Fluid Phase Equilibria 440 (2017) 77e86

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Influence of 1ealkyle3emethylimidazolium based ionic liquids on the

thermodynamic and transport properties of L(þ)elactic acid in
aqueous solutions of polyethylene glycol
Abbas Mehrdad*, Hemayat Shekaari, Narmin Noorani
Department of Physical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this study, effect of some ionic liquids on the thermodynamic and transport properties of L(þ)elactic
Received 7 January 2017 acid in aqueous polyethylene glycol solutions have been investigated. Density, speed of sound and vis-
Received in revised form cosity of L(þ)elactic acid in the aqueous solutions of polyethylene glycol, (polyethylene glycol þ 1ehexyl
25 February 2017
e3emethylimidazolium bromide) and (polyethylene glycol þ 1eoctyle3emethylimidazolium bromide)
Accepted 26 February 2017
were measured at temperatures 288.15e318.15 K. Apparent molar volumes, transfer apparent molar
Available online 2 March 2017
volume, apparent molar isentropic compressibility and viscosity Becoefficient of L(þ)elactic acid were
calculated by using experimental data and were discussed in terms of soluteesolute and soluteesolvent
Keywords:
L(þ)elactic acid
interactions. The results reveal that soluteesolvent interactions were decreased by increasing concen-
Polyethylene glycol tration of ionic liquid, length of alkyl group of ionic liquid and temperature.
Ionic liquid © 2017 Elsevier B.V. All rights reserved.
Viscosity
Volumetric

1. Introduction
L(þ)elactic acid (LaH), as an industrially important organic acid,
has widespread applications in the pharmaceutical, food, chemical,
leather, and cosmetic industries [1]. It is produced both chemical
synthesis and fermentation processes. The efficiency of the pro-
cesses mainly depends on the separation and purification of L(þ)e
lactic acid. As a result, researches in this area have been focused on
effective and economical reaction mixture to recover LaH from the
fermentation broth lately or synthesis method. The recovery pro-
cess of LaH has been made with use of several techniques such as
ion exchange resins, direct distillation, adsorption, electrodialysis,
and liquideliquid extraction [2e4]. Liquideliquid extraction based
on aqueous biphasic systems (ABS) as a method has been used
widely for separation and purification processes of biological ma-
terials [5,6]. In recent years, a new type of ABS based on ionic liq-
uids (ILs)-polymer has been reported [7e11]. Polyethylene glycol
(PEG) as an effective and useful polymer in these types of ABS is
extensively used due to its low melting points, low cost, hydrophilic
nature and low toxicity [12,13]. Recently, ILebased ABS have been
used extensively for many processes in industry and academia as
* Corresponding author.
E-mail address: a_mehrdad@tabrizu.ac.ir (A. Mehrdad).
green solvent due to their unique properties such as; low vapor
pressure, high thermal stability, noneflammability, low toxicity,
and high electrical conductivity [14e18]. Thereby, these properties
caused ionic liquids to have many attractive applications in
biotechnology for separation and purification of organic acids.
Extraction of LaH has been studied by using the ionic liquids in
recent years [19e22]. Jan Martak et al. have investigated extraction
of lactic acid by phosphonium ionic liquids [23]. Solvent extraction
of organic acids with ionic liquids was also investigated by Hud-
dleston [24]. Oliveira et al. investigated extraction of Lelactic,
Lemalic, and succinic acid from aqueous solutions by using hy-
drophobic ILs [25]. Despite abundant applications of ionic liquids in
the ABS process, there is no report with regard to their thermo-
dynamic and transport properties of LaH in the presence of ionic
liquids. Therefore, to design and optimization of the extraction
process using ABS method and selection of the proper ionic liquid,
information about the thermodynamic and transfer properties of
aqueous (LaH þ IL þ polymer) systems in order to understand
better soluteesolvent interactions between components are
necessary. On the other hand, knowledge of volumetric, acoustical
and viscometric properties are useful technique to evaluating the
soluteesolute and soluteesolvent interactions which occur in these
solutions. In the present work, volumetric and transport properties
of lactic acid in aqueous solution of (PEG þ ILs) were investigated at

