Thermodynamic study of the partitioning of organic compounds between water and octan-1-ol. Effects of water as cosolvent in the organic phase

Bernazzani, Luca; Cabani, Sergio; Conti, Giovanni; Mollica, Vincenzo

doi:10.1039/ft9959100649

Cited by 39 publications

(27 citation statements)

References 14 publications

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“…(〈f(x)〉 is equal to zero if the value of f(x) is negative; otherwise, it is equal to f(x).) This model gives a correlation coefficient R ) 0.9626 for the published set of octanol/water partition coefficients by Bernazzani et al 23 The estimated log P octanol/water partition coefficients indicate that the vinyl and hydride are between 1.4 and 2.2 units of log P more hydrophobic than the inhibitors (25-150 times more soluble in octanol). Thus, these results lend credence to the proposition that the inhibitors may form a second phase in the bath formulation.…”

Section: Solubilities and Hydrophobicitiesmentioning

confidence: 84%

Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation

et al. 2002

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The Karstedt-catalyzed hydrosilylation reaction used in curing of silicone release coatings was investigated using first-principle quantum mechanical techniques (density functional theory) as well as semiempirical methods to estimate solubility parameters. The results we obtain for the catalytic cycle indicate, in agreement with experimental results, that hydrosilylation occurs easily at room temperature. The detailed mechanism we suggest contains the key features of the models previously proposed in the literature by Lewis and ChalkHarrod and adds quantitative estimates of reaction energies and barriers. On the basis of the energy profile for the catalytic cycle in the presence of inhibitor molecules and on solubility parameters for the species involved in the reaction, we conclude that the role of the inhibitors we considered is to phase-separate the catalyst from the substrate. The reaction is thus quenched by introducing a microscopic second phase that interferes with the homogeneous reaction.

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Section: Solubilities and Hydrophobicitiesmentioning

confidence: 84%

Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation

et al. 2002

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“…[1][2][3][4][5][6][7][8][9][10] Particularly, in the solvent extraction study, since the solutes in the water-saturated organic solution are discussed, hydration of the solutes in the organic phase is a very important subject. It has been demonstrated that the water molecules are coextracted with the metal ions, [11][12][13][14] the metal complexes, [14][15][16][17] and the inorganic anions 2,3,[18][19][20] into the organic solvents, and the mean hydration numbers of these solutes in the organic phase were determined.…”

Section: Introductionmentioning

confidence: 99%

Hydration to Benzo-15-crown-5, Benzo-18-crown-6 and the Benzo-18-crown-6-Potassium Ion Complex in the Low-Polar Organic Solvents

2001

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The water in the organic solvents sometimes exerts quite a large effect on the equilibria, the existing state and the structure of solutes. [1][2][3][4][5][6][7][8][9][10] Particularly, in the solvent extraction study, since the solutes in the water-saturated organic solution are discussed, hydration of the solutes in the organic phase is a very important subject. It has been demonstrated that the water molecules are coextracted with the metal ions, 11-14 the metal complexes, [14][15][16][17] and the inorganic anions 2,3,[18][19][20] into the organic solvents, and the mean hydration numbers of these solutes in the organic phase were determined.There have been numerous studies about the ion-pair extraction of the crown ether complexes; extractability and selectivity of the metal ions have been discussed by using the overall extraction equilibrium constant and its component equilibrium constants. 21,22 On the other hand, in recent years, hydration of the crown ether molecules and complexes has been also studied by both the theoretical 23-31 and experimental [32][33][34][35][36][37] approaches, but most of these studies were in aqueous solution. Studies concerning hydration in the wet-organic solvents for the crown ether system are scarce.Iwachido et al. 14 reported on the hydration number of the alkali and alkaline earth metal ions and of those complexes with several crown ethers or cryptands in the water-saturated NB. We reported on the hydration number of the alkali metal ions and barium ion complexes with the non-cyclic poly-(oxyethylene) compounds (POE compounds) or 18-crown-6 (18C6) in the water-saturated 1,2-DCE. 17 However, the information for hydration in the wet-organic solvents for the crown ether system is still insufficient, and particularly information is lacking about hydration in various organic solvents. Therefore, in this study, we have investigated the coextraction of water with B15C5, B18C6 and the B18C6-K + complex into seven relatively low-polar solvents which are usually employed for the extraction study of crown ethers. The mean hydration number and hydration equilibrium in the solvents saturated with water are discussed. Experimental ReagentsB15C5 and B18C6 were purchased from Tokyo Kasei, and were used without further purification. Organic solvents (Wako Pure Chemicals): CTC, CF, DCM, 1,2-DCE, BZ, CB and o-DCB, were washed three times with distilled water. Potassium picrate was prepared from its hydroxide and picric acid (Wako), and was recrystallized twice from distilled water. Other chemicals were of analytical reagent grade. ProcedureFor distribution of free crown ethers, a portion of an organic solution (20 ml) containing B18C6 (0 -0.06 mol dm -3 ) or B15C5 (0 -0.1 mol dm -3 ) was shaken with an equal volume of water in a centrifuge tube (50 ml) in a thermostated water bath for 1 h at 25.0 ± 0.1˚C. After centrifugation, the water concentration of the organic phase was determined by the coulometric Karl-Fischer titration (Kyoto Electronics MKC-210).For distribution of potassium picrate ...

