New levulinic acid-based deep eutectic solvents: Synthesis and physicochem-
ical property determination

Guobing Li, Yaotai Jiang, Xiaobang Liu, Dongshun Deng

PII: S0167-7322(16)30468-8
DOI: doi: 10.1016/j.molliq.2016.07.039
Reference: MOLLIQ 6053

To appear in: Journal of Molecular Liquids

Received date: 25 February 2016

Accepted date: 13 July 2016

Please cite this article as: Guobing Li, Yaotai Jiang, Xiaobang Liu, Dongshun Deng,
New levulinic acid-based deep eutectic solvents: Synthesis and physicochemical property
determination, Journal of Molecular Liquids (2016), doi: 10.1016/j.molliq.2016.07.039

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 ACCEPTED MANUSCRIPT

New Levulinic acid-based deep eutectic solvents: synthesis

and physicochemical property determination
Guobing Li a,*, Yaotai Jiang b, Xiaobang Liu b and Dongshun Deng b, *

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a
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

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b
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

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*Corresponding author. E-mail: lgbbox@tju.edu.cn (G.B. Li), dengdsh@zjut.edu.cn (D.S. Deng)

ABSTRACT

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Recently, deep eutectic solvents (DESs) have emerged as new and inexpensive ionic
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liquids (ILs) analogues. They possess attractive and similar solvent properties with

traditional ILs. In present work a serials of DESs were prepared by pairing renewable
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levulinic acid (LA) as hydrogen donor with seven quarternary ammonium salts as
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hydrogen acceptor. The samples were further characterized in the temperature ranging
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from 293.15 to 333.15 K at atmospheric pressure with the results of density

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(0.99891-1.17735 g cm-3), dynamic viscosity (12.70-376.50 mPa s), electrical

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conductivity (0.35-8.27 mS cm-1), and refractive index data (1.44384-1.47273). The

temperature dependence of these properties was explored and correlated with simple

linear or Vogel-Fulcher-Tamman (VFT) models. The volume expansivities (β), molar

volumes (Vm), molar refractions (Rm), and free volumes (fm) values have been

calculated on the basis of density and refractive index data. The active energy of

viscosity (Eη), molar electric conductivity (Λ), and ioncity were also determined.

Partial structure-property relationship for DESs was also investigated. The tunable

properties make DESs as a potential reaction medium, electrochemical process

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medium, solvent and absorbent. Therefore, the determination and correlation can

provide relevant information for the engineering and industrial applications of DESs.

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1. Introduction

Deep eutectic solvents (DESs) are now widely acknowledged as ionic liquid (IL)

analogues because they share many characteristics with ILs. DESs are usually

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regarded as eutectic mixtures formed by mixing hydrogen bond donor (HBD) and

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hydrogen bond acceptor (HBA) which have the ability to associate with each other

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through hydrogen bond interactions or electric transfer complex. The charge

delocalization occurring through the hydrogen bond prevents HBD or HBA to

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crystallize, thus decreasing the freezing point of the DES relative to its components
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[1]. Since Abbott and co-workers reported the first DES of choline chloride (CC) and

metal halide or urea [2, 3], the family of DES has been continuously expanded. The
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HBA mainly focuses on quaternary ammonium or phosphonium salt, while the HBA
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extensively includes alcohol, carboxylic acid, amino acid, sugar, amide, inorganic salt,
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and so on [4-8]. Moreover, the applications of DES in various fields are also reported
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[8]. Electrochemistry is the first field for DESs application because of their suitable
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redox-potential window and good water-tolerance [9-11]. DESs are also used as

solvent and / or dispersion media in the material preparation [12-14]. Many

parameters of the materials can be adjusted by the choice of composition and water

content in the DES. In the synthesis, DESs are often utilized as solvents or even

catalysts with encouraging results [15-17]. The other application mainly distributes

between catalysts, bio-applications, and separation processes [18-22]. It is well known

that physical property data are important and essential to industrial and engineering

applications of DESs. However, the systematical property determination and analysis

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on DESs are few reported in the literatures. The scattered properties accompanying

the reports of usages are basically limited to melting point and viscosity data at

several temperatures. Hayyan reported several properties of five triethylene glycol

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based DESs at the temperature range of 298.15 to 353.15 K [23]. Jibril systhesed and

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characterized tetrapropylammonium bromide-based DESs [24]. Mjalli measured the

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properties of tetrabutylammonium chloride-based DESs at different temperatures

ranging from (293.15 to 353.15 K) [25]. Therefore, the related determination and

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correlation of the physical properties are still highly demanded.
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In our previous works [26, 27], six levulinic acid (LA)-based DESs were reported

as efficient absorbents for CO2 and SO2 with good performance, their counterparts
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included choline chloride (CC), choline acetyl chloride (CAC), tetraethylammonium

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chloride (TEAC), tetraethylammonium bromide (TEAB), tetrabutylammonium

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chloride (TBAC), and tetrabutylammonium bromide (TBAB). As a contination, the

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present work is turned to systematical measurement of their physicochemical

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properties such as density, dynamic viscosity, electric conductivity, and refractive

index at the temperature ranging from 293.15 to 333.15 K under atmospheric pressure.

