Thermodynamic properties of Gemini ionic liquid based deep eutectic solvents

doi:10.16085/j.issn.1000-6613.2022-1410

Abstract

Abstract:

Gemini ionic liquid, 1,1'-(1,3-trimethylene)-bis-3-methylimidazolium dibromide [C₃(MIM)₂Br₂], was synthesized using 1-methylimidazole and 1,3-dibromopropane as raw materials. A series of deep eutectic solvents were prepared by mixing C₃(MIM)₂Br₂ and ethylene glycol with various molar ratios. Melting points of all deep eutectic solvents were lower than -90℃, much lower than those of C₃(MIM)₂Br₂ and ethylene glycol, and increased with the increase of ethylene glycol composition. The thermodynamic properties of the deep eutectic solvents, including density, viscosity, electrical conductivity and specific heat capacity, were respectively determined at temperature range of 288.15K to 323.15K. The results showed that the density and viscosity decreased with increasing temperature, whereas the electrical conductivity and specific heat capacity increased. With the increase of the molar ratio of ethylene glycol in the deep eutectic solvent, the density and viscosity decreased, while the electrical conductivity and specific heat capacity increased. The correlation coefficients of the linear equations of density and specific heat capacity with temperature were greater than 0.99. VFT equation was employed to correlate viscosity and conductivity data with temperature, and the correlation coefficients of the corresponding empirical equations were all more than 0.999.

Key words: Gemini ionic liquid, deep eutectic solvent, melting point, thermodynamics

摘要：

以1-甲基咪唑、1,3-二溴丙烷为原料合成Gemini离子液体1,1'-(1,3-三亚甲基)双-3-甲基咪唑二溴盐[C₃(MIM)₂Br₂]，并以不同C₃(MIM)₂Br₂与乙二醇组成制备了一系列低共熔溶剂。熔点测试结果显示，所有的低共熔溶剂的熔点均低于-90℃，远低于C₃(MIM)₂Br₂和乙二醇的熔点，且随着乙二醇组成的增大而降低。在288.15~323.15K条件下对该低共熔溶剂的密度、黏度、电导率、比热容等热力学性质进行了测定，结果表明，密度和黏度会随着温度的升高而降低，电导率与比热容则随着温度的升高而升高。随着乙二醇物质的量的升高，密度和黏度减小，电导率和比热容增大。密度、比热容随温度变化的线性方程的相关系数大于0.99。用VFT经验方程对黏度和电导率随温度的变化进行了拟合，结果表明，黏度与电导率的相关系数均大于0.999。

关键词: Gemini离子液体, 低共熔溶剂, 熔点, 热力学性质

CLC Number:

TQ413.24

YANG Xuzhao, LI Qing, YUAN Kangkang, ZHANG Yingying, HAN Jingli, WU Shide. Thermodynamic properties of Gemini ionic liquid based deep eutectic solvents[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3123-3129.

杨许召, 李庆, 袁康康, 张盈盈, 韩敬莉, 吴诗德. 含Gemini离子液体低共熔溶剂热力学性质[J]. 化工进展, 2023, 42(6): 3123-3129.

