ‡
ABSTRACT: The extraction of 2-methylidenebutanedioic acid was investigated using N-methyl-N,N-dioctyloctan-1-ammonium chloride (trioctylmethyl ammonium chloride) (Aliquat 336) with different diluents having distinct functional groups. Nine diluents were used in the study, that is, octan-1-ol, nonan-1-ol, decan-1-ol, ethyl acetate, propyl acetate, heptan-2-one, octan-2-one, octane, and decane. The measurements were performed at temperature of 298.2 K. The experimental results of batch extractions were used to calculate distribution coefficients (KD), loading factors (Z), and extraction efficiency (E). The maximum distribution coefficient (KD = 13.01) was obtained with octan-1-ol, and its extraction efficiency was 92.86 %. Further, the maximum loading factor reached a value of 0.427 at a 0.440 mol·kg−1 amine concentration.
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al.13 separated 2-methylidenebutanedioic acid from aqueous solution by Aliquat 336 in four diluents. Waghmare et al.14 recovered picolinic acid from aqueous solution by reactive extraction, and natural nontoxic solvents were used to dilute the amine. Chang et al.15 used trioctyl phosphine oxide which was diluted in kerosene for removing 2-, 3-, and 4-aminophenol from aqueous media by the reactive extraction method. Marti et al.16 investigated pyruvic acid extraction by trioctylamine in octan-1-ol, and the kinetic and equilibrium of reactive extraction were detailed. Aşcı̧ and Iṅ ci17 determined the effect of Amberlite LA-2 on the extraction of acrylic acid with different diluents. Ren et al.18 studied the extractability of short chain fatty acids from model fermentation broth and its stripping process. In this study, the reactive extraction of 2-methylidenebutanedioic acid from aqueous solutions was investigated by Aliquat 336 in two different acetates (ethyl ethanoate and propyl ethanoate), three different alcohols (octan-1-ol, nonan-1-ol, and decan-1-ol), two different ketones (heptan-2-one and octan-2one), and two different alkanes (octane, decane).
INTRODUCTION 2-Methylidenebutanedioic acid is an intermediate in the C5branched dibasic acid metabolism and a substrate for the enzyme succinate-CoA ligase. It can be used as a monomer for the production of a plethora of products including resins, plastics, paints, and synthetic fibers. Aspergillus terreus species is considered as suitable for the production of 2-methylidenebutanedioic acid from carbohydrates during the fermentation process in the food industry.1−3 Because of the common and important uses of 2-methylidenebutanedioic acid, the removal of impurities and salt concentrations from 2-methylidenebutanedioic acid are needed prior to its commercialization.4,5 However, the separation of 2-methylidenebutanedioic acid from its aqueous fermentation broth and wastewater stream is very difficult due to the high affinity of carboxylic acids to water. Carboxylic acid extraction by using aliphatic tertiary amines and quaternary ammonium salts has been studied effectively. However, solvent extraction with alcohols, ketones, esters, and aliphatic hydrocarbons is not very efficient for carboxylic acids. A low distribution coefficient is obtained owing to the low aqueous activity of carboxylic acids.6−8 The distribution coefficients are reached to maximum when aliphatic amines are used during the extraction of carboxylic acids. The 2-methylidenebutanedioic acid extraction has not been studied efficiently. Uslu et al.9 studied the extraction of levulinic acid using different alcohols, and the solvation area of levulinic acid was determined. Tuyun and Uslu10 reported the extraction equilibrium data for picolinic acid by using tridodecyl amine. Cascaval et al.11 investigated the influence of polarity on the reactive extraction of ethanoic acid using N,N-dioctyloctan-1amine as an extractant. Blaga and Malutan12 investigated the selectivity of ascorbic acid from aqueous media. Wasewar et © 2014 American Chemical Society