Trimethyl hydrochloride (TMC) is also added to enlarge the scope of HBA.

Furthermore, the determined data were correlated with feasible model and analysized

to acquire the relevant information on the structure and properties for present seven

DESs.

2. Experimental section

2.1 Materials

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Anhydrous CC (mass fraction purity >98.5%, with the same below) was purchased

from Jinan Hualing Pharmaceutical Co., Ltd. LA, CAC, TEAB, TBAB (AR

grade, >99%) and TEAC, TMC (AR grade, >98%), TBAC (CP grade, >97%) were all

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obtained from Aladdin Chemical Company. All the chemicals were used as supplied.

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2.2 Preparation of levulinic acid-based DESs

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The DESs were prepared by direct mixing LA with various quarternary ammonium

salts under atmospheric pressure and suitable temperature until a homogeneous phase

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was obtained. The obtained DESs were further dried under vacuum at 353 K for 48 h
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before use. Karl Fischer analysis (SF-3 Karl-Fischer Titration, Zibo Zifen Instrument

Co. Ltd.) was used to determine the water content in each DES, with the results of
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less than 1.2·10−3 (mass fraction) for all DESs. The weight of the materials was
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determined by electronic balance (Mettler-Toledo AL204) with the standard

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uncertainty of 2*10−4 g.
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2.3 Determination of physical properties

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The density and refractive index data of DESs were automatically determined at

atmospheric pressure and temperatures ranging from 293.15 to 333.15 K with 10 K

intervals by DMA4500&RXA170 combined system (Anton Paar). The standard

uncertainties for density and refractive index were 0.00001g.cm-3 and 0.00004,

respectively. The instrument was calibrated periodically with double-distilled water

and dried air. Two integrated Pt 100 platinum thermometers (ur(T) = 0.01) together

with Peltier elements provide an extremely precise thermostatting of the sample. The

viscosity was detected by Pinkevitch method. The conductivity was measured by

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DDS-11A conductivity detector (Shanghai Leici Xinjing instrument limited company).

The relative standard uncertainty of viscosity as well as conductivity was 0.2%.

3. Results and discussion

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The density (ρ), dynamic viscosity (η), electrical conductivity (σ), and refractive

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index (nD) for present seven DESs at various temperatures were systematically

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determined and correlated using different models. The temperature dependences of

the abovementioned properties are graphically illustrated in Figures 1-4. For clear

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illustration, the density lines of LA + TBAB and LA + ACC, viscosity curves of LA +
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CC, LA + TEAC, and LA + TEAB, refractive index line of LA + TEAC in,

conductivity profile of LA + TEAB in were omitted in corresponding figure because

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of their overlap with other DESs.

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As shown in figures 1 and 3, the density and refractive index decreases linearly with
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increasing temperature for each DES. While for the viscosities as shown in figure 2,
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the changing tendency is nonlinear. But for electrical conductivity as illustrated in

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figure 4, they demonstrate to be increasing with increased temperature.

1.20 400

375
1.15 350
 g.cm-3

150
 / mPa.s-1

1.10
120

90
1.05
60

30
1.00
0
290 300 310 320 330 340 290 300 310 320 330
/K T/K

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Figure 1. Densities of five DESs as the function of Figure 2. Temperature dependent of viscosity for

temperature. ∆, LA-TEAB; □, LA-CC; ▽, LA based DESs. □, LA-TBAB; ○, LA-ACC; ◇,

LA-TMC; ◇, LA-TEAC; ○, LA-TBAC. LA-TBAC; ▽, LA-TMC.

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9
1.47
8

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7

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1.46 6

 / mS.cm-1
5
nD

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1.45
3
2
1.44
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1
290 300 310 320 330 340 0
/K 290 300 310 320 330 340
T/ K
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Figure 3. Temperature dependent of refractive Figure 4. Temperature dependent of conductivity

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index for LA based DESs. ∆, LA-TEAB; ▼, for LA based DESs. ●, LA-TMC; ∆, LA-TEAC; □,
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LA-TBAB; □, LA-CC; ☆, LA-ACC; ○, LA-CC; ○, LA-ACC; ◇, LA-TBAC; ▽,

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LA-TBAC; ●, LA-TMC; ○, LA-TBAC. LA-TBAB.

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3.1 Density

Density data is basic and important physical property in defining the nature of substance.

It also suggests the basis for equipment designing and operation process. The experimental

density data of present DESs are determined and listed in Table 1. All the DESs have the

density higher than unity. The quarternary ammonium salts play evident influence on the

density of DESs, with the changing sequence of LA-TEAB > LA-ACC ≈ LA-CC >

LA-TMC > LA-TBAB ≈ LA-TEAC > LA-TBAC. When the hydroxyl group in CC was

derived to be acetyl ester, the formed DESs of ACC-LA have almost the same density with

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CC-LA. The DESs containing bromide anion have slightly higher density than those of

chloride anion for the same cations. It may arise from the density difference of two halogens

themselves.

