Struct Chem (2013) 24:1841–1853 DOI 10.1007/s11224-013-0233-1
ORIGINAL RESEARCH
Enthalpy of solvation correlations for organic solutes and gases dissolved in dichloromethane and 1,4-dioxane Anastasia Wilson • Amy Tian • Nishu Dabadge • William E. Acree Jr. • Mikhail A. Varfolomeev • Ilnaz T. Rakipov • Svetlana M. Arkhipova • Michael H. Abraham
Received: 9 October 2012 / Accepted: 4 February 2013 / Published online: 15 March 2013 Ó Springer Science+Business Media New York 2013
Abstract Enthalpies of solution at infinite dilution of 53 organic solutes in dichloromethane and 10 organic solutes in 1,4-dioxane were measured using semi-adiabatic solution calorimeter. Enthalpies of solvation for 103 organic vapors and gaseous solutes in dichloromethane and for 116 gaseous compounds in 1,4-dioxane were determined from the experimental and literature data. It is shown that an Abraham solvation equation with five descriptors can be used to correlate the experimental solvation enthalpies within standard deviations of 2.07 and 2.29 kJ mol-1 for dichloromethane and 1,4-dioxane, respectively. The derived correlations provide very accurate mathematical descriptions of the measured enthalpy of solvation data at 298 K, which in the case of 1,4-dioxane span a range of 121 kJ mol-1. Division of the experimental values into a training set and a test set shows that there is no bias in predictions, and that the predictive capability of the correlations is better than
This study is honoring Maria Victoria Roux in occasion of her retirement.
Electronic supplementary material The online version of this article (doi:10.1007/s11224-013-0233-1) contains supplementary material, which is available to authorized users. A. Wilson A. Tian N. Dabadge W. E. Acree Jr. (&) Department of Chemistry, University of North Texas, 1155 Union Circle # 305070, Denton, TX 76203-5017, USA e-mail:
[email protected] M. A. Varfolomeev I. T. Rakipov S. M. Arkhipova Chemical Institute, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia M. H. Abraham Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
3.5 kJ mol-1. Enthalpies of hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons, etc.) with 1,4-dioxane were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the available literature data. Keywords Enthalpy of solvation Enthalpy of solution Enthalpy of transfer Mathematical correlation Solvation parameter model Enthalpy of hydrogen bond
Introduction This study continues development of Abraham model correlations for describing enthalpies of solvation, Dsolv H , of organic vapors and gases into water and organic solvents [1–12]. The correlation equation for Dsolv H takes the mathematical form of [1–12]: Dsolv H ¼ cl þ el E þ sl S þ al A þ bl B þ ll L ð1Þ
Dsolv H ¼ cv þ ev E þ sv S þ av A þ bv B þ vv V ð2Þ Each term on the right-hand side of Eqs. (1) and (2) represents a different type of solute–solvent interaction contribution to the dissolution process. The upper case quantities denote the properties of the dissolved solute (referred to as solute descriptors), which are defined as follows: E denotes the solute excess molar refraction that reflects the solute’s ability to interact with the surrounding solvent molecules through p- and lone-electron pairs, S is the solute dipolarity/-polarizability parameter, A and B are measures of the solute’s hydrogen bond acidity and basicity, V is the McGowan volume of the solute in units of
123
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Struct Chem (2013) 24:1841–1853
(dm3 mol-1)/100, and L is the logarithm of the solute’s gas phase dimensionless Ostwald partition coefficient into hexadecane at 298 K. The first four descriptors can be regarded as measures of the tendency of the given compound to undergo various solute–solvent interactions. The latter two descriptors, V and L, are both measures of solute size, and so will be measures of the solvent cavity term that will accommodate the dissolved solute. General dispersions are also related to solute size; thus both V and L will also describe the general solute–solvent interactions. The process coefficients in Eqs. (1) and (2) (c, e, s, a, b, v and l) represent solvent properties and are determined by regression analysis of the experimental Dsolv H data in accordance with the representative Abraham model correlation equation. Once the coefficients are known for a given solvent additional enthalpies of solvation can be calculated for more than 5000 organic and organometallic compounds for which the solute descriptors have been determined. Thus far, we have published Abraham model Dsolv H correlations for solutes dissolved into water [1]; and into four alkanes (hexane [2], heptane [3], hexadecane [3] and cyclohexane [3]); into two aromatic hydrocarbons (benzene [3] and toluene [4]); into three chloroalkanes (chloroform [5], carbon tetrachloride [4] and 1,2-dichloroethane [5]); into two ethers (dibutyl ether [6] and tetrahydrofuran [7]); into five primary alcohols (methanol [8], ethanol [8, 9], propan-1-ol [7], butan-1-ol [8], octan-1-ol [1], and 2-methylpropan-1-ol [9]), two secondary alcohols (propan2-ol [9] and butan-2-ol [9] and one tertiary alcohol (2-methylpropan-2-ol [10]); and into six other organic solvents (ethyl acetate [6], acetone [11], dimethyl sulfoxide [12], acetonitrile [11], propylene carbonate [12] and N,N-dimethylformamide [10]). In total Abraham model Dsolv H correlations have been reported for 26 different organic solvents. Mathematical expressions have also been developed for predicting enthalpies of solvation of organic vapors and gases into ionic liquid solvents based on both the ion-specific equation coefficient [13] and group contribution [14] versions of the Abraham model. Enthalpy of solvation data is important in that the numerical values provide valuable information regarding solute–solvent interactions in fluid solution. It can be used for analysis of solvent effect on different processes realized in the liquid state. In general, the enthalpy of solvation consists of two contributions: enthalpy of nonspecific solvation (van der Waals interaction term) and enthalpy of specific interaction. Dsolv H ¼ DsolvðnonspÞ H A=S þ DintðspÞ H A=S
ð3Þ
The last term in Eq. (3) presents enthalpy of donor– acceptor interactions including hydrogen bond formation. A proper separation of the enthalpy of solvation into
123
contributions from different types of intermolecular interactions will lead to further understanding of the thermodynamics of chemical reactions in a variety of solvents. Also data on Dsolv H can be used to extrapolate the gasto-condensed phase partition coefficient, K, measured at 298.15 K log Kðat TÞ log Kðat 298:15 KÞ Dsolv H ¼ ð1=T 1=298:15Þ 2:303R
ð4Þ
and water-to-organic solvent and organic solvent- toanother organic solvent partition coefficients, P, measured at 298.15 log Pðat TÞ log Pðat 298:15 KÞ Dtrans H ¼ ð1=T 1=298:15Þ 2:303R
ð5Þ
to slightly higher or lower temperatures. The enthalpy of transfer, Dtrans H , needed in Eq. (5) is defined as Dtrans H ¼ Dsolv;org H ¼ Dsolv;WðororgÞ H
ð6Þ
the difference in the enthalpy of solvation of the solute in the specified organic solvent minus its enthalpy of solvation in water (or second organic solvent). The above equations assume zero heat capacity changes. There are considerable published experimental partition coefficient data for solute transfer from water-to-water-immiscible (or partly miscible) organic solvents and for solute transfer between two partly miscible organic solvents. The latter organic biphasic systems [15–24] are used in separation processes for compounds that have very low aqueous solubilities or for compounds that are unstable in an aqueous solvent media. Most of the published partition coefficient data were determined at 298.15 K. Practical chemical separation processes and extractions often take place at temperatures other than 298.15, and there is considerable need to extrapolate measured log K and log P data to the temperature at which the chemical separation is to be performed. In the present work (which is Dedicated to Prof. Maria Victoria Roux in occasion of her retirement), enthalpy of solvation correlations for organic solutes and gases in dichloromethane and 1,4-dioxane were analyzed. These substances are widely used as solvents in industry, medicine, and science. Solution calorimetry was used to obtain experimental data necessary to determine the enthalpies of solvation of organic solutes in dichloromethane and 1,4-dioxane.
