293.15 K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用

doi:10.7503/cjcu20130448

摘要/Abstract

摘要：

用比重瓶法测定了293.15 K时1-甲基咪唑醋酸盐([Mim]Ac)/1,3-二甲基咪唑醋酸盐([Mmim]Ac)/1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)-乙醇(EtOH)二元体系在全组成范围内的密度. 计算出[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的表观摩尔体积和体系的超额摩尔体积. 用三参数多项式关联拟合了表观摩尔体积与摩尔分数的关系, 外推出组分的极限偏摩尔体积和摩尔体积. [Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的摩尔体积的外推值与实验值分别在±0.07和±0.04 cm³/mol范围内相一致. 计算出了[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH分别在无限稀溶液中的溶剂化系数. 用Redlich-Kister 方程关联拟合了超额摩尔体积与摩尔分数的关系. 分别根据极限偏摩尔体积、摩尔体积与极限偏摩尔体积的差值、溶剂化系数和超额摩尔体积对照讨论了分子间相互作用的强弱. 结果显示, 在[Mim]Ac/[Mmim]Ac/[Emim]Ac的浓度无限稀溶液中, [Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序为[Mim]Ac-EtOH>[Mmim]Ac-EtOH>[Emim]Ac-EtOH; 在EtOH的浓度无限稀溶液中, 以及体系中[Mim]Ac/[Mmim]Ac/[Emim]Ac的摩尔分数在0.15~0.95间时, [Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序都为[Emim]Ac-EtOH>[Mmim]Ac-EtOH>[Mim]Ac-EtOH.

关键词: Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH, 表观摩尔体积, 超额摩尔体积, 溶剂化系数, 分子间相互作用

Abstract:

Over the full molar fraction range and at 293.15 K, the densities of binary systems 1-methylimi-dazolium acetate([Mim]Ac)/1,3-dimethylimidazolium acetate([Mmim]Ac)/1-ethyl-3-methylimidazolium acetate([Emim]Ac)(1)-ethanol(EtOH)(2) were measured by pycnometer method. The apparent molar volumes of [Mim]Ac/[Mmim]Ac/[Emim]Ac and EtOH, and the excess molar volumes of the binary mixtures were calculated. The relations of apparent molar volumes and molar fractions were fitted by three-parameter polynomials, from which, the limiting partial molar volumes and molar volumes were extrapolated. For [Mim]Ac/[Mmim]Ac/[Emim]Ac and EtOH, the values of molar volumes from extrapolation and measurement are consistent with each other within ±0.07 and ±0.04 cm³/mol, respectively. The solvation coefficients at infinite dilutions of [Mim]Ac/[Mmim]Ac/[Emim]Ac and EtOH were calculated. The Redlich-Kister equation was used to fit the excess molar volumes and molar fractions. Finally, the solute-solvent pairs’ molecular interactions were discussed in terms of the limiting partial molar volume, the difference of molar volume and limiting partial molar volume, the solvation coefficients at infinite dilutions, and the excess molar volume. The results show that the sequence of molecular interaction at infinite dilutions of [Mim]Ac/[Mmim]Ac/[Emim]Ac is [Mim]Ac-EtOH>[Mmim]Ac-EtOH>[Emim]Ac-EtOH, and that at infinite dilutions of EtOH and [Mim]Ac/[Mmim]Ac/[Emim]Ac of x₁=0.15—0.95, the sequence is [Emim]Ac-EtOH>[Mmim]Ac-EtOH>[Mim]Ac-EtOH.

Key words: Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH, Apparent molar volume, Excess molar volume, Solvation coefficient, Molecular interaction

中图分类号:

TrendMD:

侯海云, 黄银蓉, 白博峰, 杨靖. 293.15 K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用. 高等学校化学学报, 2014, 35(1): 121.