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Table 1. Experimental density, dynamic viscosity, and electrical conductivity of present DESs

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at various temperatures.

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T/K CC+LA ACC+LA TEAC+LA TEAB+LA TBAC+LA TBAB+LA TMC+LA
Density / g cm-3

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293.15 1.14200 1.14440 1.09741 1.17735 1.03453 1.10089 1.11585
298.15 1.13842 1.14058 1.09392 1.17362 1.03096 1.09717 1.11204
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303.15 1.13483 1.13687 1.09030 1.16985 1.02729 1.09352 1.10822
308.15 1.13119 1.13301 1.08664 1.16602 1.02379 1.08987 1.10443
313.15 1.12749 1.12943 1.08328 1.16219 1.02026 1.08620 1.10066
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318.15 1.12398 1.12561 1.07967 1.15836 1.01667 1.08256 1.09683

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323.15 1.12036 1.12182 1.07612 1.15456 1.01307 1.07877 1.09305

328.15 1.11670 1.11791 1.07250 1.15116 1.00950 1.07566 1.08923
P

333.15 1.11370 1.11441 1.06920 1.14737 1.00600 1.07205 1.08536

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338.15 1.11011 1.11070 1.06574 1.14345 1.00249 1.06837 1.08183

343.15 1.10648 1.10685 1.06229 1.13974 0.99891 1.06468 1.07799
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Dynamic viscosity / mPa s

293.15 134.23 164.52 130.07 148.95 121.68 376.50 74.02
303.15 79.14 85.88 69.81 76.98 65.59 175.10 42.25
313.15 47.76 46.75 39.07 42.42 36.66 93.88 25.57
323.15 31.29 31.58 27.07 28.81 25.46 53.38 17.71
333.15 20.21 21.47 18.71 19.74 17.47 33.85 12.70
Electrical conductivity / mS cm-1
293.15 0.58 0.51 0.75 0.71 0.35 0.15 1.35
298.15 0.81 0.67 1.05 0.98 0.45 0.22 1.80
303.15 1.05 0.86 1.38 1.32 0.60 0.29 2.25

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308.15 1.38 1.12 1.72 1.67 0.72 0.42 2.75

313.15 1.75 1.43 2.15 2.12 0.89 0.55 3.35
318.15 2.10 1.78 2.65 2.53 1.13 0.73 4.02
323.15 2.63 2.30 3.18 3.09 1.29 0.92 4.71

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328.15 3.19 2.76 3.73 3.84 1.51 1.15 5.49

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333.15 3.87 3.35 4.53 4.37 1.77 1.41 6.40

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338.15 4.48 4.01 5.24 5.22 2.13 1.73 7.32

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343.15 5.22 4.70 5.87 5.88 2.38 1.99 8.27

The effect of temperature on density was also graphically presented in figure 1. As

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expected, the density of each DES decreased linearly with increasing temperature. Such
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linear relationship between density and temperature for all the DESs can be regressed by

following equation,
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  a  bT (1)
TE

where ρ demonstrates the density of DES in g.cm-3, T denotes the experimental temperature
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in Kelvin, and a and b are correlating constants. The correlated values of a and b as well as
CE

coefficients (R2) for the studied DESs are listed in Table 2. It is evident that the relationship
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between the density and temperature is highly linear because the values of R2 are more than

0.999 for all the DESs. ILs have been reported as promising materials for heat-storage or heat

transfer fluid [28]. Then, DESs, an alternative to traditional ILs, maybe possess the similar

potential. Thus, the values of volume expansivity (β) of the DESs are very important

parameter for DES application in thermodynamics and engineering fields. However, such

relevant data are still deficient. Here, the values of β for present DESs are calculated

according to the definition of volume expansivity [29],

1 V  ln 
 ( ) p  ( )p (2)
V T T
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where β is the volume expansivity in K-1, V is the molar volume in cm3.g-1, ρ is the density in

g.cm-3, and T is the temperature in K. The obtained β values of the DESs are also presented in

Table 2 and range between 6.3133 *10-4 K-1 and 7.004*10-4 K-1, which are much higher than

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the β values of metal mercury (1.8*10-4 K-1) and many traditional ILs (for example, the β

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values of 1-allyl-3-butylimidazolium dicyanamide, 1-allyl-3-octylimidazolium dicyanamide,

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and 1-vinyl-3-octylimidazolium dicyanamide are 5.97*10-4, 5.95*10-4, and 6.75*10-4 K-1,

respectively) [30]. Therefore, such inexpensive and low toxicity LA-based DESs have the

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potential utilizations in the fields of temperature sensor as well as thermal expansion.
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Table 2. The correlation coefficients of density-temperature model and regression coefficients