Experimental Dichloromethane (Acros Organics, mass fraction min. 99 %) was shaken with portions of concentrated H2SO4 until the acid layer remained colorless, then washed with water, aqueous
Struct Chem (2013) 24:1841–1853
NaHCO3, then water again. After it was pre-dried with CaCl2 and distilled from P2O5. 1,4-Dioxane (Aldrich, mass fraction min. 99 %) was distillated from LiAlH4 to remove possible traces of aldehydes, peroxides and water. Both solvents were stored in the dark without contact with air. Organic solutes used in the calorimetric measurements were supplied by Aldrich and Acros Organics (mass fraction min. 98 %). In some cases, they were dried and purified before use by standard methods [25]. The purity of chemicals was monitored by gas chromatographic analysis using a Konik 5000 B gas chromatograph; the content of the main substances in all solutes was no less than 0.995, and more than 0.999 in both dichloromethane and 1,4-dioxane. The residual water content was checked by Karl Fischer titration. It did not exceed 0.001 in the solvents and 0.003 in the solutes studied. Enthalpies of solution of organic solutes in dichloromethane and 1,4-dioxane were measured using a semi-adiabatic solution calorimeter, as previously reported [26, 27]. The calorimetric cell is a Dewar vessel charged with 110 mL of a solvent. The stirrer, sample holder, thermistor, and calibration heater (both in sealed glass tubes with silicone oil) are mounted on the Teflon lid of a Dewar vessel. The container for the weighted samples of solute consists of three brass parts with threaded connections and two Teflon film diaphragms. The Dewar vessel is placed into a thermostatted water bath with the temperature at 298.15 K. The detection limit of the apparatus is about 10 lK, which corresponds approximately to 0.005 J if the solvent is water. The reproducibility of the calorimetric data regarding the electrical calibrations only was found to be about 0.15 % for the range of calibration from 0.5 to 1.5 J. The apparatus was tested by the dissolution of potassium chloride and propan-1-ol in water. The averaged values obtained were Dsoln H KCl=H2 O = 17.41 ± 0.04 kJ mol-1 (T = 298.15 K, m = 0.02783 mol kg-1) and Dsoln H PrOH1=H2 O = -10.16 ± 0.03 kJ mol-1 (T = 298.15 K) which corresponds to the standard data [28, 29]. Each value of the solution enthalpy was reproduced several times. All experimental data obtained are presented in the supporting material (Tables SM1 and SM2). Solution enthalpies were measured at different concentrations of solutes. The absence of any concentration dependence of the solution enthalpies (at the concentrations used) confirms the performance of the experiments under infinite dilution conditions. Data obtained were statistically processed. Averaged values of solution enthalpies of organic solutes at infinite dilution in dichloromethane and 1,4-dioxane are presented in Tables 1 and 2.
1843
solvent S at temperature 298.15 K and pressure 0.1 MPa. The enthalpy of this process, Dsolv H , is equal to the molar enthalpy of solution of solute A in solvent S at infinite dilution less the solute’s standard molar enthalpy of A vaporization, Dvap H298 K , or standard molar enthalpy of A sublimation, Dsubl H298 K . A Liquid solutes: Dsolv H ¼ Dsoln H A=S Dvap H298 K
ð7Þ
A Crystalline solutes: Dsolv H ¼ Dsoln H A=S Dsubl H298 K
ð8Þ
Our search of the chemical literature found a large number of papers [30–98] that reported experimental partial molar enthalpies of solution of liquid and crystalline organic compounds in dichloromethane and 1,4-dioxane. This data were determined by either direct calorimetric methods or calculated based on the temperature dependence of measured infinite dilution activity coefficient data. Standard molar enthalpies of vaporization and sublimation of the organic solutes studied were taken from [27, 99–101]. A combination of the experimental and literature data lead to the determination of 103 enthalpies of solvation in dichloromethane and 116 enthalpies of solvation in 1,4-dioxane which were used for the regression analysis. Results and discussion We have assembled in Table 3 solvation enthalpy values for 103 organic vapors and gases dissolved in dichloromethane covering a reasonably wide range of compound type and descriptor value. Analysis of the experimental data yielded the following two Abraham model correlation equations: Dsolv HDCM ðkJ mol1 Þ ¼ 4:691ð0:505Þ
þ 4:948ð0:869ÞE 14:616ð0:900ÞS 3:187ð1:250ÞA 10:683ð1:209ÞB 7:920ð0:151ÞL ðwith N ¼ 103; SD ¼ 2:07; R2 ¼ 0:987; F ¼ 1205Þ ð9Þ Dsolv HDCM ðkJ mol1 Þ ¼ 4:540ð0:896Þ
3:986ð1:124ÞE 22:068ð1:312ÞS 6:411ð1:792ÞA
Datasets and solute descriptors Solvation can be defined as the isothermal transfer of solute A from the ideal gas state to an infinitely dilute solution in
