Studies on the Autoxidation of Phenyl Cycloalkanes

The products of the autoxidation of phenyl cyclopropane ( I ), phenyl cyclobutane ( II ), phenyl cyclopentane ( III ), phenyl cyclohexane ( IV ), phenyl cycloheptane ( V ) and phenyl cyclooctane ( VI ) were analyzed after reduction of the reaction mixtures with LiAlH₄. As products of the attack on the α-C H bonds the corresponding 1-phenyl cycloalkanols and 1-phenyl alkan-1-ols were found. In the case of phenyl cyclopropane some S_R2 ring opening probably takes place. The oxidabilities $ {\rm k}_{\rm p} /\sqrt {{\rm k}_{\rm t}} $, the chain termination constants k_t, the absolute chain propagation constants k_p and the relative chain propagation constant (k_p)_rel were determined for the phenyl cycloalkanes I — VI . As it is to be expected on the basis of the I-strain concept the autoxidation rate of phenyl cyclopentane ( III ) is considerably higher than that of phenyl cyclobutane ( II ) and phenyl cyclohexane ( IV ).     

Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.     

Studies on the base-catalyzed Solvolysis of Propane-2-sulphonic Acid p-Cresylester

Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction.     

Zur Reduktion von Schwefeldioxid-Restmengen in Getreidestärken

On the Reduction of Residual Amounts of Sulfur Dioxide in Cereal Starches. New economically applicable methods for considerable elimination of sulfur dioxide from starch products are described. Extraction experiments show that a part of the sulfur dioxide is chemically bounded. The SO₂-content of corn starches can be decreased below 20 ppm by application of less than the stoichiometrically calculated amount of sodium hydroxide or hydrogen peroxide in aqueous solution. Because of the more favourable process conditions the hydrogen peroxide-method is preferred to the others.     

Studies on the Autoxidation of Phenylacetylene

Phenylacetylene is oxidized slowly by molecular oxygen at 110°C. The main oxidation products are benzoic acid, benzoic anhydride, and benzaldehyde. Besides the oxidation, thermal dimerization, oligomerization, and polymerization processes also take place. As individual products 1,4-diphenylbut-1-yn-3-ene and 1,3,5-triphenylbenzene were identified. About 80% of the phenylacetylene consumed are converted into products of low volatility which could not be detected by gas chromatography. The autoxidation of acetylenic hydrocarbones [1] preferably yields products of the attack at C H bonds in α-position to the CC triple bond. An attack at the CC riple bond was a first proved in the case of phenylacetylene, which besides polymeric products yielded benzaldehyde, acetophenone, and organic acids [2]. Later, in the causes of the isomeric octynes [3] and of various 1-Phenylalk-1-ynes [4] an attack at the CC triple bond was also proved. As the primary products of the oxidative attack at the CC triple bond short-lived oxirenes or their valence isomers, the corresponding ketocarbenes are to be expected. Indeed, their rearrangement products were found in the oxidation mixtures of both the isomeric ocytnes [3] and the 1-phenylalk-1-ynes [4]. Other products of the oxidative attack at the CC triple bond are lower carboxylic acids, formally produced by oxidative cleavage of the CC triple bond [3, 4].     

Efficiency and degradation of a copper indium diselenide photovoltaic module and yearly output at a sunny site in Jordan

The present work mainly deals with the testing and modeling of a commercially-available copper indium diselenide (CIS) ST40 module from the former Siemens Solar Industries (SSI). For this purpose, a large quantity of current/voltage characteristics were measured in the Paul Scherrer Institute (PSI)’s photovoltaic test-facility under different cell temperatures, solar irradiation and air mass, AM, conditions. They were used to develop a semi-empirical efficiency model to correlate all measured data sets. The goal was to make available a model, allowing quick and accurate calculation of the performance of the CIS module under all relevant operating conditions.

For the undegraded state of the module, the efficiency model allowed us to deduce the efficiency at Standard Test Conditions, STC, and its temperature coefficient at STC, which were 11.58% and minus 0.050%/°C, respectively. The output of the undegraded module under STC was found to be 42.4 W, i.e., 6% higher than specified by the manufacturer (40 W). Furthermore, the efficiency does not decrease with increasing air mass. At a cell temperature of 25 °C and a relative air mass of 1.5, the module has a maximum in efficiency of 12.0% at an irradiance of about 650 W/m². This indicates that the series-resistance losses become significant at higher irradiances. Hence, improving the transparent conducting oxide (TCO) electrode on the front side of the cells might lead to a higher output at high irradiances.

Identical testing and modeling were repeated after having exposed the module to real weather conditions for one year. We found that the STC efficiency was reduced by 9.0%, from 11.58 down to 10.54%. The temperature coefficient of the efficiency had changed from minus 0.050 %/°C to minus 0.039%/°C. These results indicate possible chemical changes in the semiconductor film. The output of the module at STC was reduced by 9.0% from 42.4 W down to 38.6 W.

Using meteorological data from a sunny site in the South of Jordan (Al Qauwairah) and the efficiency model presented here allows us to predict the yearly electricity yield of the CIS module in that area. Prior to degradation, the yield was found to be 362 kWh/m² for the Sun-tracked module; and 265 kWh/m² for the fix-installed module (South-oriented, at an inclination angle of 30°). After degradation the corresponding yields were found to be 334 and 241 kWh/m²; meaning losses of 8.4% and 9.5%, respectively. (Note: all units of energy, kWh, are referred to the active cell area.) Having available efficiency models for other module types, similar predictions of the yield can be made, facilitating the comparisons of the yearly yields of different module types at the same site. This in turn allows selecting the best module type for a particular site.     

Residual stress measurements in irradiated solution-annealed type 304 stainless steel tubing

Immersion density and residual stress measurements were made on solution-annealed type 304 stainless steel capsule tubing irradiated up to fluence levels of 9 × 10²² n/cm² (E > 0.1 MeV). The measured residual stress is dependent on the competition between differential swelling which builds up differential stresses, and irradiation creep which relaxes these stresses. The measurements were analyzed using a bilinear swelling equation formulated with swelling data from the same heat of material. The temperatures and fluence levels of the swelling and slit tube data were each calculated with the same computer code. At high fluence, when swelling was in the steady-state region, the effective irradiation creep rate increased by a factor of about three. Further analysis was made assuming that stress-enhanced swelling and swelling-enhanced irradiation creep were the enhanced relaxation mechanisms.