Stability constants and thermodynamic parameters of Mn2+, Co2+, Ni2+ Cu2+, Zn2+, Cd2+, UO2(2+), Th4+, Ce3+ and Pr3+-complexes with some Schiff base hydrazones containing the pyrimidine moiety

Proton-ligand dissociation and metal-ligand formation constants of 2-amino-4-chloro-6-[alpha-(phenyl)ethylidenehydrazino]pyrimidine; (AHP) and its p-chloro (ClAHP) and p-methoxy (OMeAHP) derivatives (Str.I&II) with Mn2+, Co2+ Ni2+, Cu2+, Zn2+, Cd2+, UO2(2+), Th4+, Ce3+ and Pr3+ ions have been evaluated potentiometrically in 75% (v/v) dioxane-water and 0.1 mol dm(-3) KNO3. The thermodynamic functions (deltaG, deltaH and deltaS) for the complexation of OMeAHP were evaluated and discussed. The effect of the temperature, dielectric constant of the solvents, mole fraction of dioxane and ionic strength of the medium on the stability of Pr3+-complexes show that the stability of the chelates increases by increasing both the electron repelling property of the substituents and the organic solvent content, and by decreasing the temperature, the ionic strength and the dielectric constant of the medium.     

Studies on the reaction of salicylidenebenzoic-hydrazide (SBH) with Ce3+, Th4+ and UO2 2+

The stoichiometry and structure of salicylidenebenzoic-hydrazine (SBH) chelates with UO₂(II), Ce(III) and Th(IV) in buffer-ethanol mixtures and in pure ethanol is studied applying conductometric titration, visible spectrophotometry and ir-spectrophotometry. The ir-spectra revealed that coordination takes place through the C=O and C=N groups.Deceased December 1977.     

Surface characterization and thermodynamics of adsorption of Sr2+, Ce3+, Sm3+, Gd3+, Th4+, UO 2 2+ on activated charcoal from aqueous solution

Surface parameters of the activated charcoal were measured using precise instrumental techniques for dehydration, carbon content, trace metals impurities, anions, bulk, tap and true densities, surface area, pore volume, porosity and average particle diameter. The adsorption of Sr²⁺, Ce³⁺, Sm³⁺, Gd³⁺, Th⁴⁺ and UO ₂ ²⁺ ions on activated charcoal from aqueous solution was studied as a function of temperature. Thermodynamic parameters such as HH ⁰ and S ⁰ were calculated from the slopes and intercepts of the linear variation of lnK ₁ vs. 1/T, whereK ₃ is obtained from Langmuir equation. The results show endothermic heats of adsorption, but negative free energy values indicate that the adsorption process of metal ions on activated charcoal is favored at high temperature. The value of isosteric heat of adsorption, calculated from the Clausius-Clapeyron equation, shows that the surface of the activated charcoal is heterogeneous with respect to activity. A wavelength dispersive x-ray fluorescence spectrometer was used for measuring the concentration of metal ions.     

Determination of dissociation constants for some pyrogallol azo derivatives and stability constants of their complexes with rare-earth metals

The dissociation constants of some haloazo derivatives of pyrogallol and the stability constants of their complexes with rare-earth metals (La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) are determined by potentiometric titration in aqueous ethanol (3: 7). A correlation between the dissociation constants of the reagents and the stability constants of their complexes is found.     

Determination of the thermodynamic parameters,stoichiometry, and stability constants for complex formation of dicyclohexyl-18-crown-6 and 15-crown-5 with Y3+, La3+, and Hg2+ cations in binary solutions

The complexation of Y³⁺, La³⁺, and nd Hg²⁺ cations with macrocyclic ligands, dicyclohexyl-18-crown-6 (DCH18C6) and 15-crown-5 (15C5) have been studied in acetonitrile (AN)-N,N-dimethylformamide (DMF) binary solutions at different temperatures using conductometric method. The conductance data revealed 1: 1 [ML] stoichiometry for most complexes in pure DMF and AN-DMF binary solutions, except for the (DCH18C6-Y³⁺) complex in pure AN (1: 2, [ML₂]). The stability constants of DCH18C6-La³⁺ and 15C5-La³⁺ in pure AN were higher than in pure DMF at all temperatures. Nonlinear behavior was observed for the stability constants of complexes against the composition of AN-DMF binary solutions at all temperatures. The minimum log K _f value for the 15C5-La³⁺ complex in AN-DMF binary solutions was obtained at χ_AN = 0.5, which may be due to negative excess viscosities η^E of AN-DMF mixtures over the whole composition range with a minimum value of χ_AN = 0.5. Moreover, the selectivity order of DCH18C6 and 15C5 for Y³⁺, La³⁺, and Hg²⁺ cations 25°C depended on the AN-DMF ratio. The thermodynamic parameters (ΔH _C ⁰ ) for complex formation were obtained from the temperature dependences of the stability constants of the complexes using the van’t Hoff plots, and the standard entropy (ΔS _C ⁰ ) was calculated from the relationship: ΔG _{C, 298.15} ⁰ = ΔH _C ⁰ ? 298.15ΔS _C ⁰ .     