12:589ð1:714ÞB 30:113ð0:833ÞV ðwith N ¼ 103; SD ¼ 2:95; R2 ¼ 0:974; F ¼ 583Þ ð10Þ
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Struct Chem (2013) 24:1841–1853
Table 1 Enthalpies of solution (kJ mol-1) at infinite dilution of different organic solutes in dichloromethane, measured at 298 K N
Solute
Dsoln H A=CH2 Cl2
1
Acetone
-3.48 ± 0.02
2
Acetophenone
-2.14 ± 0.20
Table 1 continued N
Solute
Dsoln H A=CH2 Cl2
49
Propyl benzoate
-1.21 ± 0.10
50
Pyrrole
51
Pyrrolidine
3.40 ± 0.01 -1.00 ± 0.02
3
Aniline
3.03 ± 0.09
52
Tetrahydrofuran
-3.67 ± 0.20
4
Benzene
0.53 ± 0.10
53
Triethylamine
-0.58 ± 0.09
5
Butan-2-ol
14.95 ± 0.16
6
Butanone
-3.10 ± 0.10
7
Butyl acetate
-1.89 ± 0.05
8
Butyl benzoate
-0.54 ± 0.11
9
Chlorobenzene
1.16 ± 0.10
10
2-Chlorophenol
4.49 ± 0.12
11
4-Chlorophenol
22.03 ± 0.06
12
n-Decane
10.94 ± 0.07 18.94 ± 0.21
13
Decan-1-ol
14
Di-n-butyl ether
15
Diethylamine
-1.59 ± 0.04
16 17
Diethyl ether N,N-Dimethylaniline
-2.48 ± 0.03 -1.17 ± 0.02
2.34 ± 0.11
18
1,2-Dimethylbenzene
19
Diphenyl
18.77 ± 0.13
0.68 ± 0.14
20
1,3-Diphenylbenzene
22.38 ± 0.18
21
1,4-Diphenylbenzene
30.20 ± 0.48
22
n-Dodecane
13.00 ± 0.22 -2.62 ± 0.11
23
Ethyl acetate
24
Ethylbenzene
25
Ethyl benzoate
-1.29 ± 0.10
26
Formamide
12.86 ± 0.03
27
n-Hexadecane
16.37 ± 0.12
28
Hexan-1-ol
15.70 ± 0.10
29
Heptan-2-one
-1.57 ± 0.06
1.21 ± 0.07
30
Methyl acetate
-2.71 ± 0.17
31 32
N-Methylaniline Methyl benzoate
2.31 ± 0.03 -1.38 ± 0.10
33
N-Methylformamide
34
Methyl 2-hydroxybenzoate
-0.16 ± 0.02
35
Methyl 4-hydroxybenzoate
33.10 ± 0.19
36
2-Methoxyphenol
3.58 ± 0.09
37
4-Methoxyphenol
26.59 ± 0.09
38
Methyl propionate
-2.89 ± 0.09
39
Naphthalene
18.49 ± 0.27 18.53 ± 0.09
6.67 ± 0.11
40
2-Nitrophenol
41
n-Nonane
42
Octan-1-ol
18.22 ± 0.13
43
Octan-2-one
-1.01 ± 0.22
9.58 ± 0.14
44
Pentan-1-ol
15.24 ± 0.12
45
Pentan-2-one
-2.75 ± 0.24
46 47
Phenyl benzoate Piperidine
21.95 ± 0.50 -1.20 ± 0.02
48
Propyl acetate
-2.24 ± 0.14
123
All regression analyses were performed using Version 17 and Version 20 of the SPSS statistical software. The two versions gave identical results. There is little intercorrelation between the descriptors in Eqs. (9) and (10). Both correlations provide a good statistical fit of the observed data with standard deviations of 2.07 and 2.95 kJ mol-1 for a dataset that covers an approximate range of 107 kJ mol-1. See Fig. 1 for a plot of the calculated values Dsolv HDCM based on Eq. (9) against the observed values. Equation (9) is the better equation statistically, and from a thermodynamic standpoint, Eq. (9) is the enthalpic derivative of the Abraham model’s gas-to-condensed phase transfer equation. Equation (10) might be more useful in some predictive applications in instances where the L— descriptor is not known. Equation (10) uses the McGowan volume, V—descriptor, which is easily calculable from the individual atomic sizes and numbers of bonds in the molecule [102]. To our knowledge, Eqs. (9) and (10) are the first expressions that allow a prediction of the enthalpy of solvation of gaseous solutes in dichloromethane. In order to assess the predictive ability of Eq. (9), we divided the 103 data points into a training set and a test set by allowing the SPSS software to randomly select half of the experimental points. The selected data points became the training set and the compounds that were left served as the test set. Analysis of the experimental data in the training set gave
Table 2 Enthalpies of solution (kJ mol-1) at infinite dilution of different organic solutes in 1,4-dioxane, measured at 298 K N
Solute
1
Acetophenone
2
n-Decane
Dsoln H A=C4 H8 O2 0.15 ± 0.05 11.65 ± 0.11
3
Decan-1-ol
13.39 ± 0.10
4
n-Dodecane
13.57 ± 0.19
5 6
n-Hexadecane Hexan-1-ol
17.83 ± 0.13 10.08 ± 0.12
7
Methyl acetate
8
N-Methylaniline
9
n-Octane
10
Octan-1-ol
0.61 ± 0.10 -2.04 ± 0.08 9.68 ± 0.11 11.73 ± 0.07
Struct Chem (2013) 24:1841–1853
1845
Table 3 Values of the gas-to-dichloromethane solvation enthalpy in kJ mol-1 at 298 K, Dsolv HDCM , for 103 solutes, together with the solute descriptors
Dsolv H
Ref
0.0680
11.20
[34]
0.1900
3.87
[34]
-1.200
0.1086
8.85
[34]
0.000
-0.978
0.2222
5.90
[34]
0.000
0.000
-0.723
0.1830
3.57
[34]
0.050
0.100
0.058
0.2809
-10.98
[34]
Solute
E
S
A
B
L
V
Helium
0.000
0.000
0.000
0.000
-1.741
Argon
0.000
0.000
0.000
0.000
-0.688
Hydrogen
0.000
0.000
0.000
0.000
Nitrogen
0.000
0.000
0.000
Oxygen
0.000
0.000
Carbon dioxide
0.000
0.280
Iodine
1.398
0.670
0.280
0.000
3.681
0.6250
-37.93
[35]
Pentane
0.000
0.000
0.000
0.000
2.162
0.8131
-20.04
[36]
Hexane
0.000
0.000
0.000
0.000
2.668
0.9540
-24.52
[36]
2-Methylpentane
0.000
0.000
0.000
0.000
2.503
0.9540
-22.92
[36]
Heptane Octane
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
