物理化学学报(Wuli Huaxue Xuebao)

1468 Acta Phys. -Chim. Sin. 2015, 31 (8), 1468–1473 August

[Article] doi: 10.3866/PKU.WHXB201506111 www.whxb.pku.edu.cn

四种深共融溶剂的性质: 密度、电导率、动力粘度及折光率

宿洪祯1 尹静梅1 刘青山2,* 李长平1,*

( 大连大学环境与化学工程学院, 辽宁 大连 116622;
1 2
沈阳农业大学理学院, 沈阳 110866)

摘要: 制备了四种四丁基氯化铵类深共融溶剂, 包括四丁基氯化铵:丙酸[TBAC:2PA]、四丁基氯化铵:乙二醇

[TBAC:2EG]、四丁基氯化铵:聚乙二醇[TBAC:2PEG]、四丁基氯化铵:苯乙酸[TBAC:2PAA]. 在
288.15–338.15 K温度范围内, 测定了它们的密度、电导率、动力粘度及折光率. 讨论了温度对密度、电导
率、动力粘度及折光率等性质的影响. 通过经验方程估算了深共融溶剂的热膨胀系数、分子体积、标准摩尔
熵及晶格能等热力学性质参数. 利用Vogel-Fulcher-Tamman (VFT)方程和Arrhenius方程, 将测量的电导率和
动力粘度对温度拟合, 得到了动力粘度和电导率随温度变化方程式. 有关研究对深共融溶剂的工业化应用具有
重要意义.

关键词: 深共融溶剂; 密度; 电导率; 动力粘度; 折光率

中图分类号: O642

Properties of Four Deep Eutectic Solvents: Density, Electrical

Conductivity, Dynamic Viscosity and Refractive Index

SU Hong-Zhen1 YIN Jing-Mei1 LIU Qing-Shan2,* LI Chang-Ping1,*

1
( College of Chemical Engineering and the Environment, Dalian University, Dalian 116622, Liaoning Province,
P. R. China; 2School of Science, Shenyang Agricultural University, Shenyang 110866, P. R. China)

Abstract: Four deep eutectic solvents (DESs) were prepared from tetrabutylammonium chloride:
tetrabutylammonium chloride:propionic acid [TBAC:2PA], tetrabutylammonium chloride:ethylene glycol
[TBAC:2EG], tetrabutylammonium chloride:polyethylene glycol [TBAC:2PEG], and tetrabutylammonium
chloride:phenylacetic acid [TBAC:2PAA]. The density, electrical conductivity, dynamic viscosity, and
refractive index of the samples were measured at 288.15–338.15 K under atmospheric pressure. The
influence of the temperature on the density, electrical conductivity, dynamic viscosity, and refractive index
are discussed. The thermal expansion coefficient, molecular volume, standard molar entropy, and lattice
energy were determined from the measured values using empirical equations. The temperature
dependences on the electrical conductivity and dynamic viscosity of the DESs were fitted by the Vogel-
Fulcher-Tamman (VFT) equation. The Arrhenius equation is also discussed for the electrical conductivity
and dynamic viscosity. The above study will be of great significance for the industrial and engineering
applications of DESs.

Key Words: Deep eutectic solvent; Density; Electrical conductivity; Dynamic viscosity;
Refractive index

1 Introduction ing widely scientific and technological attention because of

In the recent years, deep eutectic solvents have been attract- their low cost as green solvents similar to ionic liquids (ILs).

Received: March 13, 2015; Revised: June 10, 2015; Published on Web: June 11, 2015.
*
Corresponding authors. LIU Qing-Shan, Email: [email protected]; Tel: 86-13478787524. LI Chang-Ping, Email: [email protected];
Tel: +86-13795164535.
The project was supported by the National Natural Science Foundation of China (21203193, 21306016, 21176033).
国家自然科学基金(21203193, 21306016, 21176033)资助项目
© Editorial office of Acta Physico-Chimica Sinica
No.8 SHI Xia-Xing et al.: Facile Synthesis of 0.6Li2MnO3-0.4LiNi0.5Mn0.5O2 with Hierarchi 1469