Selective preconcentration of thorium in the presence of UO(2)(2+), Ce(3+) and La(3+) using Th(IV)-imprinted polymer

We have prepared Th(IV) ion-imprinted polymers, which can be used for the selective preconcentration of Th(IV) ions, represented by uranium and lanthanides. N-methacryloyl-(l)-glutamic acid (MAGA) was chosen as the complexing monomer. In the first step, Th(IV) was complexed with MAGA and the Th(IV)-imprinted poly[ethylene glycol dimethacrylate-N-methacryloyl-(l)-glutamic acid] (Poly(MAGA-EDMA)) beads were synthesized by suspension polymerization. After that, the template Th(IV) ions were removed using 8.0 M HNO₃ solution. The breakthrough capacity was 40.44 mg Th(IV)/g beads. The relative selectivity coefficients of imprinted beads were 68, 97 and 116 for UO₂²⁺, La³⁺ and Ce³⁺, times greater than non-imprinted matrix, respectively. The Th(IV)-imprinted beads could be used many times without decreasing their breakthrough capacities significantly.     

UO2 2+, Tl+, Pb2+, Ra2+, Bi3+ and Ac3+ adsorption onto polyacrylamide-zeolite composite and its modified composition by phytic acid

The adsorption of naturally occurring radionuclides (UO₂ ²⁺, Tl⁺, Pb²⁺, Ra²⁺, Bi³⁺ and Ac³⁺) onto zeolite (Z) and polyacrylamide-zeolite composite (PAA-Z) and its modified composition by phytic acid (Z-Phy and PAA-Z-Phy) were investigated. Adsorption parameters were derived from the Langmuir and Freundlich fits to adsorption isotherms of the ions studied. The adsorption isotherms were of L and H types. The adsorption capacity of Z decreased by PAA inclusion, but the Phy modification of PAA-Z increased the capacity back to that of Z. The Phy modification made the adsorption spontaneity at least ten times better than in the absence of Phy. This investigation showed that the zeolite, as one of the most abundant natural materials and commonly used adsorbent can also be used for the removal of UO₂ ²⁺ and, in the PAA-Z form, of the studied radionuclides. The usage of Z, as PAA-Z and its Phy modification provide research materials which possess adequate practicality and effectiveness in studies of adsorption. This revised version was published online in July 2006 with corrections to the Cover Date.     

Separation of strontium from simulated waste in K2SO4/Nitrate medium containing Sr2+, Eu3+, Ce3+, Pd2+, Rh3+, Ru3+, UO 2 2+ , Fe3+, Cr3+, Ni2+, Al3+, Ca2+ and Cs+, by strongly basic anion exchanger

In this work Strontium was separated selectively form, Pd²⁺, Ni²⁺ and Ca³⁺ using anionic resins of Amberlite type IRA-900 and IRA-410 from nitrate medium. The Separation of strontium by strongly basic anion exchangers IRA-410 and IRA-900 from simulated waste containing, Sr²⁺, Eu³⁺, Ce³⁺, Pd²⁺, Rh³⁺, Ru³⁺, VO₂ ²⁺, Fe³⁺, Cr³⁺, Ni²⁺, Al³⁺, Ca²⁺, and Cs⁺, in K₂SO₄/nitrate medium which adsorbed as strontium sulphate complex was achieved through ligand- ligan exchange. The elution of strontium carried out via “loading” the column with a solution of 0.03N EDTA in presence of 0.1N NaNO₃ at pH7 where Sr²⁺ has low K_d value. An inductively Coubled Plasma — Optical Emission Spectrometry (ICP — OES) of ARL type model 3520, was used for elemental analysis.     

The solvent extraction of UO 2 2+ and Th4+ with petroleum sulfoxide

The influence of the concentration of nitric, hydrochloric and phosphoric acids, petroleum sulfoxides (PSO), salting-out agent, kind of diluent and temperature on the distribution ratio of U(VI) and Th(IV) has been systematically studied. It is found that the extraction regularity of PSO is similar to that of TBP. The distribution ratio in phosphoric acid is lower, but it increases with the increase of hydrochloric acid concentration and reaches a high value. The U(VI) exhibits the maximum distribution ratio at 3–4 mol/l HNO₃. The distribution ratio of U(VI) and Th(IV) increases rapidly in the presence of a salting out agent. The extracted compounds are determined to be UO₂(NO₃)₂2PSO and Th(NO₃)₄2PSO. The extraction enthalpies of U(VI) and Th(IV) with PSO were also calculated.     