3.173 3.677
1.0949 1.2358
-28.56 -32.69
[36] [36]
Nonane
0.000
0.000
0.000
0.000
4.182
1.3767
-37.02
This work
Decane
0.000
0.000
0.000
0.000
4.686
1.5176
-40.56
This work
Dodecane
0.000
0.000
0.000
0.000
5.696
1.7994
-49.10
This work
Hexadecane
0.000
0.000
0.000
0.000
7.714
2.3630
-65.03
This work
Cyclohexane
0.310
0.100
0.000
0.000
2.964
0.8454
-26.93
[36]
1-Octene
0.094
0.080
0.000
0.070
3.568
1.1928
-35.16
[37]
Dichloromethane
0.390
0.570
0.100
0.050
2.019
0.4943
-28.80
A Dvap H298 K
Trichloromethane
0.430
0.490
0.150
0.020
2.480
0.6167
-31.03
[36]
Tetrachloromethane
0.460
0.380
0.000
0.000
2.823
0.7391
-30.07
[36]
1-Chloropropane 1-Chlorobutane
0.216 0.210
0.400 0.400
0.000 0.000
0.100 0.100
2.202 2.722
0.6537 0.7946
-28.19 -32.75
[36] [36]
1,2-Dichloroethane
0.416
0.640
0.100
0.110
2.573
0.6352
-35.47
[38]
1,4-Dichlorobutane
0.413
0.950
0.000
0.170
3.501
0.9170
-47.44
[39]
1,6-Dichlorohexane
0.397
0.960
0.000
0.170
4.723
1.1988
-57.44
[40]
1,1,2,2-Tetrachloroethane
0.595
0.760
0.160
0.120
3.803
0.8800
-46.21
[41]
Diethyl ether
0.041
0.250
0.000
0.450
2.015
0.7309
-29.68
This work
Dibutyl ether
0.000
0.250
0.000
0.450
3.924
1.2945
-42.36
This work
Furan
0.369
0.510
0.000
0.130
1.913
0.5363
-28.16
[42]
Tetrahydrofuran
0.289
0.520
0.000
0.480
2.636
0.6223
-36.45
This work
Tetrahydropyran
0.275
0.470
0.000
0.550
3.057
0.7632
-39.65
[42]
1,4-Dioxane
0.329
0.750
0.000
0.640
2.892
0.6810
-43.77
[44]
Propanone
0.179
0.700
0.040
0.490
1.696
0.5470
-34.78
This work
Butanone
0.166
0.700
0.000
0.510
2.287
0.6879
-38.00
This work
Pentane-2-one
0.143
0.680
0.000
0.510
2.755
0.8288
-41.12
This work
Heptan-2-one Octanon-2-one
0.123 0.108
0.680 0.680
0.000 0.000
0.510 0.510
3.760 4.257
1.1106 1.2520
-49.08 -52.96
This work This work
Cyclohexanone
0.403
0.860
0.000
0.560
3.792
0.8610
-50.33
[45]
Butyl formate
0.121
0.630
0.000
0.380
2.958
0.8875
-43.17
[46]
Methyl acetate
0.142
0.640
0.000
0.450
1.911
0.6057
-35.01
This work
Ethyl acetate
0.106
0.620
0.000
0.450
2.314
0.7466
-37.62
This work
Propyl acetate
0.092
0.600
0.000
0.450
2.819
0.8875
-39.94
This work
Butyl acetate
0.071
0.600
0.000
0.450
3.353
1.0284
-44.19
This work
Methyl propionate
0.128
0.600
0.000
0.450
2.431
0.7466
-38.48
This work
Acetonitrile
0.237
0.900
0.070
0.320
1.739
0.4042
-35.85
[36]
Propionitrile
0.162
0.900
0.020
0.360
2.082
0.5451
-39.83
[36]
123
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Struct Chem (2013) 24:1841–1853
Table 3 continued Solute
E
S
A
B
L
V
Dsolv H
Ref
Butyronitrile
0.188
0.900
0.000
0.360
2.548
0.6860
-42.38
[36]
Diethylamine
0.154
0.300
0.080
0.690
2.395
0.7720
-32.89
This work
Triethylamine
0.101
0.150
0.000
0.790
3.040
1.0538
-35.98
This work
Nitromethane
0.313
0.950
0.060
0.310
1.892
0.4237
-37.46
[36]
Nitroethane
0.270
0.950
0.020
0.330
2.414
0.5646
-40.86
[36]
1-Nitropropane
0.242
0.950
0.000
0.310
2.894
0.7055
-45.32
[36]
Methanol
0.278
0.440
0.430
0.470
0.970
0.3082
-25.83
[36]
Ethanol
0.246
0.420
0.370
0.480
1.485
0.4491
-29.56
[36]
Propan-1-ol
0.236
0.420
0.370
0.480
2.031
0.5900
-34.09
[36]
Butan-1-ol
0.224
0.420
0.370
0.480
2.601
0.7309
-37.70
[36]
2-Butanol
0.217
0.360
0.330
0.560
2.338
0.7309
-34.75
This work
Pentan-1-ol
0.219
0.420
0.370
0.480
3.106
0.8718
-42.16
This work
Hexan-1-ol Octan-1-ol
0.210 0.199
0.420 0.420
0.370 0.370
0.480 0.480
3.610 4.619
1.0127 1.2945
-45.92 -53.47
This work This work
Decanol-1-ol
0.191
0.420
0.370
0.480
5.628
1.5763
-62.70
This work
Formamide
0.468
1.310
0.640
0.570
2.390
0.3650
-49.34
This work
N-Methylformamide
0.405
1.360
0.400
0.550
2.863
0.5059
-49.53
This work
N-Methylacetamide
0.350
1.280
0.400
0.710
2.974
0.6468
-54.25
[47]
N,N-Dimethylformamide
0.367
1.310
0.000
0.740
3.173
0.6468
-53.13
[47]
N,N-Dimethylacetamide
0.363
1.380
0.000
0.800
3.639
0.7877
-57.27
[47]
Diethyl carbonate
0.060
0.580
0.000
0.530
3.412
0.9462
-47.48
[48] This work
Benzene
0.610
0.520
0.000
0.140
2.786
0.7164
-33.32
Toluene
0.601
0.520
0.000
0.140
3.325
0.8573
-38.50
[49]
Ethylbenzene
0.613
0.510
0.000
0.150
3.778
0.9982
-41.19
This work
o-Xylene
0.663
0.560
0.000
0.160
3.939
0.9982
-42.22
This work
p-Xylene
0.613
0.520
0.000
0.160
3.839
0.9982
-42.82
[50]
Naphthalene
1.340
0.920
0.000
0.200
5.161
1.0854
-54.01
This work
Biphenyl 1,3-Diphenylbenzene
1.360 1.950
0.990 1.390
0.000 0.000
0.260 0.350
6.014 9.718
1.3242 1.9320
-63.03 -95.62
This work This work
1,4-Diphenylbenzene
1.950
1.430
0.000
0.350
9.814
1.9320
-90.20
This work
Chlorobenzene
0.718
0.650
0.000
0.070
3.657
0.8388
-39.84
This work
1-Chloronaphthalene
1.417
1.000
0.000
0.140
5.856
1.2078
-63.55
[51]
Aniline
0.955
0.960
0.260
0.410
3.934
0.8160
-50.25
This work
Pyrrole
0.613
0.730
0.410
0.290
2.865
0.5570
-41.80
This work
N-Methylpyrrole
0.559
0.790
0.000
0.310
2.923
0.7180
-43.37
