含非对称Gemini离子液体二元混合体系的体积和黏度性质

doi:10.11949/0438-1157.20190470

摘要/Abstract

摘要：

在温度分别为293.15、303.15、313.15、323.15和333.15 K及大气压下，系统测定了非对称Gemini离子液体，1-(3-(三甲基铵)丙-1-基)-3-甲基咪唑双氰胺盐([N₁₁₁C₃MIM][N(CN)₂]₂)，分别与乙腈(MeCN)、甲醇(MeOH)、乙醇(EtOH)所组成的二元混合物的密度和黏度。由密度和黏度值分别计算了二元混合物的超额摩尔体积( $V m E$ )和超额黏度(Δη)。 $V m E$ 和Δη随组成的变化关系由Redlich-Kister方程进行了回归，得到方程参数。结果表明， $V m E$ 和Δη值与理想溶液间为负偏差，且存在最小值，说明二元体系中[N₁₁₁C₃MIM][N(CN)₂]₂和溶剂分子间相互作用力更强，同时与所研究分子的大小和形状的差异有关。同时， $V m E$ 和Δη随温度的变化关系表明，温度对研究混合物中的分子间相互作用有很大影响。

关键词: 离子液体, 二元混合物, 密度, 黏度, 超额摩尔体积, 超额黏度

Abstract:

Densities and dynamic viscosities of binary solutions containing asymmetrical Gemini ionic liquid (GIL), 1-(3-(trimethylammonio)prop-1-yl)-3-methylimidazolium bis(dicyanamide) ([N₁₁₁C₃MIM][N(CN)₂]₂) with acetonitrile (MeCN), methanol (MeOH) or ethanol (EtOH) over the entire mole fraction range have been measured from 293.15 K to 333.15 K under atmospheric pressure. Excess molar volumes ( $V m E$ ) and excess viscosities (Δη) of the solutions were calculated based on the experimental density andviscosityvalues of pure [N₁₁₁C₃MIM][N(CN)₂]₂, molecular solvents, and their binary mixtures. The values of $V m E$ and Δη were fitted by using the Redlich–Kister equations and the optimal ?tting parameters were obtained. The results indicate thatthe values of $V m E$ and Δη reveal negative deviations from ideal solutions. There exists a minimum excess values. Negative values of $V m E$ and Δη for all the binary mixtures indicate, compared to pure [N₁₁₁C₃MIM][N(CN)₂]₂ and molecular solvents, stronger interactions between [N₁₁₁C₃MIM][N(CN)₂]₂ and MeCN, MeOH or EtOH. These negative values are also related to the difference in size and shape of the molecules studied. Moreover, the variation of $V m E$ and Δη on temperature suggests that temperature has an enormous in?uence on the intermolecular interactions between [N₁₁₁C₃MIM][N(CN)₂]₂ and molecular solvents.

Key words: ionic liquids, binary mixture, density, viscosity, excess molar volume, excess viscosity

中图分类号:

TQ 013.1

杨许召, 王军, 方云. 含非对称Gemini离子液体二元混合体系的体积和黏度性质[J]. 化工学报, 2019, 70(11): 4131-4142.

Xuzhao YANG, Jun WANG, Yun FANG. Volumetric and viscosity properties of binary mixtures containing asymmetrical Gemini ionic liquid[J]. CIESC Journal, 2019, 70(11): 4131-4142.

图/表 8

图1 [N111C3MIM][N(CN)2]2的化学结构

Fig.1 Chemical structure of [N111C3MIM][N(CN)2]2

表1 293.15～333.15 K范围内乙腈、甲醇和乙醇的黏度和密度的实验值及文献值

Table 1 Experimental and literature values of densities and viscosities for MeCN, MeOH and EtOH at temperature 293.15 K to 333.15 K under atmospheric pressure

T/K	ρ/(g?cm^-3)			η/(mPa?s)
T/K	实验值	文献值	AAPD/%	实验值	文献值	AAPD/%
MeCN
293.15	0.78210	0.782308^[24]	0.03	0.364	0.364^[24]	1.19
303.15	0.77127	0.771487^[24]		0.333	0.331^[24]
313.15	0.76032	0.760541^[24]		0.307	0.304^[24]
323.15	0.74922	0.749449^[24]		0.285	0.280^[24]
333.15	0.73797	0.738212^[24]		0.266	0.259^[24]
MeOH
293.15	0.79134	0.79123^[25]	0.01	0.584	0.587^[26]	0.29
303.15	0.78190	0.78196^[25]		0.509	0.510^[26]
313.15	0.77236	0.77243^[25]		0.446	0.447^[26]
323.15	0.76270	0.76278^[25]		0.395	0.394^[26]
333.15	0.75286	0.75296^[25]		0.352	0.351^[27]
EtOH
293.15	0.78963	0.78985^[26]	0.04	1.195	1.222^[26]	1.27
303.15	0.78102	0.78131^[26]		0.991	1.009^[26]
313.15	0.77227	0.77256^[26]		0.828	0.840^[26]
323.15	0.76335	0.76367^[26]		0.706	0.705^[26]
333.15	0.75420	0.75453^[26]		0.593	0.597^[26]

表2 0.1 MPa 下 GIL (1) + 分子溶剂 (2)二元体系在293.15 K～333.15 K范围内的密度(ρ)和超额摩尔体积(VmE)

Table 2 Experimental density (ρ), excess molar volume (VmE) for binary mixtures of GIL (1) + molecular solvent (2) from 293.15 K to 333.15 K under 0.1 MPa

