Polarography of tin(II) chloride in acetonitrile

Polarographic and spectrophotometric data show that tin(II) chloride is a weak electrolyte in dilute acetonitrile solutions. The dominant species, SnCl₂, exists in a labile equilibrium with the ions SnCl⁺ and SnCl₃^- Oxidation and reduction of these ionic species is responsible for all observed polarographic plateaux. The dichloro—tin(II) molecule is shown to be a good acceptor species in acetonitrile solution, readily forming 1:1 complexes with ligands such as 4-picoline N-oxide.     

Potentiometric stripping analysis for tin with a gold film electrode formed in situ on glassy carbon

A gold film electrode formed in situ on glassy carbon is used as the working electrode for the determination of tin over the range 0.1–10 μg ml^?1. Gold(III) added to the solution provides the film and serves as the oxidant for stripping. Two stripping curves corresponding to Sn(Au) → Sn(II) and Sn(II) → Sn(IV) were observed; either can be used for determinations of tin. The equations for the transition time (i.e., stripping signal) and stripping curve derived were verified experimentally.     

Underpotential deposition of tin(II) on a gold disc electrode and determination of tin in a tin plate sample

This work describes a study of the underpotential deposition (UPD) of Sn²⁺ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn²⁺ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, E_UPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn²⁺ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10^–7 to 3.64×10^–5 M. The method developed here has been applied to determine the tin in a tin plate sample.     

In-situ FTIR spectroelectrochemical investigation of cobalt(II)-cyanoferrate polymeric film coated on a glassy carbon electrode

Cobalt(II)-cyanoferrate polymeric film has been electrochemically deposited on a glassy carbon electrode and investigated by cyclic voltammetry and in-situ reflection FTIR spectroscopy. A reorientation of the terminal CN groups upon redox reactions was proposed. The stretching vibration mode of the terminal CN groups associated with Fe(III) was observed at 2122 cm(-1), however, the stretching vibration mode for terminal groups associated with Fe(II) did not appear. This process could result in a switch between lattice-closed and lattice-opened surface structure.     

Potentiometric determination of potassium cations using a nickel(II) hexacyanoferrate-modified electrode

Electroactive nickel(II) hexacyanoferrate (NiHCF) thin film modified electrodes are effective potentiometric sensors for the determination of potassium ions. The NiHCF films are deposited onto glassy carbon electrodes by repetitive potential cycling in K(3)Fe(CN)(6)/NaNO(3)/Ni(NO(3))(2) solution. The modified electrodes exhibit a linear response to potassium ions in the concentration range 1x10(-3) to 2.0 mol dm(-3), with a near-Nernstian slope (45-49 mV per decade) at 25 degrees C. In the determination of potassium ion in syrups used for treatment of potassium deficiency, the NiHCF-modified electrode gave comparable results to those obtained using flame emission spectrophotometry.     

Electroxidation of the alkaloids anabasine,cytisine, and lupinine at a platinum electrode in acetonitrile

The anodic behavior of anabasine, cytisine, and lupinine at a platinum electrode in anhydrous acetonitrile has been investigated and the basic kinetic parameters of their oxidation have been established.Institute of Organic Synthesis and Coal Chemistry Academy of Sciences of the Kazakh SSR, Karaganda. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 251–253, March–April, 1991.     

Influence of tin(II) chloride on the solvent extraction of platinum group metals with N,N-di-n-hexyl-N'-benzoylthiourea

Summary The solvent extraction of Rh(III) and Pt(IV) with N,N-di-n-hexyl-N'-benzoylthiourea (DHBT)/toluene is substantially accelerated in the presence of tin(II) chloride. Low concentrations of SnCl₂ from 0.02 to 0.03 mol/l and metal/ligand ratio of 1:4 (Pt) resp. 1:9 (Rh) lead to low residual metal concentrations below the detection limit of GFAAS. The extraction behaviour of Pt(II), Ru(III) and Ir(III) is not affected by the treatment with SnCl₂.     

Potentiometric response of a commercial (Ag2S+PbS)-membrane selective electrode to Hg(II) in aqueous solution

Summary The preparation and performance of an Hg(II)-ISE are described. The analytical behaviour of this electrode, made by chemical treatment of a commercial silver sulphide type Pb(II)-ISE, is discussed in terms of potentialvs. concentration curves, potentialvs. pH curves, and selectivity. The response to fixed c_Hg(II) as the pH is increased in the alkaline region corresponds to decrease in the free Hg²⁺concentration down to pHg 17. The estimated limit of detection of total Hg(II) concentration is 10^–5 M.

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Potentiometrisches Verhalten einer handelsüblichen (Ag₂S+PbS)-Membran-Elektrode gegenüber Hg(tt) in wäßriger Lösung

Zusammenfassung Herstellung und Wirkungsweise einer gegen Hg(II) ionenselektiven Elektrode wurde beschrieben. Das analytische Verhalten dieser Elektrode, die sich durch chemische Behandlung einer handelsüblichen Silbersulfidelektrode, die für Pb(II)-Ionen selektiv ist, herstellen läßt, wurde an Hand von Potential-Konzentrationskurven, Potential-pH-Kurven und ihrer Selektivität diskutiert. Das Verhalten gegenüber fixemc _Hg(ii)bei Anstieg des pH ins alkalische Gebiet korrespondiert mit der Abnahme der Konzentration an freien Hg²⁺-ionen bis herab zu pHg 17. Die Nachweisgrenze liegt schätzungsweise bei einer totalen Hg(II)-Konzentration von 10^–5 M.