The deep eutectic solvents (DESs) are composed of two or PEG, PAA) were put into a round-bottomed flask with the mol-
three cheap and green components through hydrogen bond forma- ar ratio of 1:2. The system was stirred vigorously with a mag-
tion.1 Compared to ILs, the DESs have many advantages, such netic stirrer at 353 K for 8 h. The purity and the structure of the
as the simple synthesis and purification process, low cost of raw DESs have been characterized with 1 H NMR, which were
materials, and renewable, good biocompatibility, etc.2,3 shown in literature.15 The 1H NMR spectra are also listed in Ta-
DESs have been widely used for replacing the organic ble S1 (Supporting Information). The purity of the DESs and
solvents in industrial and scientific communities, especially for the mass fraction contribution of the impurities are estimated
bioactive natural products dissolution,4 green media,5 cataly- and given in Table 1. The impurities are the H-bond acceptor
sis, 6 – 8 organic synthesis, 9 electrochemistry, 1 0 , 1 1 reaction for TBAC and H-bond donor for PA, EG, PEG, and PAA, re-
medium,12 separation process,13,14 etc. In our group, series of IL- spectively. The properties of the raw materials are listed in Ta-
type DESs were designed, synthesized, and applied for the ex- ble 2.
traction desulfurization of fuels successfully.15 Moreover, the
2.2 Measurements of the density, electrical conduct-
extraction process was optimized and extraction mechanism
was probed systematically and the hydrogen bond formed ac- ivity, dynamic viscosity, and refractive index
counting for the higher desulfurization efficiencies. The water contents were determined before determination of
Although the DESs have exhibited so many excellent proper- the properties by a Cou-Lo Aquamax Karl Fischer moisture
ties, the research on their physicochemical properties is still meter v.10.06 (Mettler Toledo, Switzerland). The water con-
scarce. The limited existing study of the properties is mainly on tents were 190 × 10–6, 160 × 10–6, 180 × 10–6, and 200 × 10–6
the melting temperature and dynamic viscosity at several (mass fraction) for [TBAC:2PA], [TBAC:2EG], [TBAC:2PEG],
points, which will hinder its industrial and engineering applica- and [TBAC:2PAA], respectively.
tions to a great extent.16–19 The density, electrical conductivity, dynamic viscosity, and
In this work, four IL-type tetrabutylammonium chloride refractive index were determined by a previous method at atmo-
based DESs, namely tetrabutylammonium chloride:propionic sphere.20,21 The uncertainties of the experimental values are also
acid [TBAC:2PA], tetrabutylammonium chloride:ethylene estimated according to literarue.22,23
glycol [TBAC:2EG], tetrabutylammonium chloride:polyethyl- The density was determined by a density meter system
ene glycol [TBAC:2PEG], and tetrabutylammonium chloride: DDM2911 (Rudolph Research Analytical Co., USA) at
phenylacetic acid [TBAC:2PAA], were synthesized. As the ba- ((288.15–338.15) ± 0.01) K within an experimental error of
sic material, the TBAC has been used for the phase transfer
catalysis in some reactions. The raw materials are cheap and
¢
0.05 kg m–3. The electrical conductivity was carried out on a
MP522 conductivity instrument (Shanghai San-Xin Instrument-
easily obtained for the syntheses of DESs. The samples have
ation, P. R. China) with the cell constants of 1 cm–1 (the cell
also exhibited highly extraction desulfurization efficiencies,
was calibrated with the aqueous KCl solution) at ((288.15–
simple and environmentally friendly synthesis process. Their
main physicochemical properties, including the density, dynam- 338.15) ± 0.05) K and the uncertainties were estimated to be
ic viscosity, electrical conductivity, and refractive index were 1%. The measurement frequency and voltage of the electrical
characterized at 288.15–338.15 K. conductivity are 50 Hz and 9 V, respectively. The dynamic vis-
cosity was determined using an Ostwald viscometer (Dalian In-
struments an Meters Co., P. R. China) at ((288.15–338.15) ±
2 Experimental
0.1) K and the uncertainties were estimated to be 1%. The re-
2.1 Materials
fractive index was carried out according to the literature.24 The
The deep eutectic solvents were synthesized and character-
data were carried on an Abbe refractometer (Shanghai Shen
ized according to our previous method.15 Tetrabutylammonium
chloride (TBAC), propionic acid (PA), thylene glycol (EG), Guang Instrument Co., P. R. China) and the frequency was 50
polyethylene glycol (PEG), and phenylacetic acid (PAA) were Hz. The degassed water refractive index was determined by the
obtained from Tianjin Kermel, Aladdin, Tianjin Kermel, and instrument at (298.15 ± 0.05) K and the value is in good agree-
Tianjin Kermel, respectively. All the materials were purified ment with the literature.25
before use according to crystallization, distillation, and vacuum The above experimental values are listed in Tables S2 to S5
drying. The purified compounds of TBAC and PA (or EG, (Supporting Information).