[N₁₁₁C₃MIM][N(CN)₂]₂ + MeCN			[N₁₁₁C₃MIM][N(CN)₂]₂ + MeOH			[N₁₁₁C₃MIM][N(CN)₂]₂ + EtOH
x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)	x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)	x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)
293.15 K
0	0.78210	0	0	0.79134	0	0	0.78963	0
0.0990	0.93960	-1.6889	0.1002	0.97302	-1.6438	0.0999	0.93424	-1.6415
0.1994	1.01699	-2.2343	0.1995	1.05047	-2.4922	0.1996	1.00801	-2.0869
0.3000	1.06096	-2.2723	0.3004	1.08668	-2.4177	0.2971	1.05299	-2.2752
0.3977	1.08690	-1.8974	0.3915	1.10502	-1.9974	0.3963	1.08397	-2.3101
0.4997	1.10606	-1.4482	0.4953	1.11931	-1.4714	0.5008	1.10518	-1.9454
0.6009	1.12088	-1.0895	0.5942	1.12987	-1.0698	0.5948	1.11951	-1.5727
0.7009	1.13251	-0.7686	0.7062	1.13973	-0.7624	0.6976	1.13197	-1.1736
0.8009	1.14195	-0.4647	0.7960	1.14597	-0.5162	0.7992	1.14177	-0.7561
0.8944	1.14955	-0.2464	0.8937	1.15159	-0.2566	0.8944	1.14939	-0.3690
1.0000	1.15674	0	1.0000	1.15674	0	1.0000	1.15674	0
303.15 K
0	0.77127	0	0	0.78190	0	0	0.78102	0
0.0990	0.93146	-1.8588	0.1002	0.96547	-1.7399	0.0999	0.92751	-1.7952
0.1994	1.00969	-2.4261	0.1995	1.04372	-2.6209	0.1996	1.00205	-2.2954
0.3000	1.05401	-2.4467	0.3004	1.08027	-2.5455	0.2971	1.04753	-2.5241
0.3977	1.08059	-2.0981	0.3915	1.09850	-2.0816	0.3963	1.07881	-2.5856
0.4997	1.10005	-1.6450	0.4953	1.11314	-1.5662	0.5008	1.09990	-2.1900
0.6009	1.11502	-1.2696	0.5942	1.12355	-1.1123	0.5948	1.11384	-1.7382
0.7009	1.12674	-0.9270	0.7062	1.13360	-0.8052	0.6976	1.12636	-1.3271
0.8009	1.13629	-0.6088	0.7960	1.14018	-0.6023	0.7992	1.13621	-0.8977
0.8944	1.14374	-0.3258	0.8937	1.14579	-0.3209	0.8944	1.14354	-0.4270
1.0000	1.15076	0	1.0000	1.15076	0	1.0000	1.15076	0
313.15 K
0	0.76032	0	0	0.77236	0	0	0.77227	0
0.0990	0.92332	-2.0430	0.1002	0.95827	-1.8659	0.0999	0.92130	-2.0068
0.1994	1.00255	-2.6446	0.1995	1.03749	-2.7968	0.1996	0.99581	-2.4866
0.3000	1.04754	-2.6820	0.3004	1.07447	-2.7363	0.2971	1.04145	-2.7087
0.3977	1.07416	-2.2868	0.3915	1.09230	-2.2010	0.3963	1.07317	-2.8016
0.4997	1.09404	-1.8411	0.4953	1.10732	-1.7037	0.5008	1.09479	-2.4595
0.6009	1.10913	-1.4393	0.5942	1.11817	-1.2945	0.5948	1.10872	-1.9897
0.7009	1.12103	-1.0864	0.7062	1.12809	-0.9460	0.6976	1.12076	-1.4717
0.8009	1.13062	-0.7359	0.7960	1.13438	-0.6690	0.7992	1.13051	-0.9954
0.8944	1.13810	-0.4225	0.8937	1.14008	-0.3836	0.8944	1.13793	-0.5173
1.0000	1.14489	0	1.0000	1.14489	0	1.0000	1.14489	0
323.15 K
0	0.74922	0	0	0.76270	0	0	0.76335	0
0.0990	0.91519	-2.2458	0.1002	0.95113	-2.0053	0.0999	0.91469	-2.2015
0.1994	0.99506	-2.8448	0.1995	1.03103	-2.9614	0.1996	0.98937	-2.6710
0.3000	1.04104	-2.9260	0.3004	1.06827	-2.8909	0.2971	1.03536	-2.9018
0.3977	1.06792	-2.5077	0.3915	1.08621	-2.3341	0.3963	1.06702	-2.9557
0.4997	1.08797	-2.0313	0.4953	1.10138	-1.8216	0.5008	1.08911	-2.6456
0.6009	1.10314	-1.5904	0.5942	1.11228	-1.3892	0.5948	1.10304	-2.1456
0.7009	1.11522	-1.2210	0.7062	1.12240	-1.0443	0.6976	1.11498	-1.5755
0.8009	1.12498	-0.8584	0.7960	1.12870	-0.7462	0.7992	1.12489	-1.0977
0.8944	1.13251	-0.5150	0.8937	1.13444	-0.4446	0.8944	1.13231	-0.5895
1.0000	1.13911	0	1.0000	1.13911	0	1.0000	1.13911	0
333.15 K
0	0.73797	0	0	0.75286	0	0	0.75420	0
0.0990	0.90707	-2.4693	0.1002	0.94401	-2.1599	0.0999	0.90757	-2.3740
0.1994	0.98830	-3.1334	0.1995	1.02464	-3.1434	0.1996	0.98267	-2.8475
0.3000	1.03439	-3.1674	0.3004	1.06216	-3.0632	0.2971	1.02883	-3.0580
0.3977	1.06184	-2.7604	0.3915	1.08019	-2.4807	0.3963	1.06085	-3.1176
0.4997	1.08198	-2.2398	0.4953	1.09529	-1.9194	0.5008	1.08322	-2.8063
0.6009	1.09754	-1.8096	0.5942	1.10634	-1.4734	0.5948	1.09751	-2.3298
0.7009	1.10952	-1.3736	0.7062	1.11671	-1.1368	0.6976	1.10951	-1.7355
0.8009	1.11944	-0.9947	0.7960	1.12313	-0.8367	0.7992	1.11929	-1.1972
0.8944	1.12698	-0.6098	0.8937	1.12882	-0.4977	0.8944	1.12680	-0.6752
1.0000	1.13340	0	1.0000	1.13340	0	1.0000	1.13340	0