DESs a /g.cm-3 104*b / K-1 104*β / K-1 R2

D

CC+LA 1.34991 -7.0971 6.3133 0.99973

TE

ACC+LA 1.36418 -7.4992 6.6515 0.99993

TEAC+LA 1.30363 -7.0375 6.5178 0.99990
P

TEAB+LA 1.39772 -7.5186 6.4900 0.99991

CE

TBAC+LA 1.24321 -7.1204 7.0040 0.99998

TBAB+LA 1.31207 -7.2093 6.6586 0.99982
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TMC+LA 1.33792 -7.5760 6.9081 0.99997

The molar volumes (Vm) of the DESs studied in this work were derived from the density

data and are presented in Table 3. Molar volume were determined at the temperature scope of

(293.15 to 343.15) K from the following equation,

Vm  M /  (3)

where M denotes the molecular mass of the DES in g mol-1, and ρ represents the density in g

cm-1. As shown in the Table 3, the molar volume slowly increases with the increasing

temperature for each DES because of the temperature dependence of density. For different

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DESs, the molar volumes demonstrated the sequence of TBAB-LA > TEAB-LA > TEAC-LA

≈ ACC-LA > CC-LA > TMC-LA, which is the similar sequence as the molar mass of HBA.

3.2 Refractive index (nD)

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Refractive index is a parameter to characterize the electronic polarizability of a molecule

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and helpful for understanding the intermolecular forces or molecule behavior in solution. The

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experimental refractive indices within the temperature range of (293.15 to 353.15) K are

listed in Table 3 and also demonstrated graphically in figure 3. In general and for all the

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DESs, the refractive indices decreased linearly with increasing temperature.
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Table 3. Values of refractive index (nD), molar volume (Vm), molar refraction (Rm), and free

volume (fm) of present DESs as a function of temperature.

D

Vm Rm Fm Vm Rm Fm
T (K) nD T (K) nD
TE

(cm mol-1)
3 3 -1
(cm mol )
CC-LA
P

293.15 1.46336 427.32 117.77 309.55 323.15 1.45424 435.57 118.01 317.57
CE

298.15 1.46185 428.66 117.81 310.85 328.15 1.45271 437.00 118.05 318.95
303.15 1.46030 430.02 117.84 312.18 333.15 1.45141 438.18 118.07 320.10
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308.15 1.45878 431.40 117.89 313.52 338.15 1.44995 439.60 118.13 321.47
313.15 1.45724 432.82 117.93 314.89 343.15 1.44844 441.04 118.17 322.87
318.15 1.45575 434.17 117.97 316.21
ACC-LA
293.15 1.45959 463.14 126.75 336.39 323.15 1.45024 472.46 127.03 345.44
298.15 1.45802 464.69 126.80 337.89 328.15 1.44861 474.12 127.07 347.04
303.15 1.45644 466.21 126.84 339.37 333.15 1.44715 475.61 127.11 348.49
308.15 1.45484 467.80 126.88 340.91 338.15 1.44561 477.19 127.16 350.04
313.15 1.45332 469.28 126.92 342.36 343.15 1.44402 478.85 127.20 351.65
318.15 1.45176 470.87 126.97 343.90
TEAC-LA

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293.15 1.46416 468.43 129.30 339.13 323.15 1.45478 477.70 129.55 348.14
298.15 1.46260 469.92 129.33 340.59 328.15 1.45324 479.31 129.61 349.70
303.15 1.46103 471.48 129.38 342.10 333.15 1.45172 480.79 129.63 351.16
308.15 1.45940 473.07 129.42 343.65 338.15 1.45028 482.35 129.70 352.65

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313.15 1.45796 474.54 129.47 345.07 343.15 1.44875 483.92 129.73 354.18

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318.15 1.45635 476.13 129.51 346.61

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TEAB-LA

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293.15 1.47273 474.39 133.01 341.37 323.15 1.46320 483.75 133.29 350.46
298.15 1.47114 475.90 133.05 342.84 328.15 1.46175 485.18 133.32 351.86

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303.15 1.46954 477.43 133.09 344.34 333.15 1.46021 486.78 133.38 353.41
308.15 1.46795 479.00 133.14 345.86 338.15 1.45859 488.45 133.43 355.02
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313.15 1.46635 480.58 133.19 347.39 343.15 1.45709 490.04 133.48 356.56
318.15 1.46479 482.16 133.24 348.92
TBAC-LA
D

293.15 1.45780 605.38 165.12 440.25 323.15 1.44783 618.20 165.44 452.76
TE

298.15 1.45612 607.47 165.17 442.30 328.15 1.44621 620.39 165.50 454.88
P

303.15 1.45444 609.64 165.23 444.41 333.15 1.44460 622.54 165.56 456.98
CE

308.15 1.45279 611.73 165.28 446.45 338.15 1.44295 624.72 165.61 459.12
313.15 1.45117 613.84 165.33 448.51 343.15 1.44137 626.96 165.68 461.28
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318.15 1.44952 616.01 165.39 450.62

