Conversion of sulphur dioxide in the atmosphere

Summary Pertinent, previous studies of the oxidation of SO₂ in the atmosphere are briefly reviewed. A project dealing with the conversion in the plume from an oil-fired power station is described in greater detail. Measurements were performed from an aircraft and included continuous registration of NO_x, SO₂ and ozone concentrations. The possibility of using NO_x as an internal tracer is discussed; also the use of the inert tracer SF₆ is treated and a special detector for the continuous registration of SF₆ in relative concentrations down to 10^–6 ppm is described. Preliminary results indicate a half-life for SO₂ in the plume of about half an hour.

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Umsetzung von Schwefeldioxid in der Atmosphäre

Zusammenfassung Einschlägige frühere Studien über die Oxidation von SO₂ in der Atmosphäre werden kurz diskutiert. Ein Projekt zum Studium der Umwandlung im Abrauch eines ölbefeuerten Kraftwerkes wird im Detail beschrieben. Die Messungen wurden mit Hilfe eines Flugzeuges vorgenommen und schließen die kontinuierliche Aufzeichnung von NO_x-, SO₂- und Ozon-Konzentrationen ein. Die Möglichkeit der Verwendung von NO_x als interner Indicator wird diskutiert. Außerdem wird der Gebrauch des inerten Indicators SF₆ behandelt und ein spezieller Detektor für die kontinuierliche Aufzeichnung von SF₆ mit relativen Konzentrationen bis herunter auf 10^–6 ppm beschrieben. Vorläufige Ergebnisse deuten auf eine Halbwertszeit von SO₂ im Abrauch von etwa 30 min hin.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria     

Theoretical study on solvation effects in chemical reactions: A vibrational coupling model

A vibrational coupling model to treat the solvation effects in chemical reaction rate calculations is proposed and applied to the intramolecular hydrogen transfer reaction CH₃O· → ·CH₂OH in the condensed phase. The effect of solvation is taken into account in two ways: (1) the solvent effect on the activation energy of the reaction is simulated by including 39 surrounding water molecules, represented by fractional charges at the assumed atomic positions, in the potential energy surface calculation; and (2) the vibrational couplings between the 10 nearest solvent molecules and the molecules constituting the reaction system are explicitly included in a vibrational frequency calculation. RRKM theory with Miller's tunneling correction included is employed to calculate the rate constants. The effect of solvation causes a significant change in the chemical reaction rate, mainly through a lowering of the activation energy. The vibrational coupling causes a slight increase of the rate constant in the tunneling region by perturbing the vibrational frequencies of the reactant and transition states, which appear in the rate-constant expression, but has little effect at higher temperatures.     

Self-assembling a molecular pegboard

This paper describes the design, construction, and application of a self-assembled, chemically addressable DNA nanogrid composed of DNA tiles of nanometer dimensions. This self-assembled structure permits precise placement of molecules at predetermined locations on a "molecular pegboard". We used the indexed DNA nanogrids to identify single molecules of DNA that hybridize at particular locations.     

Anodic stripping voltammetry with the florence mercury film electrode. determination of copper,lead and cadmium in sea water

The use of the rotating glassy carbon electrode mercury plated in situ for anodic stripping voltammetry has been investigated. The choice of electrode material is discussed. The effect of instrumental parameters on the stripping response for copper, lead and cadmium in sea water is studied, the results being in accordance with the theory of thin film electrodes. The variation in the observed sensitivity for the three metals in sea water is discussed in terms of complex-forming ligands. Lastly the performance of the film electrode is compared to that of the hanging mercury drop electrode.     

Anion radicals and dianions as electron transfer reagents

The catalytic regeneration of depolarizers by certain substrates has been demonstrated by means of cyclic voltammetry. As depolarizers we have employed anion radicals of aromatic hydrocarbons, heteroaromatic compounds, ketones, esters, nitriles, and olefins, and dianions of aromatic hydrocarbons, heteroaromatic compounds, ketones, and esters. As substrates we have investigated simple aromatic and aliphatic halides, 1,2- and 1,3-dihalides, carbon dioxide, and activated olefins. A requirement for the observation of a catalytic wave is that the reduced substrate undergoes a practically irreversible reaction after the reaction with the reduced depolarizer; for simple halides it is a cleavage reaction, for 1,2- and 1,3-dihalides an elimination, for carbon dioxide an addition, and for activated olefins a coupling. Electrochemical investigations of these kinds of reactions may be of interest in connection with the mechanism of several types of reactions in organic chemistry.     

Upper limit for thermal direct photon production in heavy-ion collisions at 60 and 200A·GeV

The production of direct photons has been investigated in reactions ofp and¹⁶O projectiles at 60 and 200A·GeV with C and Au nuclei. Photon and ⁰ spectra have been measured in the pseudorapidity range 1.52.1 for the transverse momentum region 0.4 GeV/cp _T 2.8 GeV/c employing the lead-glass spectrometer SAPHIR. An upper limit of 15% at the 90% confidence level for the direct photon signal relative to the neutral pion production is obtained from the comparison of measured photon spectra with Monte Carlo simulations of the hadronic background based on the reconstructed yield of ⁰ and mesons. Consequences for a possible phase transition to a quark-gluon plasma are discussed.     

Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A-.) have been obtained using a new laser-flash photolysis method. The radicals R. and the radical anions A-. were generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)3-. For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all the measured coupling rate constants an average value of k1 = 1.9 x 10(9) M-1 s-1 was found with a relatively small variation in the coupling rates (0.8-2.9 x 10(9) M-1 s-1). The results demonstrate that the coupling rate k1 is insensitive to changes in the steric and electronic properties of the radicals and the structure and standard potentials of the aromatic radical anions.     

[B(O–C6H4–CN)4]– based Silver and Copper Coordination Polymers

A series of new coordination polymers bearing the [B(O–C₆H₄–CN)₄]^– anion was synthesized. Two new, one dimensional coordination frameworks of the type M[B(O–C₆H₄–CN)₄] (M = Ag, Cu) were obtained by salt metathesis. The reactivity towards organic Lewis‐bases was studied. The reaction with bidentate ligands yielded two dimensional networks with the general formula [M(L)][B(O–C₆H₄–CN)₄] {L = 2,2′‐bipyridine, 4,4′‐bipyridine, 1,2‐bis(pyridyl)ethane, 1,4‐diazabicyclo[2.2.2]octane}. The synthesis, properties and single crystal structure are reported.