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  • 1985-1989  (799)
  • 1970-1974  (2,154)
  • Industrial Chemistry  (2,037)
  • Physical Chemistry  (916)
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  • 1
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid-liquid direct-contact heat transfer in a spray column was studied numerically for a low hold-up. The solutions of the conservation equations of mass, momentum and energy for both phases agree well with earlier experimental results, if one assumes a rigid liquid-liquid interface. Heat transfer inside is dominated by transient conduction and natural convection. It was found that the Nusselt number for free convection depends essentially only on the Rayleigh number.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 374-378 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wall shear rate vectors in a bubble column and an airlift-loop reactor were measured using the limiting-current electrodiffusion technique. In connection with a new circular three-segment probe, the magnitudes and directions of shear rates were determined. The results for the bubble column are in good agreement with hot film-anemometry measurements in the same column. Moreover, the spiral flow structure, postulated in the shear-zone model of Franz, has been confirmed. In addition, the measuring technique was used to determine the flow structure in an airlift-loop reactor employed for the cultivation of animal cells. The region above the gas distributor of this fermenter has been identified as critical for mechanical damage to the cells.
    Additional Material: 11 Ill.
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  • 3
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fermentation under modified gravity could be of interest in application to (a) increasing productivity of growth and growth linked production with microorganisms at high cell densities and (b) increasing the productivity of highly viscous pseudoplastic polysaccharide fermentation. In both cases, higher oxygen transfer rates in centrifugal fields result in higher productivities since these fermentations are usually oxygen limited. A further aspect of fermentation under increased gravity is the reduction of foam since foam coalescence time decreases with acceleration number. On the other hand, under microgravity, shear reduction would allow growth and production even for very shear sensitive organisms. In order to carry out fermentations under modified gravity, a special type of fermenter-the centrifugal field bioreactor CFBR-has been developed at the Institute of Chemical Engineering (Head: Prof. Mersmann) of the Technical University of Munich. For the first time, exoprotein biosynthesis of lipase with S. carnosus has been carried out under sterile and controlled conditions in this novel bioreactor, in presence of increased mass forces.
    Additional Material: 17 Ill.
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  • 4
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental technique and evaluation method is described for the determination of local heat transfer coefficients in tubes or other ducts. By means of a rotary mixing valve, cold and warm fluid flows are mixed in order to generate an arbitrarily shaped but periodically oscillating inlet temperature profile at the test tube. The propagation of the fundamental harmonic oscillation from the fluid to the outer surface of the tube wall is calculated analytically. Comparison of fluid and wall oscillations yields the heat transfer coefficient to be measured. The inaccurate measurement of fluid bulk temperature in the centre of the cross-section is compensated by an additional correction. Experiments were carried out with turbulent water flow through a copper tube. Measured heat transfer coefficients were compared to values calculated using Hausen's equation and good agreement was obtained.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 395-399 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mean droplet diameter of the dispersed phase in pulsed plate extraction columns was measured for binary and ternary systems. A change in the droplet size in the presence of solute, dependent on such factors as the direction of mass transfer, droplet size in the binary system, radio of diffusion coefficients, viscosity of the continuous phase, interfacial tension and driving force for extraction was observed. Two new empirical correlations of mean droplet sizes in mass transfer conditions are proposed. These correlations have been successfully applied to other extraction columns.
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 406-413 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During molecular distillation in a falling film apparatus, temperature and concentration of the more volatile components undergo a marked decrease in axial and radial directions, due to the distillation in vacuo. The gradients produce changes in the rate of surface evaporation and separation efficiency along the flow path. A theoretical study of this problem is presented for binary mixtures. The respective differential equations for heat and mass transfer in the liquid film are solved numerically. As the results demonstrate, the aspect ratio of an apparatus should be large when a high separation is required and small when a high distillation rate is more important.
    Additional Material: 11 Ill.
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  • 7
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Flow phenomena, local heat and mass transfer and pressure drop of corrugated passages in process equipment are examined. Based on a method for measuring local heat and mass transfer, developed in previous investigations, a procedure has been formulated for the determination of local heat and mass transfer in corrugated passages. Using the analogy between heat and mass transfer, this technique allows the determination of heat transfer distributions in any structures with high local resolution. The corresponding pressure drop is presented together with the local and integral heat and mass transfer of different structures. It is shown that differences in heat and mass transfer as well as in pressure drop are due to different flow phenomena which also characterize mixing behaviour.
    Additional Material: 16 Ill.
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  • 8
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Crystallizer design has to take into account the physical and chemical properties of the solution and solids as well as the geometry, type and operating conditions of the crystallizer. The most important property of a crystallizing system is its solubility. High solubility leads to low relative supersaturation and large mean crystal size, and vice versa. High solubility systems can be sensitive to abrasion and attrition. For low solubility systems, mixing is crucial.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 419-426 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper considers the dynamic performance of instruments in control systems. Errors connected with transient measurements are discussed. It is shown that it is not always proper to assign common statistical properties to these dynamic errors. Emphasis is placed on temperature sensors. Common industrial thermometers are described and factors affecting their response discussed. An a-priori dynamic performance prediction procedure is presented. This permits preinstallation estimation of response characteristics of sensors used in industrial processes. Sensors in service also require performance assessment since they can deteriorate with use. In-situ testing is useful for this purpose and a recently develolped procedure is described.
    Additional Material: 9 Ill.
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  • 10
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Modelling of the kinetics of a 20-N hydrazine thruster is carried out by considering two different heterogeneous reaction channels for hydrazine decomposition to the intermediate ammonia. The parameters of the reactor model are estimated by making use of temperature profiles at the wall of the decomposition chamber. Simulated ageing of the catalyst revealed an increase of the rate of deactivation with increasing total firing time.
    Additional Material: 9 Ill.
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  • 11
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The principle of ultrasonic spectrometry is based on the measurement of the ultrasonic extinction caused by the presence of particles. From measurements at different frequencies and with the knowledge of the ultrasonic extinction cross section of the particles, a system of linear equations can be established and solved to obtain the particle size distribution and particle concentration. With an experimental apparatus covering the frequency range from 1.7 MHz to 81 MHz, particles ranging from 20 to 1000 μm in diameter may be analyzed. The measurements can be carried out with particle concentrations as high as 10% by volume.
    Additional Material: 9 Ill.
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  • 12
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The “nozzle scrubber” is a wet scrubber in which the scrubbing water is dispersed in dust laden gas stream by means of one or more pneumatic nozzle. This scrubber is distinguished by an excellent collection efficiency for submicron dust at an unusually low energy and water consumption. So far, the physical effects affecting the separation cannot be explained by a well-defined theory. Therefore, it is sensible to investigate the collection efficiency with regard to the mechanisms of inertial impaction, turbulent diffusion and coalescence induced by turbulence. The experimental equipment is of a very simple design. A light scattering device was used to measure the particle distributions. In addition, electron micrographs were analyzed to obtain information about the submicron particles. The influence of operating parameters on grade efficiency has been demonstrated by their systematic variation. The contribution of turbulent diffusion to the collection efficiency has been confirmed; nevertheless, grade efficiencies were also measured when inertial impaction prevailed.
    Additional Material: 8 Ill.
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  • 13
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This study describes the gas and liquid distributions in a column with structured packings. The column is 0.5 m in diameter. It is equipped with a total of 1289 detectors in the top and bottom cross-sections. These detectors provide a detailed picture of the gas and liquid flows through elements of only 25 × 25 mm2. The maldistribution in the gas bulk flow is negligible. Only the observed wall can contribute to malperformance. The gas flows in parallel to sheet orientation, thus introducing a radial transport. Together with the change in the orientation of subsequent packing elements, this results in good gas mixing. It was observed that the liquid wall flow rate decreases when the gas velocity exceeds 1.7 m/s. Up to the loading point, the maldistribution of the liquid is constant. Above this point, the equality of the distribution deteriorates rapidly, due to the occurrence of large-scale liquid segregation.