TBAB-LA
293.15 1.47125 609.26 170.37 438.89 323.15 1.46135 621.75 170.72 451.03
298.15 1.46960 611.33 170.44 440.89 328.15 1.45985 623.55 170.74 452.82
303.15 1.46802 613.37 170.51 442.86 333.15 1.45832 625.65 170.82 454.83
308.15 1.46629 615.42 170.54 444.88 338.15 1.45671 627.81 170.89 456.92
313.15 1.46471 617.50 170.62 446.88 343.15 1.45508 629.98 170.95 459.03
318.15 1.46301 619.58 170.65 448.93
TMC-LA
293.15 1.45184 397.84 107.29 290.55 323.15 1.44228 406.14 107.52 298.62
298.15 1.45024 399.20 107.33 291.87 328.15 1.44070 407.56 107.56 300.00

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303.15 1.44862 400.58 107.37 293.21 333.15 1.43908 409.02 107.60 301.42
308.15 1.44703 401.95 107.40 294.55 338.15 1.43763 410.35 107.64 302.71
313.15 1.44546 403.33 107.44 295.89 343.15 1.43597 411.81 107.67 304.14
318.15 1.44384 404.74 107.48 297.26

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For non-electrolytes, refractive indices and density values are often reported together to

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characterize the purity of the samples concerned thanks to the high precision obtained with

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simple, quick, and inexpensive techniques. However, such two properties can be jointly

studied by Lorentz-Lorenz equation as following to acquire interesting information [31, 32],

3 0
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N A e nD2  1
 ( 2 )Vm
nD  1
(5)
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where nD is the refractive index, Vm is the molar volume, NA denotes the Avogadro’s number.

ε0 is the permittivity of free space and αe is the mean molecular polarizability. On the basis of
D
TE

above equation, the molar refraction, Rm, can be defined as eqn. (6),

nD2  1
P

Rm  ( 2 )Vm (6)
nD  1
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Simple calculations have shown that for a hardcore spherical molecular model,
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 e  4 0 a3 , where α is the sphere radius. Substituting the expression of αe into equation (5),

yields Rm  N A 4 3 / 3 ; therefore, Rm represents hard-core volume per mole molecules. The

molar free volume, Fm, which represents the volume not occupied by molecules or ions, is

simply obtained as Fm  Vm -Rm . This free volume appears in many liquid-state models, for

instance, in those based on the famous van der Waals equation. Therefore, a joint analysis of

density and refractive index can provide highly useful information about the volumetric

behavior of a system. The calculated Vm, Rm, and Fm are listed in Table 3.

For the studied DESs, the refractive index increases in the order of TBAC-LA <

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TEAC-LA < TBAB-LA ≈ TEAB-LA < TMC-LA < ACC-LA < CC-LA at each temperature.

The refractive indexes range from 0.99 to 1.15 for all DESs with the exception of CC-LA,

which has the refractive index value of higher than1.44, clearly meaning that the relatively

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strong interaction of hydroxyl group in cation with LA has a large influence on this property.

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As seen from Table 3, the molar refraction almost kept unchanged with temperature for

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each DESs. As expected, the molar free volumes increase with temperature and follow the

same changing trend with molar volumes for all DESs. It is well known that the information

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on the molar free volume can suggest important analysis and selection basis for gas solubility
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in a solvent [33, 34].

3.3 Dynamic viscosity (η)

D

The viscosity of DESs is a typical transport property to be mentioned. When DESs are
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used as green reaction and separation mediums, the dynamic viscosity data are essential
P

parameters directly influencing the mass transfer, the calculation of pipes for flow stream and
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selection of a stirrer. Furthermore, if the DESs are developed to be gas absorbents, the
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viscosity data are also basic parameter needed consideration for their suitability. The factors

affecting the viscosity behavior includes anions species, their alkalinity, size, relative ability

to form hydrogen-bond [35, 36]. Although the models based on group contribution method

were developed to predict the viscosity of pure ILs and their mixture [37, 38], they were not

suitable for deep eutectic solvents due to the absorbent of enough experimental data for

correlation. Then, it is necessary to experimentally determine the viscosity data for DESs. In

present work, the dynamic viscosity data of present seven DESs at 10 K interval in the

temperature ranging from 293.15 K to 333.15 K are measured and listed in Table 1. As shown

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in Table 1, these DESs exhibited relatively low viscosity (25.57-93.88 mPa s at 313.15 K).

