Haghbakhsh 2019

Journal Pre-proof
Simple and global correlations for the densities of deep eutectic solvents
Reza Haghbakhsh, Roghayeh Bardool, Ali Bakhtyari, Ana Rita C. Duarte, Sona
Raeissi
PII: S0167-7322(19)32946-0
DOI: https://doi.org/10.1016/j.molliq.2019.111830
Reference: MOLLIQ 111830
To appear in: Journal of Molecular Liquids
Received Date: 24 May 2019

Revised Date: 25 September 2019
Accepted Date: 26 September 2019
Please cite this article as: R. Haghbakhsh, R. Bardool, A. Bakhtyari, A.R.C. Duarte, S. Raeissi, Simple
and global correlations for the densities of deep eutectic solvents, Journal of Molecular Liquids (2019),
doi: https://doi.org/10.1016/j.molliq.2019.111830.
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1 Simple and Global Correlations for the Densities of Deep Eutectic Solvents
4
5 Reza Haghbakhsh1,2, Roghayeh Bardool1, Ali Bakhtyari1, Ana Rita C. Duarte2
6 Sona Raeissi1*
7
8
1
9 School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave., Shiraz
10 71348-51154, Iran.
2
11 LAQV, REQUIMTE, Departamento de Química da Faculdade de Ciências e Tecnologia,
12 Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
13
14
15
16
17
*
Corresponding author at: School of Chemical and Petroleum Engineering, Shiraz University,
Mollasadra Ave., Shiraz 71348-51154, Iran.
Tel.: +98 71 36133707; Fax: +98 71 36474619
E-mail address: raeissi@shirazu.ac.ir (S. Raeissi).
1
1 Abstract:
2 Deep eutectic solvents (DESs) mostly comply with the principles of green chemistry. Therefore,
3 they are being widely investigated due to their great potential for a variety of applications in the
4 industries. However, it is necessary to have accurate (thermo)-physical property information on
5 any solvent before it can pave its way into the industries. Among such properties, density as a
6 function of temperature is one of the most important. In this study, a simple, accurate and global
7 correlation is proposed to estimate the densities of a large number of DESs of different nature.
8 The proposed model is a function of the critical temperature, critical volume and acentric factor
9 of the DES, as well as the temperature of the system. In this way, the model is capable of
10 accurately predicting the density of DESs without the need for any reference-temperature density
11 data, in contrast to most of the literature models that do require a reference data point. The
12 average relative error for 149 DESs of different natures was estimated to be 3.12% by the
13 proposed model, indicating its accuracy compared to previous models.
14
15 Keywords: DES, green solvent, volumetric property, specific volume, molar volume, physical
16 property.
2
1 1. Introduction:
2 The use of toxic solvents and chemicals in the industries has led to serious environmental
3 damages in recent years. This has drawn the attention of many environmental activists with the
4 move towards green chemistry at the forefront of their agenda. Therefore, there is a need in the
5 chemical and pharmaceutical industries to find the right alternatives for these solvents, which are
6 environmentally-friendly, and at the same time, possess the properties demanded of solvents [1-
7 3]. In this respect, Ionic liquids (ILs) were introduced as appropriate alternatives to common
8 chemical solvents [4,5]. Despite their many desirable properties, there are some restrictions on
9 the use of ILs, such as issues of synthesis and high costs. Furthermore, the low biodegradability
10 and toxicity of some ILs (which are in contradiction to the principles of green chemistry) have
11 also become a concern in the literature [6–9]. Recently, Abbott and coworkers introduced the
12 Deep Eutectic Solvents (DESs) with somewhat similar properties to ILs [10].
13 DESs are formed by combining a hydrogen bond acceptor (HBA), generally ammonium
14 or phosphonium, and a hydrogen bond donor (HBD) such as acids, amides, or the chlorides of
15 metals. Upon the combination of the HBA and HBD, the melting point of the mixture is greatly
16 decreased to values lower than the melting points of the pure individual components [11]. DESs
17 possess some of the desirable properties and characteristics of ILs, such as low volatility and
18 task-specific design, yet most DESs are biodegradable, and they are less expensive than ILs [12].
19 Another advantage of DESs with respect to ILs is their ease of preparation. DESs can actually be
20 prepared by the simple mixing of two components with one-another [13]. For these reasons, in
21 the recent years, the research on DESs has increased dramatically and they have been suggested
22 as candidates for use in various industries including separations [14], synthesis and catalysis
23 [10,15–17], pharmaceuticals [18], electrochemistry [19], nanotechnology [20], and the energy
3
1 and environment sector [21]. Examples include metal extraction [19], purification of biodiesel
2 [22], organic synthesis [23], drug solubilization [18], and CO2 capture [15-17,24-32].
3 Despite the many advances in DES research, there is still the need for further research to better
4 understand their properties and behavior. Physical properties such as melting temperatures,
5 density, surface tension, polarity, conductivity, and vapor pressure are still quite scarce. Density
6 is one of the most important and fundamental physical properties of a solvent which is required
7 in the design, operation, and optimization of any application. Generally, most of the DESs have
8 densities higher than those of water. The significant differences in densities of various DESs can
9 be due to the difference in the constituent molecules or their concentrations in the DES mixture.
10 The significance of volumetric properties demands the availability of simple and easy-to-use
11 models which are also global and applicable to various types of DESs. Up to now only a few
12 studies [33-35] have been carried out to propose models to estimate the densities of DESs.
13 Shahbaz et al. [33] used Rackett’s model [36] to estimate the densities of nine DESs. The
14 Rackett equation can be considered as a pioneering model which was proposed to estimate the
15 densities of liquids. The following is Rackett’s formulation for calculating a saturated liquid’s
16 molar volume at various temperatures [36].
2
 RT  1+1−T Tc 
7
17 VS =  c Zc
 Pc 
18 (1)
 PV 
19 Z c =  c c 
 RTc 
20 (2)
4
