Interfacial equilibria with quaternary alkylammonium salts

Scibona, G.; Danesi, P.R.; Conte, A.; Scuppa, B

doi:10.1016/0021-9797(71)90221-9

Cited by 21 publications

(7 citation statements)

References 5 publications

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“…On the other hand, Scibona's group (855, 857) shows that ILN+Clin benzene as a membrane between aqueous solutions is chloride reversible, and can be made anion reversible in general. They find that the quaternary amines are aggregated in the organic phase (854) and that by converting metal cations such as zinc, palladium, and others to chloride anion complexes, the metals may be determined potentiometrically (856). Dupeyrat discussed conditions for cation or anion selective liquid membrane response in 1967, but this work has just appeared in print (%%6).…”

Section: Liquid Ion Exchange Membrane Electrodesmentioning

confidence: 99%

Ion selective electrodes, potentiometry, and potentiometric titrations

Buck¹

1972

Anal. Chem.

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Section: Liquid Ion Exchange Membrane Electrodesmentioning

confidence: 99%

Ion selective electrodes, potentiometry, and potentiometric titrations

Buck¹

1972

Anal. Chem.

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“…" ., M ,CblCN, ß. (Marcus and Kertes, 1969; Levy et al, 1971;Scibona et al, 1971). Organic-phase aggregates are frequently much smaller than their aqueous-phase counterparts.…”

Section: Resultsmentioning

confidence: 99%

“…The estimate of the area of one aggregate of stoichiometric composition ((ACN^lACblCNln) is S = 6070 A2, assuming that the hydration numbers of (ACN) is 5 and of (ACblCN) is 42 and that the aggregate behaves as a spherical "reverse micelle". Several authors have shown that the interfacial area widely depends on the nature of the counterion paired with the ammonium cation (Scibona et al, 1971;Vandegrift et al, 1980). The interfacial area occupied by one ACN molecule in p-xylene is estimated from the interfacial tension variation with concentration (Figure 2).…”

Section: Resultsmentioning

confidence: 99%

Anion exchange and aggregation of dicyanocobalamin with quaternary ammonium salts in apolar environment

Calvarin¹,

Roche²,

Renon³

1992

Ind. Eng. Chem. Res.

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Liquid-liquid extraction of dicyanocobalamin was performed, using quaternary ammonium salts (Aliquat 336) as liquid ion exchangers. A chemical model, taking into account aggregation of the cyanide and dicyanmbalamin ammonium salts in the organic phase, results in quantitative agreement with experimental data, covering the whole concentration range of practical interest. Vitamin B12 is the moat complex of all vitamin molecules. Although total chemical synthesis was achieved once in the laboratory, it is made industrially by biosynthesis. Vitamin B12 or cyanocobalamin (Cbl) is obtained as a dilute component in a fermentation broth. Its purification to obtain a pharmaceutical grade product can be achieved by a two-stage ion-exchange process using an ion-exchange resin with substituted ammonium salts (Shafer and Holland, 1955).As part of an investigation of other ways to concentrate and purify vitamin B12, (Calvarin, 1989), this article describes a liquid-liquid extraction experiment where Cbl is extracted as an anionic cyanide complex CblCN-by an organic phase containing quaternary ammonium sdta (Aliquat 336) used as anion exchangers. The results are represented by a simple, but credible, empirical ideal associated solution model assuming aggregation of species in both phases. The species involved in this extraction are presented in Figure 1. Experimental SectionMaterials. Vitamin B12 was obtained from RhonePoulenc as a pharmaceutical grade product of 96% purity. Sodium cyanide and p-xylene were purchased as Prolabo Rsctapur products, dodecane as a Prolabo technical grade product, and l-decanol as a Fluka Purum product.The mixture of trialkylmethylammonium chlorides (trialkyl= C8-Cl0, mainly capryl), known under the name of Aliquat 336, was bought as an organic solution from Fluka. It was converted to cyanide salts before extraction experiments, by repeated contacts with concentrated aqueous sodium cyanide solutions. In the conditions of the experiments, the quaternary ammonium cations form ion pairs only with CN-and CblCN-, denoted respectively as ACN and ACblCN, and various aggregates. It does not diesolve in the aqueous phase as was experimentally verified.Analytical Methods. Water Karl-Fischer titrations were performed on a Tacussel Aquaprocesseur. Interfacial tensions were measured on a Kruas K10 ring tensiometer. Cbl and CblCN-concentrations in the aqueous phase were measured on a Hewlett-Packard 8452 diode-array spectrophotometer, between 480 and 820 nm. They have absorption peaks at 551 nm for Cbl and 580 nm for CblCN-, -0888-58851 921 2631-1705$03.OO/ 0 and therefore both concentrations can be obtained simultaneously. Cyanide concentrations in aqueous phase were measured on a Metrohm 512 potentiometer by Ag+ titration: this method does not distinguish free cyanide anions and CblCN-complex, and the result is therefore an overall cyanide concentration. The total ammonium concentration in the organic phase is the sum of the ionpair [ACN] and [ACblCN] concentrations; it is measured by Ag+ potentiometric titrati...

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“…Hence, they adsorb at liquid-liquid interface and lower the interfacial tension (γ) of the system. [6][7][8][9] The drop weight method improved from drop volume method is one of the preferred methods for surface and interfacial tension measurement due to its simplicity of handling, easy temperature control, small sample size, good reproducibility and its applicability for liquid-liquid system. [10][11][12] The lowering extent of interfacial tension depends upon the chemical composition and structure of the extractant and diluents as well as extractant concentration in the bulk phase.…”

Section: Introductionmentioning

confidence: 99%

Effect of Interfacial Activity on Silver Extraction Rate with Calix[4]arene Derivatives in Nitrate Media

Kim¹,

Morisada²,

Kawakita³

et al. 2014

J.I.E.

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arene derivatives as extraction reagents have been prepared to investigate silver extraction rate in nitrate media by batch-wise method. The interfacial tension was also measured by the drop volume method to investigate the effect of interfacial activity on silver extraction rate with the calix[4]arene derivatives in chloroform / nitric acid media by varying the concentrations of the extraction reagent and nitric acid. Interfacial activities of calix[4]arene derivatives were evaluated by comparing the obtained interfacial tension values. The interfacial excess and the average area per the adsorbed extractant molecule at chloroform / nitric acid interface were estimated from the Gibbs' adsorption equation and were used to investigate the relationship with silver extraction by using calix [4]arene derivatives in nitrate media. From the result, silver extraction rate with calix[4]arene derivatives in nitrate media was significantly related to their interfacial activities.

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Interfacial equilibria with quaternary alkylammonium salts

Cited by 21 publications

References 5 publications

Ion selective electrodes, potentiometry, and potentiometric titrations

Ion selective electrodes, potentiometry, and potentiometric titrations

Anion exchange and aggregation of dicyanocobalamin with quaternary ammonium salts in apolar environment

Effect of Interfacial Activity on Silver Extraction Rate with Calix[4]arene Derivatives in Nitrate Media

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