    Additional Material: 7 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 235-244 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Film theory under consideration of one-sided diffusion is a satisfactory basis for the calculation of vapour condensation from a flowing turbulent mixture with non-condensable gases. At atmospheric pressure and low condensate flow rates, coefficient equations for smooth tubes are used as a rule. At higher pressures and thus, at higher temperatures and gas densities, there are additional parameters. For instance, non-ideal behaviour of the gas phase or the surface roughness affects the condensation process. These parameters were examined in a test plant under variation of pressure, steam concentration and temperature in a vapour/air mixture. At pressures of up to 21 bar, the Reynolds number of the gaseous phase reaches a maximum value of 128 000 and of 720 for the condensed phase. After description of the test facility, the experimental results are explained and discussed. It is shown that the experimental results are not in a good agreement with the common calculating methods. Taking into account the non-ideal behaviour of the steam/air mixture and the roughness of condensate surface by using a friction factor ξr, all the results could be calculated with an accuracy of ± 20%. This was achived with a modification of the coefficient equation of Gnielinski [1] and by using the equation of Andreussi [2] for the friction factor of a cocurrent annular flow. With respect to one-sided diffusion, the film theory is still applicable. The described method for the determination of local transfer coefficients includes the common calculating method. It represents an extension of the general validity of the film theory.
    Additional Material: 15 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 245-248 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mass transfer data are presented for absorption of oxygen in a centrifugal film apparatus. The apparatus was designed to exclude the formation of foam by gas dispersion in liquid. Cells and micro-organisms are not subjected to high shear stress. Therefore, this equipment can be applied in fermentation processes. In the present work, experimental data and correlations were obtained on splitting of the liquid film and oxygen absorption into the film through a spiral ridge formed on the conical surface. The performance of the apparatus is found to be equivalent to those of other types of absorbers.
    Additional Material: 6 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 249-254 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermally stabilized combustion has a number of unique characteristics which permit the generation of steam or other forms of process energy from the heat of combustion of a gaseous or clean liquid fuel in remarkably compact, integrated apparatus while truly minimizing the concentrations of NOx, CO and unburnt fuel in the effluent. These characteristics, which have been identified by a long-range program of research, are described and the advantages and limitations of this process are discussed.
    Additional Material: 4 Ill.
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  • 17
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 20-26 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For design and simulation of chemical process furnaces in accordance with present-day standards, the temperature distributions in the firebox and in the reactors must be generated simultaneously. This calls for coupling of the simulations of the firebox and of the reactor. For the calculation of heat transfer in the firebox, a generalized furnace simulations program, based on the zone method, is applied. Monte Carlo simulation techniques are used to determine the view factors. The location of the burners is explicitly accounted for. Absorption and emission of radiation by the flue gas are calculated by considering band contributions for carbon dioxide and water. For the simulation of the steam reforming reactors, a one-dimensional heterogeneous model, which accounts for the presence of intraparticle partial pressure gradients, is used. The simulated temperature distribution in the furnace is in excellent agreement with industrial results, as is the simulated product distribution.
    Additional Material: 3 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 333-339 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The most important investigations on liquid weeping and entrainment in plate columns with downcomers are reveiwed. The formulae for calculating column plate efficiency under conditions of liquid weeping and entrainment have been derived on the basis of mass balance equations. The presented model is a generalization of the models of AIChE and Colburn. Sample results are shown graphically. The effect of liquid entrainment on tray efficiency predicted by the model is in agreement with experimental data of FRI.
    Additional Material: 9 Ill.
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  • 20
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The knowledge of the heat transfer coefficient on the inner side of a heated vessel wall is of the utmost importance for the design of agitated vessels. In the case of large Reynolds numbers, the heat transfer is mainly determined by these numbers whereas, with small Reynolds numbers, the heat transfer is better described by considering the Grashof number. Investigations of heat transfer in agitated narrow vessels have shown that the height/diameter ratio exerts virtually no influence on the heat transfer when multi-impeller stirrers are used. The heat transfer to stirred suspensions can be described by relationships valid for liquids if the characteristic data of the liquid are replaced by those of the suspension and when the solids volume concentration is also taken into account. This relationship allows the heat transfer coefficient to be calculated for given solids volume concentrations of up to 60%.
    Additional Material: 22 Ill.
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  • 21
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to achieve optimal energy-saving, load-dependent operation of rectification columns, development and implementation of model-based control concepts are necessary. This paper reports on the design and step-by-step testing of a state observer for the estimation of two state variables which cannot be measured directly, namely the vapour rate and the location of mass transfer zone (temperature front) in the stripping section of a production column. The procedure is described, and the relevant simulation and operation results are presented and discussed. Initial experience, gained when the concept was put into practical operation, is reported.
    Additional Material: 9 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 345-350 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous crystallization of potassium carbonate was investigated in a mixed suspension mixed product removal (MSMPR) crystallizer with 7.0 1 working volume. Highly polydispersed product was obtained, with x50 varying between 320 and 670 μm. Crystal growth rates can be described by the model of Abegg, Stevens and Larson (ASL) (size dependent crystal growth rate). Values of G0 = 8.6 × 10-9 to 3.6 × 10-8 m/s and B0/ϕ = 2.7 × 108 to 4.2 × 109 1/m3s were obtained for mT = 45 to 92 kg/m3 and ε = 0.45 ± 0.05 W/kg. Nucleation kinetics at 27 °C can be described by the equation: B0/ϕ = kBϕsε0.73G02.5. Since G0 ∝ σ, convection and/or diffusion rather than surface integration are the crystal growth controlling mechanisms.
    Additional Material: 11 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 356-357 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 54-63 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When a chemical reactor is depressurized or pressure in a vessel, filled with saturated liquid, has to be decreased, generally both vapour and liquid flow out through the relief valve. Since chemical reactors are usually operated with toxic and explosive fluids, the discharged liquid which vaporizes on the ground around the vessel may reach dangerous concentrations, causing explosions or accidents with the poisonous gas. During a research project, some fundamentals were developed for the design of separation systems which separate liquid from vapour and store it in a receiver. The requirement for a separation efficiency of a least 80% is related to the condition that the separated liquid should flow back into the reactor still during the pressure relief phase. For safety reasons, both separation and re-storage are to be carried out without the supply of external energy. Theoretical and experimental investigations of pressure distribution within the piping to the relief valve and in an integrated separator show that re-storage of the separated liquid in the vessel can be achieved under certain flow conditions. Therefore, the separator must be integrated in the pipe at a certain height above the vessel, so that the hydrostatic pressure of the separated liquid, corresponding to the difference in height, is sufficient to lead it back through another pipe against the internal pressure of the vessel. First, several separators were tested with air-water mixtures. A swirl separator and a reversing separator have been developed to such an extent that they appear suitable for the set task. Experimental results with air-water mixtures and refrigerant R12 upon pressure relief show separation efficiencies of between 90 and 100% at low pressure drops within the whole operating range. As an alternative to separation outside the vessel, a rotary separator was also developed which is fixed to the outlet opening in the vessel. A centrifugal field is produced by the separator rotor and the heavier liquid is largely separated from the vapour so that only drops in the range 〈 100 μm flow together with the vapour towards the central standpipe. The outflowing vapour leaves the separator via 4 tangentially arranged nozzles, under critical conditions. The vapour flow momentum drives the separator rotor. The arrangement was developed and tested during various series of experiments, under conditions or pressure relief with refrigerant R12. So far, separation efficiencies between 60 and 95% have been achieved at stirring speeds of up to 2500 min-1.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 89-96 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Depressurization of a pressure vessel, containing a liquid or a gas is limited by the maximum possible mass flux. This flux occurs at a certain drop in pressure. The ratio of ambient pressure to that inside the vessel must be less than a certain critical value. The critical pressure ratio depends on the thermodynamic state of the fluid inside the vessel and on the geometry of the outlet cross-section. The outlet can be a pipeline, a safety valve or a rupture disk. The results of known theoretical and experimental work are presented. In previous experiments, saturated liquids, two-phase flows or pure vapours were examined. In order to predict the critical pressure ratio, certain assumptions are necessary. These are derived for three well-defined cross-sections of the vessel outlet.