1 where Vc, Zc, Tc, and T are the critical volume, critical compressibility factor, critical temperature,
2 and the desired temperature, respectively. With the above formulation, Shahbaz et al. [33]
3 estimated densities for their nine investigated DESs, based on phosponium and ammonium salts,
4 within a temperature range of 298.15-368.1 K and reported good results.
5 In another study, Shahbaz et al. [34] proposed an atomic contribution method for the refractive
6 indices of 24 DESs based on ammonium and phosphonium salts. Then, by using the relation
7 between density and refractive index, they also estimated the densities of their investigated
8 DESs. So in essence, they did not propose a density model, but rather, they calculated the
9 densities only indirectly. Mjalli et al. [35] modified the model of Spencer and Danner [37] and
10 proposed a version that could estimate the densities of DESs. Equations 3 and 4 are the original
11 Rackett-type Spencer and Danner model [37],
2 2
 T  7  T  7
 1−  −  1− R 
 T  
12 V S = V SR Z 
RA
c   Tc 
13 (3)
1
 VSR Pc  1+ 1−TR  2 7
14 Z RA =    Tc 
 RT c 
15 (4)
16 and Equations 5 and 6 present the modified Spencer and Danner model by Mjalli et al. [35].
16 16
 T  7  T  7
 1−  −  1− R 
 T  
17 VS = V SR Z 
RA
c   Tc 
(5)
16
 5 TR  7
 + 
 24 T 
V P   c 
18 Z RA =  SR c  (6)
 RTc 
5
1 where Pc, Tc, T, VSR, and TR are the critical pressure, critical temperature, desired temperature,
2 reference experimental liquid molar volume, and the corresponding reference temperature,
3 respectively.
4 To the best of our knowledge, as of yet there no accurate, easy-to-use predictive models which
5 are applicable to various types of DESs. Furthermore, the limitation of the models of Mjalli et al.
6 [35] and Spencer and Danner [37] is that they are not able to estimate the densities of DESs
7 without requiring a reference density data point, and so, they are not predictive. Therefore, the
8 main purpose of this study is to propose a model for estimating the densities of a wide range of
9 DESs of different families, which does not require a reference density point, and at the same
10 time, is simple, global, and accurate.
11
12 2. Method
13 2.1. Data
14 A general databank including experimental values of densities and the corresponding
15 temperatures for 149 DESs of various nature have been collected from open literature. This data
16 bank includes 1239 data points and all of the data are at atmospheric pressure. Table 1 presents
17 the list of investigated DESs, and the HBA and HBD for each. In this study, the DESs were
18 distributed randomly into two sets: a training dataset to develop the model (approximately 70%
19 of the total data), and the test dataset (approximately 30% of the data) to evaluate the capability
20 and performance of the proposed model.
21 Table 1
6
1 2.2. Method
2 In the last few decades, the utilization of evolutionary algorithms has significantly
3 increased due to their high susceptibilities in linear and nonlinear systems [65]. In this study, we
4 have benefited from the advantages of genetic programming to present a simple relation for
5 obtaining the densities of various DESs at different temperatures.
6 Genetic programming (GP), first introduced by Cramer [66] and later expanded by Koza [67,68],
7 is considered as an evolutionary algorithm, which is based on the Darwinian evolutionary theory.
8 Due to its accuracy, GP has been widely used in the application of artificial intelligence to solve
9 engineering problems and to determine the structure of phenomena [69,70].
10 In the GP method, blocks that contain the input and target variables, as well as their associated
11 function, are first defined, and then the proper structure of the pattern and its coefficients are
12 determined. Choosing the right inputs is one of the most important issues that should be
13 considered in this method. This is particularly important if different input data are used, because
14 providing non-related input data reduces pattern accuracy and creates more complex patterns that
15 are more difficult to interpret.
16 In this work, GP is used as the method for obtaining a precise relation for estimating the densities
17 of DESs in terms of temperature. The input data are chosen to be critical temperature (Tc),
18 critical volume (Vc), and the acentric factor (ω) of the DES. Therefore, the goal is to find an
19 equation that interconnects them in a logical manner and optimizes the coefficients of the
20 equation to result in statistically minimal errors. For this purpose, the objective function
21 proposed for use in the optimization algorithms is as follows.
7
100 N ρi ,exp − ρi ,cal
1 OF = ∑ ρ
N i i ,exp
2 (7)
3 where, ρi,exp, ρi,cal, and N denote the experimental density, calculated density, and the number of
4 data points, respectively.
6 3. Results and discussion
7 The critical properties and acentric factors of the DESs were calculated using the Lydersen-
8 Joback-Reid Method [73,74], and the Lee-Kesler mixing rules as proposed by Knapp et al. [75].
9 The results are reported in Table 2. In order to test the consistency of the calculated critical
10 properties, the liquid densities of the investigated DESs were estimated by the generalized
11 correlation given by Valderrama and coworkers [73, 76]. The details of the calculation procedure
12 and the results are presented in Tables S1 and S2 of the Supplementary Data, respectively. The
13 results of the consistency test showed that the calculated critical properties are reliable.
14 Table 2
15 Using the critical properties calculated above (Table 2) as the input data, the final resulting
16 model for calculating DES density is,
17 ρ = A + BT
18 (8)
19 A = A 1T c 2 + A 2T c + A 3ω 0.2211 + A 4V c
20 (8.1)
8
1 A 1 = − 1.13 × 10 − 6
2 (8.2)
3 A 2 = 2.566 × 10 − 3 (8.3)
A 3 = 0.2376
4 (8.4)
5 A 4 = − 4.67 × 10 −4
6 (8.5)
7 B = − 4.64 × 10 − 4
8 (8.6)
9 In the equations above, Tc, Vc, ω, ρ and T are the critical temperature (K), critical volume
10 (cm3/mol), acentric factor, density (g/cm3) and temperature (K), respectively.
11 The list of all of the investigated experimental data and the corresponding estimated densities by
12 the proposed model are given in Table S2 of the Supplementary Data.
13 Table 3 presents the values of AARD%, as given by the following equation, for the training, test
14 and overall datasets, separately.
100 N ρ i ,exp − ρ i ,cal