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“…The very useful statistic, PSD, the predicted standard deviation is obtained from the leave-one-out Finally, we combine the two data sets, together with some additional compounds taken from the literature (Alexander et al, 1977;Gharavi et al, 1983;Martin, Wu and Beerbower, 1984;Niimi, 1991;Pinsuwan, Li and Yalkowsky, 1995;Bernazzani et al, 1995;Kristl and Vesnaver, 1995;Bustamante, Pena and Barra, 1998;Martinez and Gomez, 2001;Avila and Martínez, 2002;Perlovich et al, 2003Perlovich et al, , 2010Perlovich et al, , 2011Ran et al, 2002;Sepassi and Yalkowsky, 2006;Quingzhu et al, 2007Quingzhu et al, , 2008Thimmasetty et al, 2008) or from our own previous work (Fletcher et al, 1998;Hoover et al, 2004Hoover et al, , 2005aHoover et al, , 2005bHoover et al, , 2006Charlton et al, 2005;Stovall et al, 2005aStovall et al, , 2005bFlanagan et al, 2006aFlanagan et al, , 2006bHolley et al, 2011;Ye et al, 2011;Stephens et al, 2012;Wilson et al, 2012;Bowen et al, 2013). For most of the common compounds in the Admire and Raevsky data sets, the listed log Soct(mol/L) values were the same.…”

Section: Resultsmentioning

confidence: 99%

“…Not surprisingly, there have been a number of methods put forward for the correlation and prediction of octanol solubility of liquids and solids (Li, Pinsuwan and Yalkowsky, 1995;Sepassi and Yalkowsky, 2006;Admire and Yalkowsky, 2013;Raevsky and Schaper, 2008;Raevsky, Perlovich and Schaper, 2007). It is important to note that all this work refers to dry octanol; it is well-known that solubilities in wet (water-saturated) octanol and dry octanol are not the same (Bernazzani, Cabani, Conti and Mollica, 1995;Kristl and Vesnaver, 1995;Martínez and Gómez, 2001), possibly because the microscopic structure of wet and dry octanol are not the same (Chen and Siepmann, 2006).…”

Section: Introductionmentioning

confidence: 99%

The solubility of liquid and solid compounds in dry octan-1-ol

Abraham

Acree

2014

Chemosphere

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Thermodynamic study of the partitioning of organic compounds between water and octan-1-ol. Effects of water as cosolvent in the organic phase

Cited by 39 publications

References 14 publications

Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation

Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation

Hydration to Benzo-15-crown-5, Benzo-18-crown-6 and the Benzo-18-crown-6-Potassium Ion Complex in the Low-Polar Organic Solvents

The solubility of liquid and solid compounds in dry octan-1-ol

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