Among them, TMC-LA presented the lowest viscosity of 25.57 mPa s at 313.15 K, while

TBAB-LA demonstrated the highest viscosity at each temperature level. It is clear that the

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bigger HBD molecules result in the higher viscosity of the DES. This is due to the more

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bulky molecular complexes showing slower overall mobility. Such phenomena is similar with

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those in tetrabutylammonium chloride based DESs [25]. It is worth to noting that all the

DESs have much lower viscosities than those of many pure task-specific ILs [37], meaning

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that they possess excellent property for practical usage.
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The temperature dependence of viscosity is also depicted in figure 2. As shown in figure 2,

the dynamic viscosity decreased exponentially with increasing temperature for each DES.
D

Such behavior is similar with that of common ILs. Non-Arrhenius temperature dependence
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was used to describe the viscosity behavior of present DESs, whose ions maybe suffer from
P

hindered rotation or associated to the hydrogen bond network. The temperature dependence is
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convex-curved type; therefore, the modified Vogel-Fulcher-Tamman (VFT) equation as

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suggested by Vila et al. was used to correlate the temperature dependence of the experimental

viscosity data as following [39-41],

  0 *exp(B/(T  T0 )) (7)

where η is the experimental dynamic viscosity in mPa.s. η0 is pre-exponential constant in

mPa.s. B and T0 are empirical constants in K. The best fitted values of abovementioned

parameters are listed in Table 4. From Table 4, the correlation coefficient, R2, is more than

0.998, which means that the modified VFT equation can satisfactorily describe the

temperature dependence of dynamic viscosity.

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Table 4. The parameters of dynamic viscosity-temperature model and regression coefficients

DES η0 (mPa.s) B ( K) T0 ( K) R2 Eη (298.15K) ( kJ.mol-1)

CC+LA 0.00557 1782.69 116.51 0.99967 39.93

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ACC+LA 0.17244 642.29 199.54 0.99946 48.82

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TEAC+LA 0.23720 560.09 204.36 0.99885 47.06

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TEAB+LA 0.28530 518.41 210.32 0.99920 49.67

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TBAC+LA 0.19660 586.92 201.86 0.99876 46.78

TBAB+LA 0.05910 920.85 188.02 0.99995 56.11

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TMC+LA 0.18549 568.89 198.18 0.99959 42.07

According to the definition, the activation energy can be obtained from the recovered
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parameters of VFT equation as following [40],

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d ln  T 2
E  R  RB( ) (8)
T  T0
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d ln(1/ T )
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Therefore, the activation energy at 298.15 K are calculated and presented in Table 4. As

above-mentioned, the relationship between viscosity and temperature is out of non-Arrhenius

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behavior, here these activation energies are simply provided the parameter to present the

change rate of viscosity along with temperature near room temperature.

3.4 Electrical conductivity

The conductivity of present DESs was measured between 293.15 K and 343.15 K with the

temperature interval of 10 K, and the results are shown in Table 1 and figure 4. As expected,

the electrical conductivity increases with increasing temperature. All the DESs result in low

conductivity because of the non-ionicity of the molecules. The cations have evident influence

on electric conductivity. TMC-LA showed the highest value among the DESs (1.35 mS cm-1
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at 293.15 K) due to small dimension of its trimethylammonium (therefore higher mobility).

Conversely, the biggest bulky of tetrabutyl ammonium and bromide anion is responsible for

the lowest electrical conductivity (0.15 mS cm-1 at 293.15 K, almost one order of magnitude

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lower). Similarly to dynamic viscosity, the Vogel-Fulcher-Tamman (VFT) equation is also

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applied for fitting the electrical conductivity values (σ) and temperature as shown in eqn. (9),

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   0 *exp( B /(T  T0 )) (9)

where σ is the experimental electrical conductivity at temperature T; σ0, B are fitting

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parameters. The fitted parameters are listed in Table 5 by nonlinear regression method. From
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Table 5, good-to-fitness of temperature dependence of conductivity is obtained because that

the correlation coefficients, R2, are higher than 0.999.

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Table 5. The parameters of electrical conductivity-temperature model, regression coefficients,

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and molar electric conductivity

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DES σ0(mS cm-1) B T0 (K) R2 Λ(298.15 K) (mS cm-1)

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CC+LA 536.36 720.09 187.01 0.99957 247.85

ACC+LA 1487.83 1013.05 167.06 0.99962 236.20
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TEAC+LA 248.47 527.06 202.05 0.99948 351.32

TEAB+LA 265.62 532.56 203.13 0.99902 336.82
TBAC+LA 255.06 804.94 170.74 0.99901 211.88
TBAB+LA 138.45 546.88 213.92 0.99934 91.39
TMC+LA 389.88 606.81 185.61 0.99989 537.08

3.5 Molar electrical conductivity (Λ)

The molar electrical conductivities can be calculated from density and electrical conductivity

by the following equation,

   * M *  1 (10)

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where M, ρ, Λ and σ are molecular mass, density, molar electrical conductivity at 298.15 K

and the electrical conductivity, respectively. The values of calculated molar electrical

conductivity are listed in Table 5. As shown from Table 5, the changing tendency of molar

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electrical conductivity of the seven DESs at 298.15 K is TBAB-LA<< TBAC-LA < ACC-LA

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< CC-LA < TEAB-LA < TEAC-LA << TMC-LA. Such sequence is similar with that of

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electrical conductivity itself.