15 AARD% = ∑ ρ
N i
(9)
i ,exp
16 As observed from this table, the values of AARD% are 2.82, 3.87 and 3.12% for the training,
17 test and overall datasets, respectively. Therefore, it is shown that the calculated results for both
18 the training and test datasets are in good agreement with the corresponding experimental values.
19 Also the overall AARD% value of 3.12% shows the reliability of this simple, general, and
20 straightforward correlation model.
9
1 While the majority of DESs in the literature are hydrophilic, due to the interesting potential
2 applications, hydrophobic DESs are also starting to emerge in the literature. Therefore, it is of
3 great interest to investigate if the model is suitable for this class of deep eutectic solvents.
4 Choline chloride + glycolic acid (1:1) and choline chloride + levulinic acid (1:1, 1:2, 1:3, 1:4 and
5 1:5), given in rows 65 and 66-73 of Table 1 are hydrophobic DESs [77]. The accuracy of density
6 estimations for such DESs is in the same range as the hydrophilic DESs. This confirms the wide
7 applicability of the proposed model to include hydrophobic DESs.
8 Table 3
9 Furthermore, Figures 1 and 2 are presented in order to have a more comprehensive investigation
10 of the results. These figures give insight into the behavior of the proposed model regarding
11 underestimations and overestimations of the model, using the statistical parameter of relative
12 deviation percent, RD%, as defined by Equation 10.
ρ calc . − ρ exp.
13 RD % = 100( )
ρ exp.
14 (10)
15 where, ρ exp. and ρcal. are the experimental density and calculated density, respectively. Figure 1
16 presents the behavior of relative deviation percent for the results of the model versus the
17 corresponding experimental densities for both the training and test datasets. As shown, both
18 datasets show normal behavior in the aspect of under- or overestimations. Figure 2 presents the
19 abundance of the investigated data having the corresponding relative deviation percent. As
20 observed, the percentage of data which have small relative deviation percentages (close to zero)
21 is quite high, further showing the reliable performance of the proposed model.
10
1 Figures 1 and 2
2 Figure 3 shows the ability of the proposed model to estimate the densities of 10 different
3 randomly selected DESs, with different types of HBAs and HBDs. The proposed model agrees
4 well with the experimental data for all of the different types of DESs.
5 Figure 3
6 The average absolute relative deviation, AARD%, as given by Equation 9, is given separately for
7 each DES in Table 4. The errors of the proposed model are also compared with those of previous
8 literature models in this table. For the total of 1239 experimental data points available, the
9 AARD% for the model proposed in this study, and the Rackett [36], Spencer and Danner [37]
10 and Mjalli et al. [35] models were 3.12%, 17.01%, 1.02%, and 2.25%, respectively. This
11 indicates that the suggested model is well capable of estimating the densities of DESs. It should
12 be emphasized that the models presented by Mjalli et al. [35] and Spencer and Danner [37] for
13 estimating the density of solvents, require experimental reference density data for each DES (a
14 reference DES density at a reference temperature), therefore, as they are fine-tuned by this input
15 data to the density of the particular DES under consideration, they are expected to be much more
16 accurate than the models which predict density with no density data as input. Furthermore, when
17 no density data is available for a DES, such methods are inapplicable. This can be seen from
18 Table 4, where the models of Mjalli et al. [35] and Spencer and Danner [37] could not estimate
19 the errors for the DESs which have just one density data point, because these models require a
20 reference point for calculation. Therefore, the model of this study has a greater capability and
21 applicability to estimate, and even predict, the densities of DESs.
22 Table 4
11
1 Finally, in order to have a more detailed comparison between the proposed model and the
2 literature models, the temperature-trends of the various models are compared with the
3 corresponding experimental trends in Figure 4. In this figure, four different DESs (Figures 4.A to
4 4.D), which were not investigated in Figure 3, were chosen randomly as representative DESs for
5 comparison. As can be seen, all four models observed, qualitatively, the general trend of
6 decreasing density with increasing temperature. However, it is obvious from the figure that the
7 model presented in this study estimates a far more accurate temperature-trend than some of the
8 literature models, while at the same time, it is also more global and does not require a reference
9 density data point.
10 Figure 4
11
12 4. Conclusions
13 In this study, using genetic programming (GP) and a large data bank of experimental data
14 from 149 DESs of various natures, a simple relation was proposed for estimating the densities of
15 DESs as a function of temperature. The input data required by the correlation are the critical
16 temperature, critical volume, and the acentric factor of the DES. According to the results, the
17 average absolute relative deviation for all of the data, consisting of both the training and testing
18 data sets is 3.12%, which is significantly lower than the literature model that does not require a
19 reference density data point as its input data (17.01% for the Rackett [36] model). This error is
20 close to the errors of the two density models that require a reference density data point as input
21 for calculations (1.02%, and 2.25%, for the Spencer and Danner [37] and the Mjalli et al. [35]
22 models, respectively). Furthermore, it is quite superior in estimating the temperature-trend of
12
1 DES densities, while some of the literature models fail to give a correct trend. Such accuracies in
2 density values and density trends are obtained while the proposed method is more global and
3 covers a wider range of DESs than some of the literature models, and at the same time, does not
4 require a reference DES density data point as its input parameter like some of the literature
5 models do. So in this respect, it is much more applicable than some literature models. In reality,
6 no experimental data on the DES are actually required since the input data of the proposed model
7 (the critical properties of the DESs), are themselves estimated by the suggested group
8 contribution methods and mixing rules, if not available.
10 Acknowledgments
11 The research leading to these results has received funding from the European Union Horizon
12 2020 Program under grant agreement number ERC-2016-CoG 725,034 (ERC Consolidator Grant
13 Des.solve). This work was also supported by the Associate Laboratory for Green Chemistry-
