CHEMICAL ENGINEERING THERMODYNAMICS

Chinese Journal of Chemical Engineering, 21(7) 766769 (2013)

DOI: 10.1016/S1004-9541(13)60518-2

Thermodynamic Properties of Caprolactam Ionic Liquids*

JIANG Lu (), BAI Liguang (), ZHU Jiqin ()** and CHEN Biaohua ()

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing
100029, China
Abstract A series of caprolactam ionic liquids (ILs) containing incorporated halide anions were synthesized.
Their physical properties, such as melting points, heats of fusion and heat capacities, were measured by differential
scanning calorimeter (DSC). The results indicate that these ionic liquids exhibit proper melting points, high value of
heats of fusion, and satisfying heat capacities which are suitable for thermal energy storage applications.
Keywords caprolactam ionic liquids, thermodynamic properties, thermal energy storage

INTRODUCTION

Ionic liquids (IL) are molten salts that are composed entirely of ions with melting points at ambient
temperature [1]. They have been reckoned as environmentally benign alternatives to volatile organic
solvents for reactions and separations because their
excellent physical properties such as negligible vapor
pressure, high thermal stability, low viscosity, large
liquidus range and favorable solvation behavior [2-6].
The other benefits of ionic liquids, including high heat
capacity, high thermal conductivity, non-flammability,
and designable, suggest their potential use in heat
transfer fluids and phase change materials (PCM).
Ionic liquids could be excellent liquid thermal
storage media and heat transfer fluids in a solar thermal
power plant [7-10]. Their superior physicochemical and
thermal properties have been studied by the previous
works. The calculated thermal storage density for 1-butyl3-methylimidazolium bis(trifluoromethylsulfonyl)imide
[C4MIM]+[Tf2N] was greater than 180 MJm3 when
the inlet and outlet field temperatures are 483.15 K
and 663.15 K, respectively. The sensible heat storage
density for 1-butyl-3-methylimidazolium tetrafluoroborate [C4MIM]+[BF4], 1-ethyl-3-methylimidazolium
tetrafluoroborate [C2MIM]+ [BF4] and 1-propyl-2,3dimethylimidazolium bis(trifluoromethylsulfonyl)imide
[C3MMIM]+ [Tf2N] were 156.1, 192.1 and 176.3
MJm3, respectively [11]. Comparing with the commercial
heat transfer fluid TherminolVP-1, an eutectic mixture
of 26.5% (by mass) diphenyl and 73.5% (by mass) diphenyl ether, the three ionic liquids are suited for use
as heat transfer fluids. In our previous work [12], the
melting points, heat of fusion and heat capacities for a
series of imidazolium-based ionic liquids have been measured. Among them [C16MIM]+Br and [C16MMIM]+Br
have high heats of fusion (59.11 and 50.83 kJmol1) and
moderate melting temperatures (337.06 and 368.15 K)
which indicate they are favorable candidates for PCMs.
At present, the most popular and extensive study
on ionic liquids thermal storage is the study of ILs based
on imidazolium. Compared with dialkylimidazolium

cation, lactam and its derivates are relatively cheaper,

lower toxicity, and easily available in large amounts
from industry. Ever since N-vinyl-N-alkylbutyrolactam
ionic liquids was first prepared through two-step reactions in 2002 [13], caprolactam ILs was extensively
investigated recently. Du et al. reported the preparation and characterization of lactam-based ionic liquids
containing [BF4], [CF3COO], [ClCH2COO], [NO3],
and [H2PO4] anions [14]. The heat storage densities of
lactam-cation- based Brnsted acid ILs are more than
200 MJm3, indicating that they would be more preferable to imidazolium- cation-based ILs. In their further research [15], ILs based on N-alkyl--caprolactam
as cations [Cn-CP]+ (CP is the abbreviation of caprolactam; Cn = alkyl with different number of C atoms, n = 6,
8, 10, 12, 16, or 18) containing toluene-p-sulfonate
[TS] and methanesulfonate [MS] as anion were synthesized via a one-step atom-economic reaction. The
results showed that they have higher transition enthalpies (e.g., H = 83.1 kJmol1 for C18-CPTS), higher
specific heat capacities (e.g., cp = 2.85 Jg1K1 for
C16-CPTS) and higher heat storage densities (e.g.,
sensible heat storage density Es=262.81 MJm3 for
C16-CPTS; latent heat storage density E1 = 146.0
MJm3 for C18-CPTS). On the basis of their properties, the caprolactam ionic liquids may have potential
applications as thermal storage media.
In this paper, a series of caprolactam halide ionic
liquids were synthesized as candidate PCMs for further
screening. The thermodynamic properties of caprolactam halide ionic liquids such as melting temperature,
heat of fusion, and heat capacity were measured.
2
2.1

EXPERIMENTAL
Materials

1,2-Dichloromethane, 1,2-dichloroethane and

1,2-dibromoethane were purchased from Tianjin
Fuchen Chemical Reagent Factory. 1,4-dibromobutane,
1,4-dichlorobutane, 1-bromohexane and 1-bromobutane
were purchased from Beijing Yili Fine Chemical Co.