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THEORY OF COMPLEX FORMATION Aliquat 336 was selected as an extractant for investigating the effect of extractants on the extraction of 2-methylidenebutanedioic acid from aqueous media. Aliquat 336 extracts both the dissociated and the undissociated forms of acids.19,20 For the extraction of 2methylidenebutanedioic acid (HA) by Aliquat 336 (R4N+Cl−), Received: October 13, 2013 Accepted: January 14, 2014 Published: January 17, 2014 461
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Table 1. Results for Extraction of 2-Methylidenebutanedioic Acid with the Aliquat 336 + Alcohol Systema solvents (alcohols)
pHaq
C̅ RE 4NCl/mol·kg−1
CHA/mol·kg−1
KD
100 E
Z
KE
octan-1-ol
2.395 2.516 2.615 2.916 3.064 2.361 2.453 2.530 2.738 2.967 2.278 2.442 2.503 2.701 2.937
0.440 0.871 1.310 1.751 2.210 0.440 0.871 1.310 1.751 2.210 0.440 0.871 1.310 1.751 2.210
0.287 0.190 0.129 0.084 0.044 0.298 0.221 0.158 0.111 0.050 0.312 0.229 0.174 0.123 0.062
1.146 2.245 3.756 6.297 13.007 1.064 1.779 2.890 4.540 11.222 0.971 1.682 2.530 4.002 8.921
53.41 69.18 78.96 86.29 92.86 51.56 64.01 74.29 81.95 91.82 49.26 62.72 71.68 80.01 89.92
0.427 0.328 0.269 0.232 0.205 0.418 0.311 0.258 0.223 0.202 0.407 0.306 0.251 0.219 0.200
2.605 2.578 2.867 3.596 5.885 2.419 2.042 2.206 2.593 5.078 2.206 1.932 1.932 2.286 4.037
nonan-1-ol
decan-1-ol
a
pHaq is the pH value of the aqueous phase, C̅ RE 4NCl is the equilibrium concentration of amine in the organic phase, CHA is the concentration in the aqueous phase after extraction, KD is the distribution coefficient, Z is the loading factor, E is the extraction efficiency, and KE is the equilibrium extraction constant. The uncertainty for the pH measurements was 1 %.
log KD = log KE + log C̅ RE4NCl
the distribution coefficient of itaconate ions KD(A−) can be defined as:
KD(A−) =
The plot of log KD against log C̅ ER4NCl provides a straight line with the intercept log KE, from which the equilibrium complexation constant can be obtained. C̅ RE4NCl is the equilibrium concentration of amine in the organic phase. Loading factors were used to find KE according to eq 7
C̅ R 4N+Cl‐:A‐ C HA + CA −
(1)
For the extraction of the undissociated molecules, the distribution coefficient of undissociated acid KD(HA) can be written as: KD(HA) =
Z = KEC HA (1 − Z)
C̅ R 4N+Cl−:HA C HA + C A−
(3)
The extraction of the undissociated molecules of lactic acid with Aliquat 336 has been reported more at low pH values than the dissociated molecules.21 The ratio of dissociated to undissociated molecules changes with increasing pH. Therefore, pH is the most effective parameter for concentration of undissociated acid. The extraction of the undissociated molecules of 2-methylidenebutanedioic acid by chemical interaction can be represented as:13 R 4NCl + HA ↔ R 4NCl: HA
E% =
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(1 − α)
= KEC̅ RE4NCl
KD·100 1 + KD
(8)
MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Aliquat 336 ((Sigma (CAS: 63393-96-4)) > 99 % in mass) is an anion exchange extractant and liquid with a molecular weight of 374.10. 2-Methylidenebutanedioic acid (Sigma (CAS: 97-65-4) > 99 % in mass, molecular weight: 130.10), pKa1 and pKa2 of 2-methylidenebutanedioic acid are 3.85 and 5.45, respectively. Alcohols [octan-1-ol (CAS: 111-875), nonan-1-ol (CAS: 143-08-8), decan-1-ol (CAS: 112-30-1)], alkanes [octane (CAS: 111-65-9), decane (CAS: 124-18-5)], acetates [ethyl acetate (CAS: 141-78-6), and propyl acetate (CAS: 109-60-4)], and ketones [2-heptanone (CAS: 110-43-0) and 2-octanone (111-13-7)] have been supplied from Aldrich and Fluka. Purities of all chemicals used in this study are above 98 % in mass. Experimental Procedure. Initial concentrations of acid of 0.615 mol·kg−1 were prepared with distilled water. Different ratios of Aliquat 336 to diluent were mixed for preparing organic solutions between (0.440 and 2.210) mol·kg−1. Equal volumes (20 mL) of both phases were added to 100 mL Erlenmeyer flasks. Erlenmeyer flasks were shaken in thermostat
(4)
with the extraction constant (KE) KD(HA)
(7)
In eq 7, Z is the loading factor. Extraction efficiency (E %) is defined as the ratio of 2methylidenebutanedioic acid concentration in organic phase to the sum of acid concentration in organic and aqueous phase and is defined as,
(2)
The overall distribution coefficient (KD) can be represented as: KD = KD(A−) + KD(HA)
(6)
(5)
In eqs 4 and 5, the overbar (−) indicates organic phase, C̅ ER4NCl is the equilibrium amine concentration in the organic phase, C̅ HA is the acid concentration of the organic phase, C̅ ER4NCl:HA is the acid amine complex concentration in the organic phase, KE is the extraction constant, Ka is the dissociation constant of the acid and α = Ka/(Ka + [H+]) represents the part of dissociated form of acid. The distribution coefficient and equilibrium extraction coefficients of the undissociated molecules can be determined in case of α = 0, and eq 5 is linearized 462
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Table 2. Results for the Extraction of 2-Methylidenebutanedioic Acid with the Aliquat 336 + Ketone Systema solvents (ketones)
pHaq
C̅ ER4NCl/mol·kg−1
CHA/mol·kg−1
KD
100 E
Z
KE
heptan-2-one
2.291 2.431 2.502 2.698 2.898 2.272 2.403 2.497 2.554 2.811
0.440 0.871 1.310 1.751 2.210 0.440 0.871 1.310 1.751 2.210
0.313 0.238 0.179 0.128 0.083 0.366 0.263 0.195 0.135 0.092
0.966 1.587 2.436 3.824 6.418 0.679 1.338 2.151 3.564 5.704
49.14 61.34 70.90 79.27 86.52 40.44 57.22 68.26 78.09 85.08
0.407 0.302 0.249 0.218 0.194 0.360 0.287 0.242 0.215 0.191
2.196 1.822 1.860 2.184 2.904 1.543 1.536 1.642 2.035 2.581
octan-2-one
a
pHaq is the pH value of aqueous phase, C̅ ER4NCl is the equilibrium concentration of amine in the organic phase, CHA is the concentration in the aqueous phase after extraction, KD is the distribution coefficient, Z is the loading factor, E is the extraction efficiency, and KE is the equilibrium extraction constant. The uncertainty for the pH measurements was 1 %.
Table 3. Results for the Extraction of 2-Methylidenebutanedioic Acid with the Aliquat 336 + Ester Systema solvents (esters)
pHaq
C̅ RE 4NCl/mol·kg−1
CHA/mol·kg−1
KD
100 E
Z
KE
ethyl ethanoate
2.253 2.390 2.455 2.547 2.713 2.231 2.376 2.437 2.514 2.621
0.440 0.871 1.310 1.751 2.210 0.440 0.871 1.310 1.751 2.210
0.378 0.287 0.220 0.156 0.120 0.385 0.296 0.233 0.170 0.140
0.627 1.145 1.798 2.949 4.114 0.596 1.078 1.640 2.612 3.402
38.55 53.38 64.25 74.68 80.45 37.36 51.88 62.12 72.31 77.28
0.350 0.273 0.231 0.208 0.182 0.342 0.268 0.225 0.202 0.177
1.426 1.315 1.372 1.684 1.862 1.356 1.238 1.252 1.491 1.539
propyl ethanoate
a
pHaq is the pH value of the aqueous phase, C̅ RE 4NCl is the equilibrium concentration of amine in the organic phase, CHA is the concentration in the aqueous phase after extraction, KD is the distribution coefficient, Z is the loading factor, E is the extraction efficiency, and KE is the equilibrium extraction constant. The uncertainty for the pH measurements was 1 %.
