Volumetric Properties and Molecular Interactions of Binary Mixtures Imidazolium Acetates-ethanol at 293.15 K†

doi:10.7503/cjcu20130448

Abstract

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

CLC Number:

TrendMD:

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

Figures/Tables 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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