Tunable electrochemical activity of polyaniline salt by doping anion exchange

The exchange of mobile anion of chemically synthesized polyaniline with counter anions of electrolyte solutions is studied by using cyclic voltammetry (CV). The synthesized polyaniline (PANI) doped with sulfuric acid (H2SO4) and dodecyl benzenesulfonic acid (DBSA) is soluble in a wide range of organic solvents which makes it appealing for further processability. The exchange of dopant anions (of H2SO4 and DBSA) with a variety of counter anion has been inspected by electrochemical cycling in aqueous sodium sulfate (Na2SO4), sodium perchlorate (NaClO4), and sodium hydroxide (NaOH) solution. The CV measurements have revealed that PANI remains redox active at higher scan rate and there is exchange of dopant anion with SO42- and ClO41- of electrolytes. In NaOH solution, the emeraldine salt form of PANI is transformed into emeraldine base due to deintercalation of the anion form polymer matrix. The results indicate a significant change in electrochemical conductance and behavior of PANI in each electrolyte. Furthermore, the polymer film displayed a high specific capacitance value of 588 F/g in 1.0 M NaClO4 solution in the optimized potential window of -0.2 V to 0.9 V at 20 mV/s.

Kinetic Studies on the Reactions of [(TLtBu)PtCl]+ and [Pt(tpdm)Cl]+ Complexes with Some Thiols and Thioethers

Substitution reactions of the complexes [(TLtBu)PtCl]+ and [Pt(tpdm)Cl]+, where TLtBu = 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine and tpdm = terpyridinedimethane, with nucleophiles: S-methyl-L-cysteine (S-Met-L-Cys), L-cysteine (L-Cys), glutathione (GSH) and L-methionine (L-Met) were studied in aqueous 0.1 M NaClO4 solution in the presence of 10 mM NaCl using variable-temperature UV-vis spectrophotometry. The higher reactivity of the complex with the tpdm ligand could be attributed to the influence of the bulkiness of the tert-butyl-groups from the [(TLtBu)PtCl]+ complex. The order of reactivity of the studied ligands is: S-Met-L-Cys > L-Met > GSH > L-Cys. The thioethers (S-Met-L-Cys and L-Met) are more reactive than the thiols (GSH and L-Cys). This order of reactivity is in relation with their electron properties and structures. The negative values reported for the entropy of activation confirmed the associative mode.

The correct interpretation of tetramethylthiourea electrosorption data in 3 M NaClO4 solution

Tetramethylthiourea (TMTU) electrosorption behaviour at the mercury electrode in 3 M NaClO4 has been examined. Using a new concept of adsorption isotherm, new theoretical expressions have been proposed. The application of these equations shows evident influence of the electrode charge on the TMTU adsorption. It can be concluded that TMTU molecules are largely specifically bonded and at zero electrode charge the change of adsorbed TMTU molecules orientation is observed.

Kinetic and Mechanistic Study on the Reactions of [Pd(dien)H2O]2+ and [Pt(dien)H2O]2+ with L-Cysteine and S-Methyl-L-cysteine

The reactions of [Pd(dien)H2O]2+ and [Pt(dien)H2O]2+ (dien = diethylenetriamine or 1,5-diamino-3-azapentane) with l-cysteine and S-methyl-l-cysteine were studied in an aqueous 0.10 M NaClO4 solution using stopped-flow and conventional UV-vis spectrophotometry. The second-order rate constants for the reactions of [Pd(dien)H2O]2+ at pH 1.0 are k1298 = (9.11 ± 0.11) × 102 M−1 s−1 for l-cysteine, and k1298 = (33.79 ± 0.63) × 102 M−1 s−1 for S-methyl-l-cysteine. The second-order rate constants for the reactions of [Pt(dien)H2O]2+ at pH 1.0 with l-cysteine is k1298 = (1.28 ± 0.08) × 10−2 M−1 s−1 and for S-methyl-l-cysteine is k1298 = (3.87 ± 0.02) × 10−2 M−1 s−1. Activation parameters were determined for all reactions, and the negative values of entropy of activation support an associative complex formation mechanism. Substitution reactions were also studied at pH 0.5, 1.0, and 1.5. The rate constants increase with increase in pH. These results are discussed in terms of protolitic equilibrium.

Comparative electrochemical study of some cobalt(III) and cobalt(II) complexes with azamacrocyles and β-diketonato ligands

The electrochemical properties of eight mixed-ligand cobalt(III) and co balt(II) complexes of the general formulas [CoIII(Rac)cyclam (ClO4)2 (1)?(4) and [Co2II(Rac)tpmc](ClO4)3 (5)?(8) were studied. The substances were investigated in aqueous NaClO4 solution and non-aqueous LiClO4/CH3CN solution by cyclic voltam metry at a glassy carbon electrode. In aqueous solution, cyclam and Rac ligands being soluble in water undergo anodic oxidation. Coordination to Co(III) in complexes 1?4, stabilizes these ligands but reversible peaks in catohodic region indicate the redox reaction CoIII/CoII ion. In the case of the binuclear Co(II) complexes 5?8, peaks recorded on the CVs represent oxidation of the bridged Rac ligand. The complexes examined influence the cathodic reaction of hydrogen evolution in aqueous solutions by shifting its potential to more negative values and its current is increased. In non-aqueous solution the CVs of the ligands show irreversible anodic peaks for cyclam, tpmc and for the Rac ligands soluble in acetonitrile. The absence of any peaks in the case of the investigated complexes 1?4 indicates that coordination to Co(III) stabilizes both the cyclam and Rac ligands. Cyclic voltammograms of the complexes 5?8 show oxidation processes of the Rac ligand and Co(II) ions but the absence of a highly anodic peak of the coordinated macrocycle tpmc shows its stabilization. Contrary to in aqueous solution, the redox reaction Co(III)/Co(II) does not occur in acetonitrate indicating a higher stability of the complexes 1?4 in this media in comparison with the binuclear cobalt(II)-tpmc complexes 5?8.