Hamed Peyrovedin1, Reza Haghbakhsh1,2, Ana Rita C Duarte2, Sona Raeissi1. 1. School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave., Shiraz 71348-51154, Iran. 2. LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
Abstract
Deep eutectic solvents (DESs) are newly introduced green solvents that have attracted much attention regarding fundamentals and applications. Of the problems along the way of replacing a common solvent by a DES, is the lack of information on the thermophysical properties of DESs. This is even more accentuated by considering the dramatically growing number of DESs, being made by the combination of vast numbers of the constituting substances, and at their various molar ratios. The speed of sound is among the properties that can be used to estimate other important thermodynamic properties. In this work, a global and accurate model is proposed and used to estimate the speed of sound in 39 different DESs. This is the first general speed of sound model for DESs. The model does not require any thermodynamic properties other than the critical properties of the DESs, which are themselves calculated by group contribution methods, and in doing so, make the proposed method entirely independent of any experimental data as input. The results indicated that the average absolute relative deviation percentages (AARD%) of this model for 420 experimental data is only 5.4%. Accordingly, based on the achieved results, the proposed model can be used to predict the speeds of sound of DESs.
Deep eutectic solvents (DESs) are newly introduced green solvents that have attracted much attention regarding fundamentals and applications. Of the problems along the way of replacing a common solvent by a DES, is the lack of information on the thermophysical properties of DESs. This is even more accentuated by considering the dramatically growing number of DESs, being made by the combination of vast numbers of the constituting substances, and at their various molar ratios. The speed of sound is among the properties that can be used to estimate other important thermodynamic properties. In this work, a global and accurate model is proposed and used to estimate the speed of sound in 39 different DESs. This is the first general speed of sound model for DESs. The model does not require any thermodynamic properties other than the critical properties of the DESs, which are themselves calculated by group contribution methods, and in doing so, make the proposed method entirely independent of any experimental data as input. The results indicated that the average absolute relative deviation percentages (AARD%) of this model for 420 experimental data is only 5.4%. Accordingly, based on the achieved results, the proposed model can be used to predict the speeds of sound of DESs.
Entities:
Keywords:
Deep Eutectic Systems; correlation; green solvent; modeling; physical property; sound velocity
In recent years, various studies have been published regarding the negative impacts of volatile organic solvents on our planet. Such studies put forth the concerns regarding the use of such harmful compounds, and consequently, encouraged researchers to introduce novel green solvents as environmentally friendly replacements for the commonly used polluting substances [1,2]. In this respect, different types of green substances were introduced, for example, the ionic liquids (ILs). ILs have certain advantages, such as low vapor pressures and insignificant volatilities, tunable properties, chemical and thermal stabilities and acceptable solvent power [3,4]. Such characteristics have turned them into an interesting family of green solvents for research. Consequently, their applications have been investigated in various fields, for example carbon capture, separation operations, chemical synthesis, catalysis, biodiesel production and as sustainable lubricants [5,6,7,8,9]. However, with time, some disadvantages have also been reported for ILs, such as their high price, the need for multiple-step purification and, in some cases, toxicity [3,6,10]. These issues have caused some limitations in their applications. Accordingly, it is worthwhile to propose new types of green solvents to overcome the limitations of ILs.Recently, Abbott et al. suggested a new family of solvents that can be prepared simply by the mixing of two substances [11,12]. These two components are a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD). When the HBA and HBD are mixed together, a mixture is formed with a melting point that is much lower than those of the individual HBA and HBD [13,14,15,16]. Due to this, these novel solvents are named the deep eutectic solvents (DESs). DESs have nearly all of the advantages of ILs, while they have the added benefits of easy preparation by the simple mixing of