14 LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019). The
15 authors are also grateful to Shiraz University for supporting this research.
13
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18
1 Table 1. List of the investigated DESs in this study.
Molecular No. of
Molar Ratio
Abbreviation HBA HBD weight data Ref.
HBA:HBD
(g/mol) points
DES1 Acetyl choline chloride 1,2,4-triazole 1:1 125.36 7 38
DES2 Acetyl choline chloride D-Fructose 1:1 180.91 13 39
DES3 Acetyl choline chloride D-Glucose 1:1 180.91 13 39
DES4 Acetyl choline chloride D-Mannose 1:1 180.91 13 39
DES5 Acetyl choline chloride D-Ribose 1:1 165.90 13 39
DES6 Acetyl choline chloride D-Xylose 1:1 165.90 13 39
DES7 Acetyl choline chloride Guaiacol 1:3 138.52 4 40
DES10 Acetyl choline chloride Imidazole 1:1.5 113.51 7 38
DES11 Acetyl choline chloride Imidazole 1:2 105.94 7 38
DES12 Acetyl choline chloride Imidazole 1:3 96.47 7 38
DES13 Acetyl choline chloride Levulinic acid 1:1 148.89 11 41
DES14 Acetyl choline chloride Levulinic acid 1:3 132.50 4 27
DES15 Allyl triphenylphosphonium bromide Diethylene glycol 1:4 161.54 11 42
DES18 Allyl triphenylphosphonium bromide Triethylene glycol 1:4 196.79 11 42
DES21 Benzyl tripropyl ammonium Chloride Ethylene Glycol 1:3 114.02 11 43
DES22 Benzyl tripropyl ammonium Chloride Glycerol 1:3 136.53 11 43
DES23 Benzyl tripropyl ammonium Chloride Lactic Acid 1:3 135.02 11 43
DES24 Benzyl tripropyl ammonium Chloride Oxalic acid 1:1 179.95 12 43
DES25 Benzyl tripropyl ammonium Chloride Phenol 1:3 138.05 11 43
DES26 Betaine Lactic acid 1:2 99.10 10 44
DES27 Betaine Lactic acid 1:5 94.59 11 44
DES28 Betaine Levulinic acid 1:2 116.46 11 44
benzyldimethyl(2-hydroxyethyl) D-Fructose 1:1 197.94 39
DES29 13
ammonium chloride
benzyldimethyl(2-hydroxyethyl) D-Glucose 1:1 197.94 39
DES30 13
ammonium chloride
benzyldimethyl(2-hydroxyethyl) D-Mannose 1:1 197.94 39
DES31 13
ammonium chloride
benzyldimethyl(2-hydroxyethyl) D-Ribose 1:1 182.93 39
DES32 13
ammonium chloride
19
benzyldimethyl(2-hydroxyethyl) D-Xylose 1:1 182.93 39
DES33 13
ammonium chloride
DES34 Choline chloride 1,2-propanediol 1:3 91.98 4 26
DES35 Choline chloride 1,2-propanediol 1:4 88.80 4 26
DES36 Choline chloride 1,4-butanediol 1:3 102.50 4 26
DES37 Choline chloride 1,4-butanediol 1:4 100.02 5 26,45
DES40 Choline chloride Acetamide 1:2 85.92 1 46
DES41 Choline chloride Citric acid 1:1 165.87 2 45,46
DES42 Choline chloride D-Fructose 1:1 159.89 7 47
DES43 Choline chloride D-Fructose 1.5:1 155.83 7 47
DES44 Choline chloride D-Fructose 2:1 153.13 7 47
DES45 Choline chloride D-Fructose 2.5:1 151.20 7 47
DES46 Choline chloride D-Glucose 1:1 159.89 1 46
DES47 Choline chloride D-Glucose 2:1 153.13 6 48
DES48 Choline chloride D-Mannose 1:1 159.89 13 39
DES49 Choline chloride D-Ribose 1:1 144.88 13 39
DES50 Choline chloride D-Sorbitol 1:1 159.89 1 45
DES51 Choline chloride D-Sucrose 1:1 240.96 1 46
DES54 Choline chloride D-Xylose 1:1 144.88 13 39
DES55 Choline chloride D-Xylose 3:1 142.25 1 46
DES56 Choline chloride Ethylene glycol 1:1.78 89.96 15 49
DES57 Choline chloride Ethylene glycol 1:2 87.92 30 50-52
DES60 Choline chloride Glutaric acid 1:1 135.87 13 54
DES61 Choline chloride Glycerol 1:1 115.86 15 49
DES62 Choline chloride Glycerol 1:2 107.94 18 45,50,54
DES63 Choline chloride Glycerol 1:2.03 107.78 15 49
DES64 Choline chloride Glycerol 1:3 103.98 15 49
DES65 Choline chloride Glycolic acid 1:1 107.84 13 53
DES66 Choline chloride Guaiacol 1:3 128.01 4 40
DES69 Choline chloride Levulinic acid 1:1 127.87 11 41
DES70 Choline chloride Levulinic acid 1:2 123.95 13 45,53
20
DES74 Choline chloride Malonic acid 1:1 121.84 13 51, 53
DES75 Choline chloride Malonic acid 1:2 115.91 9 51
DES76 Choline chloride Nfurfuryl alcohol 1:3 108.48 4 16
DES79 Choline chloride O-Cresol 1:2 118.63 1 55
DES81 Choline chloride O-Cresol 1:3.91 114.55 1 55
DES84 Choline chloride Oxalic acid 1:1 114.83 1 45,53
DES85 Choline chloride P-Chlorophenol 1:2 132.24 9 56
DES86 Choline chloride P-Cresol 1:2 118.63 9 56
DES87 Choline chloride Phenol 1:2 109.28 6 55
DES92 Choline chloride p-Toluenesulfonic acid 1:1 158.38 1 45
DES93 Choline chloride Tartaric acid 1:1 144.85 1 46
DES94 Choline chloride Tartaric acid 2:1 143.11 1 45
DES95 Choline chloride Triethylene glycol 1:2 146.65 6 48
DES96 Choline chloride Triethylene glycol 1:4 148.06 1 45
DES97 Choline chloride Urea 1:2 86.58 21 45,57-60
DES98 Choline chloride Xylitol 1:1 145.88 1 45
DES99 Citric acid D-Glucose 1:1 186.14 1 46
DES100 D-Glucose Tartaric acid 1:1 165.12 1 46
DES101 Diethylamine hydrochloride Guaiacol 1:3 120.50 4 40
DES104 L-proline Lactic acid 1:1 102.61 11 44
DES105 L-proline Levulinic acid 1:2 115.78 11 44
DES106 Methyl triphenylphosphonium bromide Ethylene glycol 1:3 135.86 15 49
DES107 Methyl triphenylphosphonium bromide Ethylene glycol 1:4 121.10 22 7, 49
DES108 Methyl triphenylphosphonium bromide Ethylene glycol 1:5.25 109.29 15 49
DES109 Methyl triphenylphosphonium bromide Glycerol 1:1.75 188.50 7 7
DES110 Methyl triphenylphosphonium bromide Glycerol 1:2.03 179.59 15 49
DES111 Methyl triphenylphosphonium bromide Glycerol 1:3 158.38 15 49
DES112 Methyl triphenylphosphonium bromide Glycerol 1:4 145.12 15 49
DES113 N,N diethylenethanol ammonium chloride Ethylene glycol 1:2 92.60 10 52
21
DES114 N,N diethylenethanol ammonium chloride Ethylene glycol 1:2.03 92.29 15 49
DES117 N,N diethylenethanol ammonium chloride Glycerol 1:2 112.61 10 52
DES118 N,N diethylenethanol ammonium chloride Glycerol 1:2.03 112.41 15 49
DES121 Tetrabutylammonium chloride Arginine 6:1 263.10 6 42
DES124 Tetrabutylammonium chloride Aspartic acid 9:1 263.44 6 42
DES127 Tetrabutylammonium chloride Ethylene glycol 1:2 96.61 7 61
DES130 Tetrabutylammonium chloride Glutamic acid 8:1 263.39 6 42
DES133 Tetrabutylammonium chloride Glycerol 1:3 138.55 7 61
DES136 Tetrabutylammonium chloride Phenylacetic acid 1:2 146.00 11 62
DES137 Tetrabutylammonium chloride Propionic acid 1:2 142.03 11 62
DES138 Tetrabutylammonium chloride Triethylene glycol 1:1 214.04 7 61
DES142 Tetraethylammonium bromide Levulinic acid 1:1 163.14 11 41
DES143 Tetraethylammonium chloride Levulinic acid 1:1 140.91 11 41
DES144 Tetrahexylammonium bromide Ethylene glycol 1:2 186.24 11 63
DES145 Tetrahexylammonium bromide Glycerol 1:2 206.26 11 63
DES146 Trimethylglicine 2-Chloro benzoic acid 1:2 143.43 8 64
DES147 Trimethylglicine Benzoic acid 1:2 120.46 3 64
DES148 Trimethylglicine Mandelic acid 1:2 140.48 5 64
DES149 Trimethylglicine Phenylacetic acid 1:2 129.82 5 64
Total 1239
22
1 Table 2. The values of the calculated critical properties of the investigated DESs in this study
2 using the Lydersen-Joback-Reid group contribution Method [73,74] and the Lee-Kesler mixing
3 rules presented by Knapp et al. [75].
DES Vcm(cm3/mol) Tcm(K) Pcm(bar) ωm
DES1 368.17 682.86 38.480 0.4819