http://dx.doi.org/10.1016/j.fluid.2017.02.019
0378-3812/© 2017 Elsevier B.V. All rights reserved.
78 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86
different temperatures to provide the information about the nature
of interactions LaH in aqueous solutions of (PEG þ ILs). The
apparent molar volume ðVf Þ, the infinite dilution apparent molar
volumes ðVf0 Þ, transfer volume ðDtr Vf0 Þ, the apparent molar isen-
tropic compressibility ðkf Þ and the viscosity Becoefficients were
used to interpret the soluteesolute and soluteesolvent interactions
of LaH in the aqueous solutions of (PEG þ ILs).
2. Experimental
2.1. Chemicals
The names, CAS numbers, abbreviations, purity in mass fraction
of the used chemicals and analysis method used in this work are
listed in Table 1. The doubly distilled water was used for prepara-
tion of the solutions.
2.2. Synthesis of ionic liquids
The ionic liquids, 1eAlkyle3emethylimidazolium bromide,
([Cnmim]Br, n ¼ 6 and 8) were synthesized as described in the
literature by direct alkylation of N-methylimidazole with an excess
amount of 1-haloalkane in a round bottom flask about at T ¼ 353 K
for 72 h under an argon atmosphere [26,27]. The product was dried
in high vacuum at about 353 K using a rotary evaporator for at least
4 h under reduced pressure and was used after vacuum desiccated
for at least 48 h to remove trace amount of moisture. The water
content of the ionic liquids was determined using a KarleFischer
titrator (Metrohm 756 KF) about 0.015 mass fractions. The ionic
liquids were analyzed by 1HNMR (Bruker Ave400) and FTeIR
(Bruker, Tensor 27) spectra to confirm the absence of any major
impurities were found to be in good agreement with those reported
in the literatures [28,29]. The purity of the synthesized ionic liquid
was determined using the procedure described in the literature
[30]. The ionic liquids have purity mass fraction of >0.97 and > 0.96
for [C6mim]Br and [C8mim]Br, respectively. The FT-IR and 1HNMR
spectrums of synthesized ionic liquids are shown in Figs. S1eS4
(supporting information).
2.3. Apparatus and procedure
LaH solutions were prepared in water and in the aqueous so-
lutions of (PEG þ ILs) (contain of wPEG ¼ 0.020 of polyethylene
glycol and wIL ¼ 0.010, wIL ¼ 0.015, and wIL ¼ 0.020 of ionic liquids).
The solutions were prepared in glass vials by using an analytical
balance (CP224 S Sartorius Co.) with precision of 1  107 kg. The
experimental densities and speed of sound were measured by a
vibrating tube densimeter (DSA5000 densimeter and speed of
Table 1
Table of the materials used in this study.
Chemical Name CAC No. Abbreviation Supplier
L(þ)-Lactic acid [79-33-4] LaH Sigmaaldrich 0.98
Polyethylene glycola [8-18897- PEG Merck
1]
N eMethylimidazole [616-47-7] Merck
1eBromohexane [111-25-1] Merck
1eBromooctane [111-83-1] Merck
Ethyl acetate [141-78-6] Merck
1-Hexyl-3-methyl imidazolium [C6mim]Br Synthesized
bromide
1-Octyl-3-methyl imidazolium bromide [C8mim]Br Synthesized >0.96
a
The reported nominal average molecular mass was 20 kg$mol1.
sound analyzer, Anton Paar). The apparatus was calibrated with
doubly distilled and degassed water and dry air at atmospheric
pressure. Temperature was kept constant within ±1.0  103 K
using the Peltier device built in densimeter. The experimental un-
certainty of density and speed of sound measurements were
5.0  103 kg m3 and 0.10 m s1, respectively. Viscosity of the
solutions was measured by digital viscometer (Lovis 2000M, Anton
Paar). This viscometer is based on the concept of a falling sphere
inside a capillary of known diameter. Two laser sensors at the two
ends of the capillary detect the small metal sphere and allow the
determination of the time elapsed during its fall between the two
positions. An average time is automatically recorded for the desired
number of successive runs. The temperature of the capillary is
controlled by a Peltier device within a precision of 0.01 K. In each
measurement, uncertainty of the viscosity measurements was
0.001 mPa s.
3. Results and discussion
3.1. Apparent molar volume
The experimental density (r) and speed of sound (u) for LaH in
water, the aqueous solutions of PEG and in the aqueous solutions of
(PEG þ ILs) (contain of wPEG ¼ 0.020 of polyethylene glycol and
wIL ¼ 0.010, wIL ¼ 0.015, and wIL ¼ 0.020 of ionic liquids) at T ¼
(288.15, 298.15, 308.15, and 318.15) K are reported in Table 2. In
order to study the influence of ILs on the volumetric properties of
LaH in aqueous solution of PEG, the apparent molar volume of lactic
acid were calculated by following equation [31]:
M 1000ðr0  rÞ
Vf ¼ þ (1)
r mr0 r
where M and m are the molar mass and molality of LaH, r0 and r
represent the density of the solvent and solution, respectively. In
the case of ternary systems where LaH is the solute, (PEG þ water)
were taken as the solvent and in quaternary systems
(PEG þ ILs þ water) were taken as the solvent. The values of
apparent molar volume ðVf Þ of LaH in the studied solutions are
given in Table 3. The values of apparent molar volume as a function
of LaH concentration are shown in Figs. 1 and 2. As can be seen from
Figs. 1 and 2, the apparent molar volumes of LaH in aqueous so-
lutions of (PEG þ ILs) increase by increasing both of the concen-
tration and the alkyl chain length of ILs. The apparent molar
volumes were correlated to following equation:
Vf ¼ Vf0 þ Sv m (2)
Purity (Mass Purification Method Analysis Method
Fraction)
None Karl Fischer titration
None
>0.99 None
>0.99 None
>0.99 None
>0.99 None
>0.97 Rotary/evaporator and Karl Fischer titration and 1H NMR
vacuum
Rotary/evaporator and Karl Fischer titration and 1H NMR
vacuum
 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86 79

Table 2
Density (r), speed of sound (u), and viscosity (h) of L(þ)-lactic acid in water, in the aqueous solutions of PEG and in the aqueous solutions of (PEG þ [Cnmim]Br) at different
temperatures.a