Table 1 Purity of DESs and mass fraction contribution of the impurities

Mass fraction
DES ¢
M/(g mol–1) ¢
V/(cm3 mol–1)
HBAa(TBAC) HBDb DES purity
[TBAC:2PA] 426.08 441.1 < 0.001 < 0.001 ≥ 0.99
[TBAC:2EG] 402.06 406.4 < 0.001 < 0.001 ≥ 0.99
[TBAC:2PEG] 1077.92 1000.4 < 0.001 < 0.001 ≥ 0.99
[TBAC:2PAA] 550.22 528.9 < 0.001 < 0.001 ≥ 0.99
a b
M: molar mass; H-bond acceptor, H-bond donor
1470 Acta Phys. -Chim. Sin. 2015. Vol.31

Table 2 Properties of the raw materials

Chemical name Tm/ºC ¢

M/(g mol–1) CAS No. Mass fraction
tetrabutylammonium chloride (TBAC) 83–86 277.92 1112-67-0 ≥ 0.98
propionic acid (PA) –21.5 74.08 79-09-4 ≥ 0.99
ethylene glycol (EG) –12.6 62.07 107-21-1 ≥ 0.98
polyethylene glycol (PEG) 3–7 400.00 25322-68-3 ≥ 0.98
phenylacetic acid (PAA) 76.5 136.15 103-82-2 ≥ 0.99

3 Results and discussion than those of [TBAC:2PEG], the tendency is different from the
The temperature dependence on density (ρ), electrical con- traditional ILs. Usually, the traditional ILs exhibit the high
ductivity (σ), dynamic viscosity (η), and refractive index (nD) of density which has the relative small molecule for the series ILs,
the four DESs are plotted in Figs.1–4. for example, the series of pyridinium ILs and imidazolium
It can be seen that with the increase of the temperature, the ILs.21,24
lines of density and refractive are linear one. While for the elec- For electrical conductivity, the tendency of the four DESs is
trical conductivity and dynamic viscosity, the lines are non- [TBAC:2PEG] ≈ [TBAC:2PAA] < [TBAC:2PA] < [TBAC:2EG].
linear ones with temperature increasing. From the Tables S2–S5 The samples exhibited the same tendency with the traditional
(Supporting Information) and Figs.1–4, the density, dynamic ILs. The small molecule has the low electrical conductivity.
viscosity, and refractive index decrease with the temperature in- The glycol type DESs exhibit the higher electrical conductivity
creasing. And the electrical conductivity increases with the tem- than acid type EDSs.
perature increasing. For dynamic viscosity, the tendency of the four DESs is
For density, the sequence of the four DESs is [TBAC:2PA] < [TBAC:2EG] < [TBAC:2PA] ≈ [TBAC:2PEG] < [TBAC:2PAA].
[TBAC:2EG] < [TBAC:2PAA] < [TBAC:2PEG]. The values The small molecule exhibits the better liquidity than the relat-
of the DESs of [TBAC:2PA] are lower than those of [TBAC: ive big molecule. And the glycol type DESs have the better li-
2PAA] and the values of the DESs of [TBAC:2EG] are lower quidity than acid type EDSs.

Fig.1 Density vs temperature plots for four DESs Fig.3 Dynamic viscosity vs temperature plots for the four DESs
■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA] ■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA]

Fig.2 Electrical conductivity vs temperature plots for the four DESs Fig.4 Plot of nD vs temperature for the four DESs
■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA] ■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA]
No.8 SHI Xia-Xing et al.: Facile Synthesis of 0.6Li2MnO3-0.4LiNi0.5Mn0.5O2 with Hierarchi 1471