DES2 475.71 844.60 25.637 1.3743
DES3 471.46 839.54 25.931 1.3571
DES4 511.24 846.26 23.489 1.4097
DES5 471.25 790.74 25.834 1.2391
DES6 438.35 782.87 27.631 1.2284
DES7 364.05 714.77 40.291 0.5138
DES8 351.87 716.52 41.858 0.5089
DES9 343.83 717.76 42.959 0.5056
DES10 333.19 646.03 40.667 0.4497
DES11 310.37 641.14 43.550 0.4345
DES12 282.58 635.41 47.708 0.4154
DES13 449.90 718.54 31.228 0.6509
DES14 396.93 731.12 35.600 0.6828
DES15 435.97 756.24 30.004 0.9700
DES16 366.69 709.60 32.969 1.0068
DES17 346.97 696.23 34.033 1.0176
DES18 549.25 817.24 25.162 1.0247
DES19 489.58 776.85 26.338 1.0689
DES20 472.42 765.16 26.734 1.0819
DES21 334.18 644.10 33.781 0.9375
DES22 401.61 735.27 27.577 1.2862
DES23 384.56 721.27 33.151 0.9166
DES24 512.87 774.01 27.293 0.8586
DES25 380.25 701.16 37.822 0.5152
DES26 281.96 668.50 44.088 0.7863
DES27 259.82 683.07 47.230 0.8755
DES28 356.12 701.24 38.938 0.6195
DES29 528.21 906.55 22.857 1.5331
DES30 523.81 901.37 23.127 1.5158
DES31 564.98 908.27 21.009 1.5684
DES32 523.58 851.41 23.211 1.3978
DES33 489.47 843.35 24.724 1.3871
DES34 284.11 620.93 38.436 0.9290
DES35 274.52 621.24 39.620 0.9402
DES36 330.35 637.97 33.672 0.9505
DES37 323.38 639.21 34.288 0.9631
DES38 327.68 640.23 34.358 0.9293
DES39 320.56 641.64 35.040 0.9405
DES40 267.62 602.18 45.730 0.5419
DES41 439.76 835.65 29.364 1.2310
DES42 417.09 806.24 26.725 1.4613
DES43 421.75 767.47 26.960 1.3212
DES44 424.87 742.22 27.034 1.2278
DES45 427.10 724.47 27.049 1.1611
DES46 413.03 801.26 27.058 1.4440
DES47 422.14 738.99 27.233 1.2163
23
DES48 451.13 807.51 24.301 1.4966
DES49 412.82 752.84 26.956 1.3260
DES50 417.09 806.24 26.725 1.4613
DES51 580.99 1084.19 32.369 0.9631
DES52 580.99 1084.19 32.369 0.9631
DES53 495.26 795.37 29.234 0.8418
DES54 381.39 745.40 29.037 1.3153
DES55 410.62 682.12 27.934 1.0381
DES56 266.20 602.56 40.124 0.9094
DES57 259.67 602.00 40.993 0.9155
DES58 258.86 601.93 41.105 0.9162
DES59 246.67 600.98 42.868 0.9278
DES60 397.17 713.43 32.237 0.8782
DES61 345.17 664.90 31.424 1.1093
DES62 315.17 680.67 33.459 1.2254
DES63 314.58 681.00 33.502 1.2277
DES64 300.51 688.99 34.580 1.2835
DES65 302.41 641.53 38.243 0.8667
DES66 336.95 696.74 41.799 0.5572
DES67 330.37 702.17 43.168 0.5437
DES68 326.01 705.84 44.112 0.5346
DES69 392.41 681.50 32.890 0.7378
DES70 376.78 702.19 35.396 0.7301
DES71 369.04 712.77 36.736 0.7262
DES72 364.42 719.21 37.569 0.7239
DES73 361.35 723.53 38.138 0.7224
DES74 335.84 689.82 37.159 0.8577
DES75 303.14 715.10 42.138 0.8899
DES76 310.52 647.43 40.139 0.6935
DES77 302.40 649.45 41.414 0.6890
DES78 297.02 650.84 42.300 0.6860
DES79 337.08 668.78 39.940 0.5690
DES80 324.81 675.19 42.199 0.5450
DES81 318.05 678.84 43.530 0.5317
DES82 312.69 681.79 44.634 0.5210
DES83 309.25 683.72 45.364 0.5142
DES84 303.06 676.24 40.440 0.8531
DES85 333.76 687.25 41.620 0.5575
DES86 337.08 668.78 35.458 0.8887
DES87 297.58 651.15 44.498 0.5401
DES88 281.06 655.66 47.894 0.5125
DES89 271.30 658.52 50.117 0.4959
DES90 264.85 660.49 51.686 0.4848
DES91 260.28 661.93 52.851 0.4770
DES92 403.41 801.64 30.416 1.2518
DES93 387.19 782.84 30.449 1.2866
DES94 404.73 726.83 29.269 1.1114
DES95 441.15 702.43 27.308 0.9908
DES96 441.26 718.89 27.411 1.0368
DES97 254.37 644.44 49.536 0.6509
DES98 425.23 777.37 24.760 1.5011
DES99 412.23 1042.51 26.873 1.9140
DES100 360.82 987.25 27.998 1.9696
DES101 326.53 680.55 43.476 0.4659
24
DES102 322.08 689.18 44.564 0.4706
DES103 319.13 694.99 45.308 0.4737
DES104 272.60 721.95 48.538 0.8243
DES105 333.41 745.61 42.880 0.7044
DES106 335.88 708.03 37.459 0.9031
DES107 303.04 684.73 39.865 0.9210
DES108 277.50 666.50 42.132 0.9354
DES109 475.58 843.78 28.329 1.1582
DES110 453.85 831.16 28.884 1.1859
DES111 403.41 801.64 30.416 1.2518
DES112 372.85 783.62 31.558 1.2929
DES113 272.84 610.52 39.503 0.9195
DES114 271.89 610.36 39.620 0.9203
DES115 249.04 606.72 42.693 0.9378
DES116 235.09 604.66 44.874 0.9488
DES117 329.18 689.61 32.396 1.2295
DES118 328.45 689.85 32.445 1.2317
DES119 310.85 695.61 33.703 1.2865
DES120 300.01 699.38 34.546 1.3207
DES121 968.71 808.05 14.827 0.9025
DES122 978.50 804.52 14.647 0.8969
DES123 986.15 801.79 14.509 0.8925
DES124 964.99 785.64 14.575 0.8843
DES125 972.44 785.14 14.468 0.8819
DES126 978.66 784.73 14.380 0.8799
DES127 300.81 588.75 35.684 0.8377
DES128 355.99 637.85 31.094 0.9620
DES129 251.10 590.61 41.852 0.8997
DES130 964.90 789.04 14.610 0.8895
DES131 973.11 788.15 14.489 0.8863
DES132 979.84 787.43 14.391 0.8837
DES133 422.00 718.68 25.394 1.3077
DES134 387.39 716.67 27.193 1.3377
DES135 364.81 715.64 28.558 1.3576
DES136 590.63 773.43 24.934 0.7232
DES137 449.58 650.01 28.199 0.6578
DES138 723.20 756.55 18.008 0.9818
DES139 826.71 763.73 16.172 0.9405
DES140 880.25 767.65 15.394 0.9198
DES141 912.96 770.09 14.964 0.9074
DES142 469.92 687.77 28.859 0.6275
DES143 463.24 664.78 28.360 0.6212
DES144 530.40 710.19 22.824 1.0056
DES145 600.02 793.24 19.639 1.3155
DES146 385.56 745.01 38.678 0.5852
DES147 351.57 711.92 40.881 0.5609
DES148 402.30 780.73 35.488 0.8301
DES149 389.74 725.69 37.334 0.5804
1
25
1 Table 3. The values of AARD% of the proposed model for the different datasets considered in
2 this study.
Data set Number of investigated data Number of investigated DESs AARD%
Training 888 110 2.82
Test 351 39 3.87
Overall 1239 149 3.12