mLaH/mol$kg T/K ¼ 288.15 T/K ¼ 298.15 T/K ¼ 308.15 T/K ¼ 318.15

r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s
water
0.0000 999.103 1467.20 1.138 997.048 1496.73 0.890 994.035 1520.15 0.719 990.216 1536.01 0.596
0.0347 999.850 1468.03 1.147 997.750 1497.55 0.898 994.715 1520.65 0.731 990.864 1536.43 0.601
0.0523 1000.221 1468.56 1.153 998.096 1498.05 0.902 995.048 1520.98 0.734 991.199 1536.71 0.602
0.0691 1000.572 1469.11 1.160 998.425 1498.59 0.906 995.358 1521.37 0.736 991.500 1537.04 0.604
0.0868 1000.939 1469.76 1.165 998.762 1499.22 0.910 995.685 1521.81 0.738 991.811 1537.43 0.605
0.1056 1001.324 1470.54 1.170 999.125 1499.98 0.914 996.025 1522.34 0.741 992.143 1537.92 0.607
0.1217 1001.648 1471.30 1.175 999.426 1500.65 0.917 996.311 1522.85 0.744 992.425 1538.37 0.610
0.1404 1002.022 1472.23 1.180 999.780 1501.50 0.922 996.641 1523.52 0.747 992.758 1538.94 0.612
0.1571 1002.352 1473.14 1.185 1000.088 1502.27 0.926 996.932 1524.13 0.750 993.023 1539.52 0.614
0.1751 1002.701 1474.10 1.190 1000.415 1503.17 0.929 997.242 1524.84 0.753 993.340 1540.18 0.616
Water þ PEG (wPEG ¼ 0.020)
0.0000 1002.595 1479.76 2.284 1000.314 1507.62 1.725 997.102 1528.96 1.345 993.169 1543.78 1.072
0.0391 1003.291 1480.74 2.303 1000.999 1508.53 1.735 997.763 1529.82 1.354 993.799 1544.61 1.082
0.0587 1003.639 1481.24 2.31 1001.341 1509.00 1.741 998.096 1530.26 1.357 994.121 1545.03 1.085
0.0782 1003.986 1481.74 2.319 1001.683 1509.47 1.747 998.426 1530.71 1.362 994.441 1545.46 1.089
0.0980 1004.335 1482.26 2.329 1002.030 1509.96 1.756 998.761 1531.17 1.367 994.771 1545.89 1.094
0.1176 1004.682 1482.78 2.336 1002.374 1510.45 1.761 999.097 1531.62 1.372 995.099 1546.32 1.096
0.1377 1005.037 1483.31 2.346 1002.727 1510.96 1.771 999.441 1532.10 1.38 995.436 1546.77 1.103
0.1564 1005.365 1483.81 2.357 1003.055 1511.44 1.778 999.756 1532.56 1.385 995.750 1547.19 1.105
0.1787 1005.757 1484.42 2.368 1003.447 1512.02 1.783 1000.140 1533.10 1.39 996.135 1547.69 1.109
0.1959 1006.058 1484.89 2.377 1003.750 1512.48 1.791 1000.444 1533.52 1.393 996.425 1548.08 1.113
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.010)
0.0000 1004.272 1488.13 2.310 1002.119 1515.43 1.761 998.916 1536.02 1.369 994.637 1550.18 1.029
0.0348 1004.901 1488.84 2.328 1002.722 1515.99 1.773 999.492 1536.33 1.377 995.192 1550.39 1.035
0.0519 1005.229 1489.29 2.337 1003.040 1516.33 1.779 999.806 1536.57 1.382 995.481 1550.57 1.038
0.0701 1005.595 1489.84 2.344 1003.399 1516.77 1.786 1000.154 1536.89 1.386 995.825 1550.81 1.041
0.0875 1005.948 1490.42 2.353 1003.749 1517.22 1.793 1000.499 1537.25 1.391 996.158 1551.15 1.044
0.1073 1006.365 1491.11 2.364 1004.168 1517.82 1.800 1000.911 1537.77 1.395 996.551 1551.63 1.047
0.1231 1006.719 1491.71 2.373 1004.516 1518.39 1.806 1001.252 1538.22 1.399 996.885 1552.03 1.050
0.1413 1007.119 1492.43 2.381 1004.939 1519.02 1.814 1001.659 1538.76 1.405 997.289 1552.55 1.053
0.1590 1007.530 1493.24 2.390 1005.341 1519.75 1.821 1002.065 1539.36 1.410 997.698 1553.13 1.057
0.1767 1007.969 1493.94 2.399 1005.778 1520.46 1.826 1002.491 1540.10 1.415 998.115 1553.78 1.059
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.015)
0.0000 1005.369 1489.41 2.335 1003.081 1516.34 1.774 999.844 1536.62 1.385 995.705 1550.24 1.074
0.0355 1005.993 1489.99 2.355 1003.649 1516.58 1.785 1000.347 1536.69 1.395 996.119 1550.28 1.081
0.0533 1006.341 1490.34 2.364 1003.959 1516.81 1.791 1000.624 1536.89 1.400 996.355 1550.39 1.085
0.0717 1006.711 1490.81 2.373 1004.295 1517.15 1.799 1000.928 1537.15 1.405 996.613 1550.57 1.088
0.0881 1007.059 1491.24 2.381 1004.601 1517.52 1.806 1001.213 1537.42 1.409 996.871 1550.79 1.091
0.1076 1007.497 1491.84 2.391 1004.998 1518.03 1.814 1001.568 1537.81 1.414 997.186 1551.18 1.094
0.1260 1007.928 1492.47 2.401 1005.378 1518.55 1.819 1001.926 1538.28 1.419 997.499 1551.63 1.097
0.1427 1008.319 1493.04 2.408 1005.746 1519.08 1.825 1002.271 1538.67 1.423 997.813 1552.06 1.100
0.1594 1008.744 1493.60 2.416 1006.125 1519.58 1.830 1002.631 1539.25 1.427 998.151 1552.54 1.103
0.1785 1009.241 1494.26 2.426 1006.595 1520.19 1.836 1003.026 1540.01 1.432 998.529 1553.31 1.107
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.020)
0.0000 1006.278 1490.83 2.364 1004.054 1517.18 1.789 1000.649 1537.23 1.408 996.641 1550.30 1.119
0.0352 1006.799 1491.43 2.386 1004.531 1517.41 1.802 1001.059 1537.38 1.417 997.001 1550.36 1.125
0.0542 1007.101 1491.91 2.396 1004.820 1517.63 1.809 1001.304 1537.57 1.422 997.231 1550.51 1.129
0.0701 1007.369 1492.37 2.407 1005.072 1517.93 1.815 1001.531 1537.81 1.427 997.446 1550.67 1.132
0.0879 1007.681 1492.93 2.416 1005.372 1518.28 1.823 1001.819 1538.11 1.432 997.696 1550.92 1.135
0.1076 1008.046 1493.61 2.426 1005.725 1518.81 1.831 1002.146 1538.53 1.438 997.996 1551.29 1.139
0.1234 1008.352 1494.31 2.436 1006.022 1519.32 1.837 1002.424 1539.01 1.442 998.256 1551.74 1.142
0.1420 1008.714 1495.18 2.445 1006.389 1520.05 1.844 1002.769 1539.68 1.448 998.597 1552.32 1.146
0.1595 1009.068 1495.95 2.455 1006.735 1520.78 1.852 1003.118 1540.36 1.454 998.902 1553.01 1.149
0.1769 1009.431 1496.83 2.464 1007.105 1521.52 1.858 1003.464 1540.97 1.458 999.284 1553.68 1.152
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.010)
0.0000 1004.403 1487.80 2.410 1002.210 1514.88 1.815 998.918 1534.81 1.417 994.701 1548.93 1.126
0.0354 1005.039 1488.45 2.431 1002.762 1515.45 1.830 999.429 1535.10 1.428 995.133 1549.12 1.134
0.0523 1005.362 1488.81 2.443 1003.042 1515.79 1.836 999.683 1535.31 1.433 995.362 1549.23 1.138
0.0702 1005.711 1489.22 2.454 1003.351 1516.15 1.843 999.972 1535.58 1.437 995.617 1549.45 1.141
0.0885 1006.087 1489.65 2.465 1003.681 1516.59 1.853 1000.285 1535.92 1.445 995.899 1549.69 1.145
0.1060 1006.462 1490.11 2.475 1004.018 1517.08 1.860 1000.593 1536.25 1.449 996.182 1550.02 1.150
0.1243 1006.872 1490.63 2.485 1004.385 1517.62 1.867 1000.944 1536.62 1.456 996.487 1550.35 1.154
0.1417 1007.271 1491.18 2.495 1004.746 1518.12 1.874 1001.289 1537.03 1.460 996.786 1550.79 1.158
0.1598 1007.699 1491.79 2.504 1005.134 1518.73 1.882 1001.649 1537.47 1.467 997.125 1551.19 1.163
0.1778 1008.139 1492.38 2.514 1005.536 1519.25 1.890 1002.032 1537.92 1.472 997.479 1551.59 1.167
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.015)
0.0000 1005.570 1488.94 2.469 1003.155 1515.89 1.828 999.927 1536.17 1.445 996.058 1549.42 1.156
0.0367 1006.086 1489.38 2.491 1003.654 1516.15 1.846 1000.379 1536.28 1.454 996.469 1549.51 1.164
0.0531 1006.338 1489.78 2.499 1003.894 1516.48 1.853 1000.611 1536.51 1.459 996.676 1549.71 1.167
0.0706 1006.615 1490.27 2.509 1004.167 1516.92 1.861 1000.866 1536.89 1.464 996.919 1550.06 1.171
(continued on next page)
80 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86

