Studies of Liquid-Liquid Partition Systems. V. The Formation of Mixed Dimers with Two Carboxylic Acids in Carbon Tetrachloride

Sekine, Tatsuya; Isayama, Muneo; Yamaguchi, Sumiko; Moriya, Hiromitu

doi:10.1246/bcsj.40.27

Cited by 21 publications

(2 citation statements)

References 12 publications

(8 reference statements)

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“…In this case a mechanism parallel to that for the terpyridine molecule is used. [14] The undissociated HA is known to dimerise in the organic phase, [15] Eq. (1).…”

Section: Mechanismmentioning

confidence: 99%

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Ekberg¹,

Foreman²,

Hudson³

et al. 2003

Solvent Extraction and Ion Exchange

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In this study, the extraction properties of a synergistic system consisting of 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine (BODO) and 2-bromodecanoic acid (HA) in tert-butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03-12 and 0.003-0.8 have been found for Am(III) and Eu(III), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO 4 À , NO 3 À , and H þ . The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log-log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non-linear way. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at $1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.

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“…In this case a mechanism parallel to that for the terpyridine molecule is used. [14] The undissociated HA is known to dimerise in the organic phase, [15] Eq. (1).…”

Section: Mechanismmentioning

confidence: 99%

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Ekberg¹,

Foreman²,

Hudson³

et al. 2003

Solvent Extraction and Ion Exchange

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“…For infinite dimerization constants (xi = x i = 0), if follows from [22] that which is often expressed, basing on statistical arguments, as X A~ = X?,XB? = xi, and XAB = 2 x 1~~.…”

Section: Dimerization Reaction Accompanied By a Cyclic Dimer + Linearmentioning

confidence: 99%

Dimerization and continuous association including formation of cyclic dimers

Apelblat¹

1991

Can. J. Chem.

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A. APELBLAT. Can. J. Chem. 69, 638 (1991). New aspects of the theory of ideal associated mixtures related to a differentiation between formed cyclic and linear dimers are discussed. A mathematical analysis is presented for the dimerization model, A + B + A', the continuous association (Mecke-Kempter) model, A + B + A 1 + A3 + A4 + . . ., both coupled with the cyclic dimer 4 linear dimer transformation and for the unsymmetrical (mixed) dimer formation model, A + B + A ? + B2 + AB. Introduction of the standard reaction enthalpies and volumes associated with transformations of dimers leads to a considerable change in behavior and symmetry properties of the excess thermodynamic functions. In terms of the modified Mecke-Kempter model, a consistent representation of the excess Gibbs energy of mixing G~, heat of mixing H E , and excess molar volume vE is reported for the acetic acid -water system at 298.15 K.Key words: association, dimerization, linear dimers, cyclic dimers, hydrogen bonding, carboxylic acids, alcohols, aqueous solutions.A. APELBLAT. Can. J. Chem. 69, 638 (1991). On discute de nouveaux aspects de la thtorie des mtlanges associts parfaits qui sont relies ?i une difftrentiation entre la formation de dimbres cycliques et lintaires. On presente une analyse mathtmatique du modble de dimtrisation, A + B + A 2 , du modble d'association continue (Mecke-Kempter), A + B + A2 + A3 + A4 + . . ., ainsi que deux modbles couplts avec la transformation du dimkre cyclique 4 dimbre lineaire et finalement du modble de formation du dimbre asymttrique (mixte), A+ B+A2+B2+AB. L'introduction des enthalpies standard de reaction et des volumes associts avec les transformations des dimbres conduit B un changement important dans le comportement et les propriites de symttrie des fonctions thermodynamiques en excbs. Pour le systbme acide acttiqueleau, ?i 298,15 K et utilisant le modtle de Mecke-Kempter modifii, on a obtenu une reprtsentation coherente de l'tnergie de mtlange de Gibbs en excbs, G~, de la chaleur de formation, HE et du volume molaire en excbs, vE.

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Extraction chemistry of fermentation product carboxylic acids

Kertes

King

1986

Biotech & Bioengineering

649

289

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Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathway and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase.

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Studies of Liquid-Liquid Partition Systems. V. The Formation of Mixed Dimers with Two Carboxylic Acids in Carbon Tetrachloride

Cited by 21 publications

References 12 publications

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Dimerization and continuous association including formation of cyclic dimers

Extraction chemistry of fermentation product carboxylic acids

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