26
1 Table 4. The values of AARD% for the proposed model and literature models for each DES
2 separately, over the entire temperature range of the experimental data
AARD%
DES
Proposed model Rackett [36] Spencer and Danner [37] Mjalli et al. [35]
Training Data set
DES1 1.2 3.8 1.4 2.8
DES2 0.3 40.2 0.6 1.6
DES3 0.4 40.1 0.6 1.7
DES4 2.1 31.5 0.7 1.8
DES5 3.0 21.3 0.8 2
DES6 2.3 29.5 0.8 2
DES7 0.6 9.6 0.3 0.9
DES8 1.3 11.0 0.3 0.8
DES9 1.4 11.6 0.3 0.8
DES10 3.2 6.0 1.7 3.1
DES11 2.3 6.0 1.6 3.0
DES12 5.1 9.8 2.0 3.4
DES13 0.6 0.3 0.4 1.5
DES14 2.8 2.4 0.3 1.1
DES15 0.4 20.0 0.4 1.4
DES16 2.6 19.5 0.6 1.7
DES17 3.5 18.8 0.6 1.8
DES18 0.5 21.9 0.2 1.1
DES19 3.1 22.7 0.3 1.3
DES20 4.3 23.1 0.3 1.3
DES21 6.3 17.2 1.0 2.2
DES22 6.6 30.0 0.7 1.9
DES23 6.0 18.1 0.5 1.5
DES24 7.4 4.5 0.6 1.7
DES25 7.6 12.9 0.4 1.4
DES26 2.6 2.7 0.9 2.2
DES27 0.4 10.2 0.6 1.8
DES28 0.3 4.3 0.6 1.7
DES29 3.2 54.0 0.4 1.4
DES30 1.9 52.0 0.6 1.6
DES31 0.2 43.8 0.6 1.6
DES32 0.2 32.4 0.6 1.7
DES33 2.3 42.7 0.7 1.7
DES34 5.6 9.9 0.5 1.2
DES35 6.1 10.1 0.5 1.2
DES36 6.6 8.2 0.6 1.3
DES37 7.9 9.2 0.5 1.0
DES38 7.7 9.2 0.6 1.3
DES39 9.2 10.5 0.6 1.3
DES40 0.7 6.2 - -
DES41 4.2 26.2 1.5 1.7
DES42 5.7 36.1 1.2 2.6
DES43 6.2 24.9 1.3 2.8
DES44 6.4 18.6 1.4 2.9
DES45 6.7 14.3 1.5 3.0
DES46 0.9 45.7 - -
DES47 4.0 22.0 1.2 2.5
27
DES48 2.4 34.2 1.0 2.2
DES49 4.0 22.1 1.1 2.4
DES50 1.7 43.7 - -
DES51 5.1 28.5 - -
DES52 5.3 17.8 40.6 40.6
DES53 2.8 12.7 - -
DES54 2.7 32.1 1.1 2.4
DES55 7.0 10.4 - -
DES56 0.7 5.0 2.4 4.1
DES57 0.4 6.2 1.9 3.5
DES58 0.4 5.5 2.5 4.1
DES59 0.2 6.2 2.4 4.1
DES60 1.9 6.0 1.0 2.3
DES61 0.3 12.1 2.1 3.9
DES62 0.3 18.1 1.2 2.5
DES63 0.2 16.9 2.1 3.9
DES64 0.3 20.0 2.0 3.8
DES65 5.1 5.5 1.5 2.9
DES66 0.3 9.9 0.3 0.9
DES67 1.0 11.2 0.2 0.7
DES68 1.8 12.5 0.2 0.7
DES69 0.8 0.5 0.7 1.8
DES70 1.6 1.3 0.7 1.8
DES71 2.9 2.2 0.4 1.2
DES72 3.6 2.7 0.4 1.2
DES73 4.1 3.1 0.4 1.2
DES74 4.9 6.9 1.0 2.2
DES75 2.7 19.7 0.9 2.2
DES76 0.7 4.0 0.6 1.5
DES77 0.2 4.8 0.6 1.4
DES78 0.3 5.4 0.6 1.4
DES79 4.4 8.2 - -
DES80 6.0 10.0 - -
DES81 7.0 11.1 - -
DES82 7.8 12.0 - -
DES83 8.3 12.6 - -
DES84 5.8 10.7 - -
DES85 4.1 9.7 0.2 1.1
DES86 7.9 20.3 0.3 1.2
DES87 2.4 8.9 0.3 0.9
DES88 3.8 11.1 0.3 0.9
DES89 4.7 12.5 0.3 0.8
DES90 5.3 13.6 0.2 0.8
DES91 5.7 14.3 0.2 0.7
DES92 3.7 42.5 - -
DES93 0.9 31.9 - -
DES94 7.2 12.2 - -
DES95 1.3 12.0 0.9 2.3
DES96 3.0 17.4 - -
DES97 4.4 6.0 1.6 3.1
DES98 1.0 33.2 - -
DES99 4.0 102.0 - -
DES100 3.3 109.3 - -
DES101 3.8 8.7 0.2 0.8
28
DES102 4.2 10.7 0.2 0.8
DES103 4.6 12.2 0.2 0.7
DES104 2.5 8.6 0.6 1.7
DES105 1.6 2.6 0.4 1.4
DES106 4.4 19.5 1.2 2.8
DES107 3.6 19.2 1.2 2.8
DES108 3.0 18.1 1.4 3.1
DES109 2.9 31.0 0.5 1.7
DES110 3.9 29.7 0.7 2.1
Test data set
DES111 2.8 31.6 0.9 2.4
DES112 1.9 32.7 0.9 2.5
DES113 1.5 9.3 1.4 2.7
DES114 1.8 8.4 2.2 3.9
DES115 2.3 9.1 2.2 3.9
DES116 2.6 9.4 2.2 3.9
DES117 1.3 20.1 1.1 2.4
DES118 1.8 19.7 1.8 3.6
DES119 0.5 20.6 1.8 3.6
DES120 0.2 21.7 1.8 3.6
DES121 2.6 3.7 0.4 1.5
DES122 1.8 4.8 0.2 1.3
DES123 3.0 3.7 0.4 1.6
DES124 0.2 7.4 0.4 1.6
DES125 0.2 7.4 0.5 1.6
DES126 0.3 7.2 0.4 1.6
DES127 2.6 1.4 1.6 2.8
DES128 1.2 15.7 1.2 2.4
DES129 3.5 1.3 1.6 2.9
DES130 0.2 7.5 0.4 1.5
DES131 0.3 7.2 0.4 1.5
DES132 0.5 7.0 0.4 1.5
DES133 17.2 40.5 0.6 1.9
DES134 16.9 42.2 0.7 1.9
DES135 16.8 43.4 0.6 1.9
DES136 7.6 14.5 0.4 1.3
DES137 10.0 9.9 0.5 1.5
DES138 3.4 12.3 0.6 1.7
DES139 1.0 9.0 0.5 1.6
DES140 0.3 7.6 0.5 1.6
DES141 1.1 6.6 0.5 1.6
DES142 7.0 0.4 0.6 1.7
DES143 2.2 7.2 0.7 1.9
DES144 10.4 34.8 0.5 1.5
DES145 11.6 47.8 0.3 1.3
DES146 8.1 3.0 1.4 0.8
DES147 3.1 6.8 0.2 0.4
DES148 0.3 5.9 1.1 2.6
DES149 0.9 3.2 0.7 2.3
Total 3.12 17.01 1.02 2.25
29
1 List of figures
2
3 Figure 1
4 The relative deviations of the proposed model for the entire range of investigated densities for
5 both the training and test datasets.
6 Figure 2
7 The distribution of the relative deviations of the proposed model for the overall dataset.
8 Figure 3
9 Comparison of the density calculated by the proposed model to literature data for ten random
10 DESs at atmospheric pressure.
11 Figure 4
12 Comparison of the density trends with temperature for the proposed model and literature models
13 for four random DESs at atmospheric pressure. (A): DES 27: Betaine + Lactic acid (1:5), (B):
14 DES 57: Choline Chloride + Ethylene glycol (1:2), (C): DES 59: Choline Chloride + Ethylene
15 glycol (1:2.57), (D): DES 62: Choline Chloride + Glycerol, (1:2).
30
22
Training data set
Test data set
17
12
Relative deviation %
-3
-8
-13
0.850 0.950 1.050 1.150 1.250 1.350 1.450
Experimental density (g/cm3)
1
2 Figure 1. The relative deviations of the proposed model for the entire range of investigated
3 densities for both the training and test datasets.
31
250
200
150
Abundance
100
50
0
-20 -15 -10 -5 0 5 10 15 20
1 Relative deviation %
2 Figure 2. The distribution of the relative deviations of the proposed model for the overall dataset.
32
1.400
DES 2 DES 7 DES 18
DES 56 DES 64 Series15
1.350
DES 130 DES 143 DES 141
DES 139 Proposed model
1.300
1.250
Density (g/cm3)
1.200
1.150
1.100
1.050
1.000
0.950
0.900
280 300 320 340 360 380
Temperature (K)
1
2 Figure 3. Comparison of the density calculated by the proposed model to literature data for ten
3 random DESs at atmospheric pressure.
33
1
1.400
1.300
Desnity (g/cm3)
1.200
Exp data (DES 27)