Received 2012-03-10, accepted 2012-11-06.

* Supported by the National Natural Science Foundation of China (21176010, 20706005).
** To whom correspondence should be addressed. E-mail: zhujq@mail.buct.edu.cn

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Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013

Table 1

List of room temperature ionic liquids prepared in this study

Molecular mass
/gmol1

Water content
/gm3

[BC]+Br

250.18

334

hexyl-caprolactam bromide

[HC] +Br

278.23

323

1,1-bis(caprolactam-1-yl) methane chloride

[DCM] +Cl

327.29

457

1,2-bis(caprolactam-1-yl) ethane chloride

[DCE] +Cl

341.32

426

1,4-bis(caprolactam-1-yl) butane bromide

[DCB] +Br

442.23

361

1,4-bis(caprolactam-1-yl) butane chloride

[DCB]+Cl

353.33

419

Compound

Abbreviation

butyl-caprolactam bromide

Structure

R = H, or methyl; n = 1, 2, or 4; X = Cl, or Br
Figure 1

Synthetic routes for the caprolactam ionic liquids

Caprolactam and toluene were purchased from Beijing

Chemical Plant. Their mass fraction purities were better than 98%.
2.2

Synthesis of ILs

Ionic liquids synthesized in this work are listed in

Table 1. General synthetic routes to ionic liquids in
this study are shown in Fig. 1. Representative synthesis of caprolactam ionic liquids are list below.
Butyl-caprolactam bromide: caprolactam (11.3 g,
0.1 mol) was dissolved in 30 ml of acetonitrile in a
250 ml three-neck round-bottomed flask, and then a
slight excess of butylbromide (13.7 g, 0.1 mol) was
added. The solution was stirred continuously under
refluxing conditions at 353.15 K for 72 h. After it was
cooled to room temperature, the resulted yellowish
mixture was filtered and recrystallized from ethyl

acetate and ethanol successively. The product was

obtained as fine white crystals by vacuum filtration.
1,1-bis(caprolactam-1-yl) methane chloride:
caprolactam (22.6 g, 0.2 mol) was dissolved in 60 ml
of acetonitrile in a 250 ml three-neck round-bottomed
flask, and then 1,2-dichloromethane (8.5 g, 0.1 mol)
was added. The solution was stirred continuously under refluxing conditions at 353 K for 96 h. After it was
cooled to room temperature, the resulted yellowish
mixture was filtered and recrystallized from ethyl
acetate and ethanol in turn. The product was obtained
as fine white crystals by vacuum filtration. All prepared
ionic liquids were characterized by infra-red spectrum
analysis (FI-IR) and X-ray Diffraction (XRD).
2.3

DSC measurements
Measurements of melting temperature, heat of

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Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013

fusion and heat capacity were done with a Pyris I differential scanning calorimeter, produced by PerkinElmer. The samples were weighted typically 6 mg to
7 mg and exposed to a flowing N2 atmosphere inside
the DSC furnace. The standard heating rate of the
present DSC measurement was set 2 Kmin1. The
pure samples were weighed using a balance with an
uncertainty of 0.0001 g. The temperature was controlled using a precision thermometer to determine the
temperature with an uncertainty of 0.01 K. For the
heat of fusion and heat capacity, the instrument uncertainty verified in this study by the measurement of the
pure water was 5%. The heat capacity of liquid water
is about 4.2 Jg1K1 [16, 17].
Because ionic liquids tend to pick up moisture
from the environment and the water contents of ionic
liquid have crucial influence on their properties, care
was taken during the preservation and measurements.
As mentioned above, the ionic liquids were put into
ground glass stoppered flasks. The ionic liquids were
purified by vacuum evaporation for 48 h at 373 K before use. During the procedure, taking the ionic liquids
must be as quick as possible to reduce the exposure
time and minimize the absorption of moisture. The
water contents in the ionic liquids were determined by
Karl Fischer method. The water contents in all the
samples were less than 500 gm3.
3
3.1

