Polarographic study of mixed ligand complex stability constants and kinetic parameters of reduction of zinc(II)-tartrate—Thiocyanate system

The Zn-tartrate-thiocyanate system has been investigated polarographically and the composition and stability constants of mixed complexes formed have been determined.     

Polarographic study of simple and mixed-ligand complex formation

Theoretical, experimental and statistical aspects of the polarographic method applied to simple and mixed-ligand complex formation have been studied. Some misunderstandings and erroneous interpretations have been clarified according to experimental results obtained with several systems. A criterion for establishing the number of complex species present in a simple system is proposed. For the first time the polarographic method has been applied to a mixed-ligand complex system where fourteen species co-exist.     

Polarographic studies of catalytic reduction of hydrogen in Cr(VI)−As(III) and Cr(III)—As(III) systems

In the presence of traces of Cr(VI) or Cr(III) ions in ammonia or borate buffers containing the As(III) ions a catalytic hydrogen wave arises in the dc polarogram. It was established that the complex Cr(H₂AsO₃)_n^+3?n is formed in the solution, and that its reduced form adsorbed at DME is of catalytic activity. The wave can be employed for the determination of low concentrations (2×10^?8×10^?7M) of Cr(VI) and Cr(III) ions.     

Photoredox reactions of Cr(III) mixed-ligand complexes

Irradiation of chromium(III) complexes with oxalate and pyridinedicarboxylate ligands (pda = 2,3-, 2,4-, or 2,5-dicarboxylate) leads to diverse behaviors, dictated by light energy, presence of oxygen and the ligand nature. Irradiation within the MC bands is unaffected by O₂ and results in ligand substitution. The LMCT excitation is effective only when oxalate is coordinated to Cr(III); then electron transfer from oxalate to central ion generates an intermediate, consisted of a Cr(II)species and the C₂O₄^? radicals. The species undergo fast redox reactions dependent on the presence of O₂ and the pda ligand.(1) In anoxic medium the fast outersphere electron transfer from Cr(II) to solvent, generates hydrated electrons and re-oxidizes the chromium centre to Cr^III. Then geminate recombination regenerates substrate, whereas competitive release of the C₂O₄^? radical leads to substitution of one oxalate ligand by two water molecules (aquation induced by the LMCT excitation). In the presence of the pda ligand the outersphere electron transfer is accompanied by the innersphere CT, generating Cr(III) coordinated to two radical ligands: C₂O₄^? and pda^3?; the intermediate releases also e_aq^?, but this reaction is slower than that of the homoleptic oxalate complex. Hydrated electrons are scavenged also by the released radicals. All these processes are completed within microseconds and in consequence, the Cr(III) complexes irradiated in deoxygenated solutions are insensitive to subsequent oxygenation.(2) When UV-irradiation is carried out in oxygenated medium reaction of Cr(II) species with molecular oxygen competes with the outer- or inner electron transfer observed in anoxic medium. Both these pathways result in generation of chromate(VI). Quantum yield of the Cr(VI) production is sensitive to the presence and structure of pda ligand, decreasing within the series 2,3-pda > 2,4-pda > 2,5-pda.     

Electrode processes and their kinetic parameters in the reduction and oxidation of Cr(III) and Cr(II) in molten CsCl

The reduction of chromium ions in the CsCl-CrCl₃ melt in wide concentration and temperature ranges is reported. It is assumed that the melt contains polynuclear chromium complexes. The reduction of Cr(III) to Cr(II) is a reversible one-electron process. The electroreduction of divalent chromium to chromium metal is an irreversible process involving dinuclear and mononuclear chromium complex ions. The electron transfer rate constant has been calculated for various temperatures and chromium chloride concentrations in the salt melt. The activation energy of electron transfer and its dependence on the CrCl₃ concentration in the electrolyte have been determined for the Cr(III) ↔ Cr(II) process.     

Polarographic analysis of the mixed-ligand system Cu(II)-glycine-glycinate

The polarographic method has been applied to the study of the mixed-ligand system Cu(II)-glycine-glycinate, in aqueous medium, at I = 1.0M (NaClO(4)) and 25 -/+ 0.1 degrees . The stabilization of the mixed complex [CuG(G(-))](+) has been made clear and its stability constant (beta(11) = 1 x 10(9)) has been determined. The stability constants of the complexes [CuG]I(2+) (beta(10) = 17), [CuG(2)](2+) (beta(20) = 230), [Cu(G(-))](+) (beta(01) = 2.1 x 10(8)) and [Cu(G(-))(2)] (beta(02) = 1.7 x 10(15)) have also been calculated.     

