醚基功能化离子液体[MOEMIm]Cl和[EOEMIm]Cl热力学性质

doi:10.3866/PKU.WHXB201901072

摘要/Abstract

摘要：

通过核磁共振氢谱，核磁共振碳谱，元素分析和热重分析对醚基功能化的离子液体[MOEMIm]Cl和[EOEMIm]Cl进行了表征。在温度范围T = 288.15–328.15 K内，测定了离子液体[MOEMIm]Cl和[EOEMIm]Cl的密度(ρ)、表面张力(γ)和折光率(n_D)。根据这些实验数据，讨论并计算了离子液体[MOEMIm]Cl和[EOEMIm]Cl的体积性质。计算出离子液体[MOEMIm]Cl和[EOEMIm]Cl的摩尔表面吉布斯自由能(g_s)、摩尔表面熵(s)、摩尔表面焓(h)、摩尔极化度(R_m)和摩尔极化率(α_p)，h均近似为一个常数说明这两种离子液体从内部到表面的过程是一个等库仑过程，同时这两种离子液体的R_m和α_p均与温度无关。本文还用摩尔表面Gibbs自由能改进Lorentz-Lorenz方程并预测离子液体表面张力，预测值与实验值高度相关。

关键词: 醚基功能化离子液体, 密度, 表面张力, 摩尔表面Gibbs自由能, Lorentz-Lorenz方程

Abstract:

Functionalized ionic liquids containing ether groups can be obtained through reasonable design. The unique properties of ether-based functionalized ionic liquids are attractive for a variety of practical applications. To further develop these ether-based functionalized ionic liquids, it is important to accurately describe the thermophysical properties of ether-based functionalized ionic liquids and to predict, simulate, and optimize theoretical models of thermophysical properties. Herein, the ether-functionalized ionic liquids [MOEMIm]Cl and [EOEMIm]Cl were characterized by nuclear magnetic resonance spectroscopy, elemental analysis, and thermogravimetric analysis. The density (ρ), surface tension (γ), and refractive index (n_D) of [MOEMIm]Cl and [EOEMIm]Cl were measured at 5 K intervals between 288.15 and 328.15 K. Based on the obtained experimental data, the molar volume (V), molecular volume (V_m), standard entropy (S₍₂₉₈₎⁰), and lattice energy (U_POT) of [MOEMIm]Cl and [EOEMIm]Cl were calculated and the data obtained at 298.15 K were compared. The comparison results agreed well with the literature values within the experimental error range and indicated that both [MOEMIm]Cl and [EOEMIm]Cl exhibit small lattice energies and are in the molten state at room temperature (T = 298.15 K). Based on these experimental data, the molar surface Gibbs free energy (g_s), molar surface entropy (s), molar surface enthalpy (h), molar polarization (R_m), and molar polarizability (α_p) of [MOEMIm]Cl and [EOEMIm]Cl were also calculated. The calculation results show that the molar surface enthalpy (h) is approximately constant, that is, the molar surface constant pressure heat capacity is close to zero, indicating that the process of heat capacity change from the inside to the surface of the ionic liquid is an equivalent coulomb process. Simultaneously, the calculation results showed that the molar polarization (R_m) and molar polarizability (α_p) of the ionic liquids were independent of temperature, indicating that R_m and α_p reflect the induced dipole effect of the ionic liquid. The molar surface Gibbs free energy definition equation was combined with the Lorentz-Lorenz equation to obtain a novel modified Lorentz-Lorenz equation and was used to predict the surface tension of the [MOEMIm]Cl and [EOEMIm]Cl liquids. The values predicted using this combined equation were highly correlated with the experimental values.

Key words: Ether-based functionalized ionic liquid, Density, Surface tension, Gibbs free energy of the molar surface, Lorentz-Lorenz equation

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龚燕燕,刘海春,张朵,佟静. 醚基功能化离子液体[MOEMIm]Cl和[EOEMIm]Cl热力学性质[J]. 物理化学学报, 2019, 35(11), 1224-1231. doi: 10.3866/PKU.WHXB201901072

Yanyan GONG,Haichun LIU,Duo ZHANG,Jing TONG. Thermodynamic Properties of the Ether-Based Functionalized Ionic Liquids [MOEMIm]Cl and [EOEMIm]Cl[J]. Acta Physico-Chimica Sinica 2019, 35(11), 1224-1231. doi: 10.3866/PKU.WHXB201901072