[52] [53]
N-Methylpyrazole
0.521
0.970
0.000
0.550
3.215
0.6722
-42.49
N-Methylimidazole
0.589
0.950
0.000
0.800
3.805
0.6772
-58.53
[52]
N-Methylaniline
0.948
0.900
0.170
0.430
4.494
0.9570
-52.50
This work
N,N-Dimethylaniline
0.957
0.810
0.000
0.410
4.701
1.0980
-53.97
This work
Piperidine
0.422
0.460
0.100
0.690
3.304
0.8043
-40.60
This work
Pyridine
0.631
0.840
0.000
0.520
3.022
0.6753
-42.29
[54]
Acetophenone
0.818
1.010
0.000
0.480
4.501
1.0140
-57.54
This work
Methyl benzoate
0.733
0.850
0.000
0.460
4.704
1.0726
-56.99
This work
Ethyl benzoate Propyl benzoate
0.689 0.675
0.850 0.800
0.000 0.000
0.460 0.460
5.075 5.718
1.2135 1.3544
-60.09 -66.01
This work This work
Butyl benzoate
0.668
0.800
0.000
0.460
6.210
1.4953
-69.94
This work
Phenyl benzoate
1.330
1.420
0.000
0.470
7.537
1.5395
-77.05
This work
Methyl 2-hydroxybenzoate
0.850
0.820
0.010
0.480
4.961
1.1313
-56.36
This work
123
Struct Chem (2013) 24:1841–1853
1847
Table 3 continued Solute
E
S
A
B
L
Dsolv H
V
Ref
Methyl 4-hydroxybenzoate
0.900
1.370
0.690
0.450
5.716
1.1313
-65.46
This work
2-Methoxyphenol
0.837
0.910
0.220
0.520
4.449
0.9747
-57.82
This work
4-Methoxyphenol
0.900
1.170
0.570
0.480
4.773
0.9747
-63.21
This work
2-Chlorophenol
0.853
0.880
0.320
0.310
4.178
0.8976
-47.81
This work
4-Chlorophenol
0.915
1.080
0.670
0.200
4.775
0.8975
-55.07
This work
2-Nitrophenol
1.015
1.050
0.050
0.370
4.760
0.9493
-56.87
This work
Dimethyl sulfoxide
0.522
1.740
0.000
0.880
3.459
0.6130
-59.29
[55]
Tetrahydrothiophene
0.623
0.660
0.000
0.260
3.061
0.7271
-40.85
[54]
There is very little difference in the equation coefficients for the full dataset and the training dataset correlations, thus showing that the training set of compounds is a representative sample of the total dataset. The training set values for the 51 equation was then used to predict Dsolv HDCM compounds in the test set. For the predicted and experimental values, we find SD = 2.05, average absolute error (AAE) = 1.71 and average error (AE) = 0.09 kJ mol-1. There is therefore very little bias in using Eq. (11) with AE equal to 0.09 kJ mol-1. The training set and test set analyses were performed two more times with similar results. Training and test validations were also performed for Eq. (10). To conserve journal space, we give only the test set results. The derived training set correlation for Eq. (10) predicted the 51 experimental Dsolv HDCM values in the test set to within a SD = 3.44, AAE = 2.87 and AE = -0.25 kJ mol-1. Again, there is very little bias in the predictions using Eq. (10) with AE equal to -0.25 kJ mol-1. An error/uncertainty of ±2 kJ mol-1 in the enthalpy of solvation results in an error of slightly less than 0.04 log units in extrapolating a log K value measured at 298.15 K to a temperature of 313.15 K. This level of predictive error will be sufficient for most practical chemical and engineering applications. Equation (9) can be used for analysis of solute–solvent intermolecular interactions in dichloromethane media. Such correlations were obtained earlier for other chlorinated solvents: chloroform [5], carbon tetrachloride [4],
Fig. 1 Comparison of the experimental enthalpies of solvation of solutes dissolved in dichloromethane and predicted values based on Eq. (9) Dsolv HDCM ðkJ mol1 Þ ¼ 5:163ð0:857Þ þ 5:358ð1:575ÞE 13:958ð1:520ÞS 4:493ð2:033ÞA 10:491ð2:037ÞB 8:096ð0:331ÞL with N ¼ 52; SD ¼ 2:24; R2 ¼ 0:984; F ¼ 469
ð11Þ
Table 4 Regression coefficients (solvent parameters) of Eq. (1) for chlorinated solvents Solute
c
e
s
a
b
l
Dichloromethanea
-4.691
4.948
-14.616
-3.187
-10.683
-7.920
Chloroformb
-6.516
8.628
-13.956
-2.712
-17.334
-8.739
Carbon tetrachloridec 1,2-Dichloroethaneb
-6.402 -2.345
3.583 5.555
-4.803 -18.328
-0.877 -9.599
-7.015 -7.101
-8.898 -8.045
a
Data was determined in this work
b
Data was taken from the work of Mintz et al. [5]
c
Data was taken from the work of Mintz et al. [4]
123
1848
Struct Chem (2013) 24:1841–1853
Table 5 Values of the gas-to-1,4-dioxane solvation enthalpy in kJ mol-1 at 298 K, Dsolv HDiox , for 116 solutes, together with the solute descriptors
Solute
E
S
A
B
L
V
Dsolv H
Ref
Helium
0.000
0.000
0.000
0.000
-1.741
0.0680
12.42
[56]
Neon
0.000
0.000
0.000
0.000
-1.575
0.0850
9.72
[56]
Argon
0.000
0.000
0.000
0.000
-0.688
0.1900
1.43
[56]
Krypton
0.000
0.000
0.000
0.000
-0.211
0.2460
-1.56
[56]
Xenon
0.000
0.000
0.000
0.000
0.378
0.3290
-6.62
[56]
Hydrogen
0.000
0.000
0.000
0.000
-1.200
0.1086
5.69
[56]
Deuterium
0.000
0.000
0.000
0.000
-1.200
0.1100
6.21
[56]
Nitrogen
0.000
0.000
0.000
0.000
-0.978
0.2222
4.93
[56]
Carbon dioxide Carbon tetrafluoride Sulfur hexaflouride
0.000
0.280
0.050
0.100
0.058
0.2809
-16.81
[56]
-0.580 -0.600
-0.260 -0.200
0.000 0.000
0.000 0.000
-0.817 -0.120
0.3203 0.4643