the HBA and HBD, nontoxicity (for most DESs), biodegradability and biocompatibility [17,18]. Moreover, a comparison between the costs of ILs and DESs shows that DESs are generally cheaper than ILs [17]. Accordingly, these novel solvents have attracted great attention due to their unique characteristics. Based on the desirable properties and advantages of DESs, some studies have suggested that DESs have the potential to be used for various applications in the industries, such as in extraction and separation processes, chromatography, biodiesel production, drug delivery systems and for introducing novel drugs [9,12,15,17,19,20]. Furthermore, DESs are designer solvents, i.e., suitable DESs possessing the desired (thermo-)physical properties can be designed by the engineered choice of the HBA, HBD and their molar ratios. In being so, a large number of DESs can be prepared [18]. Therefore, research on DESs is steeply on the rise, and the rate at which basic knowledge will become available on the physical properties of DESs will probably lag behind the introduction of the numerous upcoming DESs. This problem is actually an obstacle to the industrial use of DESs [21,22].The speed of sound is an important thermodynamic property, which can be used to determine various other properties, such as density, heat capacity, the Joule–Thomson coefficient, bulk modulus, virial coefficients and equation of state constants [23,24]. This characteristic has made the speed of sound a noteworthy property. This is even more pronounced for the particular family of DESs, which have even greater shortages of property data than the conventional solvents. Some of the significant thermophysical properties of DESs that are lacking can be calculated using the speed of sound. Among the most important process design and optimization properties, one can point to for example, the isentropic and isothermal compressibilities, heat capacities, and thermal conductivities of DESs. This issue is highlighted when considering that DESs are designer solvents, for which most of the thermophysical properties of the newly introduced and upcoming DESs are unknown [25,26].Accordingly, based on its value in predicting other unknown properties, different studies have already been published to estimate the speeds of sound of the older generation of designer solvents, i.e., the ionic liquids. Gardas and Coutinho [27], presented the following relation to calculate the speed of sound, u, in ILs:
where ρ and σ are the density and the surface tension, respectively, and α and β are the correlation’s optimized constants [27].In other published work, Hekayati and Esmaeilzadeh [28] introduced a correlation to predict the speed of sound of ILs. In their model, the speed of sound can be calculated as:
where M, ρ, σ and T are the molecular weight, density, surface tension and temperature, respectively, and the constants a to f are optimized parameters [28]. Based on Equation (2), Hekayati and Esmaeilzadeh calculated the speed of sound of 48 different ILs and showed that their model can estimate this property with good accuracy (1.11% and 1.62% for the training ant test datasets, respectively).In 2010, Singh and Singh [29] optimized the adjustable parameters ψ and ξ, and used Equation (3) for calculating the speed of sound in ILs.In all of these three literature models, the density and surface tension of the IL must be known to calculate the speed of sound. When such physical properties are unavailable, Haghbakhsh and his coworkers introduced a method in which the speed of sound can be calculated using an atomic contribution model [24]:In this model, ΔA and ΔB are the optimized parameters and n is the number of atoms of type i in the molecule.All of the above methods were specific to ionic liquids, and up to date, there are no general models available for estimating the speeds of sound in DESs. So far, only experimental data is available on the speeds of sound of DESs. The aim of this work was to introduce, for the first time, an accurate, simple and easy-to-use generalized model for estimating the speed of sound in various DESs. To have wide applicability, the idea was to propose a model, which does not require experimental physical property data as its input.
2. Methods
2.1. Selected Deep Eutectic Solvents (DESs) and Experimental Data
In this work, 420 speed of sound data were collected from literature references, covering 39 different DESs [21,30,31,32,33,34,35,36,37,38,39,40,41,42]. Table 1 lists these 39 DESs, including their corresponding HBAs, HBDs and molar ratios.
Table 1
The list of investigated deep eutectic solvents (DESs) in this study and the corresponding hydrogen bond acceptor (HBA), hydrogen bond donor (HBD) and molar ratio of each.
DES #
Data Set
HBA
HBD
HBA:HBD Molar Ratio
Ndp 1
Ref.