Table 2

Melting temperature and heat of fusion for the

studied ionic liquids

Ionic liquid

Melting temperature/K

Heats of fusion/Jg1

[DCM]+Cl

343.390.01

123.016.15

[DCM]+Cl

345.780.01

139.056.95

344.750.01

140.617.03

[DCB]+Br

336.400.01

126.356.32

[BC]+Br

346.170.01

141.877.09

[HC]+Br

345.240.01

137.026.85

[DCB] Cl

3.2

Heat capacity

Heat capacity (cp) is the measurable physical

quantity that characterizes the amount of heat required
to change the temperature of a compound by a given
amount. cp is related to the number of translational,
vibrational, and rotational energy storage modes in the
molecule [18]. So, a molecule containing more atoms
would have more energy modes and thus a higher heat
capacity. Data have been obtained at atmospheric pressure and within 298.15 K to 383.15 K for ionic liquids
in steps of 1 K. Fig. 3 shows the heat capacities of IL
samples varying with temperature. For simplicity, only
values at some temperatures are shown in Table 3.

RESULTS AND DISCUSSION

Melting temperatures and heats of fusion

The physicochemical properties of caprolactam

ionic liquids were obtained by differential scanning
calorimetry (DSC) according to reported procedures
and methods. The melting temperature and heat of
fusion of six caprolactam ionic liquids were shown in
Fig. 2 and listed in Table 2. According to the DSC
curves (Fig. 2), six carprolactam ILs remain stable up
to 425 K. For each IL, only one endothermic peak in the
range of 330-350 K corresponds to fusion of the sample.
There is no phase transition in the solid-phase zone
and no association or decomposition in the researched
liquid-phase zone. As shown in Table 2, all the samples
possess large heats of fusion (123.01-141.87 Jg1).

Figure 3 Heat capacities of caprolactam ionic liquids

+
+
+
+
[DCM] Cl ; [DCE] Cl ; [DCB] Cl ; [DCB] Br ;
+
+
[BC] Br ; [HC] Br

The heat capacities of these caprolactam ionic

liquids are lower than those of imidazolium ionic liquids
(e.g., cp = 2.85 Jg1K1 for C16-CPTS). The reason is
that the caprolactam ionic liquids do not have the long
alkyl chain as [C16MIM]+Br and [C16MMIM]+Br
which presents the high number of vibrational degrees.
4

Figure 2 DSC curves of caprolactam ionic liquids

1[DCM]+Cl; 2[DCE]+Cl; 3[DCB]+Cl; 4[DCB]+Br;
5[BC]+Br; 6[HC]+Br

CONCLUSIONS

A series of novel caprolactam ionic liquids were

synthesized and characterized. Their thermodynamic
properties, such as melting temperatures, heats of fusion and heat capacities were determined. The samples
possess relatively moderate melting temperatures and
large heats of fusion which are benefit to heat storage.

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Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013

