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  • 1995-1999  (1,166)
  • 1997  (1,166)
  • Theoretical, Physical and Computational Chemistry  (699)
  • Industrial Chemistry and Chemical Engineering  (228)
  • Analytical Chemistry and Spectroscopy  (212)
  • Atomic, Molecular and Optical Physics
  • Nuclear reactions
Material
Years
  • 1995-1999  (1,166)
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 687-696 
    ISSN: 0894-3230
    Keywords: bsorption ; fluorescence ; solvatochromism ; hydrogen bonding ; dipole moment ; naphthalenones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Electronic absorption and steady-state fluorescence emission of seven 3,4-dihydro-1-(2-p-substituted benzylidene)naphthalenones (1-7) show sizable solvent dependence. The charge-transfer (CT) absorption maxima of these compounds in various solvents show a red shift for the electron-donating substituted compounds (1-5), whereas a blue shift is observed for compounds possessing electron-withdrawing substituents (6, 7). Excitation into the lowest energy absorption gives emission from the locally excited state, which relaxes to the emitting intramolecular charge-transfer state for compounds with strong electron-donating substituents (1-3) in hydroxylic solvents. However, in moderately polar solvents, dual emissions are observed for these compounds. No CT emission is observed for the compounds with moderate electron-donating substituents (3 and 4) or those with electron-withdrawing substituents (6 and 7). Compound 1 with an -N(CH3)2 substituent shows an excited-state dipole moment of 17 D. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 9 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 717-724 
    ISSN: 0894-3230
    Keywords: SN1 solvolysis ; carbocation ; Grunwald-Winstein relationship ; solvent effect ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The rates of solvolysis in various solvents at 25 °C were determined for five tertiary alkyl chlorides: 2-chloro-2,4,4-trimethylpentane (4), 2-chloro-2,4-dimethylpentane, 2-chloro-2-methylpentane, 1-chloro-1,3,3-trimethylcyclopentane (7) and 1-chloro-1-methylcyclopentane. The rate data were analysed on the basis of the original and extended Grunwald-Winstein-type equation [log(k/k0)=mYCl+c and log(k/k0)=lNT+mYCl+c] and the results were compared with those reported for 2-chloro-2-methylpropane (1) and 2-chloro-2,3,3-trimethylbutane (3). The rate data for 4 in 18 solvents give an excellent correlation with l=0·00±0·02 and m=0·74±0·01. The neopentyl group in 4 more effectively shields the rear-side of the reaction center than the tert-butyl group in 3 that is correlated by l=0·10±0·04 and m=0·81±0·04. The rate ratio between 4 and 1 at 25 °C is 275 in TFE and predicted to increase to 950 in TFA. The previous 4/1 rate ratio of 21 in 80% ethanol evidently underestimates the B-strain effect on the solvolysis rate of 4 by a factor of at least 40. The remote methyl groups in 7 works to increase rear-side shielding without increasing B-strain. The marked difference in the effect of the remote methyl groups between 4 and 7 suggests that the leaving chloride ion in 4 takes a locus that is nearly antiperiplanar to the tert-butyl group. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 725-730 
    ISSN: 0894-3230
    Keywords: p-nitrophenyl N-phenylcarbamates ; stepwise mechanism ; rate-limiting breakdown of T± ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Kinetic studies of the reactions of p-nitrophenyl N-phenylcarbamates with benzylamines were carried out in acetonitrile at 25·0 °C. Second-order (k2) and third-order (k3) rate constants were observed for all the Y-substituted carbamates except for Y=m-Cl. The relatively large magnitude of ρX (for X-substituted benzylamines) and ρY together with a positive cross-interaction constant ρXY supports a stepwise mechanism involving rate-limiting breakdown of the zwitterionic tetrahedral intermediate T±. Kinetic isotope effect studies with deuterated benzylamine (XC6H4CH2ND2) indicate that in the base-catalyzed path, k3, rate-limiting deprotonation occurs at the amino group of benzylamine within the T± intermediate. The low δH≠ and δS≠ values for the k3 process are in accord with the proposed mechanism © 1997 John Wiley & Sons, Ltd.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0894-3230