1.100
Proposed model
Mjalli et al. model
Spencer and Danner model
Rackett model
1.000
290 300 310 320 330 340 350
2 Temperature (K)
3 (A)
1.250
1.200
1.150
Density (g/cm3)
1.100
1.050
Exp data (DES 57)
Proposed model
1.000 Mjalli et al. model
Rackett model
0.950
290 300 310 320 330 340 350 360 370
Temperature (K)
4
5 (B)
34
1.250
1.200
1.150
Density (g/cm3)
1.100
1.050
Exp data (DES 59)
Proposed model
1.000 Mjalli et al. model
Rackett model
0.950
290 310 330 350 370
Temperature (K)
1
2 (C)
1.550
Exp data (DES 62)
Proposed model
Mjalli et al. model
1.450 Spencer and Danner model
Rackett model
1.350
Density (g/cm3)
1.250
1.150
1.050
0.950
280 300 320 340 360
Temperature (K)
3
4 (D)
5
35
1 Figure 4. Comparison of the density trends with temperature for the proposed model and
2 literature models for four random DESs at atmospheric pressure. (A): DES 27: Betaine + Lactic
3 acid (1:5), (B): DES 57: Choline Chloride + Ethylene glycol (1:2), (C): DES 59: Choline
4 Chloride + Ethylene glycol (1:2.57), (D): DES 62: Choline Chloride
36
Highlights
• A general, simple and straightforward correlation has been proposed to estimate densities
of DESs based on a large data bank.
• The correlation is a simple function of critical temperature, critical volume and acentric
factor.
• The proposed model does not require a reference density data as input, as other models
often require.
• The AARD% of the proposed model is 3.12%