Table 3
T/K
solid

Experimental heat capacities cp for the studied ILs

cp/Jg1K1

[DCM] Cl

[DCE] Cl

[DCB] Cl

[DCB]+Br

1.440.07

1.330.07

1.620.08

1.460.07

1.590.08

1.440.07

1.720.09

1.540.08

1.950.10

2.120.11

1.910.10

1.730.09

308.15

1.760.09

1.600.08

1.990.10

2.400.12

1.960.10

1.760.09

313.15

1.810.09

1.620.08

2.030.10

1.990.10

1.790.09

318.15

1.900.10

1.750.09

2.080.10

2.020.10

1.810.09

323.15

2.070.10

1.760.09

2.180.11

2.050.10

1.850.09

2.100.11

1.940.10

1.770.09
1.830.09

2.220.11

353.15

1.990.10

2.100.11

2.250.11

2.450.12

2.480.12

358.15

1.990.10

2.100.11

2.220.11

2.440.12

2.490.12

2.140.11

363.15

2.000.10

2.100.11

2.200.11

2.430.12

2.490.12

2.150.11

368.15

2.000.10

2.110.11

2.200.11

2.440.12

2.490.12

2.160.11

373.15

2.000.10

2.110.11

2.200.11

2.440.12

2.490.12

2.180.11

378.15

2.010.10

2.120.11

2.220.11

2.440.12

2.500.13

2.180.11

383.15

2.000.10

2.130.11

2.250.11

2.440.12

2.500.13

2.200.11

REFERENCES
10
2

4
5

6
7

[HC]+Br

298.15

333.15

[BC]+Br

303.15

328.15
liquid

Wilkes, J.S., A short history of ionic liquids-from molten salts to

neoteric solvents, Green Chem., 4, 73-80 (2002).
Scovazzo, P., Kieft, J., Finan, D.A., Koval, C., DuBois, D., Noble,
R., Gas separations using non-hexafluorophosphate [PF6] anion
supported ionic liquid membranes, J. Membr. Sci., 238, 57-63
(2004).
Anthony, J.L., Maginn, E.J., Brennecke, J.F., Solubilities and
thermodynamic properties of gases in the ionic liquid 1-n-butyl-3methylimidazolium hexafluorophosphate, J. Phys. Chem. B, 106,
7315-7320 (2002).
Zhao, Z.J., Dong, H.F., Zhang, X.P., The research progress of CO2
capture with ionic liquids, Chin. J. Chem. Eng., 20 (1), 120-129
(2012).
Rogers, R.D., Huddleston, J.G., Willauer, H.D., Swatloski, R.P.,
Visser, A.E., Room temperature ionic liquids as novel media for
clean liquid-liquid extraction, Chem. Commun., 16, 1765-1766
(1998).
Cai, S.F., Wang, L.S., Epoxidation of unsaturated fatty acid methyl
esters in the presence of SO3H-functional Brnsted acidic ionic
liquid as catalyst, Chin. J. Chem. Eng., 19 (1), 57-63 (2011).
Wu, B.Q., Reddy, R.G., Rogers, R.D., Novel ionic liquid thermal
storage for solar thermal electric power systems, In: Proceedings of
Solar Forum 2001 Solar Energe: The Power to Choose, Washington,
445-451 (2001)
Reddy, R.G., Zhang, Z., Arenas, M.F., Blake, D.M., Thermal
stability and corrosivity evaluations of ionic liquids as thermal
energy storage media, High Tem. Mater. Processes, 22, 87-94
(2003).
Bai, L., Li, X., Zhu, J., Chen, B., Effects of nucleators on the

11
12
13
14
15
16

17

18

2.140.11

thermodynamic properties of seasonal energy storage materials based

on ionic liquids, Energy and Fuels, 25 (4), 1811-1816 (2011).
Liang, R., Yang, M.R., Xuan, X.P., Thermal stability and thermal
decomposition kinetics of 1-butyl-3-methylimidazolium dicyanamide,
Chin. J. Chem. Eng., 18 (5), 736-741 (2010).
Valkenburg, M.E.V., Vaughn, R.L., Williams, M., Wilkes, J.S.,
Thermochemistry of ionic liquid heat-transfer fluids, Thermochim.
Acta, 425, 181-188 (2005).
Zhu, J., Bai, L., Chen, B., Fei, W., Thermodynamical properties of
phase change materials based on ionic liquids, Chem. Eng. J., 147,
58-62 (2009).
Demberelnyamba, D., Shin, B.K., Lee, H., Ionic liquids based on
n-vinyl-g-butyrolactam: Potential liquid electrolytes and green
solvents, Chem. Commun., 2, 1538-1539 (2002).
Du, Z., Li, Z., Guo, S., Zhang, J., Zhu, L., Deng, Y., Investigation
of physicochemical properties of lactam-based bronsted acidic ionic
liquids, J. Phys. Chem. B, 109, 19542-19546 (2005).
Yang, J., Zhang, Q., Zhu, L., Zhang, S., Li, J., Zhang, X., Deng, Y.,
Novel ionic liquid crystals based on n-alkylcaprolactam as cations,
Chem. Mater., 19, 2544-2550 (2007).
Garca-Miaja, G., Troncoso, J., Roman, L., Density and heat
capacity as a function of temperature for binary mixtures of
1-butyl-3-methylpyridinium tetrafluoroborate+water, +ethanol, and
+nitromethane, J. Chem. Eng. Data., 52, 2261-2265 (2007).
Ge, R., Hardacre, C., Jacquemin, J., Nancarrow, P., Rooney, D.W.,
Heat capacities of ionic liquids as a function of temperature at 0.1
MPa. measurement and prediction, J. Chem. Eng. Data., 53, 2148-2153
(2008).
Crosthwaite, J.M., Muldoon, M.J., Dixon, J.K., Anderson, J.L.,
Brennecke, J.F., Phase transition and decomposition temperatures,
heat capacities and viscosities of pyridinium ionic liquids, J. Chem.
Thermodyn., 37, 559-568 (2005).