HOU Haiyun, HUANG Yinrong, BAI Bofeng, YANG Jing. Volumetric Properties and Molecular Interactions of Binary Mixtures Imidazolium Acetates-ethanol at 293.15 K^†. Chem. J. Chinese Universities, 2014, 35(1): 121.

图/表 6

Table 1 Molar fractions, densities, apparent molar volumes and excess molar volumes of the binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K

Binary mixture	x₁	x₂	ρ/(g·cm^-3)	^φV₁/(cm³·mol^-1)	^φV₂/(cm³·mol^-1)	$V m E$ /(cm³·mol^-1)
[Mim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0275	0.9725	0.8123	117.13	58.10	-0.162
	0.0352	0.9648	0.8184	117.38	58.06	-0.198
	0.0478	0.9522	0.8280	117.76	58.00	-0.251
	0.0629	0.9371	0.8393	117.95	57.92	-0.319
	0.1514	0.8486	0.8981	118.85	57.52	-0.631
	0.1709	0.8291	0.9098	118.93	57.42	-0.699
	0.2135	0.7865	0.9334	119.28	57.25	-0.798
	0.2603	0.7397	0.9571	119.59	57.06	-0.892
	0.3396	0.6604	0.9927	120.08	56.76	-0.997
	0.5022	0.4978	1.0505	121.03	56.26	-0.997
	0.6015	0.3985	1.0787	121.50	55.98	-0.912
	0.7299	0.2701	1.1087	122.06	55.69	-0.696
	0.9025	0.0975	1.1408	122.73	55.57	-0.263
	0.9384	0.0616	1.1467	122.84	55.49	-0.171
	1.0000	0.0000	1.1561	123.02		0.000
[Mmim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0291	0.9709	0.8147	131.67	58.06	-0.195
	0.0405	0.9595	0.8236	132.57	58.02	-0.236
	0.0513	0.9487	0.8321	132.65	57.96	-0.294
	0.0733	0.9267	0.8483	133.11	57.85	-0.387
	0.1157	0.8843	0.8773	133.47	57.62	-0.569
	0.2104	0.7896	0.9318	134.26	57.17	-0.867
	0.2315	0.7685	0.9424	134.40	57.07	-0.922
	0.2607	0.7393	0.9561	134.61	56.93	-0.984
[Mmim]Ac(1)-EtOH(2)	0.3185	0.6815	0.9805	135.05	56.71	-1.062
	0.4929	0.5071	1.0379	136.18	56.12	-1.087
	0.5903	0.4097	1.0620	136.72	55.88	-0.979
	0.7305	0.2695	1.0899	137.41	55.62	-0.714
	0.8659	0.1341	1.1115	137.94	55.40	-0.385
	0.9306	0.0694	1.1203	138.16	55.31	-0.205
	1.0000	0.0000	1.1289	138.38		0.000
[Emim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0506	0.9494	0.8320	148.70	57.96	-0.287
	0.0617	0.9383	0.8402	149.07	57.92	-0.327
	0.0701	0.9299	0.8466	148.88	57.85	-0.384
	0.0837	0.9163	0.8562	149.11	57.79	-0.440
	0.1103	0.8897	0.8741	149.28	57.64	-0.561
	0.1919	0.8081	0.9207	149.92	57.21	-0.854
	0.2246	0.7754	0.9365	150.18	57.05	-0.939
	0.2375	0.7625	0.9424	150.29	57.00	-0.968
	0.2691	0.7309	0.9559	150.52	56.85	-1.035
	0.4627	0.5373	1.0189	151.83	56.08	-1.172
	0.5714	0.4286	1.0433	152.51	55.80	-1.058
	0.7035	0.2965	1.0668	153.18	55.45	-0.834
	0.8771	0.1229	1.0899	153.93	55.14	-0.384
	0.9267	0.0733	1.0954	154.11	55.06	-0.235
	1.0000	0.0000	1.1027	154.37		0.000

Table 1 Molar fractions, densities, apparent molar volumes and excess molar volumes of the binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K

