Solvent effect on the heat of solution and partial molar volume of some non‐electrolytes and lithium perchlorate

Kiselev, V. D.; Kashaeva, E. A.; Iskhakova, G. G.; Potapova, L. N.; Коновалов, А. И.

doi:10.1002/poc.1012

Cited by 18 publications

(12 citation statements)

References 24 publications

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“…For LP, sufficient data are available on the heat of solution and partial molar volume ${\bar {V}}_{LP} $ in some organic solvents,6–9 and the salt influence on the rate of reactions 2, 4. Similar data for MP are very limited.…”

Section: Introductionmentioning

confidence: 99%

Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate

Kiselev

Bolotov

Kashaeva

et al. 2010

J of Physical Organic Chem

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For magnesium perchlorate (MP), the solvent effect on the heat of solution and partial molar volumes (PMV) at 25 °C was studied. Since the complete dissociation of magnesium perchlorate is more difficult to achieve as compared with lithium perchlorate (LP), the concentration dependence of the values of the heat of solution and partial molar volume were noted. Only in highly polar solvents with large donor numbers (DN), such as water, dimethyl sulfoxide, N,N‐dimethyl formamide, and formamide, the differential and integral values of the enthalpies of solution were the same in the range of concentrations studied. In all solvents studied, the values of the heat of solution of MP were highly exothermic and exceed that of LP by more than 30 kcal mol−1. The values of the partial molar volume of MP were changed from 82.3 cm3 mol−1 in formamide to −2.4 cm3 mol−1 in acetone, and correlate linearly with that of LP (R = 0.975). Taking into account the significant change in the properties of molecules in the solvate shell of cation Mg2+, the large increase in the reactivity of reactants, activated by such interaction with Mg2+ cation is expected. Copyright © 2010 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate

Kiselev

Bolotov

Kashaeva

et al. 2010

J of Physical Organic Chem

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“…For highly associated compounds (associates with Hbond, alkali metal salts, etc. ), a concentration dependence can occur even in water [27][28][29][30]. From the data ( Table 1) it follows that, in the series of solvents studied, the changes of PMVs of adducts are in the range of 5-12 cm 3 ·mol −1 .…”

Section: Resultsmentioning

confidence: 88%

Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

et al. 2012

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In this article negative values of the activation volume in retro-Diels-Alder reactions are interpreted in terms of the different possibilities of penetration of the solvent molecules into the sterically branched structures of the adduct and activated complex. Empty spaces, inaccessible to penetration of solvent molecules, lead to increases of the molar volume of the screened adducts in solution and, consequently, to a less negative value of the Diels-Alder reaction volume. The values of partial molar volumes of anthracene, maleic anhydride and the adducts cyclopentadiene-maleic anhydride, anthracene-maleic anhydride and anthracene-tetracyanoethylene, in several solvents, were calculated from the solution density data.

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“…It is necessary to note that the solvent influence on the values of PMVs for different planar structures of dienes and dienophiles (except tetracyanoethylene as a strong π‐acceptor) with the surface accessible for solvation is usually small . On the contrary, large differences of the partial molar volumes of the branched molecular structure of adducts were observed .…”

Section: Discussionmentioning

confidence: 99%

High-Pressure Influence on the Rate of Diels-Alder Cycloaddition Reactions of Maleic Anhydride with Some Dienes

Kiselev

2013

Int. J. Chem. Kinet.

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The rate constants for temperature and pressure range, enthalpy, entropy, and volume of activation and reaction were measured in toluene solution for the Diels–Alder cycloaddition reaction of maleic anhydride (1) with a very active diene, 9,10‐dimethylanthracene (4), and with a very inactive diene, 9‐phenylanthracene (6), which is less reactive in the reaction with 1 by five orders of magnitude. Reaction rates under pressure up to 2600 bar were measured by using a high‐pressure optical cell, adjusted to a UV‐spectrophotometer. The volume of reaction was determined by two independent methods: by the difference of the partial molar volumes of the reactants and by the dependence of a specific volume of solution on the adduct concentration during the reaction. All parameters of activation and reaction were discussed.

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Solvent effect on the heat of solution and partial molar volume of some non‐electrolytes and lithium perchlorate

Cited by 18 publications

References 24 publications

Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate

Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate

Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

High-Pressure Influence on the Rate of Diels-Alder Cycloaddition Reactions of Maleic Anhydride with Some Dienes

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