反气相色谱技术与汉森溶解参数法测定咪唑基醋酸盐类离子液体的溶解度参数

doi:10.7503/cjcu20170479

摘要/Abstract

摘要：

采用反气相色谱技术在353.15~393.15 K温度范围内测定了4种咪唑基醋酸盐离子液体的溶解度参数. 结果表明, 在实验温度范围内, 反气相色谱技术测定的离子液体的溶解度参数值随温度的升高而线性减小. 通过外推法得到333.15 K 时4种离子液体的溶解度参数分别为26.14, 24.38, 23.60和23.04 MPa^1/2. 采用Hansen溶解度参数软件在333.15 K时对4种离子液体的溶解度参数进行模拟计算, 结果分别为26.52, 23.99, 23.45和22.00 MPa^1/2. 2种方法测定结果在±1.05 MPa^1/2的误差范围内一致, 说明2种方法均适用于咪唑基醋酸盐溶解度参数的测定.

关键词: 离子液体, 溶解度参数, 反气相色谱, 汉森溶解度参数软件

Abstract:

The solubility parameters of four imidazolyl acetate ionic liquids were determined by inverse gas chromatography in the range of 353.15—393.15 K. The results show that the solubility parameter values of the four ionic liquids decrease linearly with the increase of temperature in the experimental temperature range. The solubility parameters of the four ionic liquids are 26.14, 24.38, 23.60 and 23.04 MPa^1/2 at 333.15 K by extrapolation method. The solubility parameters of the ionic liquid were also simulated by Hansen solubility parameter software at 333.15 K. The simulation results are 26.52, 23.99, 23.45 and 22.00 MPa^1/2, respectively. The results obtained by the two methods are consistent with each other in the error rang of ±1.05 MPa^1/2, indicating that the two methods are applicable to the determination of the solubility parameters of imidazolyl acetate.

Key words: Ionic liquid, Solubility parameter, Inverse gas chromatography, Hansen’s solubility parameter software;

中图分类号:

O642

TrendMD:

于开乐, 潘薪羽, 张正方, 王强. 反气相色谱技术与汉森溶解参数法测定咪唑基醋酸盐类离子液体的溶解度参数. 高等学校化学学报, 2018, 39(5): 1048.

YU Kaile,PAN Xinyu,ZHANG Zhengfang,WANG Qiang. Determination of Solubility Parameters of Imidazolyl Acetate Ionic Liquid by Inverse Gas Chromatography and Hansen Solubility Parameters^†. Chem. J. Chinese Universities, 2018, 39(5): 1048.

图/表 8

Table 1 Interaction parameter between probes and ILs at different temperatures

Probe	Ionic liquid	$χ 12 ∞$
Probe	Ionic liquid	353.15 K	363.15 K	373.15 K	383.15 K	393.15 K
n-Octane	[EMIM]OAc	3.48	3.40	3.28	3.15	3.05
	[BMIM]OAc	3.95	3.83	3.58	3.45	3.41
	[HMIM]OAc	1.68	1.65	1.61	1.64	1.62
	[OMIM]OAc	2.20	2.15	2.15	2.11	2.09
n-Nonane	[EMIM]OAc	3.51	3.51	3.47	3.41	3.37
	[BMIM]OAc	4.10	4.11	3.88	3.58	3.41
	[HMIM]OAc	2.05	1.66	1.60	1.56	1.61
	[OMIM]OAc	2.23	2.20	2.19	2.15	2.11
n-Decane	[EMIM]OAc	3.52	3.51	3.50	3.48	3.44
	[BMIM]OAc	4.22	4.18	4.01	3.66	3.67
	[HMIM]OAc	1.75	1.70	1.64	1.63	1.57
	[OMIM]OAc	2.28	2.25	2.23	2.19	2.11
n-Undecane	[EMIM]OAc	3.58	3.56	3.53	3.52	3.51
	[BMIM]OAc	4.25	4.26	4.12	3.73	3.82
	[HMIM]OAc	1.80	1.74	1.72	1.69	1.65
	[OMIM]OAc	2.37	2.33	2.30	2.26	2.22
n-Dodecane	[EMIM]OAc	3.67	3.64	3.61	3.58	3.56
	[BMIM]OAc	4.35	4.33	4.27	3.86	3.86
	[HMIM]OAc	1.69	1.84	1.80	1.75	1.73
	[OMIM]OAc	2.47	2.43	2.38	2.34	2.30
Benzene	[EMIM]OAc	0.49	0.49	0.53	0.59	0.65
	[BMIM]OAc	1.36	1.36	1.20	1.25	1.26
	[HMIM]OAc	-0.12	-0.17	-0.27	-0.12	-0.37
	[OMIM]OAc	0.59	0.55	0.56	0.56	0.55
Toluene	[EMIM]OAc	0.84	0.87	0.90	0.93	0.95
	[BMIM]OAc	1.44	1.31	1.23	1.13	1.01
	[HMIM]OAc	0.09	0.06	0.01	-0.09	-0.19
	[OMIM]OAc	0.64	0.66	0.65	0.65	0.62