Adsorption of UO2 2+, Tl+, Pb2+, Ra2+ and Ac3+ onto polyacrylamide-bentonite composite

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerization in a suspension of bentonite (B), the composite was then modified by phytic acid (PAA-B-Phy). The parameters related to adsorption of UO₂ ²⁺ in absence and presence of 0.01M CaCl₂ and of natural radionuclides (Tl⁺, Pb²⁺, Ra²⁺ and Ac³⁺ in a leaching solution) onto PAA-B and PAA-B-Phy, and thermodynamics of the adsorption were investigated. Adsorption isotherms were of L and H types for the adsorption of UO₂ ²⁺ onto PAA-B and PAA-B-Phy, whilst for Tl⁺, Pb²⁺, Ra²⁺ and Ac³⁺ they were of C type for both adsorbents. Langmuir equilibrium constants for the adsorption of all studied ions onto PAA-B-Phy were significantly higher than those found for PAA-B. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy. The composite of PAA-B and its modification by Phy have been used for the first time in this study. It is concluded that the composites can be practically used for adsorption and applied as adsorbent of radionuclides.     

Synthesis, spectral studies, and determination of stability constants and thermodynamic parameters for some aromatic diamine transition-metal complexes

The Cu(II) and Zn(II) complexes of aromatic bidentate diamines were prepared and characterized by different analytical and spectral methods. Thermodynamic parameters of complexes of Cu(II) and Zn(II) cations with 1,3-bis(p-aminophenoxy)propane were determined in 60 vol. % DMF-H₂O at various ionic strengths (0.07, 0.13, 0.2 M NaNO₃) and different temperatures (45, 50, 55, 60 ± 0.1°C) using a spectrophotometric method. The NaNO₃ solution was used to maintain the ionic strength. The stability constants show an inverse relationship with ionic strengths. The thermodynamic parameters of 60 vol. % DMF-H₂O (ΔG°, ΔH°, ΔS°) based on these formation constants were determined. The text was submitted by the authors in English.     

Collision-induced dissociation tandem mass spectrometry of desferrioxamine siderophore complexes from electrospray ionization of UO2(2+), Fe3+ and Ca2+ solutions

Desferrioxamine (DEF) is a trihydroxamate siderophore typical of those produced by bacteria and fungi for the purpose of scavenging Fe(3+) from environments where the element is in short supply. Since this class of molecules has excellent chelating properties, reaction with metal contaminants such as actinide species can also occur. The complexes that are formed can be mobile in the environment. Because the natural environment is extremely diverse, strategies are needed for the identification of metal complexes in aqueous matrices having a high degree of chemical heterogeneity, and electrospray ionization mass spectrometry (ESI-MS) has been highly effective for the characterization of siderophore-metal complexes. In this study, ESI-MS of solutions containing DEF and either UO(2)(2+), Fe(3+) or Ca(2+) resulted in generation of abundant singly charged ions corresponding to [UO(2)(DEF - H)](+), [Fe(DEF - 2H)](+) and [Ca(DEF - H)](+). In addition, less abundant doubly charged ions were produced. Mass spectrometry/mass spectrometry (MS/MS) studies of collision-induced dissociation (CID) reactions of protonated DEF and metal-DEF complexes were contrasted and rationalized in terms of ligand structure. In all cases, the most abundant fragmentation reactions involved cleavage of the hydroxamate moieties, consistent with the idea that they are most actively involved with metal complexation. Singly charged complexes tended to be dominated by cleavage of a single hydroxamate, while competitive fragmentation between two hydroxamate moieties increased when the doubly charged complexes were considered. Rupture of amide bonds was also observed, but these were in general less significant than the hydroxamate fragmentations. Several lower abundance fragmentations were unique to the metal examined: abundant loss of H(2)O occurred only for the singly charged UO(2)(2+) complex. Further, NH(3) was eliminated only from the singly charged Fe(3+) complex; this and fragmentation of C-C and C-N bonds derived from neither the hydroxamate nor the amide groups suggested that Fe(3+) insertion reactions were competing with ligand complexation. In no experiments were coordinating solvent molecules observed, attached either to the intact complexes or to the fragment ions, which indicated that both intact DEF and its fragments were occupying all of the coordination sites around the metal centers. This conclusion was based on previous experiments that showed that undercoordinated UO(2)(2+) and Fe(3+) readily added H(2)O and methanol in the ESI quadrupole ion trap mass spectrometer that was used in this study.     