    Additional Material: 17 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 103-109 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the past decade, the sintering of model supported metal catalysts, i.e. catalysts consisting of metal deposited on very thin and flat oxide films, has been intensively investigated by transmission electron microscopy. In the current paper, a mathematical model, based on an atomic migration mechanism, for the sintering of these catalysts is presented. The predictions of the model, based on Monte Carlo simulations, are in very good agreement with the experimental observations, i.e. phenomena such as ‘apparent’ particle migration, splitting and neck formation between particles are predicated by the model.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 109-112 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Anaerobic fermentation of molasses distillery slops to biogas was carried out with the aid of an adapted and selected anaerobic mixed culture. Two different types of fermenters were used, namely an agitated pretreatment fermenter and a column fermenter with glass rings as carriers for micro-organisms. The production of biogas in both fermenters amounted to between 0.6 and 0.8 dm3/g COD. The aerobic pretreatment of distillery slops by T. fermentans, yeast during a 4 to 6 h period allows a high reduction of COD in the subsequent anaerobic phase of the process. After treatment of the distillery slops by T. fermentans, it was possible to convert between 85 and 93% of the organic matter to methane. Conversion was about 93% with loading rate of 25g COD/litre day.
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 155-161 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of methanol over zeolite H-T was investigated in a fixed bed reactor. H-T was prepared from Na-T by ion exchange with HCl and NH4Cl solutions. The HCl solution caused appreciable dealumination. High yields of ethene were obtained with NH4Cl exchangeed zeolites Na-T with 45% decationization, high proprne yields with low HCl or NH4Cl Exchanged catalysts. Low methanol partial pressures and short residence times favoured the formation of lower olefins. Lowest coking rates were observed at a reaction temperature of 693 K. The catalytic activity decrased slowly with the number of reaction/regeneration cycles. The distribution of procucts 〉 C2 could be described by the most probable distribution of Schulz and Flory.
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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 170-175 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper presents a method mathematical modelling of cocurrent multitubular fixed-bed reactors. The method is adapted to the most widespread type of industrial reactor design, i.e. the system fitted with disk-and-doughnut baffles. The proposed model makes it possible to estimate the influence of non-uniformity of the heat carrier flow on the reactor characteristics, taking into account the coolant streams by-passing via the tube-to-baffle clearances. Based on the model, the effect of the operating parameters as well as of some more important geometrical parameters of the reactor on an exemplary highly exothermic process of partial benzene oxidation to maleic anhydride is discussed.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 188-195 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Collection efficiency and pressure loss of a venturi scrubber can usually be determined from the calculation models of Barth and Calvert. However, this only leads to reasonable results if the droplets are uniformly distributed throughout each cross-section of the washing zone. In this work, a two-zone models is developed which allows the calculation of the venturi scrubber at operating conditions with a non-uniform droplet distribution. The scrubber geometry is also taken into account. A venturi scrubber was developed on the basis of this new model. Its energy consumption is significantly lower than the well-Known optimum characteristic of Wicke and Holzer. For ideal operating conditions, a new optimum characteristic is given which should be the aim of future optimizations.
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  • 31
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Steady-state concentrations of the transferred reactant in the bulk phase and the non-flowing diffusion boundary layer of an isothermal, isobaric two-phase reactor with an irreversible first-order reaction and constant composition of one phase.
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  • 32
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 200-204 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A model of floc destruction resulting form mass forces in a centrifugal field is postulated and its validity examined. This model is to be regarded as a supplement to the existing shear-loading disagglomeration models. In order to verify this additional floc disintegration mechanism, appropriate investigations were carried out with flocculated suspensions of silica and Hamburg dock sludge. As a result, in addition to floc disintegration by shear forces within a turbulent flow and in the centrifuge inlet, the existence of another mechanism was demonstrated. This consists in the floc destruction in a centrifugal field where particles in excess of a certain size, or specifically heavier components, are preferentially torn out of the floc. This floc disintegration by mass forces can lead to a classification effect in centrifuges which also subject the flocs to instant high centrifugal forces.
    Additional Material: 9 Ill.
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  • 33
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 205-212 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A circular loop reactor was built for application to a heterogeneous liquid-liquid reaction. In order to investigate the dispersion behaviour of droplets in the reactor, basic experiments were performed using a number of liquid-liquid dispersions. Droplets discharged form the impeller region were found to grow due to coalescence in the circulation region. Mean droplet diameter decreased exponentially with elapsing time. An expression correlating the steady-state mean droplet diameter with the operating conditions was derived. Moreover, the transition time required for the droplet diameter to reach the equilibrium value was determined and correlated with the operating conditions.
    Additional Material: 12 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 213-217 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Important aspects of K1a measurement in agitated aerated vessels are briefly characterized from the standpoint of reliability of the measured data. An analysis of the shortcomings of dynamic methods for measuring the K1a is given. A new modification of the dynamic method is proposed, which excludes these inadequacies through a special experimental arrangement. This was verified by comparing the data with those obtained by an independent steady-state method. The new method can serve as a standard of reference, suitable for testing newly developed methods for K1a measurement. The initial response method was tested in this way in non-coalescent liquids, and shown to lead to errors of the order of hundreds of percent. K1a values obtained with the initial response method were found to depend strongly on the probe's location in the vessel.
    Additional Material: 3 Ill.
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  • 35
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Secondary nucleation in industrial crystallizers depends on both supersaturation and mechanical stress by stirring. Most models which consider mechanical stress assume that nucleation is proprotional to the energy transferred to the crystals during collisions. This is not based on any physical relationship and, in addition, the models do not satisfactorily reproduce the experimental results. Own model, based on the theory of Hertz/Huber, which accounts for the stress of the crystals caused by impact, gave better results. This well-known and proven theory allows the calculation of the volume abraded during collisions between crystals and stirrer or walls. Introducing a nucleate efficienncy, the effect of mechanical stress on the rate of secondary nucleation, due to stirring intensity and crystallizer size, can be determined.
    Additional Material: 8 Ill.
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  • 36
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 147-154 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The sintering effect of highly dispersed metals is the reason for the following phenomena: thermal deactivation, particle size effect, separable or non-separable kinetics and the isokinetic relationship ( = compensation effect). A comparison of these phenomena reveals a contradiction which can be reconciled by a new particle size effect. This effect is characterized in the following way: The dependence of specific activity on particle size is always connected with a variation of the activation energy, caused by the particle size distribution. Therefore, this effect is referred to as the partical size and distribution effect, P.S.D.E. This new concept describes all the observed phenomena of the conventional partical size effect. Moreover, it is consistent with similar effects such as non-separable kinetics and the isokinetic relationship. In consequence, the method of isothermal measurement of specific activity is inadequate.
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  • 37
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 255-261 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Carman-Kozeny equation is applicable in the viscous flow regime but, as the powder becomes finer, this equation fails. The controlling factor is the ratio of the hydraulic diameter to the mean free path of gas molecules (rH/λ) and, as this approaches unity, “slip flow” occurs. This effect increases with (a) increasing fineness, i.e. rH reduced, (b) decreasing porosity, i.e. rH reduced, and (c) decreasing pressure, i.e. λ increased. In order to account for the enhanced flow arising as a result of this failure, a second term is introduced into the equation and this includes an unknown “constant” (δK0/K), the coefficient of slip. It was considered probable that this so-called constant was a function of (rH/λ), and an attempt was made to investigate this relationship.
    Additional Material: 8 Ill.
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  • 38
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 269-273 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Ill.
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  • 39
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 262-269 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies of flow characteristics and residence time distribution, (RTD), have been undertaken in a range of geometrically similar, laboratory nozzle-type reactors. High-speed cine-photography was employed to record the complex phenomena of liquid mixing in the reactor and also to record on film the colour of an injected tracer solution leaving in the effluent. A novel atomic absorption spectrophotometric (AAS) technique was applied to transform the results of the latter film into response curves. This technique provide detailed quantitative data on the residence time distributions (RTD) for different feed rates. A multiparameter model, comprising a network of CSTR's and plug flows, was developed to simulate the experimental response data. Good agreement was obtained between model predictions and experimental results. The experimental technique and theoretical approach are recommended for analyzing the flow patterns and mixing mechanisms in such reactors.
    Additional Material: 13 Ill.
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  • 40
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A superposition of simple physical equations allows a satisfactory, comprehensive fluid dynamic description of jet-loop reactors in multiphase operation up to a dispersed phase hold-up of 15%. In the case of higher concentrations, there are further interactions which are not yet included in the model description. Apart from the drag coefficient of the single-phase jet loop, information on the particle swarm behaviour, i.e. on the slip velocity of the dispersed phase is required. Explicit formulation of the influence of the relevant geometrical parameters permits a reliable scale-up without additional adaptation parameters.