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Presented at the Fifth European Conference on Analytical Chemistry (EUROANALYSIS-V), Cracow, Poland, 26–31 August, 1984.     

Electrocatalytic oxidation of methanol on carbon ceramic electrode modified by platinum nanoparticles incorporated in poly (o-phenylenediamine) film

Carbon ceramic electrode, a new electrode substrate, was prepared by sol–gel procedure and used for the electropolymerization of o-phenylenediamine and incorporation of platinum nanoparticles into the resulting poly(o-phenylenediamine) (PoPD) film. The modified electrode was used for electrooxidation of methanol in 0.3 M H₂SO₄ as supporting electrolyte. The presence of PoPD film increased considerably the efficiency of deposited Pt nanoparticles toward the electrocatalytic oxidation of methanol. The effective parameters on the electrooxidation of methanol, i.e., amounts of polymer and Pt catalyst, medium temperature, working potential limit in anodic direction, and potential scan rate, were investigated, and the results were discussed.     

Structural and spectral studies of palladium(II) and platinum(II) complexes derived from N,N,N,N-tetradentate macrocyclic ligands

Palladium(II) and platinum(II) complexes having the general composition [M(L)] X2 (where M=Pd(II) and Pt(II), L=3,4,12,13-tetraphenyl-2,5,11,14,19,20-hexaaza tricyclo [13.3.1.1.(6-10)] cosa-1(19), 2,4,6,8,10,(20),11,13,15,17-decaene (L1); 3,4,13,14-tetraphenyl-2,5,12,15-tetraaza tricyclo [11,0,0,(6-11)] cosa-1(16),2,4,7,9,6(11),12,14,17, 19-decaene (L2); 2,3,8,9-tetraphenyl-1,4,7,10-tetraaza cyclododeca-1,3,7,9-tetraene (L3) and X=Cl(-)) have been synthesized. The ligands were characterized on the basis of elemental analyses, IR, 1H NMR and EI mass spectral studies while that of the complexes were characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, and electronic spectral techniques. All the complexes were found to be diamagnetic. The structures consist of monomeric units in which the Pd(II) and Pt(II) atoms exhibit square planar geometry.     

Determination of Hg on poly(vinylferrocenium) (PVF)-modified platinum electrode

A new surface based on poly(vinylferrocenium) (PVF⁺)-modified platinum electrode was developed for determination of Hg²⁺ ions in aqueous solutions. The polymer was electrodeposited on platinum electrode by constant potential electrolysis as PVF⁺ClO₄⁻. Cl⁻ ions were then attached to the polymer matrix by anion exchange and the modified electrode was dipped into Hg²⁺ solution. Hg²⁺ was preconcentrated at the polymer matrix by adsorption and also complexation reaction with Cl⁻. Detection of Hg²⁺ was carried out by differential pulse anodic stripping voltammetry (DPASV) after reduction of Hg²⁺. Mercury ions as low as 5 × 10⁻¹⁰ M could be detected with the prepared electrode and the relative standard deviation was calculated as 6.35% at 1 × 10⁻⁶ M concentration (n = 6). Interferences of Ag⁺, Pb²⁺ and Fe³⁺ ions were also studied at two different concentration ratios with respect to Hg²⁺. The developed electrode was applied to the determination of Hg²⁺ in water samples.     

Thermodynamic stability of polyacrylamide and poly(N,N‐dimethyl acrylamide)

Based on theoretical thermodynamic principles, the possibility of environmental degradation of polyacrylamide to its starting monomer was investigated. Theoretical electronic structure studies on the geometry and fragmentation energy of acrylamide and N,N‐dimethyl acrylamide tetramer models were carried out using a first principles gradient corrected density functional approach. Thermal degradation to form a radical would require the cleavage of carbon–carbon bonds in the polymer chain; the energy needed for this cleavage was found to depend on the structure of the repeat unit which ranged from low of 72.5 kcal for a rare head‐to‐head construct to 86.2 kcal for a normal head‐to‐tail polymer construct (therefore, for the cleavage of a normal head‐to‐tail repeat unit, temperatures of approximately 450°C would be required). The thermodynamics of the unzipping, disproportionation, and back‐biting reactions in the resulting radical fragments were also investigated; the back‐biting process was found to require the least energy and provided the most stable radical fragment with a low probability for disproportionation or releasing of monomer to occur. The effect of solvation on the hydrogen‐bonding network in the acrylamide tetramer was studied by adding explicit molecules of water to the tetramer models. The addition of water had a significant effect on the stability of the model polymer slightly stabilizing the head‐to‐head polymer, and slightly destabilizing the head to tail polymer. Copyright © 2007 John Wiley & Sons, Ltd.