Table 4. Results for the Extraction of 2-Methylidenebutanedioic Acid with the Aliquat 336 + Alkane Systema solvents (alkanes)
pHaq
C̅ RE 4NCl/mol·kg−1
CHA/mol·kg−1
KD
100 E
Z
KE
octane
2.216 2.293 2.358 2.432 2.503 2.197 2.247 2.355 2.415 2.421
0.440 0.871 1.310 1.751 2.210 0.440 0.871 1.310 1.751 2.210
0.406 0.330 0.278 0.235 0.200 0.429 0.357 0.299 0.257 0.230
0.515 0.866 1.213 1.613 2.081 0.435 0.724 1.054 1.391 1.679
34.00 46.41 54.80 61.73 67.54 30.29 41.99 51.32 58.18 62.68
0.322 0.246 0.204 0.177 0.158 0.297 0.228 0.194 0.169 0.148
1.171 0.994 0.926 0.921 0.942 0.988 0.831 0.805 0.794 0.760
decane
a
pHaq is the pH value of aqueous phase, C̅ ER4NCl is the equilibrium concentration of amine in the organic phase, CHA is the concentration in the aqueous phase after extraction, KD is the distribution coefficient, Z is the loading factor, E is the extraction efficiency, and KE is the equilibrium extraction constant. The uncertainty for the pH measurements was 1 %.
shaker for 2 h. Then, samples were kept for 3 h equilibration to separate phases. The concentration of 2-methylidenebutanedioic acid was determined by the titration method. Sodium hydroxide (relative uncertainty: ± 1 % in mass) as a standard solution was used to analyze the concentration of 2-methylidenebutanedioic acid by using phenolphthalein as an indicator. Each measurement was carried out in duplicate. In most cases, the deviation between the amount of acid analyzed and the amount of acid known did not exceed ± 3 %. The pH value of the aqueous phase was measured by pH meter (Mettler Toledo,
pH meter model S40). The uncertainty for the ph measurements was 1 %.
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DISCUSSION AND RESULTS Our study is not very similar to any published work on the extraction of 2-methylidenebutanedioic acid. Wasewar et al.13 studied 2-methylidenebutanedioic acid extraction from aqueous solution by Aliquat 336. Only four diluents (ethyl acetate, toluene, hexane, and kerosene) were used. However, here we used nine solvents to dilute Aliquat 336. Ethyl acetate is the only common diluent in both studies. Thus, our work is a 463
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complementary study for the previous study conducted by Wasewar et al.13 They found the highest distribution coefficient value to be 2.65. In contrast, the distribution coefficient value of 4.114 was reached with ethyl acetate in our study. The difference between the two values is due to the concentration of the amine used and initial concentration of the acid. Another study on the extraction of 2-methylidenebutanedioic acid belongs to Datta and Kumar.22 They used trioctylamine (a similar extractant), dissolved at least in six different solvents (kerosene, heptane, toluene, decanol, MIBK, and dichloromethane). The extraction of 2-methylidenebutanedioic acid by Aliquat 336 dissolved in esters (ethyl ethanoate and propyl ethanoate) alcohols (octan-1-ol, nonan-1-ol, and decan-1-ol), alkanes (octane and decane), and ketones (heptan-2-one and octan2-one) was studied. The results of the equilibrium data which have been used from the aqueous phase to the organic phase on the 2-methylidenebutanedioic acid reactive extraction have been presented in Tables 1 to 4. The constant concentrations of Aliquat 336 in different diluents were changed between (0.440 and 2.210) mol·kg−1. The 2-methylidenebutanedioic acid initial concentration in the aqueous phase was 0.615 mol· kg−1. It was observed that the extraction power of (Aliquat 336 + diluent) mixtures changed with increasing Aliquat 336 initial concentration in the organic phase. The order for the distribution coefficients of 2-methylidenebutanedioic acid extracted with Aliquat 336 (Tables 1 to 4) was found as follows: in alcohols, octan-1-ol > nonan-1-ol > decan-1-ol; in acetates, ethyl acetate > propyl acetate; in ketones: heptan-2one > octan-2-one; in alkanes, octane > decane. The maximum extraction efficiency of 2-methylidenebutanedioic acid was found as 92.86% by using octan-1-ol at 2.210 mol·dm−3 initial concentration of Aliquat 336. The acid concentration in the organic phase was increased from 0.186 mol·dm−3 to 0.571 mol·dm−3 when the concentration of Aliquat 336 was increased from 0.440 mol·dm−3 to 2.210 mol· dm−3. Distribution coefficients were increased from 0.4345 to 13.01 with increasing initial Aliquat 336 concentration among all diluents used in this study (Figure 1). It could be clearly seen from Tables 1 to 4 and Figure 2 that the increase in amine concentration brings about a gradual increase in the extraction efficiency. The highest extraction efficiency of the 2methylidenebutanedioic acid 92.86 %, 86.52 %, 80.45 %, and
Figure 2. Plot of extraction efficiencies, E, against the concentration of amine. ×, ethyl ethanoate; ■, heptanone; ▲, octane; ◆, octan-1-ol.