3.6 Ionicity

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The molar conductivity and dynamic viscosity have the relationship of counter-balance,
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such behavior can be described by the following Walden equation,

   k (11)
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lg   lg k   lg 1 (12)
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where Λ is the molar conductivity, η is the dynamic viscosity. α is the fitting parameter and k
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represents a temperature dependent constant. The description of lgΛ vs lgη–1 is shown in

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Fig.5 for seven DESs at the temperature ranging from 293.15 to 333.15 K. The α can be
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obtained by linear fitting as the slopes as and the values are 0.8407 for TBAC-LA, 0.9039 for

TEAB-LA, 0.9287 for TEAC-LA, 1.0154 for CC-LA, 0.9403 for ACC-LA, 0.9486 for

TBAB-LA, and 0.8905 for TMC-LA, respectively. The ideal line as the diagonal is also

included in Fig. 5. It is evident that all the Walden plots are far located to the ideal line, which

is obtained using highly diluents aqueous KCl solution as the reference without any interionic

interaction [42]. Therefore, it is reasonable to believe the non-ionic structure of the DESs.

The similar conclusion was also drawn from the literature reports [15, 43].

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Figure 5. Waldon plots of DESs. Up triangle, black, CC-LA; down triangle, magenta,

ACC-LA; square, red, TEAC-LA; down triangle, blue, TEAB-LA; square, black, TBAC-LA;
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star, black, TBAB-LA; circle, blue, TMC-LA; The diagonal is the ideal line for aqueous KCl
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solution as the reference without any ionic interaction.

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4. Conclusions
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The density, dynamic viscosity, refractive index, and electrical conductivity of the seven
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levulinic acid based DESs were determined at the temperature range of (293.15 to 333.15) K

and atmospheric pressure. The temperature dependences of density and refractive index were

satisfactorily fitted by linear equation. The VFT equation can be used for correlating the

dynamic viscosity and electrical conductivity with temperature very well. Furthermore, the

values of volume expansivity, molar volume, molar refraction, free volume, activation energy

of viscosity, molar electrical conductivity, and ionicity were derived. Walden profile implied

the non-ionic structure of present DESs. The influence of structure on property for DESs was

also investigated. This study will be significant for the engineering and industrial applications

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and helpful for the modeling or prediction of structure-property relationship for DESs.

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References

[1] D. Carriazo, M. C. Serrano, M. C. Gutiérrez, M. L. Ferrer, F. D. Monte, Chem. Soc. Rev.

41 (2012) 4496-5014.

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[2] A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, V. Tambyrajah, Chem. Commun.

R
(2003) 70-71.

SC
[3] A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, V. Chem. Commun. (2001)

2010-2011.

NU
[4] M. Francisco, A. V. D. Bruinhorst, L. F. Zubeir, C. J. Peters, M. C. Kroon, Fluid Phase
MA
Equilib. 340 (2013)77- 84.

[5] M. A. Kareem, F. S. Mjalli, M. A. Hashim, I. M. AINashef, J. Chem. Eng. Data 55 (2010)

D

4632-4637.
TE

[6] M. Francisco, A. V. D. Bruinhorst, M. C. Kroon, Green Chem. 14 (2012) 2153-2157.

P

[7] Y. T. Dai, J. V. Spronsen, , G. J. Witkamp, R. Verpoorte, Y. H. Choi, Anal. Chim. Acta 766
CE

(2013) 61-68.
AC

[8] M. Francisco, A. V. D. Bruinhorst, M. C. Kroon, Angew. Chem. Int. Ed. 52 (2013) 3074

-3085.

[9] A. P. Abbott, G. Frisch, S. J. Gurman, A. R. Hillman, J. Hartley, F. Holyoak, K. S. Ryder,

Chem. Commun. 47 (2011) 10031-10033.

[10] S. Ramesh, R. Shanti, E. Morris, J. Mater. Sci. 47 (2011) 1-7.

[11] A. P. Abbott, K. El Ttaib, G. Frisch, K. S. Ryder, D. Weston, Phys. Chem. Chem. Phys.

14 (2012) 2443-2449.

[12] J. Y. Dong, Y. J. Hsu, D. S. H. Wong, S. Y. Lu, J. Phys. Chem. C 114 (2010) 8867-8872.

21
 ACCEPTED MANUSCRIPT

[13] F. X. Chen, S. L. Xie,J. H. Zhang, R. Liu, Mater. Lett. 112 (2013) 177-179.

[14] A. Abo-Hamad, M. Hayyan, M. A. AlSaadi, M. A. Hashim, Chem. Eng. J. 273 (2015)

551-567.

T
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[15] P. M. Pawar, K. J. Jarag, G. S. Shankarling, Green Chem. 13 (2011) 2130-2134.

R
[16] D. Carriazo, M. C. Serrano, M. C. Gutieŕrez, M. L. Ferrer, F. Monte, Chem. Soc. Rev. 41

SC
(2012) 4996-5014.