DES1
Test
1-Ethyl-3-methylimidazolium chloride
Ethylene glycol
2:1
5
[30]
DES2
Training
1-Ethyl-3-methylimidazolium chloride
Ethylene glycol
1:1
5
[30]
DES3
Test
1-Ethyl-3-methylimidazolium chloride
Ethylene glycol
1:2
5
[30]
DES4
Training
Benzyl-tributyl-ammonium-chloride
Ethylene glycol
1:3
13
[31]
DES5
Training
Benzyl-tributyl-ammonium-chloride
Diethylene glycol
1:3
13
[31]
DES6
Training
Benzyl-tributyl-ammonium-chloride
Triethylene glycol
1:3
13
[31]
DES7
Test
Benzyl-tributyl-ammonium-chloride
Glycerol
1:3
13
[31]
DES8
Training
Benzyl-trimethyl-ammonium-chloride
Ethylene glycol
1:3
13
[31]
DES9
Training
Benzyl-trimethyl-ammonium-chloride
Diethylene glycol
1:3
13
[31]
DES10
Test
Benzyl-trimethyl-ammonium-chloride
Triethylene glycol
1:3
13
[31]
DES11
Training
Benzyl-trimethyl-ammonium-chloride
Glycerol
1:3
13
[31]
DES12
Training
Benzyl-tripropyl-ammonium-chloride
Phenol
1:3
11
[32]
DES13
Training
Benzyl-tripropyl-ammonium-chloride
Ethylene glycol
1:3
11
[32]
DES14
Training
Benzyl-tripropyl-ammonium-chloride
Lactic acid
1:3
11
[32]
DES15
Training
Benzyl-tripropyl-ammonium-chloride
Glycerol
1:3
11
[32]
DES16
Training
Betaine
Lactic acid
1:2
10
[21]
DES17
Training
Betaine
Lactic acid
1:5
11
[21]
DES18
Training
Betaine
Levulinic acid
1:2
11
[21]
DES19
Training
Betaine
Lactic acid/water
1:1:1
11
[21]
DES20
Test
Betaine
Citric acid/water
2:1:6
11
[21]
DES21
Training
Choline-Chloride
Urea
1:2
20
[33,34,35]
DES22
Test
Choline-Chloride
Ethylene glycol
1:2
13
[33,34]
DES23
Test
Choline-Chloride
Glycerol
1:2
38
[33,34,36]
DES24
Training
Choline-Chloride
Fructose
2:1
7
[34]
DES25
Test
Choline-Chloride
Glucose
2:1
7
[34]
DES26
Training
Choline-Chloride
1,2propanediol
1:3
10
[37]
DES27
Training
Choline-Chloride
Levulinic acid
1:2
11
[38]
DES28
Training
Choline-Chloride
Malonic acid
1:1
7
[39]
DES29
Test
Choline-Chloride
Glutaric acid
1:1
7
[39]
DES30
Training
Choline-Chloride
Oxalic acid
1:1
4
[40]
DES31
Training
Dodecanoic acid
Octanoic acid
1:3
11
[41]
DES32
Training
Dodecanoic acid
Decanoic acid
1:2
10
[41]
DES33
Training
Menthol
Octanoic acid
1:1
11
[41]
DES34
Training
Menthol
Decanoic acid
1:1
11
[41]
DES35
Training
Menthol
Salicylic acid
4:1
5
[42]
DES36
Test
Menthol
Camphor-10-sulfonic acid
5:1
5
[42]
DES37
Training
Menthol
Ethylene glycol
1:1
5
[42]
DES38
Test
Proline
Levulinic acid
1:2
11
[21]
DES39
Training
Proline
Lactic acid
1:1
10
[21]
Total
420
1 Number of data points.
The collected data points were divided randomly into training and test groups. The training dataset, consisting of 292 data (69%) and 28 DESs, was used for developing the model, while the test group, which consists of 128 data (31%) and 11 DESs, was later used to determine the accuracy of the proposed model.