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.     

Polarographic determination of Ce(III) and Tm(III) using rare earth-DBF-chlorophosphonazo complex

The electrochemical behaviour of the DBF—chlorophosphonazo (DBF—CPA)—rare earth (RE) complex has been investigated in this paper. A highly sensitive polarographic adsorption wave was found in the RE(III)—DBF—CPA system and a new method for determination of trace total RE(III) has been established. The limit of detection was 1.8 × 10⁻⁸M. The results of determination of the total RE(III) content in Chinese standard reference materials of cast-iron and alloy steel were in good agreement with the certified values. The polarographic adsorptive waves of Ce(III) and Tm(III)—DBF—CPA overlap seriously. In order to improve the selectivity of determination, a non-linear regression model was employed to fit the peak height of the polarographic wave and the concentrations of Ce(III) and Tm(III). The predictive accuracy of this model for simulant mixtures was satisfied.     

Polarographic study of composition and stability constants of Pb(II) N-(2-acetamido) imino diacetate complexes

Summary The complexation of Pb(II) by N-(2-acetamido) imino diacetate (ADA) has been studied polarographically (dc and ac polarographic techniques). Ac polarographic studies have been particularly helpful in deciding the reversibility of the reduction of both simple and complexed metal ions and for confirmation of the overall stability constants. A weighted least squares numerical technique has been applied for the calculation of the overall stability constants using both dc and ac techniques. The reduction of Pb(II) in N-(2-acetamido) iminodiacetate solutions has been found to be reversible and diffusion controlled, involving a two electron transfer process. Potential vs. concentration data at =0.1 mol dm^–3 (KNO₃) are interpreted on the basis of the formation of two complex species PbADA and Pb(ADA)^2– in thepH range 6.85–8.50. The logarithms of the stability constants (calculated from ac measurements) of these complexes are 8.73±0.12, 10.86±0.18 at 25°C, 8.31±0.28, 10.31±0.09 at 35°C and 7.61±0.20, 10.10±0.11 at 45°C, respectively. The thermodynamic parameters G, H and S have been calculated at 35°C.

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Polarographische Untersuchung von Zusammensetzung und Stabilitätskonstanten von Pb(II) N-(2-Acetamido)iminodiacetat-Komplexen

Zusammenfassung Es wurde die Komplexierung von Pb(II) mit N-(2-Acetamido)iminodiacetat (ADA) polarographisch mittels DC- und AC-Techniken untersucht. Insbesonders AC-Polarographie ergab eine klare Entscheidung bezüglich der Reversibilität der Reduktion von einfachen und komplexierten Metallionen und für die Bestätigung der Stabilitätskonstanten. Zur Bestimmung der Gesamtstabilitätskonstanten wurde eine gewichtete mittlere Fehlerquadrat-Methode auf Basis von DC- und AC-Messungen herangezogen. Die Reduktion von Pb(II) in N-(2-Acetamido)iminodiacetat-Lösung stellte sich als ein reversibler und diffusionskontrollierter Zweielektronen-Transferprozess heraus. Die Abhängigkeit des Potentials von der Konzentration bei =0.1 mol dm^–3 (KNO₃) läßt sich mit der Bildung von zwei Komplex-Spezies PbADA und Pb(ADA)^2– impH-Bereich 6.85–8.50 erklären. Die Logarithmen der Stabilitätskonstanten dieser Komplexe (aus AC-Messungen) sind 8.73±0.12 und 10.86±0.18 bei 25°C, 8.3 ±0.28 und 10.31±0.09 bei 35°C bzw. 7.61±0.20 und 10.10±0.11 bei 45°C. Die thermodynamischen Parameter G, H und S wurden für eine Temperatur von 35°C berechnet.