67.54 % was reached in the vicinity of 2.210 mol·dm−3 of Aliquat 336 concentration with octan-1-ol, heptan-2-one, ethyl acetate, and octane, respectively. Such trends could be explained by the solvents properties like the molecular size or molecular diameter of the solvent. This thickness in terms of the molecular size characterizes the “cavity” engaged by a solvent particle in the liquid solvent. Simultaneously, this could be described as the mean space between the centers of mass of two closest molecules in the liquid. While the diameter of the solvent molecules increases, solvation powers of the solvents decrease.23 The polarity of the solvent is also an important parameter for the extraction. Polarity is a function of ET which is called transition energy. Kosower24 expressed the polarity parameter (ET) as the molar transition energy, for the CT absorption band of 1-ethyl-4-(methoxycarbonyl) pyridinium iodide in the suitable solvent. A high ET value corresponds to the higher solvent polarity. Dimroth and Reichardt25,26 have explained a term ET(30) as a solvent polarity parameter. This parameter was derived from the transition energy for the highestwavelength solvatochromic absorption band of the pyridinium N-phenolate betaine dye. Due to this unusually large dislocation of the solvatochromic absorption band, the ET(30) values gives an admirable and very sensitive polarity characterization of solvents. If it gives high ET(30) values, this relates a high solvent polarity.24 Regarding ketones used in this study for the equilibrium data about the distribution of 2-methylidenebutanedioic acid between water and Aliquat 336 dissolved in octanone and heptanone have been used, and the results have been presented in Table 2. The extraction power of Aliquat 336 is shown to be more effective with heptan-2-one than with octan-2-one. The polarity of heptan-2-one is 11.9, whereas the polarity of octan2-one is 10.3. In aliphatic solvents and ester, polarities are 1.96, 2, 6, and 6.3 for octane, decane, ethyl acetate, and propyl acetate, respectively. The equilibrium complexation constant (KE) for amine concentrations have been presented in Tables 1 to 4. The resulting acid + amine complexes are believed to become constant owing to the hydrogen bonding with solvents.20,27 The first acid relates openly with the amine for forming an ion pair, and the OH of the second acid carboxyl links a hydrogen bond with the conjugated CO of the carboxylate of the first acid for forming a complex.28,29
Figure 1. Plot of distribution coefficients, K D, against the concentration of amine. ×, ethyl ethanoate; ■, heptanone; ▲, octane; ◆, octan-1-ol. 464
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(13) Wasewar, K. L.; Shende, D.; Keshav, A. Reactive Extraction of Itaconic Acid Using Quaternary Amine Aliquat 336 in ethyl acetate, Toluene, Hexane, and Kerosene. J. Chem. Eng. Data 2011, 50 (2), 1003−1011. (14) Waghmare, M. D.; Wasewar, K. L.; Sonawane, S. S.; Shende, D. Z. Natural Nontoxic Solvents for Recovery of Picolinic Acid by Reactive Extraction. Ind. Eng. Chem. Res. 2011, 50 (23), 13526−13537. (15) Chang, Z.; Xu, M.; Zhang, L.; Li, D. Reactive Extraction of o-, m-, and p-Aminophenol Using Trialkylphosphine Oxide/Kerosene. J. Chem. Eng. Data 2012, 57 (7), 2030−2036. (16) Marti, M. E.; Gurkan, T.; Doraiswamy, L. K. Equilibrium and Kinetic Studies on Reactive Extraction of Pyruvic Acid with Trioctylamine in 1-Octanol. Ind. Eng. Chem. Res. 2011, 50 (23), 13518−13525. (17) Aşcı̧ , Y. S.; Iṅ ci, I.