For refractive index, the sequence of the four DESs is [TBAC: Table 3 Estimated physicochemical property values for the four DESs
2PA] < [TBAC:2EG] < [TBAC:2PEG] < [TBAC:2PAA]. The at 298.15 K at atmospheric pressure
big molecule exhibits higher refractive index than the relative DES Vm/nm3 ¢ ¢ ¢
104α/K–1 S0/(J K–1 mol–1) UPOT/(kJ mol–1)
small molecule. [TBAC:2PA] 0.7327±0.0002 6.32±0.03 942.9±0.2 364±1
From the above results, it can be seen that, with same hydro- [TBAC:2EG] 0.6751±0.0002 6.84±0.03 871.0±0.2 371±1
gen bond acceptor (HBA) tetrabutylammonium chloride, the [TBAC:2PEG] 1.6619±0.0002 6.25±0.03 2101.0±0.2 302±1
changing of hydrogen bond donor (HBD) influences the proper- [TBAC:2PAA] 0.8785±0.0002 6.78±0.03 1124.6±0.2 349±1
ties of the DESs greatly.
3.1 Density (ρ) Table 4 Calculated values of molar electrical conductivity for the four
The lnρ vs T can be fitted according to the following straight DESs at 288.15–338.15 K under atmospheric pressure
line. The thermal expansion coefficient, α, can be obtained.
T/K
¢ ¢
Λ/(mS cm2 mol–1)
ln½ = b ¡ ®T (1) [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
288.15 0.121 0.389 0.124 0.048
where ρ is the density values, b is an empirical constant, α is the
293.15 0.151 0.457 0.148 0.064
thermal expansion coefficient, T is the experimeantal temperat-
298.15 0.185 0.534 0.178 0.084
ure. The thermal expansion coefficients are listed in Table 3.
303.15 0.227 0.625 0.212 0.109
The values in the range of 5 × 10–4 and 7 × 10–4 K–1 were ob-
308.15 0.270 0.721 0.247 0.137
tained by Jacquemin.26
313.15 0.323 0.829 0.286 0.170
The molecular volume, Vm, standard molar entropy, S0, and
318.15 0.379 0.942 0.326 0.207
lattice energy, UPOT, were calculated from density values ac-
323.15 0.438 1.061 0.368 0.248
cording to empirical equations.27
328.15 0.504 1.189 0.417 0.295
Vm = M=(N ¢ ½) (2) 333.15 0.574 1.325 0.464 0.343
0 338.15 0.650 1.475 0.516 0.396
S = 1246:5Vm + 29:5 (3)
¢ ¢ 2 –1
The uncertainty is 0.001 mS cm mol for molar electrical conductivity.
UP OT = 1981:2 (½=M )1=3 + 103:8 (4) The uncertainty is 0.05 K for temperature.
where M is molar mass, N is Avogadro's constant, ρ is density,
Vm is molecular volume, S0 is standard molar entropy, and UPOT The fitted parameters are listed in Table 5 by the equation (6)
is lattice energy. The calculated values of the above are listed in (see Fig.2). From Table 5, the correlation coefficient, R, is more
Table 3. From Table 3, the DESs have exhibited low lattice en- than 0.9999, which indicates that the VFT equation can be well
ergy which is an underlying reason for the liquid state of the used for the electrical conductivity fitting. By the Arrhenius
¢
DESs at room temperature (UPOT, CsI = 613 kJ mol–1).25 equation, the lnσ vs 1/T was plotted for the four DESs (see
3.2 Molar electrical conductivity (Λ) Fig.5).
The molar electrical conductivities can be calculated from In Fig.5, the dashed lines are straight lines for fitting of lnσ
density and electrical conductivity by the following equation: vs 1/T, the solid lines are smooth curves for lnσ vs 1/T. From
the equation, the experimental points should follow a straight
= ¾M½¡1 (5)
line, however, it is obvious that the experimental points are not
where Λ is the molar electrical conductivity, σ is the electrical
on the straight line in Fig.5. So, the electrical conductivity does
conductivity, M is the molar mass, and ρ is the density. The
not follow the Arrhenius behavior well.
molar electrical conductivity values are listed in Table 4. From
The electrical conductivity activation energies for the four
Table 4, at 298.15 K, the tendency of the four DESs is [TBAC:
DESs can be calculated by the modified VFT equation that Vila
2PAA] < [TBAC:2PA] < [TBAC:2PEG] < [TBAC:2EG].
et al.28 have built, recently.
3.3 Electrical conductivity (σ)
¾ = ¾1 exp(¡ E ¾=(k B (T ¡ T0))) (8)
Usually, the Vogel-Fulcher-Tamman (VFT) and Arrhenius
here, σ0 = σ∞ and B = Eσ/kB. σ is the electrical conductivity; σ0,
equations22 are used for the fitting of the electrical conductivity
B are fitting parameters; Eσ is the activation energy; σ∞ is the
values, σ, vs temperature, T:
maximum electrical conductivity, and kB is the Boltzmann con-
¾=¾0 ¢ exp(¡ B =(T ¡ T0)) (6) stant. The calculated values of electrical conductivity activa-
¾=¾1 ¢ exp(¡ E ¾=(k B T)) (7) tion energies are listed in Table 5.
where σ is the electrical conductivity; σ0, B are fitting paramet- 3.4 Dynamic viscosity (η)
ers; Eσ is the activation energy, which indicates the energy Like the electrical conductivity, the VFT and Arrhenius
needed for an ion to hop to a free hole; σ∞ is the maximum elec- equations were also used for the fitting of the dynamic viscos-
trical conductivity, and kB is the Boltzmann constant. ity, η, vs temperature, T.
1472 Acta Phys. -Chim. Sin. 2015. Vol.31