2.88 -2.09
[56] [56]
Methane
0.000
0.000
0.000
0.000
-0.323
0.2495
-1.14
[56]
Ethane
0.000
0.000
0.000
0.000
0.492
0.3904
-8.32
[56]
Hexane
0.000
0.000
0.000
0.000
2.668
0.9540
-24.01
[30]
Heptane
0.000
0.000
0.000
0.000
3.173
1.0949
-27.28
[57]
Octane
0.000
0.000
0.000
0.000
3.677
1.2358
-31.92
This work
Decane
0.000
0.000
0.000
0.000
4.686
1.5176
-40.56
This work
Undecane
0.000
0.000
0.000
0.000
5.191
1.6585
-43.50
[58, 59]
Dodecane
0.000
0.000
0.000
0.000
5.696
1.7994
-48.79
This work
Tridecane
0.000
0.000
0.000
0.000
6.200
1.9403
-51.07
[59]
Tetradecane
0.000
0.000
0.000
0.000
6.705
2.0810
-56.67
[30]
Pentadecane
0.000
0.000
0.000
0.000
7.209
2.2221
-59.67
[30]
Hexadecane
0.000
0.000
0.000
0.000
7.714
2.3630
-63.70
This work
Cyclopentane
0.263
0.100
0.000
0.000
2.477
0.7045
-21.97
[60]
Cyclohexane Ethene
0.305 0.107
0.100 0.100
0.000 0.000
0.000 0.070
2.964 0.289
0.8454 0.3474
-26.31 -9.04
[61] [56]
Dichloromethane
0.390
0.570
0.100
0.050
2.019
0.4943
-31.10
[62]
Chloroform
0.425
0.490
0.150
0.020
2.480
0.6167
-35.91
[61, 63]
1-Chlorobutane
0.210
0.400
0.000
0.100
2.722
0.7946
-31.50
[64]
1,1,1-Trichloroethane
0.369
0.410
0.000
0.090
2.733
0.7576
-32.89
[65]
1,1,2,2-Tetrachloroethane
0.595
0.760
0.160
0.120
3.803
0.8800
-54.76
[66]
Trichloroethylene
0.524
0.370
0.080
0.030
2.997
0.7146
-36.13
[31]
Tetrachloroethylene
0.639
0.440
0.000
0.000
3.584
0.8370
-37.90
[31]
Halothane
0.102
0.390
0.130
0.050
1.982
0.7409
-37.36
[67]
1,4-Dioxane
0.329
0.750
0.000
0.640
2.892
0.6810
-38.60
A Dvap H298K
1,2-Dimethoxyethane 15 Crown 5
0.116 0.411
0.670 1.200
0.000 0.000
0.680 1.750
2.654 6.779
0.7896 1.7025
-35.80 -78.40
[68] [69]
Acetone
0.179
0.700
0.040
0.490
1.696
0.5470
-30.28
[63]
Butan-2-one
0.166
0.700
0.000
0.510
2.287
0.6879
-33.32
[68]
Pentane-2-one
0.143
0.680
0.000
0.510
2.755
0.8288
-36.68
[31]
Nonan-2-one
0.119
0.680
0.000
0.510
4.731
1.3924
-52.59
[31]
Methyl acetate
0.142
0.640
0.000
0.450
1.911
0.6057
-31.55
This work
Ethyl acetate
0.106
0.620
0.000
0.450
2.314
0.7466
-35.10
[61]
Dimethyl carbonate
0.142
0.540
0.000
0.570
2.328
0.6644
-37.40
[70]
Diethyl carbonate
0.060
0.580
0.000
0.530
3.412
0.9462
-42.41
[70]
Diethylamine
0.154
0.300
0.080
0.690
2.395
0.7720
-29.28
[71]
Dipropylamine
0.124
0.300
0.080
0.690
3.351
1.0538
-37.42
[71]
123
Struct Chem (2013) 24:1841–1853
1849
Table 5 continued Solute
E
S
A
B
L
V
Dsolv H
Ref
Nitroethane
0.270
0.950
0.020
0.330
2.414
0.5646
-40.25
[72]
Methanol
0.278
0.440
0.430
0.470
0.970
0.3082
-32.04
[73]
Ethanol
0.246
0.420
0.370
0.480
1.485
0.4491
-35.42
[73]
Propan-1-ol
0.236
0.420
0.370
0.480
2.031
0.5900
-40.40
[74]
Butan-1-ol
0.224
0.420
0.370
0.480
2.601
0.7309
-45.10
[64]
Butan-2-ol
0.217
0.360
0.330
0.560
2.338
0.7309
-42.20
[75]
2-Methylpropan-1-ol
0.217
0.390
0.370
0.480
2.413
0.7309
-43.14
[75]
2-Methylpropan-2-ol
0.180
0.300
0.310
0.600
1.963
0.7309
-39.00
[75]
3-Methylbutan-1-ol
0.192
0.390
0.370
0.480
3.011
0.8718
-45.19
[76]
2-Methylbutan-2-ol
0.194
0.300
0.310
0.600
2.630
0.8718
-42.47
[76]
Cyclopentanol
0.427
0.540
0.320
0.560
3.241
0.7630
-49.29
[77]
Hexan-1-ol
0.210
0.420
0.370
0.480
3.610
1.0127
-51.62
This work
Octan-1-ol Decan-1-ol
0.199 0.191
0.420 0.420
0.370 0.370
0.480 0.480
4.619 5.628
1.2945 1.5763
-59.88 -62.70
This work This work
Ethan-1,2-diol
0.404
0.900
0.580
0.780
2.661
0.5078
-57.54
[74]
2-Methoxyethanol
0.269
0.500
0.300
0.840
2.490
0.6487
-42.19
[78]
2-Ethoxyethanol
0.237
0.550
0.290
0.820
2.719
0.7896
-43.89
[79]
1-Adamantanol
0.940
0.900
0.310
0.660
5.634
1.2505
-64.17
[76, 80]
Acetic acid
0.265
0.640
0.620
0.440
1.816
0.4648
-52.69
[81]
Propanoic acid
0.233
0.650
0.610
0.440
2.276
0.6057
-56.65
[82]
Butanoic acid
0.210
0.640
0.610
0.450
2.750
0.7466
-57.27
[83]
Octanoic acid
0.150
0.640
0.620
0.450
4.680
1.3102
-78.86
[83]
Adipic acid
0.350
1.210
1.130
0.760
4.474
1.1028
-108.80
[84]
Benzene
0.610
0.520
0.000
0.140
2.786
0.7176
-33.64
[61, 85, 89]
Toluene
0.601
0.520
0.000
0.140
3.325
0.8573
-37.33
[85]
4-Isopropyltoluene
0.607
0.490
0.000
0.190
4.590
1.2800
-47.21
[86]
1,3-Dimethylbenzene
0.623
0.520
0.000
0.160
3.839
0.9982
-41.47
[87]
1,4-Dimethylbenzene Biphenyl
0.613 1.360
0.520 0.990
0.000 0.000
0.160 0.260
3.839 6.014
0.9982 1.3242
-41.18 -64.74
[87] [88]
Naphthalene
1.340
0.920
0.000
0.200
5.161
1.0854
-55.60
[89, 98]
1-Methylnaphthalene
1.337
0.940
0.000
0.220
5.802
1.2263
-56.98
[90]
Anthracene
2.290
1.340
0.000
0.280
7.568
1.4544
-77.40
[89]
9-Methylanthracene
2.250
1.270
0.000
0.300
8.438
1.5953
-85.50
[91]
9,10-Dimethylanthracene
2.250
1.250
0.000
0.280
9.283
1.7362
-89.90
[91]
Phenanthrene
2.055
1.290
0.000
0.290
7.632
1.4544
-77.10
[89]
1,2-Diphenylbenzene
1.950
1.350
0.000
0.380
9.433
1.9320
-87.84
[88]
1,3-Diphenylbenzene
1.950
1.390
0.000
0.350
9.718
1.9320
-98.06
[88]
1,4-Diphenylbenzene