2.2. The Model
One of the main objectives of this work was to propose a widely applicable method. For this purpose, not only the most up-to-date and complete dataset available was used for generality, but also, attention was given to the choice of input parameters. It was the goal of this work to propose a model to be applicable to even those DESs that have not yet been prepared in the laboratories. This is of great significance by considering that, similar to ILs, DESs are designer solvents. Accordingly, a huge number of DESs are possible, and numerous new DESs will appear in future research. Due to this, it would be most desirable to predict the property of a DES, and the feasibility of its utilization in a particular task, before actually undergoing any experimental expense and time. With this idea in mind, we attempted to develop a model in which the only required input data were the critical properties and acentric factor of the DESs, which can themselves be calculated by group contrition methods. In this way, the only information necessary is practically the molecular structures of the HBA and HBD.Therefore, the aforementioned properties were selected as the input parameters and various functionalities were investigated with the aid of genetic algorithm (GA) [43], as an optimization tool. Genetic algorithm is actually an approach, which is initiated by a set of random solutions, whereupon by iteratively applying a variety of stochastic operators to the solutions, they become successively evolved. This procedure is repeated until the final solutions satisfy a minimizing condition, which is defined by an operator as an objective function. The following objective function (OF) was utilized to optimize the parameters of the function, which relates the input parameters (the critical parameters and the acentric factor) to the target parameter (the speed of sound),In Equation (7), u and u are the experimental and calculated speed of sound, and N is the number of literature data. In this manner, different possible mathematical formulations were analyzed and tested to develop the generalized model for estimating the speeds of sound in DESs.
3. Results and Discussion
The modified Lydersen–Joback–Reid method [44,45] and the Lee–Kesler mixing rules [46] were used to calculate the acentric factor, critical temperature, critical pressure and critical volume of all 39 DESs [22,47]. The calculated values are presented in Table 2.
Table 2
Calculated values of critical properties and acentric factors for all of the investigated DESs in this study [22,47].
DES #
Tc (K)
Pc (bar)
Vc (cm3/mol)
ω
Mw (g/mol)
DES1
670.98
36.65
355.99
0.6660
118.44
DES2
651.23
39.77
308.96
0.7476
104.34
DES3
632.35
43.77
264.25
0.8293
90.25
DES4
657.28
31.24
364.48
0.9659
124.53
DES5
720.58
25.62
480.62
0.9994
157.57
DES6
778.21
22.07
589.83
1.0507
190.61
DES7
749.11
25.67
433.69
1.3146
147.05
DES8
618.43
41.08
270.56
0.8745
92.97
DES9
678.15
31.88
377.22
0.9080
126.01
DES10
733.31
26.60
478.88
0.9593
159.05
DES11
708.07
32.89
333.89
1.2232
115.49
DES12
701.16
37.82
380.25
0.5152
138.05
DES13
644.10
33.78
334.18
0.9375
114.02
DES14
721.27
33.15
384.56
0.9166
135.02
DES15
735.27
27.58
401.61
1.2862
136.53
DES16
668.50
44.09
281.96
0.7863
99.10
DES17
683.07
47.23
259.82
0.8755
94.59
DES18
701.24
38.94
356.12
0.6195
116.46
DES19
637.98
61.84
206.94
0.5794
75.08
DES20
659.71
92.43
146.46
0.5139
59.39
DES21
644.44
49.54
254.37
0.6509
86.58
DES22
602.00
40.99
259.67
0.9155
87.92
DES23
680.67
33.46
315.17
1.2254
107.94
DES24
742.22
27.03
424.87
1.2278
153.13
DES25
738.99
27.23
422.14
1.2163
153.13
DES26
620.93
38.44
284.11
0.9290
91.98
DES27
702.19
35.40
376.78
0.7301
123.95
DES28
689.82
37.16
335.84
0.8577
121.84
DES29
713.43
32.24
397.17
0.8782
135.87
DES30
676.24
40.44
303.06
0.8531
114.83
DES31
737.07
24.71
559.27
0.7649
158.24
DES32
773.88
21.55
656.40
0.8307
181.61
DES33
717.72
28.79
493.39
0.6173
150.24
DES34
739.17
26.26
549.11
0.6568
164.27
DES35
744.23
33.56
445.77
0.5733
152.64
DES36
777.87
31.66
504.89
0.5094
168.94
DES37
654.33
38.54
319.91
0.7510
109.17
DES38
745.61
42.88
333.41
0.7044
115.78
DES39
721.95
48.54
272.60
0.8243
102.61
By considering the acentric factors and critical properties of the DESs presented in Table 2 as the input parameters, and by investigating various combinations of input parameters, a generalized model for estimating the speeds of sound in DESs is obtained, as Equation (8):