Table 2 (continued )

mLaH/mol$kg T/K ¼ 288.15 T/K ¼ 298.15 T/K ¼ 308.15 T/K ¼ 318.15

r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s r/kg$m3 u/m$s1 h/mPa$s
0.0891 1006.931 1490.73 2.517 1004.472 1517.38 1.868 1001.156 1537.27 1.469 997.184 1550.43 1.175
0.1070 1007.251 1491.37 2.527 1004.782 1517.98 1.876 1001.443 1537.81 1.474 997.462 1550.91 1.179
0.1224 1007.541 1492.03 2.536 1005.057 1518.66 1.881 1001.707 1538.41 1.480 997.714 1551.41 1.183
0.1429 1007.934 1492.73 2.545 1005.451 1519.32 1.891 1002.081 1538.99 1.486 998.066 1552.02 1.188
0.1599 1008.268 1493.54 2.555 1005.775 1520.15 1.897 1002.398 1539.75 1.490 998.365 1552.71 1.192
0.1788 1008.649 1494.57 2.562 1006.169 1521.05 1.903 1002.761 1540.67 1.495 998.707 1553.69 1.197
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.020)
0.0000 1006.353 1490.10 2.530 1004.009 1516.49 1.898 1000.658 1537.19 1.474 996.748 1549.91 1.175
0.0349 1006.849 1490.40 2.556 1004.463 1516.68 1.916 1001.081 1537.23 1.485 997.103 1549.95 1.183
0.0528 1007.142 1490.64 2.570 1004.735 1516.84 1.927 1001.337 1537.32 1.493 997.327 1550.06 1.189
0.0706 1007.445 1491.01 2.582 1005.022 1517.11 1.935 1001.607 1537.57 1.500 997.569 1550.26 1.194
0.0887 1007.783 1491.42 2.594 1005.335 1517.46 1.945 1001.920 1537.82 1.506 997.841 1550.51 1.197
0.1043 1008.088 1491.91 2.603 1005.627 1517.92 1.951 1002.206 1538.18 1.511 998.092 1550.93 1.202
0.1234 1008.483 1492.31 2.615 1006.004 1518.28 1.962 1002.564 1538.45 1.518 998.422 1551.22 1.207
0.1427 1008.909 1492.91 2.627 1006.413 1518.82 1.971 1002.963 1538.92 1.525 998.802 1551.66 1.214
0.1594 1009.289 1493.44 2.637 1006.763 1519.41 1.976 1003.323 1539.48 1.531 999.121 1552.17 1.217
0.1772 1009.707 1494.17 2.647 1007.156 1520.21 1.983 1003.741 1540.27 1.535 999.494 1552.93 1.221
a
Standard uncertainties are u (m) ¼ 0.0001 mol kg1, u (r) ¼ 5  103 kg m3, u (h) ¼ 0.001 mPa s, u (u) ¼ 0.10 m s1, respectively.

where Sv is the experimental slope and Vf0 the infinite dilution
apparent molar volumes. Vf0 and Sv are related to soluteesolvent
and soluteesolute interactions, respectively. The calculated values
of Vf0 and Sv for the investigated systems are listed in Table 4. The
obtained value of Vf0 for LaH in water is in agreement with literature
[32]. The values of Sv are negative in all of the investigated systems.
The value of Sv were decreased by addition ionic liquids and
increasing temperature. This behavior indicates that soluteesolute
interactions were weakened by addition ionic liquids and
increasing temperature. At infinite dilution the soluteesolute
interaction is negligible; therefore the values of the infinite dilution
apparent molar volumes provide valuable information about the
soluteesolvent interactions [33]. The obtained results were shown
that Vf0 values of LaH in the aqueous solutions of (PEG þ ILs) in-
crease with increasing concentration of ILs, alkyl chain length of ILs
as well as with increasing temperature. This phenomenon could be
interpreted in terms of hydrogen bonding formation between LaH
and ILs. It is expected that by addition of ILs some of hydrogen
bonds between LaH and eOeethoxy group of PEG molecules have
been disrupted and instead of hydrogen bond between C2eH of IL
and eOeethoxy group of PEG molecules [34e37]. On the other
hand new hydrogen bonds formed between LaH and C2eH of IL
which are depicted in Fig. 3. The values of Dtr Vf0 for transfer of LaH
from aqueous solutions of PEG to aqueous solutions of (PEG þ ILs)
[Dtr Vf0 ¼ Vf0 (water þ PEG þ IL) e Vf0 (water þ PEG)] are listed in
Table 4. As shown in this Table 4, the values of at all concentrations
of ILs are positive and increase with increasing ILs concentration
and alkyl chain length. The importance interactions which can be
occurred between LaH and (PEG þ ILs) can be classified as follows:
(i) Polar-ionic group interactions between COOH and OH of LaH,
and the cations of [Cnmim]þ.
(ii) Polar-polar group interactions between the polar groups of
LaH and imidazolium ring of [Cnmim]þ via the hydrogen
bonding.
(iii) Polar-nonpolar group interactions between the COOH and
OH of LaH and the nonpolar groups (alkyl chain) of [Cnmim]
Br.
(iv) Nonpolar-nonpolar groups interactions between the
nonpolar groups of LaH and alkyl group of imidazolium ring
of [Cnmim]þ.
By transfer LaH from aqueous solutions of PEG to aqueous so-
lutions of (PEG þ ILs) some of hydrogen bound between LaH and
PEG were replaced with hydrogen bound between LaH and ILs,
consequently Dtr Vf0 become positive.
The temperature dependence of Vf0 values can be expressed as
follows:
Vf0 ¼ A þ BT þ CT 2 (3)
where A, B and C have been evaluated by the least-square fitting of
the infinite dilution apparent molar as function temperature. The
values of Vf0 were used to calculate the apparent isobaric thermal
expansion coefficient ap according to the following equation [38]:
!
1 .
aP ¼ vVf0 vT (4)
Vf0 p
The apparent isobaric thermal expansion coefficient ap is
calculated for evaluation the response of system's volume to in-
crease in temperature. The values of a in the aqueous solutions of
PEG and in the aqueous solutions of (PEG þ ILs) are reported in
Table 4. According to Table 4, it can be seen that the values of ap
increase by increasing temperature.
3.2. Apparent molar isentropic compressibility
The apparent molar isentropic compressibility kf ; is calculated
as follow [39]:
ðkS r0  kS0 rÞ ks M
kf ¼ þ (5)
mrr0 r
where ks ¼ r1u2 is the isentropic compressibility and u is the sound
velocity. The values of kf for LaH in water, in the aqueous solutions
of PEG and in the aqueous solutions of (PEG þ ILs) at different
temperatures are given in Table 3. The apparent molar isentropic
compressibility versus concentration of LaH in the aqueous solu-
tions of (PEG þ ILs) was shown in Figs. 4 and 5. The apparent molar
isentropic compressibility of LaH was correlated versus molality of
LaH according to the following equation [40]:
kf ¼ k0f þ Sk m (6)
where k0f is the apparent molar isentropic compressibility at
infinite dilution and Sk is the experimental slope. The calculated
values of k0f and Sk for the investigated systems are listed in Table 4.
 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86 81