    Additional Material: 11 Ill.
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  • 41
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 280-288 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A cubic equation of state is modified in such a way that prediction of PVT data from 40 model compounds, typical of coal oil, becomes possible with an absolute mean deviation of less than 2% for saturated liquid volumes and vapour pressures 〉 1 bar. Additional correlations for binary interaction parameters are obtained by an optimization procedure using vapour-liquid euilibrium (VLE) data from known heavy hydrocarbon liquid/light gas systems. When the modified equation is applied to coal-derived liquids, only specific gravity and boiling analysis data of the coal liquids are required, primarily in order to determine the equation-of-state parameters. The proposed equation is shown to allow a good prediction of VLE data for systems consisting of wide-boiling-range coal oils and light gases. Experimental values were obtained at elevated temperatures and pressures with a circulation flow apparatus.
    Additional Material: 11 Ill.
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  • 42
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Heat transfer and fluid mechanical data were computed for laminar channel flows containing strong longitudinal vortex pairs. The strong vortices are generated by thin delta wings and delta winglet pairs of low aspect ratios and large angles of attack. These wings are attached to the channel walls. The data show that longitudinal vortices cause high local peaks in heat transfer and marked increases in the overall channel heat transfer. These increases occur over a wide region of channel wall, compared to the vortex generating wing area. The results are of special interest for compact heat exchangers. The heat transfer enhancement allows a considerable reduction in the heat transfer area which, in turn, reduces the manufacturing and operating costs.
    Additional Material: 8 Ill.
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  • 43
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Grade efficiencies must be measured in order to characterize particle collection in cyclones. For real, irregularly shaped partcles, the grade efficiencies depend on the shape and orientation of the particles and the flow around them. Therefore, the collection characteristics of cyclones should be defined in relation to spherical particles. Deviations occurring on the use of real, irregularly shaped dusts can then be attributed to a material influence. A fast and accurate measuring technique to determine the collection characteristic for spherical particles is described, followed by the presentation of results of extensive investigations on small model cyclones. A similarity relationship is presented. The validity of this relationship was confirmed by investigations with similar, larger cyclones.
    Additional Material: 9 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 33-37 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The absorption of nitric oxide (NO) in phosphoric acid esters and polyethylene glycol ethers which contain cupric halides has been investigated. Due to high solubility of cupric halides and high equilibrium constants of formed nitrosyl complexes, the effective solubility of nitric oxide can be enhanced to about 100-fold its solubility in the salt-free organic liquid which itself amounts to only about 5-fold the NO-solubility in water. Calculations taking into account flue gas conditions indicate that the required gas-liquid ratio in industrial absorption processes will lie in the normal range of flue gas scrubbing processes, namely in the region of 400:1 to 1000:1 in volume. Thus, such a reversible absorption process could a viable alternative to SCR-processes in flue gas denitrification.
    Additional Material: 8 Ill.
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  • 45
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 96-102 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of alkali treatment, nitrogen supplement and hydraulic retention time on methane production rate from semi-continuous anaerobic digestion of 5% wheat straw-water mixtures were investigated. The experiments were carried out in laboratory scale fermenters, fed with 1 1 of basic, alkali treated and nitrogen supplemented 5% wheat straw-water mixtures, respectively, and maintained at 55 °C. Digestion experiments were performed for hydraulic retention times of 8, 10 and 15 days. The amount and composition of produced gas were measured until steady state was attained in each run. The steady-state methane production rates were found to increase with hydraulic retention time and with the type of slurry in the following order; basic, nitrogen supplemented and alkali treated slurry. Data obtained from the experiments were employed to determine the kinetics of methane production from anaerobic digestion of wheat straw, for the assessment of pretreatment effects on process kinetics. The predicted methane production rates were found to be in a reasonably good agreement with the measurements.
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  • 46
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 71-87 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the course of polymerization in homogeneous systems, the viscosity of the reaction mass increases by several orders of magnitude. The viscosity increase is affected by reaction conditions, concentration and properties of the formed polymer. Empirical correlations for homogeneous and heterogeneous polymerizations are given. Viscosity significantly affects the polymerization kinetics as well as heat, mass and momentum balances of the polymerization reactor. The influence of viscosity and its increase on conductive heat transfer, stirrer power input and cooling capacity, molecular diffusion and mass transfer coefficients, mixing time and residence time distribution in homogeneous and heterogeneous polymerizations in stirred tank and tubular reactors is reviewed.
    Additional Material: 16 Ill.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 113-130 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Starting from the review of current industrial designs, the present paper analyzes thermal interaction between reactants and coolant in multitubular fixed-bed reactors. The interaction can be described quantitatively in terms of parameters characterizing transport processes both on the tube side and in the intertubular space. The study provides a detailed discussion of existing methods and correlations used for the evaluation of these parameters. The methods presented here can be considered as a basis for the development of a more comprehensive approach to the modeling and design of multitubular catalytic reactors.
    Additional Material: 13 Ill.
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  • 48
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The prediction of leak areas in pressure vessels is an important objective in the safety analysis of chemical plants. Using suitable design rules, a leak-before-break behaviour can be achieved. This contribution outlines a procedure for the leak-before-break design of nozzle attachments and the determination of the size of the corresponding opening area. In addition, K1-factors and leak areas for a number of nozzle geometries have been calculated and plotted.
    Additional Material: 7 Ill.
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  • 49
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 218-225 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most chemical engineers presently accept that the mass transfer rate in desorption from the solid to the gas phase or from the liquid to the gas phase is accelerated with increasing temperature in the liquid or the solid phase, or increasing partial pressure of inert gas in the gas phase, and/or decreasing total system pressure in the gas phase. Nevertheless, many reports about such mass transfer are still based on the former concept, which completely contradicts the actual phenomena mentioned above. Here, we discuss the contradiction and suggest a way of resolving it in terms of diffusion theory.
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  • 50
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 226-233 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The explosion behaviour of CH4/air mixtures inside a closed 0.065 m3 spherical and a 1 m3 cylindrical vessel was investigated to determine the effect of turbulence on the structure and propagation rate of transient turbulent flames for different initial turbulence levels generated by 4 ventilators installed inside the equipment. Laser-Doppler and hot wire anemometry were used to measure the turbulent motion. It was found that fairly uniform turbulence could be achieved in the central zones of the vessels and that the RMS-values of flow velocity were proportional to the ventilator speed. The evaluation of burning velocity from the pressure/time records showed that, starting from an initial burning velocity which depends on the initial turbulence level, the flame accelerates as a result of pressure, temperature and turbulence effects. Maximum burning velocity coincides with the inflexion point of the pressure/time curve, and is followed by a rapid deceleration of the flame front. A linear relationship between burning velocity and measured RMS-velocity is recognized in the observed range of RMS-values.
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  • 51
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Distillation has been, up to now, the standard method for separating fluid mixtures in the process industry and the consensus is that it will remain so for years to come. The only disadvantage of distillation is its high energy requirement. In the following, it will be demonstrated on the example of an ideal ternary mixture, how the energy requirement of distillation process can be reduced. Very effective are some modifications of single columns, optimization of column sequences and direct or indirect column coupling. It will be shown that, just by column coupling, the energy requirement can be reduced to a third.
    Additional Material: 15 Ill.
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  • 52
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of turbulence on local heat and mass transfer is systematically analyzed. Essential prerequisite is the availability of measurement methods, based on convective mass transfer, which allow the visualization of heat and mass transfer distributions. The results show that, even at low turbulence intensities, the flow and transport phenomena are decisively influenced by the specific design of turbulence grids and the orientation of the grid wires with respect to the stagnation line. Thereby, two different flow mechanisms occur which may interact. The anisotropy of grid turbulence leads to the “wire-gap effect” depending on the actual position of the grid wires in relation to the stagnation line. The other mechanism is based on the wavy wake velocity distribution behind screens and grid which, in conjunction with the centrifugal instability of stagnation flows, may lead to longitudinal vortices. The results indicate why turbulence has not been sufficiently considered in the available (semi-) empirical correlations. Information needed for an accurate prediction of heat and mass transfer in turbulence flows is discussed.