表2 0.1 MPa 下 GIL (1) + 分子溶剂 (2)二元体系在293.15 K～333.15 K范围内的密度(ρ)和超额摩尔体积(VmE)

Table 2 Experimental density (ρ), excess molar volume (VmE) for binary mixtures of GIL (1) + molecular solvent (2) from 293.15 K to 333.15 K under 0.1 MPa

[N₁₁₁C₃MIM][N(CN)₂]₂ + MeCN			[N₁₁₁C₃MIM][N(CN)₂]₂ + MeOH			[N₁₁₁C₃MIM][N(CN)₂]₂ + EtOH
x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)	x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)	x₁	ρ/(g·cm^-3)	$V m E$ /(cm³·mol^-1)
293.15 K
0	0.78210	0	0	0.79134	0	0	0.78963	0
0.0990	0.93960	-1.6889	0.1002	0.97302	-1.6438	0.0999	0.93424	-1.6415
0.1994	1.01699	-2.2343	0.1995	1.05047	-2.4922	0.1996	1.00801	-2.0869
0.3000	1.06096	-2.2723	0.3004	1.08668	-2.4177	0.2971	1.05299	-2.2752
0.3977	1.08690	-1.8974	0.3915	1.10502	-1.9974	0.3963	1.08397	-2.3101
0.4997	1.10606	-1.4482	0.4953	1.11931	-1.4714	0.5008	1.10518	-1.9454
0.6009	1.12088	-1.0895	0.5942	1.12987	-1.0698	0.5948	1.11951	-1.5727
0.7009	1.13251	-0.7686	0.7062	1.13973	-0.7624	0.6976	1.13197	-1.1736
0.8009	1.14195	-0.4647	0.7960	1.14597	-0.5162	0.7992	1.14177	-0.7561
0.8944	1.14955	-0.2464	0.8937	1.15159	-0.2566	0.8944	1.14939	-0.3690
1.0000	1.15674	0	1.0000	1.15674	0	1.0000	1.15674	0
303.15 K
0	0.77127	0	0	0.78190	0	0	0.78102	0
0.0990	0.93146	-1.8588	0.1002	0.96547	-1.7399	0.0999	0.92751	-1.7952
0.1994	1.00969	-2.4261	0.1995	1.04372	-2.6209	0.1996	1.00205	-2.2954
0.3000	1.05401	-2.4467	0.3004	1.08027	-2.5455	0.2971	1.04753	-2.5241
0.3977	1.08059	-2.0981	0.3915	1.09850	-2.0816	0.3963	1.07881	-2.5856
0.4997	1.10005	-1.6450	0.4953	1.11314	-1.5662	0.5008	1.09990	-2.1900
0.6009	1.11502	-1.2696	0.5942	1.12355	-1.1123	0.5948	1.11384	-1.7382
0.7009	1.12674	-0.9270	0.7062	1.13360	-0.8052	0.6976	1.12636	-1.3271
0.8009	1.13629	-0.6088	0.7960	1.14018	-0.6023	0.7992	1.13621	-0.8977
0.8944	1.14374	-0.3258	0.8937	1.14579	-0.3209	0.8944	1.14354	-0.4270
1.0000	1.15076	0	1.0000	1.15076	0	1.0000	1.15076	0
313.15 K
0	0.76032	0	0	0.77236	0	0	0.77227	0
0.0990	0.92332	-2.0430	0.1002	0.95827	-1.8659	0.0999	0.92130	-2.0068
0.1994	1.00255	-2.6446	0.1995	1.03749	-2.7968	0.1996	0.99581	-2.4866
0.3000	1.04754	-2.6820	0.3004	1.07447	-2.7363	0.2971	1.04145	-2.7087
0.3977	1.07416	-2.2868	0.3915	1.09230	-2.2010	0.3963	1.07317	-2.8016
0.4997	1.09404	-1.8411	0.4953	1.10732	-1.7037	0.5008	1.09479	-2.4595
0.6009	1.10913	-1.4393	0.5942	1.11817	-1.2945	0.5948	1.10872	-1.9897
0.7009	1.12103	-1.0864	0.7062	1.12809	-0.9460	0.6976	1.12076	-1.4717
0.8009	1.13062	-0.7359	0.7960	1.13438	-0.6690	0.7992	1.13051	-0.9954
0.8944	1.13810	-0.4225	0.8937	1.14008	-0.3836	0.8944	1.13793	-0.5173
1.0000	1.14489	0	1.0000	1.14489	0	1.0000	1.14489	0
323.15 K
0	0.74922	0	0	0.76270	0	0	0.76335	0
0.0990	0.91519	-2.2458	0.1002	0.95113	-2.0053	0.0999	0.91469	-2.2015
0.1994	0.99506	-2.8448	0.1995	1.03103	-2.9614	0.1996	0.98937	-2.6710
0.3000	1.04104	-2.9260	0.3004	1.06827	-2.8909	0.2971	1.03536	-2.9018
0.3977	1.06792	-2.5077	0.3915	1.08621	-2.3341	0.3963	1.06702	-2.9557
0.4997	1.08797	-2.0313	0.4953	1.10138	-1.8216	0.5008	1.08911	-2.6456
0.6009	1.10314	-1.5904	0.5942	1.11228	-1.3892	0.5948	1.10304	-2.1456
0.7009	1.11522	-1.2210	0.7062	1.12240	-1.0443	0.6976	1.11498	-1.5755
0.8009	1.12498	-0.8584	0.7960	1.12870	-0.7462	0.7992	1.12489	-1.0977
0.8944	1.13251	-0.5150	0.8937	1.13444	-0.4446	0.8944	1.13231	-0.5895
1.0000	1.13911	0	1.0000	1.13911	0	1.0000	1.13911	0
333.15 K
0	0.73797	0	0	0.75286	0	0	0.75420	0
0.0990	0.90707	-2.4693	0.1002	0.94401	-2.1599	0.0999	0.90757	-2.3740
0.1994	0.98830	-3.1334	0.1995	1.02464	-3.1434	0.1996	0.98267	-2.8475
0.3000	1.03439	-3.1674	0.3004	1.06216	-3.0632	0.2971	1.02883	-3.0580
0.3977	1.06184	-2.7604	0.3915	1.08019	-2.4807	0.3963	1.06085	-3.1176
0.4997	1.08198	-2.2398	0.4953	1.09529	-1.9194	0.5008	1.08322	-2.8063
0.6009	1.09754	-1.8096	0.5942	1.10634	-1.4734	0.5948	1.09751	-2.3298
0.7009	1.10952	-1.3736	0.7062	1.11671	-1.1368	0.6976	1.10951	-1.7355
0.8009	1.11944	-0.9947	0.7960	1.12313	-0.8367	0.7992	1.11929	-1.1972
0.8944	1.12698	-0.6098	0.8937	1.12882	-0.4977	0.8944	1.12680	-0.6752
1.0000	1.13340	0	1.0000	1.13340	0	1.0000	1.13340	0