Table 5 Fitted values of electrical conductivity vs temperature for the Table 6 Fitted values of dynamic viscosity vs temperature for the four
four DESs by VFT and modified VFT equations DESs by VFT and modified VFT equations

DES ¢
σ0/(S cm ) –1
B/K 3
10 Eσ/eV T0/K R DES η0/(mPa s)¢ B/K 103Eη/eV T0/K R
[TBAC:2PA] 0.075±0.007 671.9±26.9 58.0 168.5±3.0 0.99997 [TBAC:2PA] 0.0272±0.0028 1210.8±28.9 104.5 158.1±1.7 0.99999
[TBAC:2EG] 0.198±0.029 820.2±53.2 70.8 134.4±5.9 0.99994 [TBAC:2EG] 0.0067±0.0016 1742.7±89.2 150.4 120.3±4.6 0.99998
[TBAC:2PEG] 0.013±0.001 540.8±30.9 46.6 172.0±4.1 0.99993 [TBAC:2PEG] 0.0479±0.0191 1223.8±121.8 105.6 149.0±7.6 0.99989
[TBAC:2PAA] 0.038±0.004 567.6±23.0 49.0 194.4±2.5 0.99996 [TBAC:2PAA] 0.2288±0.1196 665.8±97.9 54.4 204.9±6.8 0.99962

Fig.5 Plots of lnσ vs 1/T for the four DESs Fig.6 Plots of lnη vs 1/T for the four DESs
■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA]. ■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA].
The dashed lines are straight lines. The dashed lines are straight lines.

´ = ´0 exp(B =(T ¡ T0)) (9)

´ = ´1 exp(E ´=(k BT)) (10)
where η is the dynamic viscosity; η0, B are fitting parameters;
Eη is the activation energy for dynamic viscosity; η∞ is the max-
imum dynamic viscosity, and kB is the Boltzmann constant. The
best fitted parameters are listed in Table 6 by the equation (9)
(see Fig.3). From Table 6, the correlation coefficient, R, is more
than 0.999, which indicates that the VFT equation can also be
used for the dynamic viscosity fitting.
According to equation (10), the lnη vs 1/T was described in
Fig.6 for the four DESs.
Fig.7 Plots of lgΛ vs lgη–1 for the four DESs from 288.15 to 338.15 K
In Fig.6, the dashed lines are straight lines for fitting of lnη
■ [TBAC:2PA]; ● [TBAC:2EG]; ▲ [TBAC:2PEG]; ▼ [TBAC:2PAA].
vs 1/T, the solid lines are smooth curves for lnη vs 1/T. From
The solid straight line is the ideal line for aqueous KCl solutions.
the Fig.6, similar to the electrical conductivity, the same result
was obtained that the experimental dynamic viscosity does not Table 7 Fitted values of refractive index vs temperature for the four
follow the Arrhenius behavior well. DESs according to equation (14)
The same for dynamic viscosity, the modified VFT equation
DES A –104B R
was obtained by Vila et al:28
[TBAC:2PA] 1.5431±0.0005 2.94±0.02 0.9997
´ = ´1 exp(E a =(k B(T ¡ T0))) (11) [TBAC:2EG] 1.5466±0.0007 2.70±0.02 0.9993
here, η0=σ∞ and B=Ea/kB. η is the dynamic viscosity; η0, B are [TBAC:2PEG] 1.5616±0.0007 3.04±0.02 0.9994
fitting parameters; Ea is the activation energy for dynamic vis- [TBAC:2PAA] 1.6021±0.0003 3.15±0.01 0.9999
cosity; η∞ is the maximum dynamic viscosity, and kB is the
Boltzmann constant. The dynamic viscosity activation energies where Λ is the molar conductivity, η is the dynamic viscosity, k
for DESs are listed in Table 6. is a temperature dependent constant, α is the fitting parameter.
3.5 Walden product The description of lgΛ vs lgη–1 is shown in Fig.7 for four DESs
The relationship of molar conductivity and dynamic viscos- from 288.15 to 338.15 K.
ity can be built by the following Walden equation: The slopes, α, can be obtained and the values are 0.653 for
[TBAC:2PA], 0.564 for [TBAC:2EG], 0.621 for [TBAC:2PEG],
´® = k (12)
and 0.710 for [TBAC:2PAA], respectively. From Fig.7, all of
¡1
lg = lg k + lg ´ (13) the Walden plots are lower than the ideal line, the position of
No.8 SHI Xia-Xing et al.: Facile Synthesis of 0.6Li2MnO3-0.4LiNi0.5Mn0.5O2 with Hierarchi 1473

