Studies on complexation and solvent extraction of lanthanides in the presence of diaza-18-crown-6-di-isopropionic acid.
Stability constants of some lanthanides with K22DAP (diaza-18-crown-6-diisopropionic acid) were determined by potentiometric titration method. The logarithmic values of these constants for La(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III), and Lu(III) are 11.14, 11.43, 11.78, 11.74, 11.95, 12.09, 11.49, and 10.88, respectively. Solvent extraction studies were carried out on the K22DAP complexes of La(III), Nd(III) and Lu(III) using TTA (thenoyltrifluoroacetone) as an extractant in different diluents. It appears that nitrobenzene, a diluent with high dielectric constant, favors the extraction of the complexes. Extraction rates of the K22DAP complexes of lanthanides were investigated at pH 5.5 and 8.0 with TTA in chloroform. The rates of extraction are found to be dependent upon the nature of the extracted species. Competitive extractions were carried out to see if selective extractions could be achieved.
Kinetics of interaction of copper ion with four diaza-crown-alkanoic acid complexes
Cinetique de complexation avec: acides tetraoxa-1,4,10,13 diazacyclooctadecane-diacetique-7,16, -di-α-propionique-7,16 et acetique-7 et l'acide trioxa-1,4,10 diazacyclopentadecanediacetique-7,13
An Ultrasensitive Analytical Method Based on Chemiluminescence Sensing Electrochemical Parallel Catalytic Reaction Event
An ultrasensitive electrochemiluminescence (ECL) method on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed for improving ECL analytical characteristics using vanadate(V) as a representative. Vanadate(V) could be electrochemically reduced to generate vanadate(II) which could be chemically oxidized by potassium periodate to regenerate vanadate(V) and give parallel catalytic wave effect. Then, the reduced product of potassium periodate could react with butyl-rhodamine B to emit a sensitive chemiluminescence signal. The chemiluminescence intensity was correlative with vanadate(V) concentration. The investigation on the electrochemical reaction rate constant (k0) confirmed that the speed of electrochemical reaction was faster than that of the subsequent chemiluminescence reaction. The possibility of the combination of electrochemical parallel catalytic reaction with chemiluminescence signal sensing was proved. The similar ECL behaviors could be observed at zirconia nanowires-Nafion modified electrode. Because of the separation and enrichment effect of the modified electrode on vanadate(V), the selectivity and sensitivity was further improved greatly. Based on these findings, a new concept on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed and an ultrasensitive ECL method for the determination of vanadate(V) was developed at zirconia nanowires-Nafion modified electrode. Under the optimum experimental conditions, the ECL intensity was linear with the concentration of vanadate(V) in the range of 2.0×10−12 mol/L–2.0×10−10 mol/L. The detection limit was 8.0×10−13 mol/L, which was more than 6 orders of magnitude lower than that observed by electrochemical current transduction for electrochemical parallel catalytic reaction at zirconia nanowires-Nafion modified electrode.