图2 不同温度下GIL (1) + 分子溶剂(2)二元体系的VmE随组成的变化关系

Fig.2 Plot of VmE against x1 for binary system of GIL (1) + molecular solvent (2) at various temperatures□ 293.15 K; ● 303.15 K; ○ 313.15 K; ▲ 323.15 K; △ 333.15 K

表3 VmE 值的Redlich-Kister参数及标准偏差

Table 3 Coefficients of Redlich-Kister equation and corresponding standard deviations (σ) for VmE values

T/K	A₀	A₁	A₂	A₃	σ
[N₁₁₁C₃MIM][N(CN)₂]₂+ MeCN
293.15	-7.928	0.999	1.128	1.726	0.0467
303.15	-8.377	0.976	-0.004	2.580	0.0382
313.15	-8.958	1.162	-1.309	3.411	0.0383
323.15	-9.707	0.774	-1.934	5.355	0.0507
333.15	-10.782	1.401	-2.813	6.107	0.0561
[N₁₁₁C₃MIM][N(CN)₂]₂+ MeOH
293.15	-6.018	9.844	-8.386	0.295	0.0049
303.15	-6.291	10.338	-9.368	-0.207	0.0047
313.15	-6.898	10.320	-9.986	0.887	0.0064
323.15	-7.342	10.625	-10.933	1.287	0.0060
333.15	-7.762	11.061	-12.119	1.613	0.0060
[N₁₁₁C₃MIM][N(CN)₂]₂+ EtOH
293.15	-7.727	6.244	-4.049	3.441	0.0053
303.15	-8.648	6.914	-4.441	3.137	0.0075
313.15	-9.557	6.790	-4.827	4.769	0.0119
323.15	-10.177	6.974	-5.793	5.757	0.0153
333.15	-10.821	6.761	-6.674	7.201	0.0175

表4 0.1 MPa 下 GIL (1) +分子溶剂 (2)混合物在293.15 K～333.15 K范围内的黏度(η)和超额黏度(Δη)

Table 4 Experimental viscosity (η), excess viscosity (Δη) for binary mixtures of GIL (1) + molecular solvent (2) from 293.15 K to 333.15 K under 0.1 MPa