Table 1 Interaction parameter between probes and ILs at different temperatures

Probe	Ionic liquid	$χ 12 ∞$
Probe	Ionic liquid	353.15 K	363.15 K	373.15 K	383.15 K	393.15 K
n-Octane	[EMIM]OAc	3.48	3.40	3.28	3.15	3.05
	[BMIM]OAc	3.95	3.83	3.58	3.45	3.41
	[HMIM]OAc	1.68	1.65	1.61	1.64	1.62
	[OMIM]OAc	2.20	2.15	2.15	2.11	2.09
n-Nonane	[EMIM]OAc	3.51	3.51	3.47	3.41	3.37
	[BMIM]OAc	4.10	4.11	3.88	3.58	3.41
	[HMIM]OAc	2.05	1.66	1.60	1.56	1.61
	[OMIM]OAc	2.23	2.20	2.19	2.15	2.11
n-Decane	[EMIM]OAc	3.52	3.51	3.50	3.48	3.44
	[BMIM]OAc	4.22	4.18	4.01	3.66	3.67
	[HMIM]OAc	1.75	1.70	1.64	1.63	1.57
	[OMIM]OAc	2.28	2.25	2.23	2.19	2.11
n-Undecane	[EMIM]OAc	3.58	3.56	3.53	3.52	3.51
	[BMIM]OAc	4.25	4.26	4.12	3.73	3.82
	[HMIM]OAc	1.80	1.74	1.72	1.69	1.65
	[OMIM]OAc	2.37	2.33	2.30	2.26	2.22
n-Dodecane	[EMIM]OAc	3.67	3.64	3.61	3.58	3.56
	[BMIM]OAc	4.35	4.33	4.27	3.86	3.86
	[HMIM]OAc	1.69	1.84	1.80	1.75	1.73
	[OMIM]OAc	2.47	2.43	2.38	2.34	2.30
Benzene	[EMIM]OAc	0.49	0.49	0.53	0.59	0.65
	[BMIM]OAc	1.36	1.36	1.20	1.25	1.26
	[HMIM]OAc	-0.12	-0.17	-0.27	-0.12	-0.37
	[OMIM]OAc	0.59	0.55	0.56	0.56	0.55
Toluene	[EMIM]OAc	0.84	0.87	0.90	0.93	0.95
	[BMIM]OAc	1.44	1.31	1.23	1.13	1.01
	[HMIM]OAc	0.09	0.06	0.01	-0.09	-0.19
	[OMIM]OAc	0.64	0.66	0.65	0.65	0.62

