Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

Benzenoid Molecules with Uniform Distribution of π-Electrons within Rings

In a recent work it was demonstrated that in linear hexagonal chains the distribution of π-electrons into rings (as computed by means of the Randić–Balaban method) is uniform, irrespective of the nature of the terminal fragments. We now establish that an analogous, yet somewhat more complex, uniformity in the π-electron distribution exists also in double linear hexagonal chains, as well as in some other benzenoid systems.     

A fixed-point equation for the high-temperature phase of discrete lattice spin systems

A fixed-point equation on an infinite-dimensional space is proposed as an alternative to the usual definition of the infinite-volume limit in discrete lattice spin systems in the high-temperature phase. It is argued heuristically that the free energy and correlation functions one obtains by solving this equation agree with the usual definitions of these quantities. A theorem is then proved that says that if a certain finite-volume condition is satisfied, then this fixed-point equation has a solution and the resulting free energy is analytic in the parameters in the Hamiltonian. For particular values of the temperature this finite-volume condition may be checked with the help of a computer. The two-dimensional Ising model is considered as a test case, and it is shown that the finite-volume condition is satisfied for0.77 _critical.     

Valence bond ground states in isotropic quantum antiferromagnets

Haldane predicted that the isotropic quantum Heisenberg spin chain is in a massive phase if the spin is integral. The first rigorous example of an isotropic model in such a phase is presented. The Hamiltonian has an exactSO(3) symmetry and is translationally invariant, but we prove the model has a unique ground state, a gap in the spectrum of the Hamiltonian immediately above the ground state and exponential decay of the correlation functions in the ground state. Models in two and higher dimension which are expected to have the same properties are also presented. For these models we construct an exact ground state, and for some of them we prove that the two-point function decays exponentially in this ground state. In all these models exact ground states are constructed by using valence bonds.Supported in part by N.S.F. Grant PHY-80-19754. Fellow of the A.P. Sloan Foundation and the Canadian Institute for Advanced ResearchN.S.F. Post-doctoral FellowSupported in part by N.S.F. Grant PHY-85-15288-A01     

Forward-backward multiplicity correlations in σ+ p,K + p andpp collisions at 250 GeV/c

Forward-backward multiplicity correlations in σ⁺,K ⁺ p andpp collisions at 250 GeV/c ( \(\sqrt s \) =22 GeV) are given for all charges and for the different charge combinations. The correlations are found to be caused predominantly by centrally produced particles. It is demonstrated that this result is an agreement with observations at the ISR and the CERNp \(\bar p\) -Collider. The results are compared to expectations from LUND, DPM and FRITIOF Monte Carlo models and a geometrical picture relating correlations in hadron-hadron collisions toe ⁺ e ^? data in terms of impact parameters is tested.     

Inductively coupled plasma compared with direct current arc spectrometry for analysis of minor elements in aluminium baths

A validation study was carried out in order to evaluate the efficiency of inductively coupled plasma-optical emission spectrometry (ICP-OES) for the analysis of minor elements (manganese, chromium, copper, iron, and titanium) in aluminium alloys. Aluminium casting samples were obtained by adding compressed powder compacts of each alloying element and aluminium (minitablets) to aluminum baths in a laboratory crucible furnace. Digestion of solid samples was performed using concentrated HCI and H202 35% (v/v) previous to analysis by ICP-OES without any matrix separation. This solution-based method was validated considering direct current arc spectrometry as the reference method based on direct analysis without any pretreatment of the solid samples considered. Univariate statistical procedures were carried out, for which precision <3% and trueness of the analytical results were taken into account.     

Application of stir bar sorptive extraction for wine analysis

Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used.     

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.