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  • 53
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An independent preliminary mechanistic prediction method for leakage rates through small slit-shaped through-wall cracks, based on coupled pressure drop and (critical) mass flux calculation is presented. The predictions are verified against initially subcooled liquid refrigerants and water data collected during experiments in real and model cracks in a wide range of parameters. The achieved accuracy of prediction is already comparable to that of the experimental results. Further model modifications are put forward.
    Additional Material: 11 Ill.
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  • 54
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To improve the rate of convergence of random search optimization procedures, the incorporation of a gradient-oriented one-dimensional search is investigated. With this modification to the random search procedure based on uniform sampling and region contraction [1], convergence to within 0.01% of the global optimum was obtained substantially faster for typical chemical engineering problems. It was also found that the reliability of obtaining the global optimum was improved.
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  • 55
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 318-323 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A special stress measuring device for determining the normal and shear stresses acting on silo walls was developed and tested. The load cell can be used for measuring simultaneously the normal stress as well as the intensity and direction of the shear stress.
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  • 56
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The chlorination of an alumina with BET surface area of 100 m2/g has been studied in situ by transmission IR measurements at about 670 K. The chlorinating gases consisting of Cl2 and CO were employed individually and in equimolar proportion. The IR results do not reveal the presence of a phosgene surface species which could support the only mechanism proposed so far to explain the chlorination. A detailed alternative reaction mechanism is suggested for the high temperature chlorination reaction, taking into account the IR results, together with the known electron donor-acceptor properties of the activated alumina and the reaction gases: Cl2 molecules accept electrons from oxide ions with a lower coordination number on the alumina surface, leading to the formation of Cl-and Oad. While Cl- yields AlCl3, Oad reacts further with CO producing CO2.
    Additional Material: 4 Ill.
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  • 57
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The vapour phase hydrogenation of 1,3-cyclo-octadiene (COD) over Pd on alumina has been studied in the gas phase, using a recycle reactor. The dependences of COD hydrogenation rates and those of the consecutive cyclo-octene (COE) hydrogenation on the reaction conditions are well described by a model which takes into account mass transfer in the porous layer of palladium. The kinetics of the COE hydrogenation is of a Langmuir-Hinshelwood type. The hydrogenation of COD is of first order with respect to hydrogen. The reaction order with respect to COD is -0.15. If the catalyst surface is completely covered by COD, the hydrogenation of COE is totally suppressed. This indicates a much stronger adsorption of COD than of COE. Hydrogenation of COE can only occur in the innermost part of the pores when the transport of COD by diffusion is insufficient to supply the entire active surface of the catalyst. This happens if the ratio PH2/PCOD exceeds 2/ϕ2 with ϕ being the Thiele's modulus. This relationship permits a simple evaluation of the effective diffusion coefficient in the porous Pd-layer.
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  • 58
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 63-70 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is shown in this report that, under certain conditions, cleaning of exhaust air by absorption presents an interesting alternative to the existing methods. In particular, this process can be used with advantage for small quantities of exhaust air, high and strongly fluctuating solvent concentrations and solvent mixtures such as those occurring in batch operation. A washing agent was employed which had not been previously used for this purpose. Its properties, which were investigated in the laboratory, were confirmed during a 15-months' trial period in a semi-industrial plant. The process and plant were optimized for practical use. Through its option of solvent recovery from exhaust air, this physical absorption process contributes to environmental control.
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  • 59
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Combustion rate of flat graphite plates in oxidizing flows with velocities of up to 80 m/s and stagnation temperatures between 1600 and 2500 K were investigated. The flow field and its local properties were recorded in addition to surface temperature of the solid sample and change in surface structure. The experiments, in which the surface temperature of graphite was adjusted and carefully controlled by radiation shields, indicated that, under these experimental conditions, between 15 and 20 wt-% of carbon was lost as particles of up to 100 μm which burnt rapidly in the boundary layer region. Subtraction of erosion rates from the recorded global combustion rates yield the heterogeneous chemical reaction rates, which are approximated by an Arrhenius type function for the mathematical modelling. Since steep temperature and concentration gradients occur in the boundary layer, the local values of the multicomponent transport coefficients were evaluated in order to design a more realistic computational procedure which, in addition, also includes radiative heat transfer. Computational checks revealed that, in the past, the assumption of mean constant values for the transport coefficients has led to errors of up to 100% in the evaluation of the chemical reaction and global combustion rates.
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  • 60
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    Chemical Engineering & Technology - CET 12 (1989), S. 358-364 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The energy consumption of ammonia plants based on steam reforming of naphtha or natural gas can be reduced by shifting the reforming load from the primary to the secondary reformer. It is shown that lowering of the primary reformer operating temperature 20 °C results in 2% increase of unconverted methane content in the outlet stream. The increased methane content can be processed in the secondary reformer if the process air inlet temperature is increased to 400 °C. The lower operating temperature reduces the energy consumption of the primary reformer by about 6% (and the overall consumption by about 2%) and also prolongs the service life of reformer tubes.
    Additional Material: 7 Ill.
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  • 61
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 62
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    Chemical Engineering & Technology - CET 12 (1989), S. 1-11 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of micromixing limits on a process of crystallization in an MSMPR crystallizer is studied with respect to power law growth and nucleation kinetics. Three limiting cases corresponding to maximum mixedness and complete segregation in an MSMPR crystallizer and plug flow configuration were analyzed for processes in which supersaturation is generated by conventional techniques. The sensitivity of these three limiting cases to the supersaturation generation term in each mode of operation was investigated using several numerical examples. The study demonstrates the effects of mixing on the overall crystallizer performance and, in particular, the enormous micromixing influence at high supersaturation generation rates. The difference in the product CSD arise from the variations of supersaturation profiles experienced by the elementary volumes throughout their sojourn. Characterization of mixing in a real crystallizer at some intermediate levels is emphasized with the aid of relevant industrial examples.
    Additional Material: 8 Ill.
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  • 63
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    Chemical Engineering & Technology - CET 12 (1989), S. 15-19 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effective interfacial area a and volumetric liquid-side mass transfer coefficient kLa of an RTL contactor were obtained at different stirring speeds by absorption of oxygen from air into 0.8 kmol/m3 sodium sulphite solution, in the presence of Co++ ions. The values of a and kLa ranged from 80 to 150 m2/m3 and 0.0003 to 0.00053 s-1, respectively, when stirrer speed was increased from 8 to 40 rpm. When kL alone was evaluated, it was found to be practically constant, irrespective of stirring speed.
    Additional Material: 5 Ill.
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  • 64
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution reports on the theory underlying a uniform representation of heat transfer to submerged surfaces in fixed bed reactors and of gas convective part of heat transfer in fluidized beds with coarse-grained bulk solids and/or at elevated pressure. Based on an analysis of the pressure drop behaviour of fixed bed percolation at different gas pressures and with different bulk solids, a new dimensionless pressure drop parameter was developed. Fixed bed heat transfer data are very well correlated by this new dimensionless number. As soon as fluid throughput is in excess of minimum fluidization velocity, the pressure drop parameter transforms into the well-known Archimedes number. These two dimensionless numbers are connected by the condition of equilibrium for pressure drop and mass of practices in a fluidized bed. This equilibrium is fulfilled as soon as fluidization commences. Up to now, the Archimedes number has been generally accepted as the significant parameter, determining the gas convective part of heat transfer in fluidized beds; however, without any physical interpretation of this parameter. Introduction of the pressure drop number, which is consistent with the Archimedes number, reduces the heat transfer behaviour to pressure drop characteristics. The usefulness of this concept is proven by the comparison of experimental results and prediction.
    Additional Material: 6 Ill.
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  • 65
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    Journal of Physical Organic Chemistry 2 (1989), S. 646-652 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using a series of equations connecting experimental and theoretical values, it is possible to discuss the origin of the N-methylation effect in azoles dissolved in water and dimethyl sulphoxide. The existence in the azoles studied of a linear relationship between the gas → solution transfer enthalpies and the charge on the pyrrole hydrogen atom demonstrated the fundamental importance of the loss of an active centre for solvation. For the imidazole-N-methylimidazole pair, the complete thermochemical cycle has been determined, allowing the apparent lack of an effect of N-methylation on the basicity in solution to be discussed.