Table 1 (Xu) Continued

Probe	Ionic liquid	$χ 12 ∞$
Probe	Ionic liquid	353.15 K	363.15 K	373.15 K	383.15 K	393.15 K
Phenylethane	[EMIM]OAc	1.20	1.23	1.26	1.30	1.30
	[BMIM]OAc	1.92	1.79	1.74	1.71	1.70
	[HMIM]OAc	0.15	0.13	0.10	0.03	-0.05
	[OMIM]OAc	0.80	0.80	0.79	0.77	0.77
Phenylpropane	[EMIM]OAc	1.53	1.54	1.56	1.59	1.59
	[BMIM]OAc	2.16	2.14	1.99	1.94	1.91
	[HMIM]OAc	0.27	0.22	0.20	0.12	0.07
	[OMIM]OAc	0.93	0.91	0.90	0.88	0.87
Cyclohexene	[EMIM]OAc	2.39	2.43	2.37	2.37	2.39
	[BMIM]OAc	3.10	2.91	3.08	2.79	2.69
	[HMIM]OAc	1.23	1.26	1.31	1.41	1.38
	[OMIM]OAc	1.45	1.44	1.42	1.38	1.32
Octene	[EMIM]OAc	3.31	3.35	3.27	3.22	3.25
	[BMIM]OAc	2.84	2.63	2.50	2.34	2.18
	[HMIM]OAc	1.69	1.71	1.84	1.88	1.86
	[OMIM]OAc	1.87	1.90	1.86	1.82	1.81
Methanol	[EMIM]OAc	-2.25	-2.17	-2.15	-2.12	-2.08
	[BMIM]OAc	-0.64	-0.64	-0.64	-0.64	-0.66
	[HMIM]OAc	-1.25	-1.35	-1.27	-1.25	-1.24
	[OMIM]OAc	-0.67	-0.66	-0.65	-0.64	-0.63
Ethanol	[EMIM]OAc	-1.90	-1.85	-1.84	-1.84	-1.81
	[BMIM]OAc	-0.38	-0.39	-0.43	-0.48	-0.51
	[HMIM]OAc	-1.18	-1.22	-1.19	-1.19	-1.19
	[OMIM]OAc	-0.61	-0.62	-0.63	-0.64	-0.65
Propanol	[EMIM]OAc	-1.84	-1.81	-1.80	-1.76	-1.71
	[BMIM]OAc	-0.40	-0.42	-0.44	-0.45	-0.46
	[HMIM]OAc	-1.40	-1.44	-1.39	-1.35	-1.32
	[OMIM]OAc	-0.80	-0.58	-0.79	-0.78	-0.77
Isopropanol	[EMIM]OAc	-1.55	-1.52	-1.51	-1.48	-1.46
	[BMIM]OAc	-0.07	-0.11	-0.15	-0.18	-0.20
	[HMIM]OAc	-1.14	-1.13	-1.14	-1.11	-1.10
	[OMIM]OAc	-0.53	-0.55	-0.56	-0.56	-0.57
Butanol	[EMIM]OAc	-1.70	-1.67	-1.66	-1.63	-1.58
	[BMIM]OAc	-0.30	-0.36	-0.36	-0.39	-0.41
	[HMIM]OAc	-1.15	-1.44	-1.44	-1.40	-1.35
	[OMIM]OAc	-0.85	-0.86	-0.85	-0.85	-0.84