[N₁₁₁C₃MIM][N(CN)₂]₂ + MeCN			[N₁₁₁C₃MIM][N(CN)₂]₂ + MeOH			[N₁₁₁C₃MIM][N(CN)₂]₂ + EtOH
x₁	η/(mPa·s)	Δη/(mPa·s)	x₁	η/(mPa·s)	Δη/(mPa·s)	x₁	η/(mPa·s)	Δη/(mPa·s)
293.15 K
0	0.364	0	0	0.584	0	0	1.195	0
0.0990	2.580	-156.891	0.1002	4.521	-155.148	0.0999	6.109	-155.556
0.1994	10.38	-310.451	0.1995	12.76	-308.243	0.1996	14.18	-307.630
0.3000	26.36	-456.143	0.3004	29.34	-453.316	0.2971	26.07	-452.356
0.3977	59.14	-580.387	0.3915	48.43	-591.223	0.3963	40.38	-597.399
0.4997	117.2	-686.206	0.4953	80.19	-723.370	0.5008	71.47	-734.160
0.6009	195.5	-770.622	0.5942	148.2	-817.993	0.5948	148.7	-807.914
0.7009	336.8	-789.978	0.7062	244.1	-882.787	0.6976	253.4	-868.400
0.8009	504.9	-782.619	0.7960	368.4	-919.226	0.7992	396.0	-889.002
0.8944	862.0	-575.800	0.8937	534.7	-903.063	0.8944	630.0	-807.892
1.0000	1608	0	1.0000	1608	0	1.0000	1608	0
303.15 K
0	0.333	0	0	0.509	0	0	0.991	0
0.0990	2.132	-63.797	0.1002	3.731	-62.355	0.0999	4.760	-62.356
0.1994	7.918	-124.533	0.1995	9.71	-122.879	0.1996	10.66	-122.447
0.3000	18.99	-180.116	0.3004	21.24	-177.993	0.2971	18.64	-179.006
0.3977	38.47	-225.371	0.3915	32.83	-231.116	0.3963	27.89	-235.417
0.4997	69.58	-261.841	0.4953	55.71	-275.803	0.5008	46.02	-286.461
0.6009	110.6	-287.852	0.5942	88.40	-310.145	0.5948	90.72	-303.977
0.7009	174.6	-290.138	0.7062	130.9	-333.864	0.6976	139.9	-322.817
0.8009	250.0	-281.035	0.7960	186.7	-344.278	0.7992	205.6	-324.385
0.8944	391.2	-201.770	0.8937	264.8	-328.141	0.8944	303.3	-289.691
1.0000	662.9	0	1.0000	662.9	0	1.0000	662.9	0
313.15 K
0	0.307	0	0	0.446	0	0	0.828	0
0.0990	1.802	-30.614	0.1002	3.185	-29.357	0.0999	3.886	-29.291
0.1994	6.313	-58.666	0.1995	7.656	-57.435	0.1996	8.255	-57.206
0.3000	14.37	-83.241	0.3004	15.91	-81.797	0.2971	13.88	-83.150
0.3977	26.89	-102.406	0.3915	23.60	-105.782	0.3963	20.72	-108.433
0.4997	45.10	-117.272	0.4953	35.66	-126.789	0.5008	31.46	-131.537
0.6009	68.39	-126.813	0.5942	55.50	-139.760	0.5948	55.59	-137.843
0.7009	102.2	-125.403	0.7062	80.43	-147.243	0.6976	85.36	-141.363
0.8009	138.9	-121.169	0.7960	108.30	-151.798	0.7992	120.5	-139.104
0.8944	207.7	-82.687	0.8937	147.9	-142.471	0.8944	165.5	-124.985
1.0000	324.6	0	1.0000	324.6	0	1.0000	324.6	0
323.15 K
0	0.285	0	0	0.395	0	0	0.706	0
0.0990	1.551	-16.646	0.1002	2.803	-15.493	0.0999	3.286	-16.352
0.1994	5.223	-31.140	0.1995	6.217	-30.234	0.1996	6.614	-31.918
0.3000	11.25	-43.315	0.3004	10.42	-44.223	0.2971	10.68	-46.329
0.3977	19.75	-52.492	0.3915	14.85	-57.459	0.3963	15.83	-59.984
0.4997	31.63	-59.072	0.4953	22.60	-68.156	0.5008	24.74	-70.875
0.6009	45.61	-63.396	0.5942	35.95	-73.104	0.5948	38.01	-75.423
0.7009	64.54	-62.562	0.7062	51.22	-75.912	0.6976	55.69	-77.225
0.8009	86.01	-59.190	0.7960	68.96	-76.258	0.7992	76.53	-75.633
0.8944	118.8	-43.311	0.8937	91.28	-70.847	0.8944	99.92	-70.292
1.0000	181.2	0	1.0000	181.2	0	1.0000	190.2	0
333.15 K
0	0.266	0	0	0.352	0	0	0.593	0
0.0990	1.364	-9.958	0.1002	2.529	-8.870	0.0999	2.866	-8.851
0.1994	4.463	-18.070	0.1995	5.243	-17.360	0.1996	5.529	-17.289
0.3000	9.219	-24.549	0.3004	8.892	-24.937	0.2971	8.547	-25.127
0.3977	15.40	-29.279	0.3915	12.008	-32.722	0.3963	12.09	-32.627
0.4997	23.41	-32.664	0.4953	17.57	-38.541	0.5008	17.22	-39.141
0.6009	32.67	-34.697	0.5942	26.34	-41.068	0.5948	26.17	-40.649
0.7009	44.77	-33.771	0.7062	37.14	-41.428	0.6976	37.05	-41.220
0.8009	57.81	-31.896	0.7960	48.67	-41.052	0.7992	50.26	-39.326
0.8944	77.20	-22.948	0.8937	63.06	-37.099	0.8944	68.42	-31.763
1.0000	111.9	0	1.0000	111.9	0	1.0000	111.9	0

表4 0.1 MPa 下 GIL (1) +分子溶剂 (2)混合物在293.15 K～333.15 K范围内的黏度(η)和超额黏度(Δη)

Table 4 Experimental viscosity (η), excess viscosity (Δη) for binary mixtures of GIL (1) + molecular solvent (2) from 293.15 K to 333.15 K under 0.1 MPa