Binary mixture	x₁	x₂	ρ/(g·cm^-3)	^φV₁/(cm³·mol^-1)	^φV₂/(cm³·mol^-1)	$V m E$ /(cm³·mol^-1)
[Mim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0275	0.9725	0.8123	117.13	58.10	-0.162
	0.0352	0.9648	0.8184	117.38	58.06	-0.198
	0.0478	0.9522	0.8280	117.76	58.00	-0.251
	0.0629	0.9371	0.8393	117.95	57.92	-0.319
	0.1514	0.8486	0.8981	118.85	57.52	-0.631
	0.1709	0.8291	0.9098	118.93	57.42	-0.699
	0.2135	0.7865	0.9334	119.28	57.25	-0.798
	0.2603	0.7397	0.9571	119.59	57.06	-0.892
	0.3396	0.6604	0.9927	120.08	56.76	-0.997
	0.5022	0.4978	1.0505	121.03	56.26	-0.997
	0.6015	0.3985	1.0787	121.50	55.98	-0.912
	0.7299	0.2701	1.1087	122.06	55.69	-0.696
	0.9025	0.0975	1.1408	122.73	55.57	-0.263
	0.9384	0.0616	1.1467	122.84	55.49	-0.171
	1.0000	0.0000	1.1561	123.02		0.000
[Mmim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0291	0.9709	0.8147	131.67	58.06	-0.195
	0.0405	0.9595	0.8236	132.57	58.02	-0.236
	0.0513	0.9487	0.8321	132.65	57.96	-0.294
	0.0733	0.9267	0.8483	133.11	57.85	-0.387
	0.1157	0.8843	0.8773	133.47	57.62	-0.569
	0.2104	0.7896	0.9318	134.26	57.17	-0.867
	0.2315	0.7685	0.9424	134.40	57.07	-0.922
	0.2607	0.7393	0.9561	134.61	56.93	-0.984
[Mmim]Ac(1)-EtOH(2)	0.3185	0.6815	0.9805	135.05	56.71	-1.062
	0.4929	0.5071	1.0379	136.18	56.12	-1.087
	0.5903	0.4097	1.0620	136.72	55.88	-0.979
	0.7305	0.2695	1.0899	137.41	55.62	-0.714
	0.8659	0.1341	1.1115	137.94	55.40	-0.385
	0.9306	0.0694	1.1203	138.16	55.31	-0.205
	1.0000	0.0000	1.1289	138.38		0.000
[Emim]Ac(1)-EtOH(2)	0.0000	1.0000	0.7895		58.27	0.000
	0.0506	0.9494	0.8320	148.70	57.96	-0.287
	0.0617	0.9383	0.8402	149.07	57.92	-0.327
	0.0701	0.9299	0.8466	148.88	57.85	-0.384
	0.0837	0.9163	0.8562	149.11	57.79	-0.440
	0.1103	0.8897	0.8741	149.28	57.64	-0.561
	0.1919	0.8081	0.9207	149.92	57.21	-0.854
	0.2246	0.7754	0.9365	150.18	57.05	-0.939
	0.2375	0.7625	0.9424	150.29	57.00	-0.968
	0.2691	0.7309	0.9559	150.52	56.85	-1.035
	0.4627	0.5373	1.0189	151.83	56.08	-1.172
	0.5714	0.4286	1.0433	152.51	55.80	-1.058
	0.7035	0.2965	1.0668	153.18	55.45	-0.834
	0.8771	0.1229	1.0899	153.93	55.14	-0.384
	0.9267	0.0733	1.0954	154.11	55.06	-0.235
	1.0000	0.0000	1.1027	154.37		0.000

Table 2 Least-square fitting parameters φVB0, a, b and standard deviations σ of Eq. (4) for binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2)