     

Composition of a mixed-ligand gadolinium(III) complex in fluoride-dimethylformamide electrolyte

The gadolinium(III) complex formed in a fluoride-dimethylformamide (DMF) electrolyte was studied by linear-sweep voltammetry and IR spectroscopy. The composition of the mixed-ligand complex formed was found to correspond to the component ratios Gd: DMF: F = 1: 3: 4. It has been found that the coordination link in the complex is via two oxygen atoms and one nitrogen atom of dimethylformamide and involves four fluoride ions.     

Stoichiometry, stability constants and coordination geometry of Eu(III) 5-sulfosalicylate complex in aqueous system-A TRLIFS study

The complex formation between Eu(III) and 5-sulfosalicylate, (HSSA)(2-), has been investigated by means of TRLIFS (time resolved laser induced fluorescence spectroscopy). The concentration of free ligand in the solution was determined from the fluorescence emission of 5-sulfosalicylate by subtracting the dynamic quenching effect from the observed quenching of fluorescence emission by means of lifetime analysis, and the stoichiometry and the corresponding formation constants were obtained. A carboxylate coordinated complex, Eu(HSSA)(+), and also a chelate complex, Eu(SSA), were identified, and the formation constants of the complex Eu(HSSA)(2+) for the reaction, Eu(3+)+ HSSA(2-)[rightward arrow] Eu(HSSA)(+), and the deprotonation constant of the chelating reaction, Eu(HSSA)(+)--> Eu(SSA)+ H(+), were calculated at log beta(1,1)= 1.79 and log K'=-5.78, respectively. TRLIFS using the fluorescence emission from Eu(III) was performed in order to determine the number of coordination waters of the complex Eu(HSSA)(2+). The quenching of the Eu(III) fluorescence caused by (SSA)(3-) disturbed the lifetime analysis of the 'intrinsic lifetime' of Eu(III) in Eu(HSSA)(2+), however the problem was successfully solved by the analysis of emission intensity and lifetime, and the formulation of the complex was determined as [Eu(HSSA)8H(2)O](2+) with the explicit involvement of the coordinated waters.     

Polarographic study of dioxo-uranium(VI)-8-hydroxyquinoline-succinate system and thermodynamic parameters

The dioxo-uranium(VI)-8-hydroxyquinoline-succinate system has been studied polarographically at constant ionic strength (μ = 0.6 M KCl) in aqueous alcohol (7 : 3) at different temperatures. The reduction of the simple and mixed complexes is reversible and diffusion controlled. The DeFord-Hume and Schaap-McMaster methods have been applied in the determination of composition and stability constants of the simple and mixed complexes respectively. The thermodynamic parameters ΔG, ΔH and ΔS have also been calculated.     

Polarographic study of Eu(III)-succinate-ethylenediamine and Eu(III)-malonate-ethylenediamine mixed systems

The mixed complexes of Eu(III) with succinate (succ^2?) and malonate (mal^2?) and ethylenediamine (en) have been studied polarographically at 25°C and at constant ionic strength, μ = 0.1 (NaNO₃) and pH 6. The reduction of the complexes in each case is quasi-reversible and diffusion-controlled. In each system three mixed complexes are formed, viz. [Eu(succ)(en)]⁺, [Eu(succ)(en)2]⁺ and [Eu(succ)₂(en)]^? with stability constants log β₁₁ = 9.2, log β₁₂ = 17.5 and log β₂₁ = 11.7; and [Eu(mal)(en)]⁺, [Eu(mal)₂(en)₂]^? and [Eu(mal)₃(en)]^3? with stability constants log β₁₁ = 11.4, log β₂₂ = 19.08 and log β₃₁ = 13.5 respectively.     

Synthesis,characterisation, and antioxidant study of Cr(III)-rutin complex

The article describes the synthesis and characterisation of the Cr(III)-rutin complex along with an estimate of its antioxidant activity. The complex was characterised using elemental analysis, UV-VIS, IR, conductance data, thermal, and gravimetric analyses. In the UV-VIS study, a bathochromic shift of approximately 98 nm indicates the formation of a rutin complex by more than one chelating site. The FT-IR spectra clearly show the formation of the Cr—O bond between rutin and Cr(III) at 494 cm^?1, while the thermal study shows the presence of eight coordinated water molecules in the complex. The gravimetric analysis quantitatively proves the presence of four chloride ions. From these data, the formula of the Cr(III)-rutin complex was deduced as [Cr₂(C₂₇H₂₈O₁₆)(H₂O)₈]Cl₄. Moreover, the antioxidant study of the complex was evaluated by using 2,2′-diphenyl-1-picrylhydrazyl (DPPH) free-radical, ferric-reducing, and phosphomolybdenum assays, which show that the complex has a higher antioxidant activity than rutin.     