[17] E. Durand, J. Lecomte, B. Baréa, E. Dubreucq, R. Lortiec, P. Villeneuvea, Green Chem.

15 (2013) 2275-2282.
NU
MA
[18] B. Singh, H. Lobo, G. Shankarling, Catal. Lett. 141 (2011) 178-182.

[19] S.Wang, X. W. Peng, L. X.n Zhong, S. S. Jing, X. F. Cao,F. C. Lu, R. C. Sun, Carbohydr.
D

Polym. 117 (2015) 133-139.

TE

[20] M. Sharma, C. Mukesh, D. Mondala, K. Prasad, RSC Adv. 3 (2013) 18149-18155.

P

[21] A. García, E. R.Juan, G. R. Gutiérrez, J. J. Rios, J. F. Bolaños, Food Chem. 197 (2016)
CE

554-561.
AC

[22] T. T. Jiao, C. S. Li, X. L. Zhuang, S. S. Cao, H. N. Chen, S. J. Zhang, Chem. Eng. J. 266

(2015) 148-155.

[23] M. Hayyana,T. Aissaoui, M. A. Hashim, M. A. AlSaadia, A.Hayyan, J. Taiwan Inst.

Chem. Eng. 50 (2015) 24-30.

[24] B. Jibril, F. Mjalli, J. Naser, Z. Gano, J. Mol. Liq. 199 (2014) 462-469

[25] F. S. Mjalli, J. Naser, B. Jibril, V. Alizadeh, Z. Gano, J. Chem. Eng. Data 59 (2014)

2242-2251.

[26] D. S. Deng, G. Q. Han, Y. T. Jiang, New J. Chem., 39 (2015) 8158-8164.

22
 ACCEPTED MANUSCRIPT

[27] M. Z. Lu, G. Q. Han, Y. T. Jiang, X. D. Zhang, D. S. Deng, N. Ai, J. Chem. Thermodyn.

88 (2015) 72-77.

[28] J. Liu, F. X. Wang, L. Zhang, Renew. Energy 63 (2014) 519-523.

T
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[29] J. M. Smith, H. C. Van Ness, M. M. Abbott, Introduction to chemical engineering

R
thermodynamics, 7th ed., McGraw-Hill, New York, 2005.

SC
[30] Q. H. Zhang, X. Y. Ma, S. M. Liu, B. Q. Yang, L. J. Lu, Y. D. He, Y. Q. Deng, J. Mater.

Chem. 21 (2011) 6864-6868.

NU
[31] M. A. Iglesias-Otero, J. Troncoso, E. Carballo, L. Romaní, J. Chem. Thermodyn. 40
MA
(2008) 949-956.

[32] M. Deetlefs, K. R. Seddon, M. Shara, Phys. Chem. Chem. Phys. 8 (2006) 642-649.
D

[33] M. S. Shannon, J. M. Tedstone, S. P. O. Danielsen, M. S. Hindman, A. C. Irvin, J. E.

TE

Bara, Ind. Eng. Chem. Res. 51 (2012) 5565-5576.

P

[34] Y. F. Hu, Z. C. Liu, C. M. Xu, X. M. Zhang, Chem. Soc. Rev. 40 (2011) 3802-3823.
CE

[35] D. R. McFarlane, J. Sun, J. Golding, P. Meakin, M. Forsyth, Electrochim. Acta 45 (2000)

AC

1271-1278.

[36] G. H. Tao, L. He, N. Sun, Y. Kou, Chem. Commun. (2005) 3562-3564.

[37] J. A. Lazzús, G. Pulgar-Villarroel, J. Mol. Liq. 209 (2015) 161-168.

[38] F. Gharagheizi, P. Ilani-Kashkouli, A. H. Mohammadi, D. Ramjugernath, D. Richon,

Chem. Eng. Sci. 80(2012)326-333.

[39] H. Jin, B. O’Hare, J. Dong, S. Arzhantsev, G. A. Baker, J. F. Wishart, A. J. Benesi, M.

Maroncelli, J. Phys. Chem. B 112 (2008) 81-92.

[40] A. Yadav, S. Pandey, J. Chem. Eng. Data 59 (2014) 2221-2229.

23
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[41] A. Boisset, S. Menne, J. Jacquemin, A. Balducci, M. Anouti, Phys. Chem. Chem. Phys.

15 (2013) 20054-20063.

[42] C. Schreiner, S. Zugmann, R. Hartl, H. J. Gores, J. Chem. Eng. Data 55 (2010)

T
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1784-1788.

R
[43] H. Z. Su, J. M. Yin, Q. S. Liu, C. P. Li, Acta Phys. Chim. Sin. 31 (2015) 1468-1473.

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Highlights
 Levulinic acid was paired with seven quarternary ammonium salts to form new DESs
 Physical properties of the levulinic acid-based DESs were determined and fitted
 Partial structure-property relationship for DESs was investigated

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 Present DESs have the potential of industrial applications

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