where u, V and T are the speed of sound, critical molar volume, molecular weight and the desired temperature in m/s, cm3/mol, g/mol and kelvins, respectively, and ω is the acentric factor.In Figure 1, a comparison between the calculated speeds of sound of nine different DESs and the corresponding literature data is shown. It can be seen that the proposed model could successfully calculate the speeds of sound of the different-natured DESs, having different families of HBAs and HBDs. Within the temperature range of Figure 1, it was observed that at a constant pressure, the speed of sound had an almost linear relation to temperature in DESs. This linearity of the experimental data was followed reliably by the proposed model, having the constant slope of −2.012ω for each DES.
Figure 1
Comparison of the behavior of the speed of sound versus temperature for the proposed model and experimental data for nine randomly selected DESs.
Following Equation (8), and using the available literature data, the average absolute relative deviation percentages (AARD%) of the proposed model for the training, test, and overall datasets were calculated using Equation (9)According to the results presented in Table 3 for all three data sets, the calculated AARD% of all 420 data points was only 5.4%, which shows the accuracy and reliability of the proposed model. However, even more important was the AARD% of the test dataset, consisting of 128 data points, which was found to be 6.8%. Since all of the data in this dataset were unseen by the model (not used when developing the model), this shows the capability of the proposed model in predicting the speed of sound of new and upcoming DESs.
Table 3
The number of investigated data in the different datasets and the corresponding AARD% of the proposed model.
Data Set
Number of Investigated Data
AARD%
Training
292
4.8
Test
128
6.8
Overall
420
5.4
While AARD% is a good indication of the average errors, it does not give any information on the over- and under-estimations of the model. Therefore, for further investigations, the relative deviation percentages (RD%) were also calculated using Equation (10) and presented in Figure 2; Figure 3.
where, u and u express the calculated and experimental speeds of sound, respectively.
Figure 2
The relative deviation percent for the entire investigated data range for both the training and test datasets.
Figure 3
The distribution behavior of the relative deviation percent of the proposed model for the overall dataset.
In the calculation of RD%, both the test and training datasets were considered and the behavior of the relative deviation percent of these two datasets can be compared in Figure 2. Based on this figure, a rather normal behavior can be seen for both the test and training datasets, i.e., there are no systematic over- or under-estimations by the model for either of the two datasets. These observations not only provide the confidence of use of the model regarding any systematic errors, but also validate that apart from the correlative ability, the predictive use of the model is trustworthy. Furthermore, based on Figure 3, the distribution of the relative deviation percent is mostly concentrated close to zero. This further indicates the reliability of the proposed model. According to both Figure 2 and Figure 3, the maximum deviations of the proposed model with respect to experimental values were about ±20%. Such high error values occur for only a small number of the DESs, and again, are symmetric with respect to positive and negative deviations.In order to compare the accuracy of the proposed model to published literature, the ionic liquid models of Gardas and Coutinho [27], Hekayati and Esmaeilzadeh [28], Singh and Singh [29] and Haghbakhsh et al. [24], which were presented as Equations (1)–(6), were considered as the next closest systems to DESs. In order to use Equations (1)–(3), the surface tensions and the densities of all of the DESs needed to be calculated. For this purpose, the densities of the DESs under study were calculated using the method proposed by Haghbakhsh et al. [22], and the surface tensions were calculated with the aid of Equation (11), proposed by Curl and Pitzer [48].The results of the calculated AARD% values for all the aforementioned methods are given in Table 4. According to the calculated AARD% values, the proposed correlation was the most accurate model among the compared literature models. In general, the proposed model decreased the AARD% values by almost 40% in comparison to the other three models. Of course, it must be emphasized that there were no literature models available specifically for DESs. All of the four literature models compared in Table 4 were proposed for ionic liquids, and not DESs, and so, one does not expect high accuracies when they are used to predict the speeds of sound in DESs. Apart from Singh and Singh’s model, which had very poor results for DESs, the other three models showed acceptable results, even though they were developed for ionic liquids.