[N₁₁₁C₃MIM][N(CN)₂]₂ + MeCN			[N₁₁₁C₃MIM][N(CN)₂]₂ + MeOH			[N₁₁₁C₃MIM][N(CN)₂]₂ + EtOH
x₁	η/(mPa·s)	Δη/(mPa·s)	x₁	η/(mPa·s)	Δη/(mPa·s)	x₁	η/(mPa·s)	Δη/(mPa·s)
293.15 K
0	0.364	0	0	0.584	0	0	1.195	0
0.0990	2.580	-156.891	0.1002	4.521	-155.148	0.0999	6.109	-155.556
0.1994	10.38	-310.451	0.1995	12.76	-308.243	0.1996	14.18	-307.630
0.3000	26.36	-456.143	0.3004	29.34	-453.316	0.2971	26.07	-452.356
0.3977	59.14	-580.387	0.3915	48.43	-591.223	0.3963	40.38	-597.399
0.4997	117.2	-686.206	0.4953	80.19	-723.370	0.5008	71.47	-734.160
0.6009	195.5	-770.622	0.5942	148.2	-817.993	0.5948	148.7	-807.914
0.7009	336.8	-789.978	0.7062	244.1	-882.787	0.6976	253.4	-868.400
0.8009	504.9	-782.619	0.7960	368.4	-919.226	0.7992	396.0	-889.002
0.8944	862.0	-575.800	0.8937	534.7	-903.063	0.8944	630.0	-807.892
1.0000	1608	0	1.0000	1608	0	1.0000	1608	0
303.15 K
0	0.333	0	0	0.509	0	0	0.991	0
0.0990	2.132	-63.797	0.1002	3.731	-62.355	0.0999	4.760	-62.356
0.1994	7.918	-124.533	0.1995	9.71	-122.879	0.1996	10.66	-122.447
0.3000	18.99	-180.116	0.3004	21.24	-177.993	0.2971	18.64	-179.006
0.3977	38.47	-225.371	0.3915	32.83	-231.116	0.3963	27.89	-235.417
0.4997	69.58	-261.841	0.4953	55.71	-275.803	0.5008	46.02	-286.461
0.6009	110.6	-287.852	0.5942	88.40	-310.145	0.5948	90.72	-303.977
0.7009	174.6	-290.138	0.7062	130.9	-333.864	0.6976	139.9	-322.817
0.8009	250.0	-281.035	0.7960	186.7	-344.278	0.7992	205.6	-324.385
0.8944	391.2	-201.770	0.8937	264.8	-328.141	0.8944	303.3	-289.691
1.0000	662.9	0	1.0000	662.9	0	1.0000	662.9	0
313.15 K
0	0.307	0	0	0.446	0	0	0.828	0
0.0990	1.802	-30.614	0.1002	3.185	-29.357	0.0999	3.886	-29.291
0.1994	6.313	-58.666	0.1995	7.656	-57.435	0.1996	8.255	-57.206
0.3000	14.37	-83.241	0.3004	15.91	-81.797	0.2971	13.88	-83.150
0.3977	26.89	-102.406	0.3915	23.60	-105.782	0.3963	20.72	-108.433
0.4997	45.10	-117.272	0.4953	35.66	-126.789	0.5008	31.46	-131.537
0.6009	68.39	-126.813	0.5942	55.50	-139.760	0.5948	55.59	-137.843
0.7009	102.2	-125.403	0.7062	80.43	-147.243	0.6976	85.36	-141.363
0.8009	138.9	-121.169	0.7960	108.30	-151.798	0.7992	120.5	-139.104
0.8944	207.7	-82.687	0.8937	147.9	-142.471	0.8944	165.5	-124.985
1.0000	324.6	0	1.0000	324.6	0	1.0000	324.6	0
323.15 K
0	0.285	0	0	0.395	0	0	0.706	0
0.0990	1.551	-16.646	0.1002	2.803	-15.493	0.0999	3.286	-16.352
0.1994	5.223	-31.140	0.1995	6.217	-30.234	0.1996	6.614	-31.918
0.3000	11.25	-43.315	0.3004	10.42	-44.223	0.2971	10.68	-46.329
0.3977	19.75	-52.492	0.3915	14.85	-57.459	0.3963	15.83	-59.984
0.4997	31.63	-59.072	0.4953	22.60	-68.156	0.5008	24.74	-70.875
0.6009	45.61	-63.396	0.5942	35.95	-73.104	0.5948	38.01	-75.423
0.7009	64.54	-62.562	0.7062	51.22	-75.912	0.6976	55.69	-77.225
0.8009	86.01	-59.190	0.7960	68.96	-76.258	0.7992	76.53	-75.633
0.8944	118.8	-43.311	0.8937	91.28	-70.847	0.8944	99.92	-70.292
1.0000	181.2	0	1.0000	181.2	0	1.0000	190.2	0
333.15 K
0	0.266	0	0	0.352	0	0	0.593	0
0.0990	1.364	-9.958	0.1002	2.529	-8.870	0.0999	2.866	-8.851
0.1994	4.463	-18.070	0.1995	5.243	-17.360	0.1996	5.529	-17.289
0.3000	9.219	-24.549	0.3004	8.892	-24.937	0.2971	8.547	-25.127
0.3977	15.40	-29.279	0.3915	12.008	-32.722	0.3963	12.09	-32.627
0.4997	23.41	-32.664	0.4953	17.57	-38.541	0.5008	17.22	-39.141
0.6009	32.67	-34.697	0.5942	26.34	-41.068	0.5948	26.17	-40.649
0.7009	44.77	-33.771	0.7062	37.14	-41.428	0.6976	37.05	-41.220
0.8009	57.81	-31.896	0.7960	48.67	-41.052	0.7992	50.26	-39.326
0.8944	77.20	-22.948	0.8937	63.06	-37.099	0.8944	68.42	-31.763
1.0000	111.9	0	1.0000	111.9	0	1.0000	111.9	0

图3 不同温度下GIL (1) + 分子溶剂(2)二元体系的Δη随组成的变化关系

Fig.3 Plot of Δη against molar fraction (x1) for binary system of GIL (1) + molecular solvent (2) at various temperatures□ 293.15 K; ● 303.15 K; ○ 313.15 K; ▲ 323.15 K; △ 333.15 K

表5 Δη值的Redlich-Kister参数及标准偏差

Table 5 Coefficients of Redlich-Kister equation and corresponding standard deviations (σ) for Δη values

T/K	A₀	A₁	A₂	A₃	A₄	σ
[N₁₁₁C₃MIM][N(CN)₂]₂+ MeCN
293.15	-2715.91	-1795.18	-1950.01	-1717.72	—	64.34
303.15	-1037.83	-592.87	-633.73	-566.10	—	10.80
313.15	-465.60	-234.86	-249.66	-206.53	—	3.00
323.15	-234.19	-98.36	-138.40	-130.56	—	0.59
333.15	-129.35	-47.91	-75.59	-64.03	—	0.20
[N₁₁₁C₃MIM][N(CN)₂]₂+ MeOH
293.15	2937.49	1696.94	285.85	4893.11	6428.83	451.61
303.15	1121.53	619.73	211.55	1722.77	2111.40	44.01
313.15	511.69	261.39	50.60	736.58	959.31	7.22
323.15	274.27	122.58	-14.56	370.43	500.81	1.43
333.15	155.11	65.66	-22.04	183.08	268.22	0.40
[N₁₁₁C₃MIM][N(CN)₂]₂+ EtOH
293.15	2925.41	1806.99	613.49	3834.42	4702.49	163.04
303.15	1132.63	604.71	108.43	1382.52	1751.69	18.02
313.15	520.42	240.15	-49.61	594.05	862.28	5.31
323.15	284.05	119.13	-23.97	355.78	493.61	2.43
333.15	154.30	74.17	1.86	119.61	161.84	0.13