the ideal line is obtained using aqueous KCl solutions at high (8) Serrano, M. C.; Gutiérrez, M. C.; Jiménez, R.; Ferrer, M. L.;
dilution.29 The lines of the four DESs lie below the ideal KCl Monte, F. D. Chem. Commun. 2012, 48, 579. doi:
line. So, the four DESs are called "sub-ionic".30 According to 10.1039/C1CC15284J
the fitted values of the slopes, α, the values are lower than the (9) Zhang, Z. H.; Zhang, X. N.; Mo, L. P.; Li, Y. X.; Ma, F. P. Green
other traditional ILs.21,30 Chem. 2012, 14, 1502. doi: 10.1039/c2gc35258c
(10) Carriazo, D.; Gutirrez, M. C.; Pic, F.; Rojo, J. M.; Fierro, J. L.
3.6 Refractive index (nD)
G.; Ferrer, M. L.; Monte, F. D. ChemSusChem 2012, 5, 1405.
The relationship of refractive index and temperature can be
doi: 10.1002/cssc.v5.8
described by a linear equation:
(11) Abbott, A. P.; Ttaib, K. E.; Frisch, G.; Ryder, K. S.; Weston, D.
nD = A + B T (14) Phys. Chem. Chem. Phys. 2012, 14, 2443. doi:
where nD is the refractive index; A, B are fitting parameters; T is 10.1039/c2cp23712a
experimental temperature. The fitted values of A and B are lis- (12) Monte, F. D.; Carriazo, D.; Serrano, M. C.; Gutirrez, M. C.;
ted in the Table 7. From Table 7, the correlation coefficients for Ferrer, M. L. ChemSusChem 2014, 7, 999. doi:
the four DESs are higher than 0.999. 10.1002/cssc.201300864
(13) Abbott, A. P.; Cullis, P. M.; Gibson, M. J.; Harris, R. C.; Raven,
E. Green Chem. 2007, 9, 868. doi: 10.1039/b702833d
4 Conclusions
(14) Shahbaz, K.; Mjalli, F. S.; Hashim, M. A.; AlNashef, I. M.
The density, electrical conductivity, dynamic viscosity, and
Energy Fuels 2011, 25, 2671. doi: 10.1021/ef2004943
refractive index of the four DESs were determined at atmo-
(15) Li, C. P.; Li, D.; Zou, S. S.; Li, Z.; Yin, J. M.; Wang, A. L.; Cui,
spheric pressure at 288.15–338.15 K. The DESs exhibited
Y. N.; Yao, Z. L.; Zhao, Q. Green Chem. 2013, 15, 2793. doi:
lower lattice energies than the traditional melt salts, it is the
10.1039/c3gc41067f
reason that the DESs are liquids in room temperature. The VFT
(16) Abbott, A. P.; Capper, G.; Davias, D. L.; Rasheed, R. K.;
equation can be used for fitting of the electrical conductivity
Tambyrajah, V. Chem. Commun. 2003, 70, 70.
and dynamic viscosity to temperature very well and Arrhenius
(17) Maugeri, Z.; María, P. D. D. RSC Adv. 2012, 2, 421. doi:
equation can not. The relative big molecule DESs exhibited the
10.1039/C1RA00630D
higher density, electrical conductivity, and refractive index than
(18) Ruß, C.; König, B. Green Chem. 2012, 14, 2969. doi:
the relative small molecule, but, the poorer liquidity. Accord-
10.1039/c2gc36005e
ing to the Walden rule, the slopes were obtained and the values
(19) Bahadori, L.; Manan, N. S.; Chakrabarti, M. H.; Hashim, M. A.;
are 0.653 for [TBAC:2PA], 0.564 for [TBAC:2EG], 0.621 for