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  • 66
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    Journal of Physical Organic Chemistry 2 (1989), S. 26-34 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of 4-monosubstituted cyclopentenes, , were synthesized and their relative rates (kX/kH) for bromination and chlorination were determined in methanol, ethanol and acetic acid at 25 °C by competitive method. log(kX/kH) for most of the substituents can be correlated by means of Taft's equation, log(kX/kH) = ρI σI + C. In methanol ρI, Br2 = -2·91, ρI, Cl2 = -0·49, in ethanol ρI, Br2 = -3·07, ρI, Cl2 = -0·70 and in acetic acid ρI, Br2 = -1·64, ρI, Cl2 = -0·65. The presence of C(〈0) is due to a constant steric effect. The deviation of X = H is ascribed to the absence of the steric effect and that of X = CO2Me and CO2Et is accounted for in terms of anchimeric assistance. For chlorination no anchimeric assistance was observed.
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  • 67
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    Journal of Physical Organic Chemistry 2 (1989), S. 43-50 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cyclic vinyl ether dihydro-1,4-dioxin is converted to its cyclic hemiacetal hydration product, 2-hydroxy-1,4-dioxane, in aqueous solution by an acid-catalyzed reaction for which kH+ = 1·80 × 10-5 M-1 S-1 at 25°C. This reactivity and the solvent isotope effect kH+/kD+ = 2·2 show that the reaction occurs by rate-determining proton transfer from catalyst to substrate and not by a pre-equilibrium mechanism as recently proposed.2
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  • 68
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanisms of the reactions between 1-phenylethyl benzenesulfonates (1-PEB) with N,N-dimethylanilines are investigated in methanol at 35·0°C. Reactivity and selectivity trends were found to be similar to those for the reactions of 1-PEB with anilines, but the magnitudes of cross interaction constants, ρXZ, between substituents X in the nucleophile and Z in the leaving group were substantially smaller indicating no hydrogen-bond bypass bridge formation in the transition state. However, the magnitude of ρXZ suggested a direct electrostatic interaction between the reaction centers in the nucleophile and leaving group in the frontside nucleophilic attack with a loose transition state structure.
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  • 69
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: IR spectroscopy is presented as a convenient means to monitor the formation of acyl (and alkyl) cations from corresponding acid chlorides, with Lewis acids at low temperature in the solid state. Phenylacetyl chloride is co-deposited (under vacuum at -173°C with antimony pentafluoride on a KBr window), as in the ‘molecular beam’ method of cation generation. The initial IR spectrum of the deposition shows (in addition to starting materials) that a small amount of phenylacetyl cation (2274 cm-1) has been formed. Warming the solid matrix to -123°C Promotes the smooth conversion of acid chloride to acyl cation. Ultraviolet irradiation (through quartz windows) at -123°C to -73°C facilitates this conversion but does not result in the loss of carbon monoxide from the acyl cation to form benzyl cation. When benzyl chloride is used in place of phenylacetyl chloride, there is no noticeable difference between IR spectra taken before and after warming and/or photolysis of the solid deposition.
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  • 70
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The formation of a σ-like complex by reaction between 1,3,5-trinitrobenzene and 1,8-diazabicyclo [5.4.0]-undec-7-ene was investigated in toluene at various temperatures. The kinetic data showed autocatalytic behaviour. Inspection of the reaction mixtures at zero reaction time indicated the presence of an equilibrium preceding the attack of the nucleophile, affording a molecular complex (substrate-nucleophile) which is responsible for the observed kinetic features. The present and the previous data led to the conclusion that the catalytic behaviours usually observed in SNAr reactions (in apolar solvents with amines as nucleophiles) are better explained by the presence of substrate-catalyst interactions than by catalysis on departure of the proton and leaving group from the zwitterionic intermediate.
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  • 71
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    Journal of Physical Organic Chemistry 2 (1989), S. 93-102 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Organocerium(III) reagents reacted with α,β-unsaturated carbonyl compounds to give 1, 2-addition products (allylic alcohols) in good to high yields. The reaction was studied from a mechanistic point of view by the use of (E)- and (Z)-1-(4′-methoxyphenyl)-3-phenyl-2-propen-1-ones and 4,4-ethylenedioxy-2,6-dimethyl-2,5-cyclohexadienone as the probe compounds. A polar pathway was suggested for the reaction with the former enones. On the other hand, the operability of single electron transfer processes was demonstrated in the reaction with the latter probe compound.
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  • 72
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    Journal of Physical Organic Chemistry 2 (1989), S. 103-109 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preliminary theoretical study of the mechanisms for the reactions of the perchlorofluoroethanes CF2ClCCl3 (1), CF2ClCCl2F (2) and CF3CCl3 (3), with nucleophiles has been carried out by the MNDO method, following the experimentally suggested process shown in Scheme 1. The unlikely chlorophilic attack in the first step of Scheme 1 has been shown to be feasible for 1, 2 and 3 by analysis of the MO interactions. The second step has been found to be affected by the anionic hyperconjugation which stabilizes the anions CF2ClCCl2- (4), CF2ClCClF- (5) and CF3CCl2- (6) and would make reactions (2) (the second step) unfeasible in gas phase, but in solution reaction (2) may still easily occur for 4 and 5.
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  • 73
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    Journal of Physical Organic Chemistry 2 (1989), S. 110-116 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transamination reaction of α-amino acids with glyoxylic acid as catalyzed by copper(II) ions was investigated kinetically in an aqueous medium at pH 5·0 and 30·0°C. L-Phenylalanine transferred its amino group to glyoxylic acid most readily among seven different amino acids used here in the single-walled bilayer vesicle formed with N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C16). Such rate enhancement was found to originate from the cooperative trifunctional catalysis: a coordination effect exercised by copper(II) ions, a general acid-base catalysis by the imidazolyl group of the lipid, and a hydrophobic field effect provided by the bilayer vesicle. Lack of any of the three functions failed to give out significant rate enhancement. As regards correlation between the reactivity and the nature of α-amino acids, the copper(II)-catalyzed transamination was progressively enhanced as hydrophobicity of the α-amino acid was increased in the N+C5His2C16 vesicle.
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  • 74
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    Journal of Physical Organic Chemistry 2 (1989), S. 117-130 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas phase ion/molecule reactions have been used to probe the structure of ions obtained by electron impact upon 1-(diphenylmethylene)cyclopropane and 2,2-diphenyl-1-methylenecyclopropane. The resulting ions of molecular composition C16H14 (m/z 206+) were reacted with charge transfer reagents (6·9 〈 IP 〈 8·8eV), giving evidence for the presence of isomeric ions with different reactivities. The less reactive ion is identified as a trimethylenemethane species (TMM+) in which one cyclopropane bond is broken; the more reactive ions are assigned as vertical ions in which the cyclopropane ring is unaffected. The vertical ions have recombination energies of 8·44 ± 0·05eV, whereas TMM+ has one of 7·41±0·05eV. The TMM+ fraction is not constant; it increases with increasing IP of the reagent. This is attributed to a reagent-catalyzed isomerization of the vertical ion to TMM+. In addition, the reagent ions are observed to undergo a unique reaction with the neutral methylenecyclopropane derivatives: electron transfer and ring opening to yield TMM+. These findings limit the application of the customary equilibrium measurements as a method to determine the substrate IP.
    Additional Material: 7 Ill.
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  • 75
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bis(1,2-diaryl-1,2-ethylenedithiolato)metal(0) complexes (1; metal = Ni, Pd, and Pt) react with quadricyclane (Q) to give selectively 1:1 adducts which are identical with the adducts between 1 and norbornadiene (NBD). In the adducts, two sulfur atoms of the different dithiolato ligands are added to one of the double bonds of NBD. The reactions of 1 with Q are 103-104 times faster than those with NBD. The more electropositive dithiolatometal complexes react faster with Q and NBD. The adducts are dissociated to the free dithiolatometal complexes and NBD by UV-irradiation (254-436 nm). Upon irradiation with 254 nm light, the photodissociation occurs before the decomposition of the dithiolatometal complexes.
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  • 76
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    Journal of Physical Organic Chemistry 2 (1989), S. 161-176 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclobutanediyl (2) has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C2h and C2v forms which interconvert via a Cs transition state. For the singlet, only a C2h form is found. It passes, via a Cs transition state, onto the C2v surface on which bicyclobutane (3) is the only minimum. The ring-flipping (inversion) process in 3 includes the singlet biradical as an intermediate, and involves a novel, non-least motion path similar to one previously proposed by Gassman. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.
