ARTICLE pubs.acs.org/JPCB
A New Method for the Determination of Vaporization Enthalpies of Ionic Liquids at Low Temperatures Sergey P. Verevkin,* Dzmitry H. Zaitsau, Vladimir N. Emelyanenko, and Andreas Heintz* Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059, Rostock, Germany
bS Supporting Information ABSTRACT: A new method for the determination of vaporization enthalpies of extremely low volatile ILs has been developed using a newly constructed quartz crystal microbalance (QCM) vacuum setup. Because of the very high sensitivity of the QCM it has been possible to reduce the average temperature of the vaporization studies by approximately 100 K in comparison to other conventional techniques. The physical basis of the evaluation procedure has been developed and test measurements have been performed with the common ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C2mim][NTf2] extending the range of measuring vaporization enthalpies down to 363 K. The results obtained for [C2mim][NTf2] have been tested for thermodynamic consistency by comparison with data already available at higher temperatures. Comparison of the temperature-dependent vaporization enthalpy data taken from the literature show only acceptable agreement with the heat capacity difference of 40 J K1 mol1. The method developed in this work opens also a new way to obtain reliable values of vaporization enthalpies of thermally unstable ionic liquids.
1. INTRODUCTION Ionic liquids (ILs) have very low but detectable vapor pressure at ambient temperatures. First measurements1,2 of vapor pressures and quantitative results for enthalpies of vaporization have already been performed before the principal volatility of ILs at elevated temperatures between 473 and 573 K has been demonstrated qualitatively.3,4 Since then much attention has been paid to the challenging task of measuring vapor pressures of ILs. Traditional techniques for vapor pressure measurements with the exception of the Knudsen method5,6 have been developed for measuring reliable vapor pressures and vaporization enthalpies for moderately volatile compounds but not for extremely low volatile substances such as ILs. This situation has inspired the development of new experimental methods extending and improving traditional methods toward measurements of reliable vaporization enthalpies, Δgl Hom, of ILs. Among these methods are transpiration,7,8 temperature-programmed desorption with line of sight mass spectrometry (LOSMS),912 thermogravimetry,1315 high-temperature spectroscopic technique,16 and drop microcalorimetry17 (see Table 1). Each of these methods has peculiarities, advantages, and disadvantages, and their crucial drawback has in common that ILs under study could easily undergo decomposition at elevated temperatures. Typically vaporization processes have been studied between 420 and 600 K.716 In this work we describe a method for determining enthalpies of vaporization of very low volatile ILs using a commercially available quartz crystal microbalance (QCM). The combination of a highvacuum chamber with the extremely sensitive QCM has turned r 2011 American Chemical Society
out to allow measurements of mass loss rates for ILs at temperatures down to 363 K. In contrast to the conventional Knudsen method, our method is more sensitive since the total open surface is exposed to the QCM under vacuum conditions. This requires also a new physical evaluation procedure different from the Knudsen method. Test measurements have been performed with the common ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C2mim][NTf2], which has widely been studied in the literature and where experimental data are available obtained by other techniques at higher temperatures.
2. METHODOLOGY OF QCM FOR VAPORIZATION ENTHALPY DETERMINATION FOR ILS QCMs have been used in microgravimetry for determining very small masses deposited on a quartz crystal surface, since the increasing thickness leads to a change in the resonance frequency.1824 It has been shown that the QCM is a sensitive mass sensor for measurements of the solid depositions.2528 However, there are some intricacies with measurements of liquid depositions due to a nonlinear dependency of the frequency change in a case where viscous liquid films of different thicknesses are deposited on the quartz crystal. Moreover, shifts in frequency and bandwidth of the QCM could also be influenced by diverse varieties of Received: August 3, 2011 Revised: September 28, 2011 Published: September 28, 2011 12889
dx.doi.org/10.1021/jp207397v | J. Phys. Chem. B 2011, 115, 12889–12895
The Journal of Physical Chemistry B
ARTICLE
Table 1. Enthalpies of Vaporization of [C2mim][NTf2] from the Literature and This Work (kJ mol1) temperature
Δgl Hm°
Δgl Hm°
range, K
Tav, K
at Tav
at 298.15 Ka
442484 300550
462.6 430.0
118.8 ( 2.7 119.0 ( 2.0
135.2 ( 2.7 133.2 ( 2.0
ref 2 9
577.8
577.8
110.4 ( 2.4
138.4 ( 2.4
17
473523
495.5
120.6 ( 2.1
140.3 ( 2.1
13
499538
516.5
114.7 ( 6.8
136.5 ( 6.8
7
359436
398.0
122.0 ( 3.0
132.0 ( 3.0
11
545600
573.0
109.3 ( 1.7
136.8 ( 1.7
16
362395
378.2
118.6 ( 1.0
126.6 ( 1.0b
this work
a
Enthalpies of vaporization for ILs were adjusted to 298.15 K with Δgl Cp,m° = 100 J K1 mol1. b Calculated using eq 8 with Δgl Cp,m° = 100 J K1 mol1.