Mjalli, F. S.; AlNashef, I. M.; Hussain, M. A.; Low, C. T. J.
[TBAC:2PEG], and 0.710 for [TBAC:2PAA], respectively. The
Phys. Chem. Chem. Phys. 2013, 15, 1707. doi:
temperature dependence on refractive index was fitted by the
10.1039/C2CP43077K
linear equation. This study will be significant for DESs' indus-
(20) Liu, Q. S.; Yang, M.; Yan, P. F.; Liu, X. M.; Tan, Z. C.; Welz-
trial and engineering applications.
Biermann, U. J. Chem. Eng. Data 2010, 55, 4928. doi:
10.1021/je100507n
Supporting Information: The 1H NMR spectra and the ex- (21) Liu, Q. S.; Li, P. P.; Welz-Biermann, U.; Chen, J.; Liu, X. X.
perimental values of density, dynamic viscosity, electrical con- J. Chem. Thermodyn. 2013, 66, 88. doi:
ductivity, and refractive index have been included. This inform- 10.1016/j.jct.2013.06.008
ation is available free of charge via the internet at http://www.whxb. (22) Chen, Y.; Zhuo, K.; Chen, J.; Bai, G. J. Chem. Thermodyn. 2015,
pku.edu.cn. 86, 13 doi: 10.1016/j.jct.2015.02.017
(23) Chen, Y.; Zhang, H.; Li, A.; Zhuo, K. Fluid Phase Equilibr.
References 2015, 388, 78. doi: 10.1016/j.fluid.2014.12.038
(24) Tong, J.; Hong, M.; Chen, Y.; Wang, H.; Guan, W.; Yang, J. Z.
(1) Zhang, Q. H.; Vigier, K. D. O.; Royer, S.; Jérôme, F. Chem. Soc.
J. Chem. Thermodyn. 2012, 54, 352. doi:
Rev. 2012, 41, 7108. doi: 10.1039/c2cs35178a
10.1016/j.jct.2012.05.012
(2) Jhong, H. R.; Wong, D. S. H.; Wan, C. C.; Wang, Y. Y.; Wei, T.
(25) Lide, D. R. Handbook of Chemistry and Physics, 82nd ed.; CRC
C. Electrochem. Commun. 2009, 11, 209. doi:
Press: Boca Raton, FL, 2001–2002.
10.1016/j.elecom.2008.11.001
(26) Jacquemin, J.; Husson, P.; Padua, A. A. H.; Majer, V. Green
(3) Singh, B. S.; Lobo, H. R.; Shankarling, G. S. Catal. Commun.
Chem. 2006, 8, 172. doi: 10.1039/B513231B
2012, 24, 70. doi: 10.1016/j.catcom.2012.03.021
(27) Glasser, L. Thermochim. Acta 2004, 421, 87. doi:
(4) Dai, Y.; Sprosen, J. V.; Witkamp, G. J.; Verpoorte, R.; Choi, Y.
10.1016/j.tca.2004.03.015
H. Anal. Chim. Acta 2013, 766, 61. doi: 10.1016/j.aca.
(28) Vila, J.; Ginés, P.; Pico, J. M.; Franjo, C.; Jiménez, E.; Varela, L.
2012.12.019
M.; Cabeza, O. Fluid Phase Equilibr. 2006, 242, 141. doi:
(5) Francisco, M.; Bruinhorst, A. V. D.; Kroon, M. C. Angew. Chem. 10.1016/j.fluid.2006.01.022
Int. Edit. 2013, 52, 3074. doi: 10.1002/anie.201207548 (29) Schreiner, C.; Zugmann, S.; Hartl, R.; Gores, H. J. J. Chem. Eng.
(6) Krystof, M.; Pérez-Sánchez, M.; María, P. D. D. ChemSusChem Data 2010, 55, 1784. doi: 10.1021/je900878j
2013, 6, 630. doi: 10.1002/cssc.201200931 (30) Belieres, J. P.; Angell, C. A. J. Phys. Chem. B 2007, 111, 4926.
(7) Maugeri, Z.; María, P. D. D. ChemCatChem 2014, 6, 1535. doi: 10.1021/jp067589u
Supplementary Information for Acta Phys. -Chim. Sin. 2015, 31 (8), 1468–1473
doi: 10.3866/PKU.WHXB201506111