Table 1 (Xu) Continued

Probe	Ionic liquid	$χ 12 ∞$
Probe	Ionic liquid	353.15 K	363.15 K	373.15 K	383.15 K	393.15 K
Phenylethane	[EMIM]OAc	1.20	1.23	1.26	1.30	1.30
	[BMIM]OAc	1.92	1.79	1.74	1.71	1.70
	[HMIM]OAc	0.15	0.13	0.10	0.03	-0.05
	[OMIM]OAc	0.80	0.80	0.79	0.77	0.77
Phenylpropane	[EMIM]OAc	1.53	1.54	1.56	1.59	1.59
	[BMIM]OAc	2.16	2.14	1.99	1.94	1.91
	[HMIM]OAc	0.27	0.22	0.20	0.12	0.07
	[OMIM]OAc	0.93	0.91	0.90	0.88	0.87
Cyclohexene	[EMIM]OAc	2.39	2.43	2.37	2.37	2.39
	[BMIM]OAc	3.10	2.91	3.08	2.79	2.69
	[HMIM]OAc	1.23	1.26	1.31	1.41	1.38
	[OMIM]OAc	1.45	1.44	1.42	1.38	1.32
Octene	[EMIM]OAc	3.31	3.35	3.27	3.22	3.25
	[BMIM]OAc	2.84	2.63	2.50	2.34	2.18
	[HMIM]OAc	1.69	1.71	1.84	1.88	1.86
	[OMIM]OAc	1.87	1.90	1.86	1.82	1.81
Methanol	[EMIM]OAc	-2.25	-2.17	-2.15	-2.12	-2.08
	[BMIM]OAc	-0.64	-0.64	-0.64	-0.64	-0.66
	[HMIM]OAc	-1.25	-1.35	-1.27	-1.25	-1.24
	[OMIM]OAc	-0.67	-0.66	-0.65	-0.64	-0.63
Ethanol	[EMIM]OAc	-1.90	-1.85	-1.84	-1.84	-1.81
	[BMIM]OAc	-0.38	-0.39	-0.43	-0.48	-0.51
	[HMIM]OAc	-1.18	-1.22	-1.19	-1.19	-1.19
	[OMIM]OAc	-0.61	-0.62	-0.63	-0.64	-0.65
Propanol	[EMIM]OAc	-1.84	-1.81	-1.80	-1.76	-1.71
	[BMIM]OAc	-0.40	-0.42	-0.44	-0.45	-0.46
	[HMIM]OAc	-1.40	-1.44	-1.39	-1.35	-1.32
	[OMIM]OAc	-0.80	-0.58	-0.79	-0.78	-0.77
Isopropanol	[EMIM]OAc	-1.55	-1.52	-1.51	-1.48	-1.46
	[BMIM]OAc	-0.07	-0.11	-0.15	-0.18	-0.20
	[HMIM]OAc	-1.14	-1.13	-1.14	-1.11	-1.10
	[OMIM]OAc	-0.53	-0.55	-0.56	-0.56	-0.57
Butanol	[EMIM]OAc	-1.70	-1.67	-1.66	-1.63	-1.58
	[BMIM]OAc	-0.30	-0.36	-0.36	-0.39	-0.41
	[HMIM]OAc	-1.15	-1.44	-1.44	-1.40	-1.35
	[OMIM]OAc	-0.85	-0.86	-0.85	-0.85	-0.84

Fig.1 Relationship between δ12/(RT)-χ12∞/V1 and δ1 at 353.15 K Note:(A) [EMIM]OAc; (B)[BMIM]OAc; (C)[HMIM]OAc; (D)[OMIM]OAc.

Table 2 δ2(MPa1/2) values of four ILs at different temperatures

Ionic liquid	353.15 K	363.15 K	373.15 K	383.15 K	393.15 K	333.15 K	298.15 K
[EMIM]OAc	25.80	25.62	25.46	25.29	25.11	26.14	26.74
[BMIM]OAc	23.79	23.55	23.31	22.93	22.70	24.38	25.36
[HMIM]OAc	23.07	22.99	22.70	22.48	22.18	23.60	24.40
[OMIM]OAc	22.54	22.25	22.06	21.80	21.50	23.04	23.93

Fig.2 Relationship between δ2 and T Note: a. [EMIM]OAc; b. [BMIM]OAc; c. [HMIM]OAc; d. [OMIM]OAc.

Fig.3 Three-dimensional solubility graphs of four ILs Note: (A) [EMIM]OAc; (B)[BMIM]OAc; (C)[HMIM]OAc; (D)[OMIM]OAc.

Table 3 Three-dimensional solubility parameters of four ILs at 333.15 K

Ionic liquid	δ_D/MPa^1/2	δ_P/MPa^1/2	δ_H/MPa^1/2	δ_T/MPa^1/2
[EMIM]OAc	18.80	9.80	15.93	26.52
[BMIM]OAc	17.85	9.60	12.84	23.99
[HMIM]OAc	17.95	8.24	12.65	23.45
[OMIM]OAc	15.42	9.63	12.39	22.00

Table 4 Three-dimensional solubility parameters of four ILs at 298.15 K

Ionic liquid	δ_D/MPa^1/2	δ_P/MPa^1/2	δ_H/MPa^1/2	δ_T/MPa^1/2
[EMIM]OAc	17.03	14.84	14.48	26.83
[BMIM]OAc	15.40	14.29	13.71	25.08
[HMIM]OAc	16.99	10.52	14.23	24.54
[OMIM]OAc	17.77	9.46	13.02	23.98

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