Figures/Tables 10

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热力学性质	实验值	文献值	相对误差/%	T/K
ρ/g·mL^-1	1.1162	1.11676^[16]	-0.050	288.15
	1.1021	1.1030^[17]、1.10293^[18]、1.1019^[19]、1.10272^[16]	-0.082、-0.075、0.018、-0.056	308.15
	1.0986	1.0999^[17]、1.0936^[20]、1.099201^[21]	-0.118、0.457、-0.055	313.15
	1.0949	1.0978^[17]、1.0955^[22]、1.095640^[21]	-0.264、-0.055、-0.068	318.15
	1.0906	1.09105^[23]、1.09202^[16]、1.0847^[24]	-0.0412、-0.130、0.544	323.15
η/mPa·s	26.0965	26.343^[21]	-0.936	288.15
	10.0952	9.2122^[17]、10.472^[25]、11.236^[26]	9.585、-3.598、-10.153	308.15
	8.6371	7.9605^[17]、9.404^[26]	8.499、-8.155	313.15
	6.8190	6.2933^[17]、7.945^[26]、8.126^[21]	8.353、-14.172、-16.084	318.15
	6.4921	6.992^[20]、6.933^[21]、6.774^[26]、5.4468^[17]	-7.150、-6.359、-4.161、19.191	323.15
κ/μS·m^-1	0.413	0.400^[27]	3.250	303.15
	0.516	0.502^[27]	2.789	313.15
	0.609	0.600^[27]	1.500	323.15
c_p /J·g^-1·K^-1	2.3462	2.3533^[27]、2.376^[20]	-0.302、-1.1254	293.15
	2.3891	2.3826^[27]、2.3922^[20]	0.273、-0.130	298.15
	2.4286	2.4160^[27]、2.412^[20]、2.394^[28]	0.522、0.688、1.445	303.15
	2.5671	2.478^[20]	3.596	323.15

热力学性质	实验值	文献值	相对误差/%	T/K
ρ/g·mL^-1	1.1162	1.11676^[16]	-0.050	288.15
	1.1021	1.1030^[17]、1.10293^[18]、1.1019^[19]、1.10272^[16]	-0.082、-0.075、0.018、-0.056	308.15
	1.0986	1.0999^[17]、1.0936^[20]、1.099201^[21]	-0.118、0.457、-0.055	313.15
	1.0949	1.0978^[17]、1.0955^[22]、1.095640^[21]	-0.264、-0.055、-0.068	318.15
	1.0906	1.09105^[23]、1.09202^[16]、1.0847^[24]	-0.0412、-0.130、0.544	323.15
η/mPa·s	26.0965	26.343^[21]	-0.936	288.15
	10.0952	9.2122^[17]、10.472^[25]、11.236^[26]	9.585、-3.598、-10.153	308.15
	8.6371	7.9605^[17]、9.404^[26]	8.499、-8.155	313.15
	6.8190	6.2933^[17]、7.945^[26]、8.126^[21]	8.353、-14.172、-16.084	318.15
	6.4921	6.992^[20]、6.933^[21]、6.774^[26]、5.4468^[17]	-7.150、-6.359、-4.161、19.191	323.15
κ/μS·m^-1	0.413	0.400^[27]	3.250	303.15
	0.516	0.502^[27]	2.789	313.15
	0.609	0.600^[27]	1.500	323.15
c_p /J·g^-1·K^-1	2.3462	2.3533^[27]、2.376^[20]	-0.302、-1.1254	293.15
	2.3891	2.3826^[27]、2.3922^[20]	0.273、-0.130	298.15
	2.4286	2.4160^[27]、2.412^[20]、2.394^[28]	0.522、0.688、1.445	303.15
	2.5671	2.478^[20]	3.596	323.15

溶剂	熔点/℃
C₃(MIM)₂Br₂	171^[29]
乙二醇	-13^[27]
DES1	-98
DES2	-108
DES3	-110
DES4	-114

溶剂	熔点/℃
C₃(MIM)₂Br₂	171^[29]
乙二醇	-13^[27]
DES1	-98
DES2	-108
DES3	-110
DES4	-114

热力学性质	溶剂	A	B	R²	σ
密度	DES1	1.57066	-6.78488×10^-4	0.99997	0.00011
	DES2	1.53140	-6.82138×10^-4	0.99998	0.00011
	DES3	1.51577	-6.82252×10^-4	0.99999	0.00011
	DSE4	1.48676	-6.83652×10^-4	0.99998	0.00009
比热容	DES1	0.95372	0.00308	0.99766	0.0025
	DES2	0.55713	0.00531	0.99847	0.0034
	DES3	0.01762	0.0078	0.99858	0.0048
	DES4	-0.51295	0.01004	0.99900	0.0051