Designing A Reactor to Generate Hydrogen Bubbles

Hydrogen is produced by the reaction between zinc and hydrochloric acid. This reaction is used to illustrate the importance of considering thermodynamics when designing a chemical reactor. The gas released is collected in soap bubbles that rise in the air, indicating that a lighter than air gas has been produced. The bubbles can be lit to add a dramatic effect to the demonstration. The reaction is highly exothermic, raising the temperature of the reaction materials and the reactor. Batch operation of this reactor would require short cooling periods between reactions. Alternatively, a modification of the design is suggested to allow for continuous cooling of the vessel, which would allow semicontinuous operation of the reactor. (Zinc would have to be periodically replenished as it is consumed in the reaction.) The consequences associated with the cooling of the vessel are discussed.     

Chemical identification of icosahedral structure for cobalt and nickel clusters

Reactions of bare and hydrogenated cobalt and nickel clusters with ammonia and with water are used to determine cluster geometrical structure. Saturation measurements determine the total number of ammonia binding sites on cluster surfaces. A pattern of minima in the number of such sites is found to correlate with the sequence of closed shells and subshells expected for icosahedral packing in the 50- to 120-atom size range (50- to 200-atom range for hydrogenated clusters). In many cases there are 12 sites at the minima, the number that would be expected for preferred ammonia binding sites on closed (sub)shells of icosahedral clusters. The equilibrium adsorption of a single water molecule provides a sensitive measure of changes in cluster-water binding energy. A pattern of binding energy maxima is found, once again correlating with icosahedral structure, but for clusters having one metal atom more than the closed (sub)shells. In general, hydrogenation enhances the patterns of minima and maxima. These observations are explained in terms of the expected nature of ammonia and water binding to icosahedral clusters.     

Trace speciation by HPLC?GF AA for tin- and leadbearing organometallic compounds,with signal increases induced by transition-metal ions

High-performance liquid chromatography coupled with graphite furnace atomic absorption spectroscopy (HPLC? GF AA) gives element-specific detection of environmental samples containing trace amounts of organotin or organolead species. The direct GF AA of organotin and organolead species is subject to errors arising primarily from loss of analyte prior to atomization, probably through the formation of refractory carbides and of compounds or complexes that are volatile at low temperatures. Examples abound in the literature of signal suppression in the GF AA of organometallic species in environmental samples, and several furnace tube modifications have been developed to overcome this suppression. Here, the analyte and a modifier are co-pipetted into a conventional furnace tube, from either a solution of analyte or an HPLC effluent. Oxides of transition metals (e.g. chromium, manganese, or tungsten) are shown to enhance both tin and lead signals, whereas chlorides do not, suggesting the low-temperature formation of relatively involatile metal oxides or volatile metal chlorides, respectively. In the absence of modifier, GF AA signal intensities decrease consecutively for equal quantities of mono-, di-, tri- and tetra-butyltin species, but are nearly equal for the first three in the presence of complexing dichromate (Cr₂O₇^2?). The lesser signal increase for tetrabutyltin indicates a dissimilar low-temperature complexation chemistry for the fully ligated neutral organometal to that for the ligated ions. similar results are demonstrated in post-column addition of a matrix modifier to effluent containing either organotin or organolead species.     

High-temperature emissivities of complex gas mixtures in the 4.8 μ region

Emissivities of dilute C-H-O and C-H-O-N gas mixtures have been measured in the 4.8 μ region behind reflected shock waves (2399≤T, °K≤3093) under near-equilibrium and equilibrium conditions. The emission may be satisfactorily accounted for in terms of emission from equilibrium mixtures of CO₂, CO and H₂O.     

Photon stimulated ion desorption of H+ ions from GaAs (110)/H2O

The photon stimulated ion desorption yield of H⁺ ions from a H₂O dosed GaAs (110) surface has been measured in the range 18eV ? hυ ? 30eV. There is a direct correspondence between the PSID H⁺ yield, reflectance, and the secondary electron yield spectrum of GaAs (110). The data provides evidence that the initial stages of PSID involve core level (Ga(3d), O(2s)) → conduction band excitation followed by Auger decay.