Table 3
The apparent molar volume ðVf Þ and apparent molar isentropic compressibility ðkf Þ of L(þ)-lactic acid in water, in the aqueous solutions of PEG and in the aqueous solutions of
(PEG þ [Cnmim]Br) at different temperatures.a

mLaH/ T/K ¼ 288.15 T/K ¼ 288.15 T/K ¼ 288.15 T/K ¼ 288.15

mol$kg1
106Vf 1014 106Vf 1014 106Vf 1014 106Vf 1014
/m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1
water
0.0347 68.573 0.669 69.974 0.804 70.766 1.387 71.904 1.581
0.0523 68.667 0.543 70.114 0.718 70.944 1.317 71.728 1.492
0.0691 68.747 0.445 70.189 0.622 71.135 1.229 71.912 1.422
0.0868 68.840 0.337 70.358 0.532 71.261 1.156 72.110 1.357
0.1056 68.934 0.210 70.412 0.411 71.403 1.074 72.216 1.268
0.1217 69.032 0.089 70.52 0.334 71.527 1.001 72.294 1.201
0.1403 69.119 0.039 70.568 0.232 71.638 0.905 72.309 1.118
0.1571 69.212 0.156 70.661 0.163 71.744 0.838 72.537 1.054
0.1751 69.321 0.246 70.76 0.081 71.848 0.762 72.541 0.971
Water þ PEG (wPEG ¼ 0.020)
0.0391 72.082 0.933 72.488 1.057 73.283 1.173 74.312 1.276
0.0587 72.066 0.922 72.480 1.041 73.225 1.158 74.175 1.259
0.0782 72.054 0.915 72.460 1.031 73.218 1.145 74.117 1.244
0.0980 72.058 0.902 72.427 1.015 73.192 1.132 74.007 1.232
0.1176 72.045 0.891 72.400 1.001 73.135 1.123 73.921 1.220
0.1377 72.034 0.883 72.370 0.987 73.091 1.108 73.846 1.207
0.1564 72.023 0.873 72.334 0.972 73.074 1.094 73.772 1.195
0.1787 72.016 0.861 72.303 0.958 73.019 1.080 73.652 1.180
0.1959 72.008 0.853 72.271 0.944 72.935 1.066 73.605 1.172
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.010)
0.0348 71.727 1.188 72.588 1.480 73.544 1.922 74.400 2.109
0.0519 71.330 1.034 72.137 1.369 72.912 1.774 74.051 1.999
0.0701 70.900 0.874 71.625 1.224 72.398 1.630 73.357 1.861
0.0875 70.588 0.738 71.224 1.111 71.934 1.499 72.884 1.707
0.1073 70.208 0.607 70.728 0.964 71.400 1.329 72.394 1.533
0.1231 69.815 0.493 70.330 0.827 70.992 1.207 71.942 1.413
0.1413 69.517 0.385 69.815 0.704 70.525 1.083 71.399 1.272
0.1590 69.156 0.250 69.488 0.576 70.109 0.959 70.888 1.133
0.1767 68.703 0.165 69.022 0.461 69.657 0.805 70.428 0.996
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.015)
0.0355 72.154 1.473 73.851 2.124 75.875 2.503 78.667 2.733
0.0533 71.486 1.347 73.366 1.965 75.395 2.291 78.116 2.596
0.0717 70.995 1.179 72.895 1.782 74.896 2.120 77.630 2.458
0.0881 70.495 1.058 72.539 1.631 74.442 1.988 77.024 2.318
0.1076 69.878 0.894 71.953 1.448 73.933 1.835 76.467 2.135
0.1260 69.337 0.744 71.528 1.307 73.419 1.675 75.976 1.970
0.1427 68.948 0.640 71.057 1.170 72.907 1.565 75.412 1.828
0.1594 68.422 0.542 70.610 1.067 72.403 1.404 74.807 1.686
0.1785 67.881 0.441 69.997 0.943 72.037 1.235 74.304 1.494
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.020)
0.0352 74.864 1.675 76.240 2.344 78.358 2.586 80.059 2.819
0.0542 74.459 1.466 75.637 2.191 77.899 2.436 79.375 2.644
0.0701 74.072 1.310 75.239 2.020 77.391 2.283 78.762 2.517
0.0879 73.654 1.157 74.746 1.873 76.640 2.123 78.219 2.375
0.1076 73.158 0.995 74.184 1.674 76.009 1.955 77.597 2.206
0.1234 72.776 0.821 73.757 1.512 75.527 1.785 77.087 2.030
0.1420 72.406 0.642 73.239 1.304 74.957 1.580 76.370 1.831
0.1595 72.048 0.523 72.853 1.136 74.382 1.400 75.944 1.645
0.1769 71.689 0.381 72.386 0.983 73.919 1.277 75.141 1.462
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.010)
0.0354 71.825 1.321 74.311 1.630 75.668 2.144 78.188 2.465
0.0523 71.451 1.230 73.991 1.529 75.469 2.052 77.742 2.408
0.0702 71.131 1.146 73.623 1.456 75.058 1.938 77.307 2.280
0.0885 70.714 1.068 73.234 1.352 74.603 1.812 76.793 2.173
0.1060 70.282 0.974 72.765 1.227 74.213 1.720 76.322 2.040
0.1243 69.816 0.873 72.297 1.112 73.687 1.620 75.896 1.941
0.1417 69.426 0.773 71.884 1.030 73.237 1.521 75.532 1.818
0.1598 69.012 0.668 71.454 0.921 72.850 1.433 75.045 1.721
0.1778 68.597 0.583 71.018 0.855 72.396 1.347 74.557 1.635
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.015)
0.0367 75.644 1.929 76.254 2.220 77.739 2.532 79.122 2.637
0.0531 75.207 1.720 75.898 2.006 77.139 2.328 78.646 2.466
0.0706 74.859 1.532 75.470 1.789 76.706 2.096 78.071 2.234
0.0891 74.377 1.373 75.012 1.591 76.200 1.904 77.613 2.044
0.1070 73.922 1.159 74.567 1.377 75.802 1.691 77.103 1.848
0.1224 73.511 0.988 74.213 1.184 75.407 1.505 76.671 1.697
0.1429 73.054 0.810 73.666 1.003 74.854 1.331 76.124 1.501
0.1599 72.697 0.639 73.320 0.817 74.444 1.144 75.716 1.332
0.1788 72.332 0.447 72.829 0.651 74.027 0.956 75.305 1.117
(continued on next page)
82 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86