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To appear in: Journal of Molecular Liquids

Received Date: 24 May 2019

© 2019 Published by Elsevier B.V.

4 industries. However, it is necessary to have accurate (thermo)-physical property information on

13 proposed model, indicating its accuracy compared to previous models.

16 molar volume at various temperatures [36].

4 within a temperature range of 298.15-368.1 K and reported good results.

11 Rackett-type Spencer and Danner model [37],

10 time, is simple, global, and accurate.

14 A general databank including experimental values of densities and the corresponding

20 and performance of the proposed model.

5 obtaining the densities of various DESs at different temperatures.

7 is considered as an evolutionary algorithm, which is based on the Darwinian evolutionary theory.

9 engineering problems and to determine the structure of phenomena [69,70].

15 are more difficult to interpret.

21 proposed for use in the optimization algorithms is as follows.

4 data points, respectively.

6 3. Results and discussion

16 model for calculating DES density is,

10 (cm3/mol), acentric factor, density (g/cm3) and temperature (K), respectively.

12 the proposed model are given in Table S2 of the Supplementary Data.

14 and overall datasets, separately.

100 N ρ i ,exp − ρ i ,cal

20 straightforward correlation model.

7 applicability of the proposed model to include hydrophobic DESs.

12 deviation percent, RD%, as defined by Equation 10.

21 applicability to estimate, and even predict, the densities of DESs.

9 density data point.

22 models, respectively). Furthermore, it is quite superior in estimating the temperature-trend of

8 contribution methods and mixing rules, if not available.

14 LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019). The

DES Vcm(cm3/mol) Tcm(K) Pcm(bar) ωm

DES1 368.17 682.86 38.480 0.4819

Data set Number of investigated data Number of investigated DESs AARD%

Training 888 110 2.82

Test 351 39 3.87

Overall 1239 149 3.12

Exp data (DES 27)

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