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  • 77
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    Journal of Physical Organic Chemistry 2 (1989), S. 177-182 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 4-O2NC6H4OCH2CH2NHPh undergoes clean base-catalyzed Smiles photorearrangement to 4-O2NC6H4N(Ph)CH2CH2OH in dimethyl sulfoxide-water (25:75). A linear plot of φ-1 vs [OH-]-1 indicated that the limiting quantum yield at high [OH-] is 0·12 and that uncatalyzed photorearrangement does not occur. Rate constants for the deprotonation step were determined for a variety of bases having conjugate acid pKa values in the range 5-10. When plotted according to the Brønsted Catalysis Law, these data gave a non-linear plot approaching slopes of zero and unity above and below a pKa of 6-7. This indicates that the proton-donating intermediate in this photo-Smiles rearrangement is the zwitterion diradical (pKa ≈ 7) rather than the Meisenheimer complex (pKa ≈ 2).
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  • 78
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    Journal of Physical Organic Chemistry 2 (1989), S. 146-160 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of several alkylphosphonates and alkylphosphonyl chlorides has been investigated by molecular mechanics calculations (MM2, 1985 version). The difference of the steric energies (ΔE) between tetracoordinate substrate and pentacoordinate transition state of phosphorus compounds represents the activation energy (ΔE≠) in hydrolysis. The change of ΔE for various alkyl groups relative to methyl group (ΔΔER) is suggested as a measure of the steric effect of substituents. Thus the correlation analysis involving log k and ΔΔER of the branched alkyl group gives good results and it is reasonable to anticipate that analogous treatment using ΔΔER for the straight chain alkyl group is not satisfactory owing to the minor contribution of steric effect of the latter. However, the multiple regression analysis of log k with ΔΔER and Taft's σ* provides very good results. As shown by us, for the hydrolytic reactions studied, the proposed ΔΔER is much better than Taft's Es and Charton's ν, the commonly used well-known steric parameters in the chemistry of carbon compounds.
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  • 79
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    Journal of Physical Organic Chemistry 2 (1989), S. 183-186 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The harmonic vibrational frequencies were calculated analytically at the 6-31** level for azetidine using the GAUSSIAN 82 program. The results strongly indicate the presence of several errors in a recent assignment of the fundamentals of azetidine based on a normal coordinate analysis and a revised assignment is suggested. It is concluded that reliable vibrational data for azetidine in the gas phase are needed in order to resolve the remaining ambiguities in the interpretation of the spectra.
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  • 80
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    Journal of Physical Organic Chemistry 2 (1989) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 81
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    Journal of Physical Organic Chemistry 2 (1989), S. 187-204 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction products of bifunctional chain molecules with structure X—(CH2)n—Y may critically depend on the chain length n. When the chain length is short (n ≤ 5), reaction products particular to an intramolecular reaction can be dominant, while a process corresponding to an intermolecular reaction between X—CH3 and H3C—Y may take place for higher homologues having large n (≥10). The reaction switching dependent on n is explained in terms of the encounter probability for both end groups (X and Y) with conformations pertinent to product formation. The reaction switching of this sort is discussed on the basis of a reactivity profile recorded as a function of the chain length. Similar reactivity profiles have been observed for thermal Friedel-Crafts cyclization and photo-Smiles rearrangement/photoredox reaction. It is anticipated that the magic methylene chain length of 7 may give rise to an appreciable decrease in reaction yields (e.g. ‘difficulty in medium-sized ring closure’) or an anomalous switching of reaction pathways due to chain length effects.
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  • 82
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    Journal of Physical Organic Chemistry 2 (1989), S. 205-213 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanism of the Grignard reactions of aromatic ketones in THF was studied by spectroscopic and kinetic methods. The stable radical intermediates generated in the initial electron transfer from Grignard reagent to ketones are in a state of aggregated dimer of corresponding ion-radical pairs; in which two ketone anion radicals are bridged by a dimer di-cation of Grignard reagent. Subsequent alkyl radical transfer from dimeric Grignard reagent cation moiety to ketone anion radical aggregated each other are promoted by a participation of another neutral Grignard reagent. Proposed mechanism by present authors is able to explain well addition products/reduction products ratios in the Grignard reactions.
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  • 83
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    Journal of Physical Organic Chemistry 2 (1989), S. 214-224 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solvolysis of 21 different 3- or 17-androstanyl tosylates or chlorides with halogen, hydroxy or oxo substituents in 17- or 3-position shows rate constant variations in hexafluoro isopropanol of up to 6·3 with regular differences for epimeric substituents. Similar variations ae seen over a distance of ∼10 Å in 13C-NMR shifts at C-17-ones of androstan-17-ones with varied halogen substituents in C-3, whereas the shielding observed at other distant carbon atoms excludes significant through bond effects. It is shown how, on the basis of suitable Coulomb-type equations and of force field minimized geometries, both the stability variation of carbocationic transition states and the carbonyl group polarization are predictable by linear electric field effects, using the same parametrization.
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  • 84
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    Journal of Physical Organic Chemistry 2 (1989), S. 225-231 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gas-phase pyrazole elimination of N-alkyl pyrazoles has been studied using MNDO semi-empirical molecular orbital (MO) theory with complete geometry optimization of all stationary points. We found that the activation energies (Ea) of the concerted processes are around 80 kcal/mol, 25 Kcal/mol higher than experimental values. But the differences in Ea between compounds with different substituents are in good agreement with the experimental ones.
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  • 85
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    Journal of Physical Organic Chemistry 2 (1989), S. 232-242 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic vector analysis of a set of six physical and empirical parameters of 103 commonly used organic solvents (bp, ∊r, μ, nD, ETN, and δ) gives four vectors describing 95% of the total data variability. Non-hierarchical cluster analysis, applied to our results, leads to ten separate classes of organic solvents.
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  • 86
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    Journal of Physical Organic Chemistry 2 (1989), S. 255-262 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photostimulated reaction of neopentyl halides with different nucleophiles by the SRN1 mechanism of nucleophilic substitution has been studied. Neopentyl halides do not react with carbon nucleophiles, diethylphosphite, diphenylphosphonite and azide ions, but they react with arsenide and selenide ions. The photostimulated reaction of neopentyl bromide with diphenylarsenide ions gave only the straightforward substitution product neopentyldiphenylarsine. On the other hand, the photostimulated reaction of bromobenzene with dineopentyl arsenide ions gave three arsines: dineopentylphenylarsine, neopentyldiphenylarsine and triphenylarsine. Neopentyl chloride reacts under irradiation with diphenylphosphide ions giving good yields of the substitution product.
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  • 87
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    Journal of Physical Organic Chemistry 2 (1989), S. 300-322 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various modifications of the Marcus equation have been applied to the problem of photochemical proton transfer, using available data on general acid-catalyzed photohydration reactions. These include incorporation of asymmetry and tightness parameters, as well as distance variation as a function of exoor endothermicity. The intersecting state model of Formosinho has also been successfully applied to these reactions. The overall conclusion from all of these approaches is that the reactions are characterized by somewhat asymmetric and ‘loose’ transition states, with a small but significant degree of charge development on the in-flight proton at the transition state. Estimates of the intrinsic barriers and work terms place these in the 5-7 kcal and 2-3 kcal ranges respectively. A simple valence bond configuration mixing model leads to similar qualitative conclusions about the nature of the transition states in these reactions.
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  • 88
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 323-330 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoreactions of Cr(CO)5(Im) (Im = 1,3-dimethyl-4-imidazolin-2-ylidene) have been investigated by laser flash and continuous photolysis. Quantum yields for the disappearance of Cr(CO)5(Im) in benzene under Ar or CO were very low, although transients observed by laser flash photolysis reacted rapidly with CO. This suggests that photodissociation of the carbene ligand is very minor. The laser flash photolysis at 337 nm in benzene (B) gave a transient (λmax = 630 nm), which converted to the second transient (λmax = 455 nm) within ∼100 ns. The kinetic studies of these transients revealed that the first one is a ‘free’ coordinatively unsaturated species (Cr(CO)4(Im)) and the second one carries a solvent molecule as a ligand (Cr(CO)4(Im)(B)). From the comparison of Cr(CO)4(Im) and Cr(CO)5, apparently lower reactivity of Cr(CO)5 was found to be due to the strong coordination of a solvent molecule. The Im ligand neutralizes the deficit of electron density on Cr. A simple synthesis of Cr(CO)5(Im) was also described.