Table 3 (continued )

mLaH/ T/K ¼ 288.15 T/K ¼ 288.15 T/K ¼ 288.15 T/K ¼ 288.15

mol$kg1
106Vf 1014 106Vf 1014 106Vf 1014 106Vf 1014
/m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1 /m3$mol1 kf /m3$mol1$Pa1
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.020)
0.0349 75.427 2.217 76.768 2.442 77.872 2.708 80.097 2.847
0.0528 74.707 2.027 76.034 2.289 77.134 2.555 79.297 2.672
0.0706 74.156 1.830 75.408 2.121 76.522 2.348 78.602 2.505
0.0887 73.479 1.625 74.783 1.922 75.708 2.167 77.879 2.330
0.1043 72.958 1.469 74.209 1.746 75.080 2.008 77.298 2.140
0.1234 72.313 1.310 73.535 1.584 74.452 1.866 76.590 1.991
0.1427 71.638 1.113 72.829 1.392 73.708 1.674 75.726 1.807
0.1594 71.114 0.993 72.380 1.239 73.127 1.499 75.209 1.659
0.1772 70.583 0.847 71.874 1.061 72.419 1.287 74.568 1.462
a
Standard uncertainties are u ðVf Þ ¼ 5  105 m3 mol-1, u ðkf Þ ¼ 3  103 m3 mol1 Pa1.

Table 4 indicate that the values of k0f are positive and increase with
increasing concentration of ionic liquid, alkyl chain length of ionic
liquid and temperature. Therefore, solute-solvent interactions were
decreased by increasing concentration of ILs, alkyl chain length of
ILs and temperature. Also the results of Table 4 indicate that the
values of k0f were increased by increasing temperature. Therefore it
can be concluded that solute-solvent interactions were decreased
by increasing temperature. This behavior can be attributed to the
stronger interactions of LaH and water with respect to interactions
of LaH and PEG or ILs.

3.3. Viscosity B-coefficients

Viscosity is a transport property which provides valuable in-

Fig. 1. The Apparent molar volumes of LaH as a function of molality m of LaH (◊) in
water, (D) in the aqueous solutions of PEG (wPEG ¼ 0.020), in the aqueous solutions of
(PEG þ C6mim]Br), (A)wIL ¼ 0.010; (:)wIL ¼ 0.015; (C)wIL ¼ 0.020 at T ¼ 298.15 K.
formation on soluteesolute and soluteesolvent interactions and
this can be confirming volumetric results. Therefore, experimental
viscosity (h) for the LaH in water, in the aqueous solutions of PEG
and in the aqueous solutions of (PEG þ ILs) were measured at T ¼
(288.15e318.15) K and are listed in Table 2. The concentration de-
pendency of viscosity was given by JoneseDole equation [41]:
 
h ¼ h0 1 þ AC 1=2 þ BC (7)

where h and h0 are the viscosities of the solution and solvent,

Fig. 2. The Apparent molar volumes of LaH as a function of molality, m, of LaH (◊) in
water, (D) in the aqueous solutions of PEG (wPEG ¼ 0.020), in the aqueous solutions of
(PEG þ C8mim]Br) (A)wIL ¼ 0.010; (:)wIL ¼ 0.015; (C)wIL ¼ 0.020 at T ¼ 298.15 K.
The infinite dilution apparent molar isentropic compressibility is
important properties and provides valuable information about the
interactions soluteesolvent and hydration of molecules because at
infinite dilution, each solute is surrounded only by the solvent
molecules and is infinitely distant with other solutes. The results of
respectively, C is molarity of the solution. The Aecoefficient is
related to soluteesolute interactions but is often small; hence it is
neglected in many correlations. The viscosity Becoefficient is an
experimental constant which can be attributed to the sol-
uteesolvent interactions and depends on shape and size of solute
molecules [42]. The plots of h versus C are illustrated in Fig. 6. The
viscosity Becoefficients were calculated from the slope of linear
plot of h versus C and the obtained Becoefficients are given in
Table 5. As can be seen from Table 5, viscosities Becoefficient in-
crease by increasing both the concentration and the alkyl chain
length of the ILs which can be attributed to formation hydrogen
bonds between LaH and ILs. The values of Becoefficients for all the
investigated systems are positive and decrease with increasing
temperature, therefore, the thermal coefficient ðdB=dTÞ is negative
and this phenomena may be due to stronger soluteesolvent in-
teractions in the lower temperature. The negative thermal coeffi-
cient ðdB=dTÞ indicate that hydrodynamic volume of solute were
decreased by increasing temperature; in other words LaH mole-
cules are hydrated in low temperature rather than high tempera-
ture. The solvation number of a solute can be obtained from ðB=Vf0 Þ
ratio. The solvation number of LaH which calculated from the
Becoefficients and infinite dilution apparent molar volume are
reported in Table 5. The results of Table 5 show that the solvation
number of LaH was decreased by increasing temperatures while the
 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86 83