参考文献 38

1	WeltonT. Room-temperature ionic liquids. Solvents for synthesis and catalysis[J]. Chemical Reviews, 1999, 8: 2071-2084.
2	胡甜甜, 赵地顺, 武宇, 等. 醚基功能化离子液体催化合成乙酸正丁酯[J]. 化工学报, 2017, 68(1): 136-145.
	HuT T, ZhaoD S, WuY, et al. Synthesis of n-butyl acetate by ether-functionalized ionic liquid[J]. CIESC Journal, 2017, 68(1): 136-145.
3	Abo-HamadA, HayyanM, AlSaadiM A, et al. Potential applications of deep eutectic solvents in nanotechnology[J]. Chemical Engineering Journal, 2015, 273: 551-567.
4	RogersR D, SeddonK R. Ionic liquids: solvents of the future?[J]. Science, 2003, 302: 792-793.
5	ZhangS, ChenY, LiF, et al. Fixation and conversion of CO₂ using ionic liquids[J]. Catalysis Today, 2006, 115: 61-69.
6	ZhaoY, YuB, YangZ, et al. A protic ionic liquid catalyzes CO₂ conversion at atmospheric pressure and room temperature: synthesis of quinazoline-2, 4(1H, 3H)-diones[J]. Angewandte Chemie International Edition, 2014, 53: 5922-5925.
7	AntoniettiM, KuangD, SmarslyB, et al. Ionic liquids for the convenient synthesis of functional nanoparticles and other inorganic nanostructures[J]. Angewandte Chemie International Edition, 2004, 43: 4988-4992.
8	BösmannA, DatsevichL, JessA, et al. Deep desulfurization of diesel fuel by extraction with ionic liquids[J]. Chemical Communications, 2001, (23): 2494-2495.
9	LimaS, NevesP, AntunesM M, et al. Conversion of mono/di/polysaccharides into furan compounds using 1-alkyl-3-methylimidazolium ionic liquids[J]. Applied Catalysis A: General, 2009, 363(1/2): 93-99.
10	BrandtA, GräsvikJ, HallettJ P, et al. Deconstruction of lignocellulosic biomass with ionic liquids[J]. Green Chemistry, 2013, 15(3): 550-583.
11	AndersonJ L, DingR, EllernandA, et al. Structure and properties of high stability geminal dicationic ionic liquids[J]. Journal of the American Chemical Society, 2005, 127(2): 593-604.
12	QiM, ArmstrongD W. Dicationic ionic liquid stationary phase for GC-MS analysis of volatile compounds in herbal plants[J]. Analytical and Bioanalytical Chemistry, 2007, 388(4): 889-899.
13	HuangK, HanX, ZhangX, et al. PEG-linked geminal dicationic ionic liquids as selective, high-stability gas chromatographic stationary phases[J]. Analytical and Bioanalytical Chemistry, 2007, 389(7/8): 2265-2275.
14	BhawalS S, PatilR A, ArmstrongD W. Rapid, effective deprotection of tert-butoxycarbonyl (Boc) amino acids and peptides at high temperatures using a thermally stable ionic liquid[J]. RSC Advances, 2015, 5(116): 95854-95856.
15	JinC M, YeC, PhillipsB S, et al. Polyethylene glycol functionalized dicationic ionic liquids with alkyl or polyfluoroalkyl substituents as high temperature lubricants[J]. Journal of Materials Chemistry, 2006, 16(16): 1529-1535.
16	YangX, WangJ, ZouW, et al. Synthesis and thermodynamic properties of a novel pyridinium-based asymmetrical gemini ionic liquid[J]. Korean Journal of Chemical Engineering, 2015, 32(12): 2369-2374.
17	WangX, ZhangP, CuiP, et al. Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids[J]. Chinese Journal of Chemical Engineering, 2017, 25(9): 1182-1186.
18	LuX, ZhuJ, QianX, et al. Separation of methyl linolenate and its analogues by functional mixture of imidazolium based ionic liquid-organic solvent-cuprous salt[J]. Chinese Journal of Chemical Engineering, 2019, 27(4): 811-817.
19	LiC, ZhangZ, ZhaoZ. Direct conversion of glucose and cellulose to 5-hydroxymethylfurfural in ionic liquid under microwave irradiation[J]. Tetrahedron Letters, 2009, 50(38): 5403-5405.
20	HouQ, ZhenM, LiuL, et al. Tin phosphate as a heterogeneous catalyst for efficient dehydration of glucose into 5-hydroxymethylfurfural in ionic liquid[J]. Applied Catalysis B: Environmental, 2018, 224: 183-193.
21	QiX, WatanabeM, AidaT M, et al. Efficient catalytic conversion of fructose into 5-hydroxymethylfurfural in ionic liquids at room temperature[J]. ChemSusChem, 2009, 2(10): 944-946.
22	CarneiroA P, RodríguezO, MacedoE A. Fructose and glucose dissolution in ionic liquids: solubility and thermodynamic modeling[J]. Industrial & Engineering Chemistry Research, 2013, 52(9): 3424-3435.
23	YangX, WangJ, FangY. Properties of pure 1-(3-(trimethylammonio)prop-1-yl)-3-methylimidazolium bis(dicyanamide) asymmetrical gemini ionic liquid and its binary mixture with isopropanol at T = (283.15—333.15) K[J]. The Journal of Chemical Thermodynamics, 2019, 134: 84-95.
24	ChenF, YangZ, ChenZ, et al. Density, viscosity, speed of sound, excess property and bulk modulus of binary mixtures of γ-butyrolactone with acetonitrile, dimethyl carbonate, and tetrahydrofuran at temperatures (293.15 to 333.15) K[J]. Journal of Molecular Liquids, 2015, 209: 683-692.
25	GołdonA, DabrowskaK, HofmanT. Densities and excess volumes of the 1, 3-dimethylimidazolium methylsulfate + methanol system at temperatures from (313.15 to 333.15) K and pressures from (0.1 to 25) MPa[J]. Journal of Chemical & Engineering Data, 2007, 52(5): 1830-1837.
26	YangC, SunY, HeY, et al. Volumetric properties and viscosities of binary mixtures of N,N-dimethylformamide with methanol and ethanol in the temperature range (293.15 to 333.15) K[J]. Journal of Chemical & Engineering Data, 2008, 53(1): 293-297.
27	YangC, LaiH, LiuZ, et al. Densities and viscosities of diethyl carbonate + toluene, + methanol, and + 2-propanol from (293.15 to 363.15) K[J]. Journal of Chemical & Engineering Data, 2006, 51(2): 584-589.
28	DjojoputroH, IsmadjiS. Density and viscosity of binary mixtures of ethyl-2-methylbutyrate and ethyl hexanoate with methanol, ethanol, and 1-propanol at (293.15, 303.15, and 313.15) K[J]. Journal of Chemical & Engineering Data, 2005, 50(4): 1343-1347.
29	KurniaK A, MutalibM I A. Densities and viscosities of binary mixture of the ionic liquid bis(2-hydroxyethyl)ammonium propionate with methanol, ethanol, and 1-propanol at T = (293.15, 303.15, 313.15, and 323.15) K and at P = 0.1 MPa[J]. Journal of Chemical & Engineering Data, 2011, 56(1): 79-83.
30	CiocirlanO, CroitoruO, IulianO. Densities and viscosities for binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid with molecular solvents[J]. Journal of Chemical & Engineering Data, 2011, 56(4): 1526-1534.
31	LuX, XieH, LeiQ, et al. Densities and viscosities of binary mixtures of 2, 2-diethyl-1, 1, 3, 3-tetramethylguanidinium bis (trifluoromethylsulfonyl) imide with methanol and ethanol[J]. The Journal of Chemical Thermodynamics, 2019, 136: 44-53.
32	ZecN, Bešter-RogačM, VranešM, et al. Physicochemical properties of (1-butyl-1-methylpyrrolydinium dicyanamide+ γ-butyrolactone) binary mixtures[J]. The Journal of Chemical Thermodynamics, 2015, 91: 327-335.
33	AnoutiM, JacqueminJ, LemordantD. Volumetric properties, viscosities, and isobaric heat capacities of imidazolium octanoate protic ionic liquid in molecular solvents[J]. Journal of Chemical & Engineering Data, 2010, 55(12): 5719-5728.
34	LiX, ZhouQ, LuX, et al. Densities and viscosities of binary mixtures of magnetic ionic liquids 1-alkyl-3-methylimidazolium tetrachloroferrate with ethyl acetate at temperatures (293.15 to 323.15) K[J]. Journal of Molecular Liquids, 2017, 243: 285-292.
35	YeF, ZhuJ, YuK, et al. Physicochemical properties of binary mixtures of 1, 1, 3, 3- tetramethylguanidine imidazolide ionic liquid with water and alcohols[J]. The Journal of Chemical Thermodynamics, 2016, 97: 39-47.
36	MoosaviM, MotahariA, OmraniA, et al. Investigation on some thermophysical properties of poly (ethylene glycol) binary mixtures at different temperatures[J]. The Journal of Chemical Thermodynamics, 2013, 58: 340-350.
37	AnwarN, Riyazuddeen. Excess molar volumes, excess molar isentropic compressibilities, viscosity deviations, and activation parameters for 1-ethyl-3-methyl-imidazolium trifluoro-methanesulfonate + dimethyl sulfoxide and/or acetonitrile at T = 298.15 to 323.15 K and P = 0.1 MPa[J]. Journal of Chemical & Engineering Data, 2018, 63(2): 269-289.
38	ChenJ, ChenL, XuY. Properties of pure 1, 1, 3, 3-tetramethylguanidine imidazole ionic liquid and its binary mixtures with alcohols at T=(293.15 to 313.15)K[J]. The Journal of Chemical Thermodynamics, 2015, 88: 110-120.

