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Mar 15, 2013 - Abstract Enthalpies of solution at infinite dilution of 53 organic solutes in dichloromethane and 10 organic solutes in 1,4-dioxane were ...
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

1846

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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