Acetates, polycrystalline

Aqueous electrolytes proposed in the literature for cathodic electrodeposition of lead selenide are generally composed of dissolved selenous anhydride and a lead salt, such as nitrate or acetate. Polycrystalline PbSe films have been prepared by conventional electrosynthesis from ordinary acidic solutions of this kind on polycrystalline Pt, Au, Ti, and Sn02/glass electrodes. The main problem with these applications was the PbSe dendritic growth. Better controlled deposition has been achieved by using EDTA in order to prevent PbSeOs precipitation, and also acetic acid to prevent lead salt hydrolysis. 

The 3M Company manufactures a continuous polycrystalline alurnina—sihca—boria fiber (Nextel) by a sol process (17). Aluminum acetate is dissolved in water and mixed with an aqueous dispersion of colloidal sihca and dimethylform amide. This mixture is concentrated in a Rotavapor flask and centrifuged. The viscous mixture is then extmded through spinnerettes at 100 kPa (1 atm) the filaments are collected on a conveyor and heat-treated at 870°C to convert them to metallic oxides. Further heating at 1000°C produces the 10-p.m diameter aluminum borosihcate fibers, which are suitable for fabrication into textiles for use at temperatures up to 1427°C. 

It was reported recently [216] that optical-quality PbTe thin films can be directly electrodeposited onto n-type Si(lOO) substrates, without an intermediate buffer layer, from an acidic (pH 1) lead acetate, tellurite, stirred solution at 20 °C. SEM, EDX, and XRD analyses showed that in optimal deposition conditions the films were uniform, compact, and stoichiometric, made of fine, 50-100 nm in size, crystallites of a polycrystalline cubic structure, with a composition of 51.2 at.% Pb and 48.8 at.% Te. According to optical measurements, the band gap of the films was 0.31 eV and of a direct transition. Cyclic voltammetry indicated that the electrodeposition occurred via an induced co-deposition mechanism. 

We have also investigated adsorption of acetate on a polycrystalline Pt electrode, which is of interest in the context of catalysts for ethanol oxidation, where acetate is an unwanted oxidation intermediate, and have demonstrated the capacity of the BB-SFG method to examine Pt nanoparticles. 

Cadmium acetate and sodium tellurite solutions have similarly been used to grow CdTe films by SILAR. The films were polycrystalline (hexagonal), and the grain size was on the order of 22nm (film thickness 272nm). The optical band gap was 1.41 eV.85... 

The lead precursor in PbSe film deposition was lead acetate complexed with triethanolamine. The growth rate for PbSe was 0.18-0.16nm/cycle. The films were polycrystalline (i.e., cubic) without preferred orientation. The stoichiometry of SILAR-grown PbSe was found to be 1 1 within the limits of the RBS technique. Impurities detected were 5 at.% of oxygen and 8 at.% of hydrogen.103... 

Adsorption of acetic acid on Pt(lll) surface was studied the surface concentration data were correlated with voltammetric profiles of the Pt(lll) electrode in perchloric acid electrolyte containing 0.5 mM of CHoCOOH. It is concluded that acetic acid adsorption is associative and occurs without a significant charge transfer across the interface. Instead, the recorded currents are due to adsorption/desorption processes of hydrogen, processes which are much better resolved on Pt(lll) than on polycrystalline platinum. A classification of adsorption processes on catalytic electrodes and atmospheric methods of preparation of single crystal electrodes are discussed. 

Case Studies Adsorption of Acetic Acid on Pt(111) Single Crystal Electrodes. Acetic acid is one of a very few organic compounds which is reversibly adsorbed on platinum at room temperature (20,25). We report below our radiochemical results on adsorption of this compound on Pt(111) and on polycrystalline Pt. 

Figure 5. A combined figure representing the following relationships cyclic voltammogram of the polycrystalline Pt electrode in 0.1 M HCIO (solid line) cyclic voltammogram following addition of 1 mM CH COOH to the 0.1 M HClOi electrolyte (broken line) surface concentration of adsorbed acetic acid plotted as a function of the electrode potential (solid line and circles). (Reprinted with permission from ref. 23. Copyright 1988 Elsevier.)...