Binary mixture	^φ $V B 0$ = $V ? B 0$ /(cm³·mol^-1)		a/(cm³·mol^-1)		b/(cm³·mol^-1)		σ/(cm³·mol^-1)
Binary mixture	(1)	(2)	(1)	(2)	(1)	(2)	(1)	(2)
[Mim]Ac(1)-EtOH(2)	117.05	55.54	10.12	0.27	-4.31	2.54	0.07	0.02
[Mmim]Ac(1)-EtOH(2)	131.91	55.38	11.11	0.22	-4.78	2.73	0.07	0.02
[Emim]Ac(1)-EtOH(2)	148.25	55.10	9.07	0.54	-2.95	2.70	0.07	0.02

Table 2 Least-square fitting parameters φVB0, a, b and standard deviations σ of Eq. (4) for binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2)

Binary mixture	^φ $V B 0$ = $V ? B 0$ /(cm³·mol^-1)		a/(cm³·mol^-1)		b/(cm³·mol^-1)		σ/(cm³·mol^-1)
Binary mixture	(1)	(2)	(1)	(2)	(1)	(2)	(1)	(2)
[Mim]Ac(1)-EtOH(2)	117.05	55.54	10.12	0.27	-4.31	2.54	0.07	0.02
[Mmim]Ac(1)-EtOH(2)	131.91	55.38	11.11	0.22	-4.78	2.73	0.07	0.02
[Emim]Ac(1)-EtOH(2)	148.25	55.10	9.07	0.54	-2.95	2.70	0.07	0.02

Fig.1 Fitting curves of the apparent molar volumes vs. molar fractions for binary mixtures[Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K(A) φV1-x1; (B) φV2-x2. a. [Mim]Ac(1)-EtOH(2); b. [Mmim]Ac(1)-EtOH(2); c. [Emim]Ac(1)-EtOH(2).

Table 3 Molar volumes, the differences of the molar volumes and limiting partial molar volumes, solvation coefficients at infinite solutions of components (1) and (2) for [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K

Binary mixture	$V m (B) *$ /(cm³·mol^-1)				δ_B/(cm³·mol^-1)		$γ B 0$
Binary mixture	(1)^a	(1)^b	(2)^a	(2)^b	(1)	(2)	(1)	(2)
[Mim]Ac(1)-EtOH(2)	122.97	122.91	58.37	58.35	6.14	2.83	0.050	0.048
[Mmim]Ac(1)-EtOH(2)	138.36	138.29	58.37	58.33	6.45	2.99	0.047	0.051
[Emim]Ac(1)-EtOH(2)	154.37	154.37	58.37	58.34	6.12	3.27	0.040	0.056

Binary mixture	$V m (B) *$ /(cm³·mol^-1)				δ_B/(cm³·mol^-1)		$γ B 0$
Binary mixture	(1)^a	(1)^b	(2)^a	(2)^b	(1)	(2)	(1)	(2)
[Mim]Ac(1)-EtOH(2)	122.97	122.91	58.37	58.35	6.14	2.83	0.050	0.048
[Mmim]Ac(1)-EtOH(2)	138.36	138.29	58.37	58.33	6.45	2.99	0.047	0.051
[Emim]Ac(1)-EtOH(2)	154.37	154.37	58.37	58.34	6.12	3.27	0.040	0.056

Table 4 Redlich-Kister coefficients A0, A1, A2, A3 and standard deviation σ of Eq.(11) for binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K

Binary mixture	A₀	A₁	A₂	A₃	σ/(cm³·mol^-1)
[Mim]Ac(1)-EtOH(2)	-4.017	-1.064	-0.181	-0.488	0.005
[Mmim]Ac(1)-EtOH(2)	-4.309	-1.484	-0.218	-0.118	0.006
[Emim]Ac(1)-EtOH(2)	-4.572	-1.524	-0.078	0.224	0.005

Fig.2 Fitting curves of the excess molar volumes vs. the molar fractions for binary mixtures [Mim]Ac/[Mmim]Ac/[Emim]Ac(1)-EtOH(2) at 293.15 K

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