KINETICS AND INTERFACIAL PHENOMENA

ABSTRACT

Kinetics and interfacial phenomena in solvent extraction of metal ions are reviewed. The importance of interfacial reactions is discussed. The use of new modern techniques to study extraction is also presented.     

Composition and interfacial activity of hydrophobic sulphide-type extractants

The composition and interfacial activity of dihexyl sulphide (Elf), dodecyl methyl sulphide (two samples from Elf and Penwalt) and n-dodecyl hydroxyethyl sulphide (Elf) which are commercially available sulphide-type extractants have been investigated. Recrystallized n-dodecyl hydroxyethyl sulphide was found to be of high purity (i.e. impurities, if any, are below the detection level of a gas chromatograph equipped with an efficient capillary column), whereas it was shown that all the other sulphides contained many components which were separated and, for most of them, indentified by a GC/MS technique. Recrystallized n-dodecyl hydroxyethyl sulphide starts to adsorb at the 2 M HCI/dodecane interface at concentrations (typically 10^?3 M ) of about one order of magnitude lower than dodecyl methyl sulphide (Elf or Penwalt). Dihexyl sulphide exhibits a very weak interfacial activity and the observed decrease in the interfacial tension in the system containing about 0·4 M dihexyl sulphide cannot be attributed with certainty to its own interfacial activity.     

Synthesis and surface activity of sodium salts of branched perfluorocarboxylic acids and their analogs containing one chlorine atom

Individual sodium salts of branched perfluorocarboxylic acids, (CF₃)₂CF(CF₂CF₂)_nCOONa, and their analogs containing one chlorine atom, CF₃CF(CF₂CI)(CF₂CF₂)_nCOONa, were synthesized by telomerization of 2-iodoheptafluoropropane and l-chloro-2-iodohexafluoropropane with tetrafluoroethene, the addition of ethylene to both types of iodides considered, HI elimination and the oxidation of perfluoroalkylethylenes with potassium bichromate. The surface tension measurements demonstrated the high surface activity of sodium salts containing 9 and 11 carbon atoms in the hydrophobe. Perfluorocompounds were more surface active than their analogs having one chlorine atom but the differences were not great.     

Structure—activity relationships for hydroxyoxime metal extractants

The distance-based topological indices and connectivity indices were computed for various homologues of hydroxyoximes and correlated with the partition data and the rate of copper extraction from acidic sulphate solutions. The distance-based topological indices are more sensitive to the structural changes in extractant molecule than the connectivity indices.     

Surface complexation modeling of proton and Cd adsorption onto an algal cell wall

This study quantifies Cd adsorption onto the cell wall of the algal species Pseudokirchneriella subcapitata by applying a surface complexation approach to model the observed adsorption behavior. We use potentiometric titrations to determine deprotonation constants and site concentrations for the functional groups on the algal cell wall. Adsorption and desorption kinetics experiments illustrate that adsorption of Cd onto the cell wall is rapid and reversible, except under low pH conditions. Adsorption experiments conducted as a function of pH and total Cd concentration yield the stoichiometry and site-specific stability constants for the important Cd-algal surface complexes. We model the acid/base properties of the algal cell wall by invoking four discrete surface functional group types, with pKa values of 3.9 +/- 0.3, 5.4 +/- 0.1, 7.6 +/- 0.3, and 9.6 +/- 0.4. The results of the Cd adsorption experiments indicate that the first, third, and fourth sites contribute to Cd adsorption under the experimental conditions, with calculated log stability constant values of 4.1 +/- 0.5, 5.4 +/- 0.5, and 6.1 +/- 0.4, respectively. Our results suggest that the stabilities of the Cd-surface complexes are high enough for algal adsorption to affect the fate and transport of Cd under some conditions and that on a per gram basis, algae and bacteria exhibit broadly similar extents of Cd adsorption.     

Hydrophilicity and Solubility in Water of Block Copolymers of Ethylene and Butylene Oxides of Type EBE

The solubility of ethylene and butylene oxide block copolymers in water was investigated. The turbidity of water dispersion and the water number were determined, and empirical statistically valid equations correlating these parameters with the molecular mass of the polyoxyethylene chain were derived. The hydrophilicity of block copolymers defined by the degree of transmittance and the water number was compared with hydrophilicity derived from the polarity index.     

Surface activity of mixtures of oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate

Surface and interfacial tension and detergency of mixtures containing oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate were determined. Synergism in the surface tension reduction was not observed. The competition for adsorption at the air/water interface between oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate depended on the considered surface tension, the weight ratio of surfactants in the aqueous phase, and the hydrophile-lipophile balance of the nonionic surfactant. Generally, coverage of the interface with oxyethylated methyl dodecanoate increased when surface tension decreased. Nonionics were the dominant species at the interface in the important region of surface activity, i.e., for surface tensions below 40 mN m⁻¹. The mole fraction of the hydrophobic nonionic at the interface was higher than the contribution of hydrophilic oxyethylates. An increase of the surfactant ratio in the bulk phase affects the interfacial ratio of surfactants in the same way. The lowest interfacial tension (1.5 mN m⁻¹) at the hexadecane/water interface was observed for oxyethylated methyl dodecanoate having an average degree of oxyethylation equal to 8 and 10. Nearly 5 min was needed to achieve equilibrium value. Mixtures with sodium dodecylbenzenesulfonate decreased the interfacial tension somewhat less efficiently but the equilibrium was rapidly established. The standard washing powders containing oxyethylated methyl dodecanoates exhibited washing ability similar to that obtained for the powder with traditional alcohol oxyethylate.     

COPPER EXTRACTION FROM CHLORIDE SOLUTIONS WITH MIXTURES OF SOLVATING AND CHELATING REAGENTS

ABSTRACT

Equimolar mixtures of N,N,N',N'-tetrahexylpyridine-3,5-dicarboxamide (L) with 2-hydroxy-5-t-octylbenzophenone oxime or l-phenyldecane-l,3-dione (HB), were used to extract copper from chloride solutions of various concentration of chloride ions. Chloride ions were then scrubbed out with water or ammoniacal solutions and copper was transferred from the solvate CUCl₂L₂ to chelate CuB₂- Both studied systems permit effective extraction of copper and removal of chloride ions from the organic phase. Some protonation of solvating reagent L occurs, however, when copper is stripped from the chelate with hydroxyoxime. This negative effect can be suppressed when 1-phenyl decane-1,3-dione is used as a chelating agent. The scrubbing of chloride ions must be then carried out with ammoniacal solutions to avoid simultaneous stripping of copper.     

Photocatalytic activity of thin TiO2 films deposited using sol–gel and plasma enhanced chemical vapor deposition methods

Thin titanium dioxide films, deposited using RF PECVD and sol–gel techniques, were studied comparatively with respect to their bactericidal as well as self-cleaning properties. The effect of the deposition process on film morphology, chemical and crystalline structure, bactericidal activity and hydrophilic properties was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), surface profilometry, optical microscopy and contact angle measurements. It was found that the bactericidal activity of amorphous TiO₂ films, produced using the RF PECVD method, as either comparable to or better than those of crystalline (anatase) films deposited by means of the sol–gel technique. One reason for such advantageous behavior of plasma deposited materials is thought to be their substantially higher surface roughness, as revealed by AFM measurements. The hydrophilic effect, induced with UV irradiation, was strongest in the case of sol–gel films, but the RF PECVD synthesized coatings were found to be only slightly less hydrophilic. The conclusion follows that both sol–gel and RF PECVD techniques are equally capable of producing titanium dioxide films of high photocatalytic quality.