四种深共融溶剂的性质: 密度、电导率、动力粘度及折光率

宿洪祯 1 尹静梅 1 刘青山 2,* 李长平 1,*

(1 大连大学环境与化学工程学院, 辽宁 大连 116622; 2
沈阳农业大学理学院, 沈阳 110866)

Properties of Four Deep Eutectic Solvents: Density, Electrical

Conductivity, Dynamic Viscosity and Refractive Index

SU Hong-Zhen1 YIN Jing-Mei1 LIU Qing-Shan2,* LI Chang-Ping1,*

(1College of Chemical Engineering and the Environment, Dalian University, Dalian 116622, Liaoning Province,
2
P. R. China; School of Science, Shenyang Agricultural University, Shenyang 110866, P. R. China)

∗
Corresponding authors. LIU Qing-Shan, Email: [email protected]; Tel: 86-13478787524.
LI Chang-Ping, Email: [email protected]; Tel: +86-13795164535.
 1
Table S1 H NMR spectrum δH (500MHz) in CDCl3 of [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] and [TBAC:2PAA]
[TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
Radical Chemical Chemical Chemical Chemical
nH nH nH nH
shift shift shift shift
-CH3 0.777-0.885(t) 12 0.949-1.058(t) 12 0.809-0.870(t) 12 0.720-0.819(t) 12
-CH2-CH3 0.918-1.003(t) 6
-CH2-CH3 1.218-1.349(m) 8 1.410-1.493(m) 8 1.250-1.333(m) 8 1.111-1.208(m) 8
N-CH2-CH2- 1.446-1.585(m) 8 1.627-1.710(dt) 8 1.476-1.562(dt) 8 1.296-1.424(dt) 8
-CH2-CH3 2.179-2.300(q) 4
N-CH2- 3.048-3.265(m) 8 3.259-3.331(m) 8 3.176-3.221(m) 8 2.931-2.994(m) 8
-CH2-OH 3.418-3.447(m) 8
-CH2-COOH 3.458-3.518(s) 4
-O-(CH2)2-O-
3.469-3.508(m) 57
-OH
-CH2-CH2-OH 3.529-3.560(m) 8
-CH2-OH 3.586-3.702(s) 8
-CH2-OH 4.295-4.509(s) 4
C(4)H 7.042-7.091(dd) 2
C(2,,3, 5,6)H 7.092-7.150(m) 8
-COOH 9.011-9.238(s) 2
-COOH 9.021-10.304(s) 2

nH: the number of the H

 Table S2 Values of density, ρ/kg·m-3, for four DESs at atmospheric pressure
T/K [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
288.15 972.38 995.35 1084.62 1046.76
293.15 969.18 992.32 1081.04 1043.55
298.15 965.91 989.34 1077.45 1040.39
303.15 962.67 986.27 1073.82 1037.14
308.15 959.38 983.21 1070.23 1033.88
313.15 956.11 980.13 1066.61 1030.59
318.15 952.83 977.03 1062.94 1027.34
323.15 949.51 973.91 1059.34 1023.99
328.15 946.26 970.85 1055.74 1020.74
333.15 943.01 967.84 1052.12 1017.56
338.15 939.73 964.78 1048.51 1014.31
The uncertainty is 0.05 kg·m-3 for density. The uncertainty is 0.05 K for temperature.

S3
 Table S3 Electrical conductivity values (σ/(mS·cm–1)) for four DESs at
atmospheric pressure
T/K [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
288.15 0.276 0.964 0.1247 0.0907
293.15 0.343 1.128 0.148 0.1214
298.15 0.420 1.314 0.178 0.1587
303.15 0.512 1.532 0.211 0.205
308.15 0.609 1.763 0.245 0.257
313.15 0.725 2.02 0.283 0.319
318.15 0.847 2.29 0.321 0.386
323.15 0.975 2.57 0.362 0.461
328.15 1.120 2.87 0.408 0.547
333.15 1.270 3.19 0.453 0.635
338.15 1.434 3.54 0.502 0.730

The uncertainty is 1% for electrical conductivity. The uncertainty is 0.05 K for

temperature.

S4
 Table S4 Values of dynamic viscosity (η/(mPa·s)) for four DESs
at atmospheric pressure
T/K [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
288.15 301.2 216.7 315.5 677.0
293.15 213.0 160.6 232.8 430.6
298.15 155.0 121.2 177.1 286.8
303.15 114.9 92.8 133.4 205.5
308.15 87.3 71.6 104.1 134.9
313.15 67.2 56.1 82.0 109.2
318.15 52.3 44.7 65.9 83.3
323.15 41.5 35.9 53.4 64.7
328.15 33.6 29.5 44.9 51.2
333.15 27.6 24.4 37.5 40.4
338.15 22.8 20.4 31.6 33.2
The uncertainty is 1% for dynamic viscosity. The uncertainty is 0.05 K for
temperature.

S5
Table S5 Values of refractive index, nD, for four DESs at atmospheric pressure
T/K [TBAC:2PA] [TBAC:2EG] [TBAC:2PEG] [TBAC:2PAA]
288.15 1.4580 1.4686 1.4740 1.5115
293.15 1.4567 1.4674 1.4724 1.5099
298.15 1.4553 1.4661 1.4708 1.5083
303.15 1.4538 1.4648 1.4692 1.5067
308.15 1.4523 1.4635 1.4676 1.5051
313.15 1.4509 1.4622 1.4661 1.5035
318.15 1.4494 1.4608 1.4646 1.5020
323.15 1.4479 1.4594 1.4632 1.5004
328.15 1.4464 1.4580 1.4618 1.4988
333.15 1.4449 1.4566 1.4603 1.4973
338.15 1.4433 1.4551 1.4586 1.4958
The uncertainty is 0.0002 for refractive index. The uncertainty is 0.05 K for
temperature.

S6