Table 4
Standard partial molar volume ðVf0 Þ, experimental slope (Sv), transfer volumes ðDtr Vf0 Þ, apparent isobaric thermal expansion (ap), partial molar isentropic compressibility ðk0f Þ,
experimental slope ðSK Þ for L(þ)-lactic acid in water, in the aqueous solutions of PEG and in the aqueous solutions of (PEG þ [Cnmim]Br) at different temperatures.a

T/K 106Vf0 /m3$mol1 106Sv/m3$mol2$kg 106DtrVf0 /m3$mol1 1014k0f /m3$mol1$Pa1 1014 Sk/kg m3$mol2$Pa1 104 ap/K1

water
288.15 68.38 ± 0.01 5.29 ± 0.05 0.899 ± 0.01 6.622 ± 0.12 19.903
298.15 69.83 ± 0.03 5.41 ± 0.24 0.983 ± 0.01 5.256 ± 0.13 16.34
a
69.38
308.15 70.57 ± 0.04 7.59 ± 0.31 1.545 ± 0.006 4.499 ± 0.06 13.051
70.15a
318.15 71.58 ± 0.07 5.56 ± 0.67 1.783 ± 0.006 4.292 ± 0.05 9.793
Water þ PEG (wPEG ¼ 0.020)
288.15 72.10 ± 0.005 0.45 ± 0.04 3.72 0.953 ± 0.001 0.510 ± 0.01 4.397
298.15 72.56 ± 0.01 1.44 ± 0.09 2.73 1.085 ± 0.001 0.715 ± 0.01 8.710
308.15 73.37 ± 0.02 2.03 ± 0.20 2.80 1.198 ± 0.002 0.664 ± 0.02 12.907
318.15 74.46 ± 0.02 4.44 ± 0.16 2.88 1.298 ± 0.002 0.657 ± 0.02 16.949
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.010)
288.15 72.41 ± 0.05 20.76 ± 0.42 0.31 1.397 ± 0.03 7.186 ± 0.28 13.078
298.15 73.42 ± 0.04 25.05 ± 0.40 0.86 1.739 ± 0.01 7.289 ± 0.09 13.307
308.15 74.34 ± 0.08 26.85 ± 0.74 0.97 2.178 ± 0.01 7.776 ± 0.12 13.546
318.15 75.41 ± 0.06 28.33 ± 0.55 0.95 2.402 ± 0.01 7.986 ± 0.12 13.751
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.015)
288.15 73.11 ± 0.06 29.46 ± 0.56 1.01 1.717 ± 0.03 7.413 ± 0.29 17.604
298.15 74.81 ± 0.06 26.51 ± 0.50 2.25 2.389 ± 0.04 8.377 ± 0.33 25.358
308.15 76.85 ± 0.05 27.39 ± 0.46 3.48 2.761 ± 0.03 8.553 ± 0.24 32.622
318.15 79.77 ± 0.06 30.68 ± 0.50 5.31 3.064 ± 0.02 8.682 ± 0.15 39.075
Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.020)
288.15 75.65 ± 0.05 22.73 ± 0.44 3.55 1.964 ± 0.03 9.108 ± 0.23 23.437
298.15 77.13 ± 0.05 27.08 ± 0.43 4.57 2.712 ± 0.02 9.794 ± 0.17 24.154
308.15 79.55 ± 0.09 32.28 ± 0.78 6.18 2.945 ± 0.02 9.496 ± 0.22 24.551
318.15 81.21 ± 0.08 33.78 ± 0.73 6.75 3.185 ± 0.03 9.551 ± 0.31 25.157
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.010)
288.15 72.69 ± 0.05 22.92 ± 0.41 0.59 1.513 ± 0.01 5.207 ± 0.11 27.858
298.15 75.23 ± 0.06 23.54 ± 0.53 2.67 1.831 ± 0.02 5.618 ± 0.17 27.981
308.15 76.66 ± 0.09 23.83 ± 0.78 3.29 2.334 ± 0.02 5.670 ± 0.15 28.502
318.15 79.06 ± 0.04 25.28 ± 0.37 4.60 2.702 ± 0.02 6.107 ± 0.18 28.541
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.015)
288.15 76.48 ± 0.06 23.66 ± 0.53 4.38 2.286 ± 0.01 10.754 ± 0.14 8.002
298.15 77.17 ± 0.02 24.22 ± 0.22 4.61 2.595 ± 0.03 11.553 ± 0.26 13.049
308.15 78.56 ± 0.07 25.70 ± 0.67 5.19 2.908 ± 0.02 11.522 ± 0.22 17.846
318.15 80.04 ± 0.07 27.06 ± 0.66 5.58 3.014 ± 0.02 11.045 ± 0.15 22.451
Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.020)
288.15 76.54 ± 0.06 34.05 ± 0.52 4.44 2.534 ± 0.04 10.101 ± 0.34 12.007
298.15 77.87 ± 0.09 34.60 ± 0.84 5.31 2.810 ± 0.01 10.233 ± 0.14 17.452
308.15 79.15 ± 0.06 38.12 ± 0.57 5.78 3.071 ± 0.02 10.269 ± 0.15 22.729
318.15 81.36 ± 0.07 38.80 ± 0.64 6.90 3.197 ± 0.01 10.083 ± 0.08 27.520
a
Reported by Ref. [32].

Fig. 3. Hydrogen bond interaction between the 1-Hexyl 3-methylimidazolium cation and polyethylene glycol.
84 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86
Fig. 4. The isentropic compressibility of L(þ)-lactic acid in the aqueous solutions of
(PEG þ C6mim]Br (wPEG ¼ 0.020, wIL ¼ 0.015); A, 288.15 K; :, 298.15 K; C, 308.15 K;
-, 318.15 K.
Fig. 5. The isentropic compressibility of L(þ)-lactic acid in the aqueous solutions of
(PEG þ C8mim]Br (wPEG ¼ 0.020, wIL ¼ 0.015); A, 288.15 K; :, 298.15 K; C, 308.15 K;
-, 318.15 K.
solvation number values were increased at high the concentration
of ILs and the alkyl chain length of the ILs. Consequently, sol-
uteesolvent interactions were increased by increasing concentra-
tion and number of carbon atoms in the alkyl chain of ILs.
The viscosity data were analyzed on the basis of transition state
treatment of relative viscosity of solutions which suggested by
Feakins et al. [43]. The viscosity Becoefficient in this theory was
given by following equation:
  !
Dm0s
2  Dm1
0s
B¼ V10  V20 þ V10 (8)
RT
where V10 and V20 are the partial molar volume of the solvent and
solute. In the case solvent is mixture V10 ¼ S(xi Mi/r) and xi and Mi
denote the mole fractions and molar masses of solvent component
and r is the density of the solvent. Dm0s 1 and Dm0s2 are the free
molar activation energy of the solvent and solute, respectively and
were calculated according to Eyring's simple model by following
equations:
Fig. 6. Viscosity of L(þ)-lactic acid in the aqueous solutions of (PEG þ Cnmim]Br) at
T ¼ 298.15 K; [C6mim]Br; A, wIL ¼ 0.010; :,wIL ¼ 0.015; C,wIL ¼ 0.020; [C8mim]Br; ◊,
wIL ¼ 0.010; D, wIL ¼ 0.015; B,wIL ¼ 0.020.
h0 V10
Dm0s
1 ¼ DG1
0s
¼ RT ln (9)
hNA
  