[1]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[2]	张龙, 宋孟杰, 邵苛苛, 张旋, 沈俊, 高润淼, 甄泽康, 江正勇. 管翅式换热器迎风侧翅片末端霜层生长模拟研究[J]. 化工学报, 2023, 74(S1): 179-182.
[3]	王琪, 张斌, 张晓昕, 武虎建, 战海涛, 王涛. 氯铝酸-三乙胺离子液体/P₂O₅催化合成伊索克酸和2-乙基蒽醌[J]. 化工学报, 2023, 74(S1): 245-249.
[4]	车睿敏, 郑文秋, 王小宇, 李鑫, 许凤. 基于离子液体的纤维素均相加工研究进展[J]. 化工学报, 2023, 74(9): 3615-3627.
[5]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[6]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[7]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[8]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[9]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[10]	王俐智, 杭钱程, 郑叶玲, 丁延, 陈家继, 叶青, 李进龙. 离子液体萃取剂萃取精馏分离丙酸甲酯+甲醇共沸物[J]. 化工学报, 2023, 74(9): 3731-3741.
[11]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[12]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.
[13]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[14]	刘爽, 张霖宙, 许志明, 赵锁奇. 渣油及其组分黏度的分子层次组成关联研究[J]. 化工学报, 2023, 74(8): 3226-3241.
[15]	陈吉, 洪泽, 雷昭, 凌强, 赵志刚, 彭陈辉, 崔平. 基于分子动力学的焦炭溶损反应及其机理研究[J]. 化工学报, 2023, 74(7): 2935-2946.