1.950
1.430
0.000
0.350
9.814
1.9320
-100.89
[88]
Chlorobenzene
0.718
0.650
0.000
0.070
3.657
0.8388
-41.43
[92]
Fluorobenzene
0.477
0.570
0.000
0.100
2.788
0.7341
-35.42
[32]
Bromobenzene
0.882
0.730
0.000
0.090
4.041
0.8914
-45.51
[32]
Iodobenzene
1.188
0.820
0.000
0.120
4.502
0.9746
-48.11
[32]
1,2-Dichlorobenzene
0.872
0.780
0.000
0.040
4.518
0.9612
-50.48
[32]
1,4-Dichlorobenzene 1-Chloronaphthalene
0.825 1.417
0.750 1.000
0.000 0.000
0.020 0.140
4.435 5.856
0.9612 1.2078
-48.51 -61.83
[32] [32]
1-Nitronaphthalene
1.600
1.590
0.000
0.290
7.056
1.2596
-76.30
[33]
Aniline
0.955
0.960
0.260
0.410
3.934
0.8160
-57.50
[31]
N-Methylaniline
0.948
0.900
0.170
0.430
4.494
0.9570
-57.34
This work
123
1850
Struct Chem (2013) 24:1841–1853
Table 5 continued Solute
E
S
A
B
L
Dsolv H
V
Ref
Pyrrole
0.613
0.730
0.410
0.290
2.865
0.5774
-50.23
[85]
N-Methylimidazole
0.589
0.950
0.000
0.800
3.805
0.6772
-52.56
[53]
N-Methylpyrrole
0.559
0.790
0.000
0.310
2.923
0.7180
-40.92
[53, 85]
N-Methylpyrazole
0.521
0.970
0.000
0.550
3.215
0.6772
-39.91
[53]
Pyridine
0.631
0.840
0.000
0.520
3.022
0.6753
-39.84
[93]
Piperidine
0.422
0.460
0.100
0.690
3.304
0.8043
-36.54
[31]
Phenol
0.805
0.890
0.600
0.300
3.766
0.7751
-66.10
[64]
Anisole
0.710
0.750
0.000
0.290
3.890
0.9160
-46.65
[64]
4-Fluorophenol
0.670
0.970
0.630
0.230
3.844
0.7928
-69.67
[64]
4-Fluoroanisole
0.571
0.740
0.000
0.280
3.904
0.9337
-49.62
[64]
2-Aminophenol
1.110
1.310
0.610
0.600
4.975
0.8749
-83.40
[94]
3-Aminophenol
1.130
1.640
0.740
0.570
5.304
0.8749
-97.70
[94]
4-Aminophenol Acetophenone
1.150 0.818
1.470 1.010
0.660 0.000
0.730 0.480
5.200 4.501
0.8749 1.0140
-92.10 -55.15
[94] This work
Benzophenone
1.447
1.500
0.000
0.500
6.852
1.4810
-76.20
[33]
Benzaldehyde
0.820
1.000
0.000
0.390
4.008
0.8730
-50.30
[33]
a-Pinene
0.446
0.140
0.000
0.120
4.308
1.2574
-37.93
[86]
b-Pinene
0.530
0.240
0.000
0.190
4.394
1.2574
-39.98
[86]
2-Methylfuran
0.368
0.510
0.000
0.140
2.465
0.6772
-33.20
[95]
Water
0.000
0.450
0.820
0.350
0.260
0.1673
-37.92
[96]
Ferrocene
1.350
0.850
0.000
0.200
5.622
1.1210
-58.10
[97]
and 1,2-dichloroethane [5]. Table 4 contains parameters of these correlations together with dichloromethane data. The correlations allow us to perform a term by term analysis. It is evident from Table 4 that the l coefficient is the same for all solvents. At the same time, chloroform has the highest value of the coefficient b, hence, it is the hydrogen bond acid among the studied solvents. Dichloromethane is a weaker hydrogen bond acid. The large value of parameter b for carbon tetrachloride (Table 4) may look surprising, but previously it has been shown [102, 103] that carbon tetrachloride can act as an electron acceptor in donor– acceptor interactions with bases. That is, carbon tetrachloride is a (weak) Lewis acid. 1,2-Dichloroethane is the strongest hydrogen bond base among the studied solvents as shown by the value of the parameter a. Other solvents have very weak hydrogen bond acceptor properties, which can be neglected. In Table 5, values of the enthalpies of solvation of 116 gaseous solutes in 1,4-dioxane are collected. Preliminary analysis of the experimental Dsolv HDiox data yielded correlation equations having very small b coefficients. This would be expected in the case of Eq. (1) from the molecular structure considerations because 1,4-dioxane does not have any acidic hydrogen. The b-coefficient was set equal to zero, and the final regression analyses performed to give:
123
Dsolv HDiox ðkJ mol1 Þ ¼ 3:845ð0:443Þ þ 5:825ð0:798ÞE
19:873ð0:984ÞS 35:905ð1:066ÞA 7:842ð0:132ÞL ðwith N ¼ 116; SD ¼ 2:29; R2 ¼ 0:991; F ¼ 3174Þ ð12Þ Dsolv HDiox ðkJ mol1 Þ ¼ 5:087ð0:715Þ
1:871ð0:984ÞE 28:459ð1:228ÞS 38:323ð1:401ÞA 29:845ð0:665ÞV ðwith N ¼ 116; SD ¼ 3:01; R2 ¼ 0:985; F ¼ 1839Þ ð13Þ Both Eqs. (12) and (13) are statistically very good with standard deviations of 2.29 and 3.01 kJ mol-1 for a dataset that covers an approximate range of 121.0 kJ mol-1. Both equations were validated through training and test set analyses. Figure 2 compares the calculated values of Dsolv HDiox based on Eq. (12) against the observed data. To our knowledge, there has been no previous attempt to
Struct Chem (2013) 24:1841–1853
1851 Table 6 Regression coefficients (solvent parameters) of Eq. (1) for three ether solvents Solute 1,4-Dioxanea
c
e
s
a
l
-35.905
-7.842
-3.845
5.825
-19.873
b
-6.040
3.640
-14.478
-40.652
-8.537
Di-n-butyl etherc
-6.366
3.943
-5.105
-33.970
-9.324
Tetrahydrofuran a
Data were determined in this work
b
Data were taken from the work of Stephens and coworkers [7]
c
Data were taken from Mintz et al. [6]
Table 7 Enthalpies of hydrogen bonding of proton donor solutes with 1,4-dioxane (DHB H A=Diox ), kJ mol-1 at 298 K