Figure 3. The current (a) and the second harmonic signal (b) obtained during the potential cycling (10 mV s-1 scan rate) from a polycrystalline silver electrode in a 0.1M TBABF4 + 35mM acetic acid acetonitrile solution.

Figure 8. The cyclic voltammogram of polycrystalline Pt electrode in lO Af acetic acid + Q.5M H2SO4 solution, and simultaneously recorded...

We then designed model studies by adsorbing cinchonidine from CCU solution onto a polycrystalline platinum disk, and then rinsing the platinum surface with a solvent. The fate of the adsorbed cinchonidine was monitored by reflection-absorption infrared spectroscopy (RAIRS) that probes the adsorbed cinchonidine on the surface. By trying 54 different solvents, we are able to identify two broad trends (Figure 17) [66]. For the first trend, the cinchonidine initially adsorbed at the CCR-Pt interface is not easily removed by the second solvent such as cyclohexane, n-pentane, n-hexane, carbon tetrachloride, carbon disulfide, toluene, benzene, ethyl ether, chlorobenzene, and formamide. For the second trend, the initially established adsorption-desorption equilibrium at the CCR-Pt interface is obviously perturbed by flushing the system with another solvent such as dichloromethane, ethyl acetate, methanol, ethanol, and acetic acid. These trends can already explain the above-mentioned observations made by catalysis researchers, in the sense that the perturbation of initially established adsorption-desorption equilibrium is related to the nature of the solvent. 

Reduction of substituted nitrobenzenes under alkaline conditions, usually with aqueous sodium acetate as electrolyte and a nickel cathode, is the classical method due to Elbs [45] for the formation of azo- and azoxy-compounds. Protons are used in the electrochemical reaction so that the catholyte becomes alkaline and under these conditions, phenylhydroxylamine reacts rapidly with nitrosobenzene to form azoxybenzene. Finely divided copper has long been known to catalyse the reduction of nitrobenzene to aniline in alkaline solution at the expense of azoxybenzene production [46]. Modem work confirms that whereas reduction of nitrobenzene at polycrystalline copper in alkaline solution gives mainly azoxybenzene, if the electrode is pre-oxidised in alkaline solution and then reduced just prior to the addition of nitrobenzene, high yields of aniline are obtained with good current efficiency... 

Chelates 589 (3.27) and 590 (3.28) [16] were obtained by refluxing the methanol (or ethanol in the case of 590) solutions of corresponding ligands and metal acetate in a 2 1 ratio for 15 min. Polycrystalline precipitates were filtered out, washed by corresponding solvent, and dried in vacuo at 150°C. Yields 40-50%. 

Single pulse, shock tube decomposition of acetic acid in argon inv olves the same pair of homogeneous, molecular first-order reactions as thermolysis (19). Platinum on grapliite catalyzes the decomposition at 500—800 K at low pressures (20). Ketene, methane, carbon oxides, and a variety of minor products are obtained. Photochemical decomposition yields methane and carbon dioxide and a number of free radicals, wliich have complicated pathways (21). Electron impact and gamma rays appear to generate these same products (22). Electron cyclotron resonance plasma made from acetic acid deposits a diamond [7782-40-3] film on suitable surfaces (23). The film, having a polycrystalline stmcture, is a useful electrical insulator (24) and widespread industrial exploitation of diamond films appears to be on the horizon (25). 

In-situ FTIR studies on the electrooxidation of ethanol on polycrystalline Pt [97-99] as well as on single-crystal Pt electrodes [lOO/lOl] have shown the formation of acetaldehyde and acetic acid in addition to cmbon dioxide as soluble products. Figure 29 shows the typical features for thesq/products, which were assigned according to Ihble 1. 

First, Harrison et al. [3.36] studied Me UPD in the systems Ag(lll)/Pb, Cf, Ag(polycrystalline)/Tl, Cf, and Ag (polycrystalline)/Pb, acetate by cyclic voltammetry and potentiostatic pulse measurements. The authors claimed that a non-monotonous current transient represents a necessary criterion for 2D nucleation and growth involved in the 2D Meads overlayer formation. However, the experimental results presented did not give evidence for a first order phase transition. 

---