Determination of stability constants and thermodynamic parameters for interaction of thiosemicarbazones with divalent metal ions

The Calvin–Bjerrum pH titration technique as modified by Irving and Rossotti has been applied to determine the stability constants of complexes of a series of thioligands, namely benzaldehyde thiosemicarbazone, pyridine-2-carbaldehyde thiosemicarbazone, and cyclopentanone thiosemicarbazone with divalent metal ions (Cu, Cd, Co, Ni, Pb, and Zn). The studies were carried out in 50% v/v dioxane-water at different temperatures (293 K, 303 K, and 313 K) keeping ionic strength at 0.1 mol KNO₃. The thioligands undergo deprotonation of only one proton (–N²H–) of a thiosemicarbazone [R¹R²C²=N³–N²(H)–C¹(=S)N¹H₂]. Thermodynamic parameters, such as free energy, enthalpy, and entropy have also been evaluated. The investigations represent the first report of the solution phase studies in metal–thiosemicarbazone chemistry.     

Polarographic determination of stability constants and thermodynamic parameters of lead(II) propanoate and 2-hydroxypropanoate complexes with a computer-controlled system

A computer-controlled electrometric system is described. It is used for d.c. polarographic determinations of the stability constants of lead(II) propanoate and 2-hydroxypropanoate complexes at four temperatures. From the values of the monoligand complex stability constants obtained at different temperatures, standard thermodynamic functions (ΔH_j and ΔS_j) for the first and second steps of complex formation were obtained. Closed-loop interaction between the minicomputer and electrometric instrument was achieved through computer control of the potentiostat, drop-life timer, burette and valve for nitrogen purging. Computer programs are outlined for numerical and statistical evaluation of the experimental data giving E_{$\text{1}\text{2}$}i_d and slope of logarithmic presentation of polarograms, F_o functions and cumulative stability constants, β_j as well as for calculation of the standard thermodynamic functions.     

Thermodynamic parameters and stability constants of some tervalent lanthanide complexes of 1-(3-aryl-5-hydroxy 4-isoxazolylazo) 4-sulphonic acids

The stability constants of some tervalent lanthanide chelates of 1-(3-aryl-5-hydroxy 4-isoxazolylazo) 4-sulphonic acid (PHI-4S) and its substituents have been carried out by potentiometric and spectrophotometric methods. The results indicated the formation of 1:1 and 1:2 complexes with an order: Yb(III) > Y(III) > Gd(III) > Dy(III) > Tb(III) > Sm(III) > Nd(III) > Pr(III) > La(III). The stabilities increase with a decrease in the ionic or crystal radii [except a small break at Gd(III)], indicates the absence of extensive covalent bonding due to the non-availability of 4f-orbitals for bond formation. Structure-reactivity relationships of complex formation have been discussed by Hammett’s and Irving-Rossotti theories. Thermodynamic parameters have been discussed in terms of iso-equilibrium relationship.     

Thermodynamics of substituted rhodanine II: Binary complexes of Th(IV), UO2(II), Ce(III), and La(III) with 3-benzamidorhodanine and its derivatives

Summary Th(IV), UO₂(II), Ce(III) and La(III) chelates with 3-benzamidorhodanine and its derivatives have been investigated potentiometrically in 0.1M KCl and 20% (v/v) ethanol-water medium. The stability of the formed complexes increases in the order Th(IV)>UO₂(II)>Ce(III)>La(III). For the same metal ion, the stability of the chelates is found to increase with decreasing temperature, ionic strength, dielectric constant of the medium and by increasing the electron repelling property of the substituent. The thermodynamic parameters (G, H and S) for complexation are evaluated and discussed. The formation of the complexes has been found to be spontaneous, exothermic and entropically favourable.

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Thermodynamik von substituiertem Rhodanin II: Binäre Komplexe von Th(IV), UO₂(II), Ce(III) und La(III) mit 3-Benzamidorhodanin und seinen Derivaten

Zusammenfassung Th(IV)-, UO₂(II)-, Ce(III)- und La(III)-Chelate mit 3-Benzamidorhodanin und seinen Derivaten wurden in 0.1M KCl und 20% (/) Ethanol-Wasser potentiometrisch untersucht. Die Stabilität der gebildeten Komplexe steigt in der Reihenfolge Th(IV)>UO₂(II)>Ce(III)>La(III). Für ein- und dasselbe Metallion steigt die Stabilität der Chelate mit sinkender Temperatur, Ionenstärke und Dielektrizitätskonstante des Mediums und mit steigender Elektronenabstoßungsfähigkeit des Substituenten. Die thermodynamischen Parameter (G, H und S) für die Komplexbildungsreaktion werden bestimmt und diskutiert. Die Bildung der Komplexe erweist sich als spontan, exotherm und entropisch begünstigt.