Polarographic study of As(III)—Triethanolamine reaction

pH, conductometric titration and polarographic measurements revealed that the interaction of As(III) with triethanolamine is based on hydrogen ion liberation with the formation of only [As(OH)₂HX]^? species. The polarographic reduction waves for this reaction are irreversible and of diffusion controlled process. The conditional stability constant is calculated and found to be independent of both As(III) and TEA concentrations. The average log β value amounts to 14.33±0.11 and the average log γ value equals 5.63.     

Thermal decomposition reactions and kinetic parameters of nitritobismuthates(III)

Thermal studies have been carried out on nitritobismuthates(III) of the silver group having the general formula M₂Ag[Bi(NO₂)₆] where M = Cs, Rb, K, and the sodium group having the formula M₂Na[Bi(NO₂)₆] where M = Cs, Rb.Typical thermal curves, temperatures of the endothermic peaks and percentage weight loss, calculated from the TG curve, are shown. On the basis of the results of thermal and X-ray analysis the mechanisms of the thermal decomposition reaction were determined for nitritobismuthates(III).The thermal curves were used to calculate kinetic parameters, activation energy E_a and order of reaction n by Zsako's and Coats and Redfern's methods. A comparison of the thermal stabilities of the salts under study was made. Within the same group of nitritobismuthates(III), the activation energy and the decomposition temperatures of the salts increases when the difference between the radii of outer sphere cations increases.     

Complex formation constants and thermodynamic parameters for La(III) and Y(III)L-serine complexes

Summary The stoichiometric stability constants for La(III) and Y(III)L-serine complexes were determined by potentiometric methods at different ionic strengths adjusted with NaClO₄ and at different temperatures. The overall changes in free energy (G ^o), enthalpy (H ^o), and entropy (S ^o) during the protonation ofL-serine and that accompanying the complex formation with the metal ions have been evaluated.

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Komplexbildungskonstanten und thermodynamische Parameter für La(III)- und Y(III)-L-Serin-Komplexe

Zusammenfassung Die stöchiometrischen Komplexbildungskonstanten für La(III)- und Y(III)-L-Serin-Komplexe wurden mittels potentiometrischer Methoden bei verschiedenen Ionenstärken (mit NaClO₄ adjustiert) und bei verschiedenen Temperaturen bestimmt. Die Änderungen in der freien Energie (G ^o), Enthalpie (H ^o) und Entropie (S ^o) während der Protonierung und der Komplexbildung mit den Metallionen wurden ermittelt.

     

Mössbauer study of mixed-ligand complexes of europium(III)

A series of europium(III) mixed complexes was prepared containing 1,10-phenanthroline or 2,2-bipyridine as neutral ligand and simple inorganic anions or benzoate and its derivatives as ionic ligands. The Mössbauer spectra of the products indicated that both types of ligands were directly coordinated to the central europium(III) atom. The Mössbauer isomer shift values reflected both electron shifting and steric effects of the substituents on the ligand. The quadrupole splitting values pointed to the similar symmetry of the electron shell of the europium in almost all complexes with analogous composition. The IR spectra provided evidence of the binding mode of the carboxylate groups in the complexes containing benzoate or its derivatives. The x-ray photoelectron spectra of the compounds demonstrated the effects of electrophilic and nucleophilic substituents on the electron binding energies in the europium, oxygen, and nitrogen orbitals.     

Polarographic analysis of the reduction waves of Pt(II)-SATSC complex

A polarographic study of the Pt(II)-salicylaldehyde thiosemicarbazone complex in sodium perchlorate as supporting electrolyte is described. In addition to the reduction wave of the complex, a catalytic hydrogen wave is also recorded. The characteristics of this catalytic hydrogen wave are studied under different experimental conditions such as varying acid/complex/supporting electrolyte/surfactant concentrations and also with mercury droptime. Based on these, a probable mechanism for the electrode process has been postulated. Presented at the 12th Annual Symposium in Chemistry held at the Indian Institute of Technology, Madras in March 1987.