A comparison of the electrode kinetics of dissolution of Pb and Hg

Mercury dissolution in HCl and Pb in H₂SO₄ have been investigated using automated equipment of new design. The characteristic electrochemical parameter curves derived from the steady-state impedance and current-potential curves are reported. The data spans the active-passive transition and the passive region. An interpretation of the data in the passive region, based on a reaction kinetic model, is discussed.     

Modification of thermal techniques: Derivative,digital filter,Fourier transform

Continued efforts to identify compatible or incompatible blends have demonstrated a need to separate overlapping curves or peaks in a thermal trace. One way to do this is by using the derivatives of these curves. While the function is available on most modern thermal analysis units, its usefulness is often limited by noise in the system. Two techniques which can help to greatly reduce noise are digital filtering and Fourier transformation of the data. Both approaches have been used on identical sets of noisy data. The FT method appears to offer greater potential for producing useful derivatives from noisy composite curves.

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Zusammenfassung Ständige Versuche zur Identifizierung kompatibler und nichtkompatibler Gemische haben die Notwendigkeit mit sich gebracht, sich überlappende Kurven oder Peaks in thermischen Kurvenverläufen zu trennen. Eine Möglichkeit dafür bietet die Registrierung difierenzieller Kurven. Diese können mit den meisten modernen Geräten aufgenommen werden, ihre Brauchbarkeit wird aber oft durch den Geräuschpegel im System limitiert. Der Geräuschpegel kann durch digitale Filterung und durch Fourier-Transformation der Daten herabgesetzt werden. Beide Methoden wurden unter Verwendung identischer Datenserien geprüft. Die FT-Methode scheint bessere Möglichkeiten zu bieten, geeignete Differentialkurven aus starkes Rauschen aufweisenden Kurvenverläufen zu erhalten.

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Gel routes to environmental catalysts

Various methods for the preparation of metal oxide catalysts for environmental control purposes are described. These include coprecipitation, sol-gel, and impregnation, and are used to prepare mixed oxide catalysts of the types SnO₂-MO₂ (M=Ce or Zr), SnO₂-Ln₂O₃ (Ln = lanthanide), Ln-doped CeO₂, Cr (VI)-doped SnO₂, and Cu(II)-doped SnO₂. The aggregation in stable colloidal sols of SnO₂, CeO₂ and ZrO₂ is dependent on the concentration of the metal oxide. Techniques for the characterisation of these catalyst materials include gas adsorption, X-ray diffraction, and TEM/EDXA.     

Line sources in absorption spectroscopy

Hollow-cathode tubes and discharge lamps are studied as spectral sources for absorption spectrophotometry. Comparisons are made of monochromatic versus conventional continuous sources with respect to several experimental parameters, particularly the effect of slitwidth. Working curves are shown to indicate the possible advantages of using line sources for narrow band absorption systems.     

Metal complex-substituted polysiloxanes as novel coatings for capillary electrophoresis and capillary electrochromatography

Two novel polysiloxane-based polymers, which contain metal complexes, have been prepared. To prepare the Co(TACN)3+(2) (TACN= 1,4,7-triazacyclononane) based polymers, an orthoamide derivative of TACN was added to bromobutane-substituted methylpolysiloxane and hydrolyzed with base. Co(II) was then coordinated to the TACN, followed by cobalt oxidation to make polymer A or followed by N-octyl TACN coordination and cobalt oxidation to make polymer B. In both materials, TACN forms thermodynamically and kinetically stable Co(TACN)3+(2) complexes in which the six coordination sites of the Co(III) are occupied by nitrogens from the TACN. The polymers were coated on fused-silica capillary columns and spherical silica particles, which were used for capillary electrophoresis and capillary electrochromatography, respectively. The open and packed columns showed strong and pH-independent reversed electroosmotic flow.     

The effect of bubbles on the measured electrochemical parameters during hydrogen evolution on nickel

The hydrogen evoluton reaction has been investigated at nickel rotating and vertical stationary electrodes in 1 M HC1. Steady state current—potential, impedance—potential and potential step—current—time transients results are reported. The impedance is analysed by equivalent circuit to produce double layr capacity—potential, ohrnic resistance—potential (and charge transfer resistance—potential) curves. Some deductions are made about the bubble layer and its effect on the electron transfer mechanism for the reaction.     

Electrokinetic control of fluid flow in native poly(dimethylsiloxane) capillary electrophoresis devices

Capillary zone electrophoresis (CZE) devices fabricated in poly(dimethylsiloxane) (PDMS) require continuous voltage control of all intersecting channels in the fluidic network in order to avoid catastrophic leakage at the intersections. This contrasts with the behavior of similar flow channel designs fabricated in glass substrates. When the injection plugs are shaped by voltage control and leakage from side channels is controlled by the application of pushback voltages during separation, fluorescein samples give 64 200 theoretical plates (7000 V separation voltage, E = 1340 V/cm). Native PDMS devices exhibit stable retention times (+/- 8.6% RSD) over a period of five days when filled with water. Contact angles were unchanged (+/- 1.9% RSD) over a period of 16 weeks of dry storage, in contrast to the known behavior of plasma-oxidized PDMS surfaces. Electroosmotic flow (EOF) was observed in the direction of the cathode for the buffer systems studied (phosphate, pH 3-10.5), in the presence or absence of hydrophobic ions such as tetrabutylammonium or dodecyl sulfate. Electroosmotic mobilities of 1.49 x 10(-5) and 5.84 x 10(-4) cm2/Vs were observed on average at pH 3 and 10.5, respectively, the variation strongly suggesting that silica fillers in the polymer dominate the zeta potential of the material. Hydrophobic compounds such as dodecyl sulfate and BODIPY 493/503 adsorbed strongly to the PDMS, indicating the hydrophobicity of the channel walls is clearly problematic for CZE analysis of hydrophobic analytes. A method to stack multiple channel layers in PDMS is also described.     

Synthesis, molecular and crystal structure of bis(triethanolamine)manganese(II) saccharinate: a seven-coordinate manganese complex with tri- and tetradentate triethanolamine ligands

The synthesis, molecular and crystal structure of bis(triethanolamine)Mn(II) saccharinate, [Mn(tea)₂](sac)₂ are reported. The configuration of the tea ligands results in an unusual example of coordination number seven for the Mn(II) ion. The two triethanolamine (tea) ligands coordinate to the Mn(II) ion forming a monocapped trigonal prism geometry, in which one of the tea ligands behaves as a tridentate ligand, while the other one acts as a tetradentate donor. The free and coordinated hydroxyl hydrogens of the tea ligands are involved in hydrogen bonding with the amine nitrogen, carbonyl and sulfonyl oxygens of the neighbouring sac ions to form a three-dimensional infinite network. A weak π–π interaction between the phenyl rings of the sac ions also occurs.     

Thermal characterization of portland cement-magnesia blends

Summary Due to growing environmental concerns and the need to use less energy-intensive building products, alternatives and improvements to Portland cement (PC) are being actively researched worldwide. Use of supplementary materials is now a common practice where PC is the predominant component of inorganic building products. This study aims to investigate the potential of magnesia (MgO), derived from a naturally occurring raw material magnesite, as a supplementary material. Results from mortar samples prepared with 10 and 20% replacements of ordinary Portland cement (OPC) by MgO are presented. DTA-TG was used to study and characterise the hydration behaviour of MgO in OPC environment after 3, 7, 14, 28, 56 and 90 days of moist curing. Microstructural and compressive strength determinations providing additional information on the influence of hydrated phases are also reported.