Kinetics of solvent extraction of metal ions with HEDHP. III. The kinetics and mechanism of solvent extraction of Cr(III) from acidic aqueous solutions with bis-(2-ethyl hexyl) phosphoric acid in benzene

1979 ◽  
Vol 57 (23) ◽  
pp. 3011-3016 ◽  
Author(s):  
Muhammad Fakhrul Islam ◽  
Ranjit Kumar Biswas

The rate of solvent extraction of chromium(III) from aqueous sulphuric acid solutions (containing 0.05 mol dm−3 sulphate ion and 0.25 mol dm−3 acetate buffer, ionic strength, I = 0.40 mol dm−3) with bis-(2-ethyl hexyl) phosphoric acid (HDEHP or H2A2) in benzene has been measured under various conditions. The rate of backward extraction measurement of Cr(III) from organic phase to aqueous phase is not possible due to the inert property of Cr(III)–DEHP chelate. The forward rate is found to be first-order w.r.t. Cr(III) concentration in the aqueous phase and HDEHP concentration in the organic phase. The order w.r.t. H+ concentration varies from −1 to 1 over the pH range 1.5 to 5.25. The rate is found to decrease with increasing sulphate and nitrate ions concentrations in the aqueous phase. At (30 ± 1) °C, the rate expression, in the presence of sulphate, acetate, and nitrate ions, is found to be represented by:[Formula: see text]In the absence of the anions, the formation of CrHA22+ intermediate complex (Cr(OH)2+ + H2A2(0) → CrHA22+ + H2O) is the rate determining step at all acidities. The effects of the anions on the rate are discussed.

Author(s):  
Ruiyang Miao ◽  
Lidong Shao ◽  
Richard G. Compton

AbstractThe mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.


1982 ◽  
Vol 35 (11) ◽  
pp. 2345 ◽  
Author(s):  
R Paimin ◽  
RW Cattrall

The extraction of cobalt(II) by Aliquat 336R from 7 M lithium chloride solutions involves two species from the aqueous phase, COCl42 and CoCl3-, with the former being the predominant one. The equilibrium constants for the formation of the extracted complexes (R3MeN+)2 CoCl42- and R3MeN+CoCI3- are: logKll 5.01 and logK12 9.55. From the results of experiments by means of the single-drop technique, a mechanism is proposed based on the formation of interfacial complexes by fast ion-exchange with a rate-determining step which involves the replacement at the interface of the complex (R3MeN+)2 COCl42- by two molar proportions of reagent from the bulk organic phase.


RSC Advances ◽  
2015 ◽  
Vol 5 (60) ◽  
pp. 48659-48664 ◽  
Author(s):  
Shao-Hua Yin ◽  
Shi-Wei Li ◽  
Jin-Hui Peng ◽  
Li-Bo Zhang

The extraction kinetics of Pr(iii) from chloride medium containing two complexing agents lactic acid (HLac) and citric acid (H3cit) with di-(2-ethylhexyl)phosphoric acid (D2EHPA, H2A2) have been investigated by constant interfacial area cell with lamina flow.


DYNA ◽  
2020 ◽  
Vol 87 (213) ◽  
pp. 85-90
Author(s):  
Patricio Navarro Donoso ◽  
Cristian Vargas Riquelme ◽  
Jonathan Castillo ◽  
Rossana Sepúlveda

The entrainment of the organic phase in the aqueous applied to typical solutions in a solvent extraction of copper process was studied. The organic phase used is composed of the commercial extractant LIX 984-N diluted in Shellsol 2046 AR. The aqueous phase contains 6 g/L of Cu2+, at pH 2  and 20 ºC. The variables studied were: mixing speed of 400 to 1000 rpm; mixing time of 3 to 30 minutes; initial pH of the electrolyte 2, 3, and 4; percentage of extractant in the organic phase 10 to 30% v/v; and copper concentration in the aqueous phase 1 to 6 g/L. It was determined that the entrainment of the organic phase in the aqueous is determined by the physical properties of the phases in equilibrium and by the system’s hydrodynamics, and it is a phenomenon that involves the advancing speed of the interphase (or dispersion band) and the displacement speed of the organic drops.


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