    Additional Material: 3 Ill.
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  • 89
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The difference in reactivity of small [n]cyclophanes towards CF3CO2H is discussed in terms of charge densities, strain energies and proton affinities. These data are calculated with MNDO and MINDO/3 for para-, meta- and ortho-cyclophanes and for their ipso-protonation products; an attempt is made to transform gas phase ΔHf0 values into liquid phase ΔH0f values. Experimental evidence is presented that the acid catalyzed rearrangement of [5]paracyclophane to its ortho-isomer proceeds via two consecutive 1,2-carbon shifts without deprotonation; intermediate adducts were identified by NMR-spectroscopy. Thus, a gradual shift in reaction pattern in the series [4]-, [5]- and [6]paracyclophane is observed experimentally, in line with the calculational results.
    Additional Material: 2 Tab.
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  • 90
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    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 91
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 359-362 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction pathway of urea formation by selenium-catalysed carbonylation of secondary amines with carbon monoxide in the presence of oxygen was studied using piperidine as a secondary amine. It was established that selenium reacts with carbon monoxide and piperidine to give carbamoselenoate as an intermediate, which affords biscarbamoyl diselenide by the oxidation with molecular oxygen. Aminolysis of biscarbamoyl diselenide gives the urea derivative, accompanying the regeneration of selenium catalyst.
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  • 92
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An excellent linear correlation of oxygen-17 substituent chemical shifts (SCS) for twelve α, α, α-trifluoroacetophenones with single σ+ constants, δ = 24·6σ+ + 556·3 (correlation coefficient 0·998) has been observed. However, from this plot, an SCS of 34·3 ppm for 1,1,1-trifluoroacetone will give a corresponding σ+ (γ+) value of 1·44 for a methyl group, which is not in agreement with 0·63-0·79 obtained from solvolytic rate data.
    Additional Material: 1 Ill.
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  • 93
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 377-382 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of N-methylation of pyridine and its ring-substituted derivatives by trimethyl phosphate were measured in D2O and in CDCl3. Relative rates, together with the solvent activity coefficients of substrates for the transfer form chloroform to water, were used for determining the solvent activity coefficients of the activated complexes for this SN2 reaction. The results indicate early activated complexes for all pyridines, with the most nucleophilic substrate showing the most reactant-like activated complex.
    Additional Material: 2 Tab.
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  • 94
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 367-376 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative rates of hydrogen atom abstraction from a series of twelve saturated cyclic ethers and sulfides were determined at 70°C. The abstracting radical could be generated from bromotrichloromethane both photolytically or by the thermal decomposition of AIBN. The reaction rates did not show a dependence upon method of radical generation. Reaction occurred only at the position adjacent to the heteroatom. The reactivity of the cyclic ethers was in the order C4H8O 〉 C6H12O 〉 C3H6O 〉 C5H10O. This trend would indicate appreciable influence by ring strain, however, the slightly greater reactivity of tetrahydrofuran relative to oxepane suggests a contribution by stereoelectronic factors as well. The reactivity of the cyclic sulfides, which reacted faster than the corresponding ethers, was in the order C4H8S 〉 C5H10S 〉 C6H12S. This would imply little influence of ring strain. The major structural effect would be that of variable electron donating ability of the sulfur atom. The rate of reaction of thietane was also determined. It was found to preferentially undergo SH2 attack at the sulfur atom followed by ring opening rather than hydrogen abstraction. The reactivities of both series of compounds were decreased by the inductive effect of a second heteroatom beta to the reaciton site.
    Additional Material: 1 Ill.
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  • 95
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 383-388 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Norbornadiene, isolated in argon, xenon and nitrogen matrices at 20 K, was irradiated with UV light. Characterized by UV-VIS-IR absorption spectroscopy the photoproduct, representing a single species, was assigned to quadricyclane. This result is compared with the literature data on photochemistry of norbornadiene in the gas and liquid phase. The role of the rigid matrix environment on selectivity of the photochemical reaction is discussed.
    Additional Material: 3 Ill.
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  • 96
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 389-409 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A gas-phase experimental investigation of the competition between carbon and oxygen alkylation of a series of cyclic and acyclic enolate ions is described. Perfluoropropylene is shown to react in a characteristic way with oxyanions and carbanions to produce distinctive ionic products. The relative yields of these products formed in reactions with ambident enolate ions provides a measure of their intrinsic carbon vs. oxygen regioselectivity. The results for a series of enolates derived from aldehydes, ketones, esters, amides and related compounds show a wide range of reactivity which is a function of the nature of the central substituent. Most aldehyde and ketone enolates react mainly through oxygen, while enolates with σ-acceptor of π-donor type central substituents react mainly thorugh carbon. Ring-size in cyclic ketone enolates also influences C vs. O regioselectivity, i.e. small-ring enolates react mainly through carbon, while larger ring enolates (C7-C9) react preferentially through oxygen. The enolate reactivity patterns can be generally accounted for by the keto-enol energy differences for the parent carbonyl compounds, although some exceptions are evident. The origins of the highly variable, kinetically determined regioselectivities are discussed.
    Additional Material: 5 Tab.
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  • 97
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 580-584 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants were determined for the combination reactions of a series of cation radicals derived from substituted anthracenes with acetate, p-nitrobenzoate, trifluoroacetate, nitrate and perchlorate ions. Rate constants, depending on the identities of the cation radicals and the nucleophiles, ranging from about 200 to 2 × 1010 1 mol-1 s-1 were observed in acetonitrile at 293 K. The key steps in the reaction are (1) reversible complex formation between the anion and the cation radical followed by (2) irreversible bond formation \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\rm{Ar}^{ + \cdot } + \rm{X}^ - \rightleftharpoons {{\rm{Ar}^{ + \cdot } } \mathord{\left/ {\vphantom {{\rm{Ar}^{ + \cdot } } {\rm{X}^ - }}} \right. \kern-\nulldelimiterspace} {\rm{X}^ - }}} &&&&& {(1)} \\ {{{\rm{Ar}^{ + \cdot } } \mathord{\left/ {\vphantom {{\rm{Ar}^{ + \cdot } } {\rm{X}^ - }}} \right. \kern-\nulldelimiterspace} {\rm{X}^ - }} \to \rm{Ar}^ \cdot - \rm{X}} &&&&& {(2)} \\ \end{array} $$\end{document}.The preliminary results show that cation radical-anionic nucleophile reactions can be very facile. The cation radicals of 9-nitro- and 9-cyanoanthracene are particularly reactive, giving rise to rate constants close to the diffusion-controlled limit with all anionic nucleophile studied and even react moderately rapidly with perchlorate ion. The reaction with perchlorate ion can be compared to the behavior of stable carbenium ions that coexist with the anion in solution and in crystalline salts.
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  • 98
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 602-610 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to assist in the interpretation of the D5h molecular structure of [45] (1,2,3,4,5)ferrocenophane (1) obtained from x-ray crystallographic analysis, a hypothetical hydrocarbon C30H40 (2) was derived from 1 by removing the iron atom and subjected to geometry optimization by molecular mechanics. A stable D5 conformer was found for 2, which has a g+ g- g+ helical bridge conformation and a ring-ring distance almost identical with that in 1 and ferrocene itself. Optimization of a perhydrogenated hydrocarbon model gave a highly strained C1 structure.
    Additional Material: 2 Ill.
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  • 99
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 611-622 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solvent effect on two SN2 reactions was evaluated by discrete, continuum and discrete-continuum models. The potential energy profiles were found to change dramatically on introduction of the solvent effect. The double-well shape which characterizes the F- + CH3F → FCH3 + F- reaction in the gas phase becomes unimodal when the solvent is introduced, in good agreement with experimental data. The solvation parameters are found to intervene in the reaction coordinate. Recent Monte Carlo and molecular dynamics calculations are discussed.
    Additional Material: 4 Ill.
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  • 100
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 1-14 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth-order kinetics (third-order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non-nucleophilic tertiary bases, spectacular effects of hydrogen-bond donor (HBD) and hydrogen-bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed.
    Additional Material: 5 Ill.
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