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201901072

https://www.whxb.pku.edu.cn/CN/Y2019/V35/I11/1224

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ILs	T/K	ρ/(g·cm^-3)	γ/(mJ·m^-2)	n_D
[MOEMIm]Cl	288.15	1.16860 + 0.00007	49.6 + 0.31	1.5201 + 0.0003
	293.15	1.16546 + 0.00007	49.2 + 0.31	1.5185 + 0.0003
	298.15	1.16231 + 0.00007	48.7 + 0.31	1.5160 + 0.0003
	303.15	1.15917 + 0.00007	48.4 + 0.31	1.5142 + 0.0003
	308.15	1.15604 + 0.00007	48.0 + 0.31	1.5121 + 0.0003
	313.15	1.15291 + 0.00007	47.6 + 0.31	1.5103 + 0.0003
	318.15	1.14978 + 0.00007	47.1 + 0.31	1.5083 + 0.0003
	323.15	1.14663 + 0.00007	46.7 + 0.31	1.5069 + 0.0003
	328.15	1.14327 + 0.00007	46.2 + 0.31	1.5046 + 0.0003
[EOEMIm]Cl	288.15	1.14313 + 0.00007	47.8 + 0.31	1.5269 + 0.0003
	293.15	1.13998 + 0.00007	47.3 + 0.31	1.5255 + 0.0003
	298.15	1.13683 + 0.00007	46.9 + 0.31	1.5240 + 0.0003
	303.15	1.13369 + 0.00007	46.5 + 0.31	1.5225 + 0.0003
	308.15	1.13057 + 0.00007	46.0 + 0.31	1.5206 + 0.0003
	313.15	1.12745 + 0.00007	45.6 + 0.31	1.5184 + 0.0003
	318.15	1.12437 + 0.00007	45.2 + 0.31	1.5159 + 0.0003
	323.15	1.12128 + 0.00007	44.8 + 0.31	1.5142 + 0.0003
	328.15	1.11821 + 0.00007	44.3 + 0.31	1.5119 + 0.0003

ILs	ρ/(g·cm^-3)	V_m/(nm³)	10⁴V/(m³·mol^-1)	S⁰/(J·K^-1·mol^-1)	ΔU_POT/(kJ·mol^-1)
[C₂2O1IM][DCA]	1.11360²²	1.987	0.3300	441	443
[C₂2O1IM][OAC]	1.19238²³	1.797	0.2985	402	455
[C₂2O1IM][SCN]	1.122107²³	1.901	0.3158	423	448
[C₂2O1IM][TfO]	1.355886²³	2.244	0.3728	494	430
[C₂2O1IM][NTF₂]	1.463127²³	2.976	0.4944	646	401
[MOEMIm]Cl	1.16231	1.520	0.2524	344	475
[EOEMIm]Cl	1.13683	1.677	0.2786	377	463

ILs	T/K	g_s/(kJ·mol^-1)	s/(J·mol^-1·K^-1)	h/(kJ·mol^-1)	g_s(pre)/(kJ·mol^-1)
[MOEMIm]Cl	288.15	11.89	15.99	16.49	11.89
	293.15	11.81	15.99	16.50	11.81
	298.15	11.71	15.99	16.48	11.73
	303.15	11.66	15.99	16.51	11.65
	308.15	11.59	15.99	16.51	11.57
	313.15	11.51	15.99	16.52	11.49
	318.15	11.41	15.99	16.50	11.41
	323.15	11.33	15.99	16.50	11.33
	328.15	11.23	15.99	16.48	11.25
[EOEMIm]Cl	288.15	12.23	17.81	17.36	12.22
	293.15	12.13	17.81	17.35	12.13
	298.15	12.05	17.81	17.35	12.05
	303.15	11.96	17.81	17.36	11.96
	308.15	11.86	17.81	17.34	11.87
	313.15	11.78	17.81	17.35	11.78
	318.15	11.69	17.81	17.36	11.69
	323.15	11.61	17.81	17.37	11.60
	328.15	11.50	17.81	17.35	11.51

ILs	T/K	n_D	R_m/(cm³·mol^-1)	10²⁴α_p/(cm³)	γ_(pre)/(mJ·m^-2)
[MOEMIm]Cl	288.15	1.5201	45.96	18.23	49.6
	293.15	1.5185	45.96	18.23	49.2
	298.15	1.5160	45.90	18.20	48.8
	303.15	1.5142	45.89	18.20	48.4
	308.15	1.5121	45.86	18.19	47.9
	313.15	1.5103	45.85	18.18	47.5
	318.15	1.5083	45.82	18.17	47.1
	323.15	1.5069	45.84	18.18	46.7
	328.15	1.5046	45.80	18.16	46.3
[EOEMIm]Cl	288.15	1.5269	51.27	20.33	47.8
	293.15	1.5255	51.30	20.34	47.3
	298.15	1.5240	51.32	20.35	46.9
	303.15	1.5225	51.34	20.36	46.5
	308.15	1.5206	51.32	20.35	46.0
	313.15	1.5184	51.28	20.34	45.6
	318.15	1.5159	51.21	20.31	45.2
	323.15	1.5142	51.21	20.31	44.8
	328.15	1.5119	51.16	20.29	44.3

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