Table 4
Comparison of the values of AARD% for the proposed model and literature models for each of the investigated DESs.
DES
Proposed Model
Haghbakhsh et al.’s Model [24]
Hekayati and Esmaeilzadeh’s Model [28]
Gardas and Coutinho’s Model [27]
Singh and Singh’s Model [29]
DES1
13.9
14.5
8.6
15.0
4.9
DES2
7.5
16.6
3.6
9.0
11.8
DES3
1.3
17.6
2.6
1.3
31.6
DES4
5.8
2.4
8.1
5.2
33.0
DES5
1.8
3.3
6.6
7.1
36.5
DES6
0.9
8.3
5.0
9.3
43.8
DES7
5.4
9.0
4.7
14.2
84.5
DES8
0.7
68.8
2.8
1.9
27.2
DES9
1.1
1.4
3.6
1.1
28.0
DES10
2.8
7.0
2.1
2.9
32.1
DES11
4.6
7.6
0.9
6.8
76.5
DES12
1.9
2.7
3.6
3.6
4.4
DES13
2.5
1.8
4.8
1.2
26.1
DES14
8.9
22.0
11.9
13.7
54.0
DES15
1.3
9.0
2.1
10.9
77.4
DES16
1.6
1.3
4.6
2.8
37.4
DES17
12.5
7.6
16.7
20.1
82.7
DES18
2.8
2.0
4.9
1.0
15.8
DES19
1.1
1.4
0.8
3.8
29.6
DES20
2.4
1.5
1.8
6.2
79.5
DES21
12.6
25.2
10.4
15.5
7.8
DES22
4.7
10.4
2.6
7.9
13.8
DES23
8.1
5.2
4.5
4.1
66.2
DES24
1.0
4.7
4.6
3.6
55.2
DES25
21.4
25.5
25.7
19.5
19.1
DES26
2.5
11.6
8.8
4.0
36.6
DES27
4.5
4.6
2.7
1.3
18.9
DES28
5.9
3.6
3.7
4.2
30.9
DES29
8.7
1.3
4.0
4.5
26.4
DES30
3.9
6.8
2.6
2.7
39.3
DES31
3.3
15.4
31.7
25.5
36.0
DES32
7.1
6.6
27.3
25.3
39.1
DES33
7.7
13.1
29.0
19.5
22.7
DES34
2.1
11.6
26.1
18.9
23.5
DES35
9.2
3.1
24.3
17.8
36.8
DES36
2.6
5.7
19.7
13.3
26.7
DES37
21.2
2.6
28.0
20.8
53.8
DES38
6.0
2.2
12.8
13.7
56.8
DES39
4.8
2.6
7.8
13.1
75.8
Total
5.4
9.7
8.8
9.1
40.8
Furthermore, the model of Haghbakhsh et al., similar to the model proposed in this study, does not require surface tension and density data of the DESs in order to calculate the speed of sound, which can be considered as an advantage of these two models over the other three.In addition to the comparisons of AARD%, the behavior of the speed of sound versus the temperature of the proposed model and the literature models are shown on Figure 4 for DES4, DES5, DES6 and DES7, and on Figure 5 for DES8, DES9, DES10 and DES11. Based on the results shown on Figure 4; Figure 5, it is obvious that all the studied models did indeed estimate a negative slope for the speed of sound versus temperature. However, the model of Singh and Singh [29] shows slopes that are much steeper than the experimental data, while the slopes of the other four models do not differ greatly from one another.