interactions of the crystal with the liquid sample.29 The classical “load” on a QCM consists of a thin homogeneous film, which shifts the resonance frequency due to its inertia. Other possible types of loading include semi-infinite viscoelastic media, rough objects contacting the crystal via isolated asperities, mechanically nonlinear contacts, and dielectric films. Thus, for the liquid depositions the knowledge of their density and viscosity under the experimental conditions is required for the correct determination of the mass of the thin film on the quartz crystal,2831 but the theoretical treatment is complicated. In contrast, the viscosity of a crystalline sample is very high, and therefore its effect on the frequency shift is very low and determined only by the mass load on the crystal. Vapor pressure and vaporization enthalpy measurements of low volatile pure organic compounds has been a long-standing goal in our laboratory.32 During the last years we have focused our efforts on studies of ILs.2,7,8,10 The high sensitivity of the QCM, offers a method of measuring the mass loss of an IL sample caused by evaporation as function of time. The amount of the IL deposited from the vapor phase on the QCM is a measure not only for the rate of vaporization but also for the equilibrium pressure of the IL. However, very few studies dealing with QCM vapor pressure measurements exist in the literatures which are restricted exclusively to vapor pressure measurements of solids. Surprisingly the QCM method has never been applied for studies of low volatile liquids. From our knowledge, the first attempt to determine enthalpies of sublimation of some nucleic acids by mass loss rates using a QCM has been made in 1974.33 In this and in further works3436 no absolute values of the vapor pressure have been determined but attempts have been made to derive enthalpies of sublimation from the temperature-dependent change in resonance frequency (df/dt) using the linear correlation ln(df/dt 3 T1/2) vs 1/T. Sublimation of samples on to the QCM was performed as a rule from a Knudsen effusion cell or simply from the surface of the sample placed in the open crucible. A very first trial to obtain absolute vapor pressures for crystalline agrochemicals combining the Knudsen cell with the QCM was made by Goodman.37 However, it is not clear in this article how the frequency change of the QCM was related to the mass loss of the sample. Several experimental runs with different orifices of the effusion cell are documented by this author, but our analysis of the data revealed a very low reproducibility.
More successful was the work done by Freedman et al.38 To determine the absolute vapor pressure of solids the frequency change of the QCM was adjusted to the mass uptake through the constant C = 2.26 106 g1 Hz1 according to calculations made by Sauerbrey.22 Provided that the Knudsen cell is kept at a fixed distance (and fixed orientation) to the QCM, the measured mass gain rate is related to the vapor pressure by the equation38 dm=dt ¼ F 5:830 102 PðTorrÞ½Mðg 3 mol1 Þ=TðKÞ1=2 where F is a viewing factor representing the fraction of molecules leaving the cell orifice which hit the QCM surface. The F value was calculated in the small angle approximation supposing the validation of cosine law distribution of the molecules leaving the effusion cell orifice. The estimated uncertainty of the vapor pressure determination was (7%. The device and procedure were tested with benzoic acid, and the absolute vapor pressure values agreed with the reliable experimental data3941 within experimental uncertainties. Another way to determine the sublimation rate of a sample was proposed by Gershanik et al.42 A solution of 2,4,6-trinitrotoluene in acetonitrile was placed on the surface of a QCM. After evaporation of the acetonitrile the sample was exposed to the continuous air stream. The mass loss rate of trinitro-toluene from microcrystals was directly monitored. A new Knudsen effusion apparatus with simultaneous gravimetric and quartz crystal microbalance mass loss detection has been described just recently.43 This modification has also been developed for accurate vapor pressure measurements of solid polyaromatic hydrocarbons (PAHs). To obtain vapor pressures the frequency change of the QCM and the mass loss of the sample in the Knudsen effusion cell were used simultaneously. The frequency change of the QCM and the mass loss of the Knudsen cell (measured gravimetrically) were correlated empirically. The mass loss of the effusion cell during these experiments was typically in the range of 1020 mg. Because of the much lower vapor pressure of ILs compared to PAH this method is too slow for determining vapor pressures of ILs. We have estimated that few years are required for evaporating 10 mg of any aprotic IL at 380 K under the experimental conditions described by Santos et al.43 As a consequence we decided to use an open cell instead of the traditional Knudsen cell. This modification provides a large surface for vaporization leading to shorter and acceptable measurement times, usually of 10 to 24 h. Absolute vapor pressures cannot be measured by this method due to unknown empirical parameters of apparatus but enthalpies vaporization of ILs can be determined at lower temperatures not reachable by other techniques used so far. In the focus of the current work has been a development of a new technique for reliable measurements enthalpies of vaporization of very low volatile liquid samples such as ILs. For this purpose we have combined evaporation of the sample from the open surface into vacuum with a monitoring of the mass deposition rates using the QCM.
3. EXPERIMENTAL SECTION 3.1. Chemicals. 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C2mim][NTf2] supplied by IoLiTec has been used for our studies. Prior to experiments, the IL was 12890
dx.doi.org/10.1021/jp207397v |J. Phys. Chem. B 2011, 115, 12889–12895
The Journal of Physical Chemistry B
ARTICLE
Figure 1. The scheme of the experimental setup.
subjected to vacuum evaporation at 333 K at least for 24 h to remove possible traces of solvents and moisture. The water concentration (