̇ Extraction Equilibria of Acrylic Acid from Aqueous Solutions by Amberlite LA-2 in Various Diluents. J. Chem. Eng. Data 2010, 55 (7), 2385−2389. (18) Ren, Y. P.; Wang, J. J.; Li, X. F.; Wang, X. H. Reactive Extraction of Short-Chain Fatty Acids from Synthetic Acidic Fermentation Broth of Organic Solid Wastes and Their Stripping. J. Chem. Eng. Data 2012, 57 (1), 46−51. (19) Martak, J.; Schlosser, S. L/L Equilibria of Dimethylcyclopropanecarboxylic Acid in Water-Solvent Systems with Trioctylamine as an Extractant. Chem. Pap. 2000, 54, 413−422. (20) Yang, S. T.; White, S. A.; Hsu, S. T. Extraction of Carboxylic Acids with Tertiary and Quaternary Amines: Effect of pH. Ind. Eng. Chem. Res. 1991, 30, 1335−1342. (21) Kyuchoukov, G.; Marinova, M.; Albet, J.; Molinier, J. New Methods for the Extraction of Lactic Acid by Means of Modified Extractant (Aliquat336). Ind. Eng. Chem. Res. 2004, 43, 1179−1184. (22) Datta, D.; Kumar, S. Reactive Extraction of 2-Methylidenebutanedioic Acid with N,N-Dioctyloctan-1-amine Dissolved in Six Different Diluents: Experimental and Theoretical Equilibrium Studies at (298 ± 1) Datta. J. Chem. Eng. Data 2011, 56 (5), 2574−2582. (23) Yizhak, M. The properties of solvents; Wiley Series in Solution Chemistry; Wiley: New York, 1999. (24) Kosower, E. M. An Introduction to Physical Organic Chemistry; Wiley: New York, 1968. (25) Reichardt, C. Solvent and solvent effect in organic chemistry; Wiley: New York, 2004. (26) Dimroth, K.; Reichardt, C.; Siepmann, T.; Bohlmann, F. K.; Dimroth, C. Reichardt, Ü ber Pyridinium-N-phenol-betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln. Just. Liebigs Ann. Chem. 1963, 661, 1−37. (27) Wennersten, R. Extraction of Carboxylic Acid from Fermentation Broth in Using Solution of Tertiary Amine. J. Chem. Technol. Biotechnol. 1983, 33, 85. (28) Barrow, G. M.; Yerger, E. A. Acid-Base Reactions in Nondissociating Solvents Acetic Acid and Triethylamine in Carbon Tetrachloride and Chloroform. J. Am. Chem. Soc. 1954, 76, 5211− 5216. (29) Yerger, E. A.; Barrow, G. M. Acid-Base Reactions in Nondissociating Solvents: n- Butyl Amine and Acetic Acid in Carbon Tetrachloride. J. Am. Chem. Soc. 1955, 7, 620.
CONCLUSION The extractability of 2-methylidenebutanedioic acid by Aliquat 336 dissolved in (four diluent categories) two alkanes, three alcohols, two acetates, and two ketones, all of which have been used as diluents, was investigated. The distribution coefficients, loading factors, and extraction efficiency were calculated according to experimental results. The extraction equilibrium was interpreted as a result of consecutive formation of acid− amine with a stoichiometry of 1:1. Equilibrium extraction constants KE were calculated for each of solvents and each concentration. The maximum synergistic extraction efficiency was found for the Aliquat 336 + octan-1-ol extractant system with a KD value of 13.01 and equilibrium extraction constant (KE) giving the highest value of 5.885.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Funding
This work was supported by the Research Fund of Istanbul University Project No: 16710. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work is a part of master thesis entitled “Reactive Extraction of Some Organic Acid” which is pursued by Institute of Science of Istanbul University.
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REFERENCES
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