Figure 4
Comparison of the behavior of the speed of sound versus the temperature for the proposed model and literature models for four members of the DES family having benzyl tributyl ammonium chloride as the HBA and the different HBDs of ethylene glycol (DES4) (A), diethylene glycol (DES5) (B), triethylene glycol (DES6) (C) and glycerol (DES7) (D). Experimental data o, proposed model ―, Haghbakhsh et al.’s model [24] ---, Gardas and Coutinho’s model [27] ― ―, Hekayati and Esmaeilzadeh’s model [28] · – · – and Singh and Singh’s model [29] ···.
Figure 5
Comparison of the behavior of the speed of sound versus the temperature for the proposed model and literature models for four members of the DES family having benzyl trimethyl ammonium chloride as the HBA and the different HBDs of ethylene glycol(DES8) (A), diethylene glycol (DES9) (B), triethylene glycol (DES10) (C) and glycerol (DES11) (D). Experimental data o, proposed model ―, Haghbakhsh et al.’s model [24] ---, Gardas and Coutinho’s model [27] ― ―, Hekayati and Esmaeilzadeh’s model [28] · – · – and Singh and Singh’s model [29] ···.
According to Figure 4 for the family of benzyl tributyl ammonium chloride as the HBA, it was concluded that the models of Hekayati and Esmaeilzadeh and Gardas and Coutinho had similar trends, and in most cases, they overestimate, while the model of Haghbakhsh et al. shows the least slopes and mostly underestimates the experimental data and the slopes. In Figure 5, which shows similar graphs, but for the family of benzyl trimethyl ammonium chloride as the HBA, again the models of Hekayati and Esmaeilzadeh and Gardas and Coutinho had almost the same slopes in most cases, and the model of Haghbakhsh et al. underestimates the data and the slopes in most cases, except for the case of ethylene glycol as the HBD, which has completely erroneous results.The behavior of the speed of sound versus the temperature of the other DESs not presented in Figure 4; Figure 5 are presented in Figures S1–S4 of the Supplementary file. Based on all these results, it is clear that the proposed model was generally the most precise model, yet it is a simple and user-friendly model that can be utilized to estimate the speed of sound of different DESs.
4. Conclusions
In this work, a general correlation was introduced for the first time for estimating the speed of sound in DESs. For this purpose, 28 different DESs were used for establishing a proper model, and 11 other DESs were used for testing the capability of the proposed model. The only input parameters of the proposed model were the molecular weight, critical molar volume and the acentric factor of the DES, where the latter two could themselves be calculated with an appropriate group contribution method. Therefore, this model was essentially needless of any input data, making it very widely applicable in comparison to other literature models. For example, the ionic liquid models of Gardas and Coutinho, Hekayati and Esmaeilzadeh and Singh and Singh all require density and surface tension properties as the input parameters for calculating the speed of sound, which can be a limitation for designer solvents. Since no generalized models were, as of yet, available for DESs, the model of this study was compared to literature models proposed for a close relative, the ionic liquids. The results indicated that the AARD% of the proposed model was only 5.4%, while those for the models of Gardas and Coutinho, Hekayati and Esmaeilzadeh, Singh and Singh and Haghbakhsh et al. were 9.1%, 8.8%, 40.8% and 9.7%, respectively. Furthermore, such a low value of AARD%, obtained for 39 different DES types having different HBAs and HBDs, indicates that the proposed model is general and can be applied for estimating the speed of sound of various types of DESs accurately.
Authors: Andrew P Abbott; Glen Capper; David L Davies; Raymond K Rasheed; Vasuki Tambyrajah Journal: Chem Commun (Camb) Date: 2003-01-07 Impact factor: 6.222
Authors: Daniel Carriazo; María Concepción Serrano; María Concepción Gutiérrez; María Luisa Ferrer; Francisco del Monte Journal: Chem Soc Rev Date: 2012-06-13 Impact factor: 54.564