RT
Dm0s
2 ¼ Dm1 þ
0s
B  V10  V20 (10)
V10
where h is the Planck constant, NA is the Avogadro number and R
universal gas constant. The values of Dm0s 1 , and Dm2  Dm1
0s 0s are
given in Table 5. According to this table, the values of are greater
than. The positive values of Dm0s 2  Dm1
0s reveal that the solute
(LaH) has a maker structure nature. Also, Table 5 shows that maker
structure nature of LaH was deceased by addition of PEG to water.
This behavior can be attributed to the weak interactions between
LaH and aqueous solutions of PEG with respect to those of LaH and
water. The results of Table 5 indicate that maker structure nature of
LaH was increased by addition of ILs to aqueous solutions of PEG.
Perhaps this behavior may be due to the stronger interactions be-
tween LaH and aqueous solutions of (PEG þ ILs) with respect to
those of LaH and aqueous solutions of PEG. Also, the maker struc-
ture nature of LaH in aqueous solutions of (PEG þ [C8mim]Br) are
greater than to those of LaH in aqueous solutions of (PEG þ [C6mim]
Br). Therefore it can be concluded that both hydrophilic in-
teractions between LaH and ILs the hydrophobic interactions be-
tween LaH and ILs are important. The values of Dm0s 2  Dm1 were
0s
decreased with increasing temperature It might be related to the
decreasing the maker structure nature of LaH in the solvent.
4. Conclusions
In this work volumetric and viscometric properties of LaH in the
aqueous solutions of PEG and in the aqueous solutions of
(PEG þ ILs) were investigated. The calculated infinite dilution
apparent molar volume Vf0 , transfer volumes, the limiting value of
apparent molar isentropic compressibility k0f and B-coefficient
viscosity reveal that soluteesolvent interaction were decreased by
increasing temperature, concentration ionic liquids and alkyl chain
length of ionic liquids.
 A. Mehrdad et al. / Fluid Phase Equilibria 440 (2017) 77e86 85

Table 5
The viscosity B-coefficients, free energy of activation per mole of solvent ðDm0s
1 Þ and solute ðDm2 Þ, and salvation number ðB=Vf Þ for L(þ)-lactic acid in water, in the aqueous
0s 0

solutions of PEG and the aqueous solutions of (PEG þ [Cnmim]Br) at different temperatures.

T/K B/(dm3$mol1) Dm0s

1 /kJ$mol
1
Dm0s
2 /kJ$mol
1
Dm0s
2  Dm1 /kJ$mol
0s 1
B=Vf0

LaH þ water
288.15 0.267 ± 0.005 9.43 51.64 42.21 3.90
298.15 0.258 ± 0.002 9.16 51.69 42.53 3.69
308.15 0.231 ± 0.006 8.94 49.05 40.11 3.27
318.15 0.193 ± 0.007 8.73 44.59 35.86 2.69
LaH þ Water þ PEG (wPEG ¼ 0.020)
288.15 0.203 ± 0.004 11.46 44.73 33.27 2.82
298.15 0.188 ± 0.007 10.84 43.54 32.7 2.59
308.15 0.181 ± 0.008 10.58 43.40 32.82 2.47
318.15 0.170 ± 0.006 10.35 42.66 32.31 2.28
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.010)
288.15 0.219 ± 0.002 11.19 46.60 35.41 3.02
298.15 0.212 ± 0.002 10.91 46.67 35.76 2.88
308.15 0.187 ± 0.004 10.64 44.15 33.51 2.51
318.15 0.169 ± 0.002 10.24 42.27 32.03 2.24
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.015)
288.15 0.222 ± 0.002 11.22 46.98 35.76 3.04
298.15 0.215 ± 0.005 10.94 47.14 36.2 2.87
308.15 0.195 ± 0.003 10.68 45.5 34.82 2.54
318.15 0.176 ± 0.003 10.37 43.54 33.17 2.21
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C6mim]Br (wIL ¼ 0.020)
288.15 0.248 ± 0.003 11.26 50.55 39.29 3.28
298.15 0.224 ± 0.003 10.97 48.53 37.56 2.90
308.15 0.201 ± 0.003 10.73 46.59 35.86 2.53
318.15 0.192 ± 0.003 10.48 46.31 35.83 2.36
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.010)
288.15 0.250 ± 0.004 11.29 50.74 39.45 3.44
298.15 0.233 ± 0.003 10.99 49.77 38.78 3.10
308.15 0.219 ± 0.004 10.73 48.94 38.21 2.86
318.15 0.204 ± 0.005 10.48 47.97 37.49 2.58
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.015)
288.15 0.263 ± 0.004 11.35 52.79 41.44 3.44
298.15 0.240 ± 0.006 11.01 50.82 39.81 3.11
308.15 0.222 ± 0.004 10.78 49.50 38.72 2.83
318.15 0.206 ± 0.004 10.56 48.31 37.75 2.57
LaH þ Water þ PEG (wPEG ¼ 0.020)þ[C8mim]Br (wIL ¼ 0.020)
288.15 0.271 ± 0.006 11.43 53.72 42.29 3.54
298.15 0.267 ± 0.007 11.12 54.42 43.3 3.43
308.15 0.243 ± 0.005 10.86 52.34 41.48 3.07
318.15 0.226 ± 0.005 10.62 51.19 40.57 2.78

Appendix A. Supplementary data 226e229.

Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.fluid.2017.02.019.
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