Fig. 2 Comparison of experimental enthalpies of solvation for solutes dissolved in 1,4-dioxane and predicted values based on Eq. (12)
correlate enthalpies of solvation for gaseous solutes in 1,4dioxane. The predictive ability of Eq. (12) was assessed as before by allowing the SPSS software to randomly divide the 116 experimental data points into training and test sets. Analyses of the experimental data in the training set gave Dsolv HDiox ðkJ mol1 Þ ¼ 2:998ð0:667Þ þ 5:677ð1:241ÞE 20:034ð1:641ÞS 37:337ð1:656ÞA 8:172ð0:231ÞL with N ¼ 58; SD ¼ 2:23; R2 ¼ 0:993; F ¼ 1573
ð14Þ There is very little difference in the equation coefficients for the full dataset and the training dataset correlations, thus showing that the training set of compounds is a representative sample of the total dataset. The training set equation was then used to predict Dsolv HDiox values for the 58 compounds in the test set. For the predicted and experimental values, a SD = 2.70, AAE = 1.91 and AE = 0.098 kJ mol-1 was found. There is therefore very little bias in using Eq. (14) with AE equal to 0.098 kJ mol-1. The training set and test set analyses were performed two more times with similar results. Training and test validations were also performed for Eq. (13). To conserve journal space, we give only the test set results. The derived training set correlation for Eq. (13) predicted the 58 experimental Dsolv HDiox values in the test set to within a SD = 3.28, AAE = 2.35 and AE = 0.078 kJ mol-1. Again, there is very little bias in
Solute (A)
Eq. (15)
Eq. (16)
Lit.
Methanol
-15.4
-16.5
-8.3a, -11.7b
Butan-1-ol Phenol
-13.3 -21.5
-14.2 -23.0
-9.4a, -13.0b -20.6a, -21.3b, -20.9c
Aniline
-9.3
-10.0
-10.3a
N-Methylaniline
-6.1
-6.5
-6.5a
-14.7
-15.7
-10.8a
Chloroform
-5.4
-5.7
-7.0a, -6.9d, -9.2b
Trichloroethylene
-2.9
-3.1
-3.3a
Pyrrole
a
Solomonov et al. [104]
b
Joesten and Schaad [105]
c
Arnett et al. [64]
d
Iogansen [106]
the predictions using Eq. (13) with AE equal to 0.078 kJ mol-1. The process coefficients c, e, s, a, b, l in Eq. (12) for 1,4dioxane were compared with analogous values for other ethers obtained previously [6, 7]. Table 6 shows that coefficients c, e and l for 1,4-dioxane, tetrahydrofuran and di-n-butyl ether are similar. At the same time, these solvents have different values for the s-coefficient (Table 6) responsible for dipolarity/polarizability interactions (van der Waals interactions). Di-n-butyl ether has the smallest value of s due to the large alkyl groups. Also ethers possess different proton acceptor ability in accordance with values of the a-coefficient (Table 6) which decreases in the order tetrahydrofuran [ 1,4-dioxane [ di-n-butyl ether. For aprotic organic solvents, including ethers, the term alA in Eq. (1) gives the total contribution of hydrogen bond formation to the enthalpy of solvation (because the blB is zero). It must be noted that H-bonds play a crucial role in the effect of solvents on the reactivity of solute molecules. In accordance with Eqs. (12) and (13), the enthalpy of hydrogen bond formation of organic substances with 1,4-dioxane, DHB H A=Diox , can be calculated:
123
1852
Struct Chem (2013) 24:1841–1853
DHB H A=Diox ¼ 35:905ð1:066ÞA
ð15Þ
DHB H A=Diox ¼ 38:323ð1:401ÞA
ð16Þ
Data on DHB H A=Diox for several hydrogen bond acid solutes calculated using Eqs. (15) and (16) are presented in Table 7. It is evident that they are in good agreement with the available literature data [64, 104–106]. Consequently, enthalpies of solvation correlations based on the Abraham model provide a good tool for the prediction of hydrogen bonding enthalpies in aprotic solvents.
Conclusions The correlations presented in this study further document the applicability of the Abraham solvation parameter model to describe enthalpies of solvation for organic vapors and gaseous solutes dissolved in organic solvents. The derived Dsolv H correlations for dichloromethane and 1,4-dioxane permit extrapolations of gas-to-dichloromethane (or 1,4-dioxane) and water-to-dichloromethane (or 1,4dioxane) transfers measured at 298.15 K to other temperatures. Since not all manufacturing processes occur at 298.15 K, there is a growing need in the chemical industry to know solute transfer and partition properties at other temperatures as well. The Abraham model can also be useful for analysis of intermolecular interactions. Acknowledgments Nishu Dabadge and Amy Tian thank the University of North Texas’s Texas Academy of Math and Science (TAMS) program for a summer research fellowship. Mikhail A. Varfolomeev and Ilnaz T. Rakipov acknowledge the financial support by the Russian Federal Program ‘‘Scientific and Scientific-Pedagogical Personnel of Innovative Russia 2009–2013’’ (N P1349).
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