    Keywords: ureido sugars ; amino acids ; 1H NMR ; IR ; H-D exchange ; intramolecular hydrogen bonding ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Ureido 2-deoxy-β-D-glucopyranosides with seven different amino acid ester residues were studied by means of IR and 1H NMR spectroscopy. The H-D exchange rates increase in the order L-Val〈L-Leu〈L-Ala〈Gly for both NH protons; however, the exchange rate at N-1-H (linked to the glucopyranoside) is significantly faster than that at N-3-H (at the amino acid residue). The analysis of IR spectra in the region of the NH stretching vibrations shows, in agreement with other investigations, that the signals at 3454, 3423 and 3355 cm-1 are due to the free and the intramolecular associated NH groups forming a five- and seven-membered ring, respectively. It was found that the C7 associated ring is formed by hydrogen bonding between the N-1-H function and the C=O of the acetyl group at the C-3 position in the glucopyranoside. The N-3-H group is involved in a hydrogen bond with the C=O; function of the ester group protecting the amino acid residue. Furthermore, it was found that the ureido sugar with L-Val exhibits a stronger C7 hydrogen bond than the other amino acid residues. This result conforms with the lowest H-D exchange rate at the N-1 position of this compound. Steric effects resulting in the shielding of this hydrogen bond against OD attack are considered as a reason for this peculiarity. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 5
    ISSN: 0894-3230
    Keywords: solvent effects ; aromatic nucleophilic substitutions ; empirical polarity parameter ; halonitrobenzenes ; aliphaticamines ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Empirical solvent polarity parameters ET(30) were determined by UV/VIS spectroscopy, using Dimroth-Reichardt's betaine dye, as a function of composition, for several binary solvent mixtures [i.e. polar hydrogen bond acceptor (PHBA) solvents+chloroform or dichloromethane]. Each solvent system was analyzed according to its deviations from additivity due to preferential solvation of the chemical probe and also from complicated intermolecular interactions of the mixed solvents. The ET(30) parameter of many of these mixtures has presented synergism. The synergetic effects were more significant for those binary solvent systems in which chloroform is the co-solvent. These results were related to the solvent effects on some aromatic nucleophilic substitution reactions. The kinetics of the reactions between 1-halo-2,4-dinitrobenzenes and primary or secondary aliphatic amines were studied in three solvent systems (PHBA+chloroform) where the synergism for the ET(30) polarity parameter is the rule. In all the aminodehalogenation reactions discussed the formation of the intermediate is the rate-determining step. The kinetic data show a tendency to decrease with decrease in the overall solvation capability of the binary mixture. In general, the reaction rates presented a gradual decrease in the PHBA solvent-rich zone and a large decrease at high co-solvent concentrations. The ET(30) values corresponding to binary dipolar hydrogen bond acceptor-hydrogen bond donor mixtures may be not generally valid for interpreting solvation effects on the reactions under consideration. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 835-840 
    ISSN: 0894-3230
    Keywords: N-methylaminopyridines ; polar properties ; spectroscopic properties ; solvent effect ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dipole moments of 2-N-methylamino-5-nitro-6-methylpyridine (I) and 2-N-methylamino-3-nitro-6-methylpyridine (II) were determined in solvents of different polarity and basicity. The solvent effect is discussed in terms of the two-parameter (π*-β) Kamlet-Taft expression. The solvent dependences of the energy of intramolecular charge-transfer transition and the frequency of the ν(NH) stretching vibration are in keeping with the dielectric results. It was found that the solvent-induced disturbance in the electronic structure of I is brought about by hydrogen bond interaction with the NH group. The strong intramolecular hydrogen bond in II is stable in weakly basic solvents and the electronic structure is insensitive to the environment. However, in more basic solvents the intramolecular hydrogen bond is partly broken and an N - H· · ·solvent hydrogen bond is formed, bringing about distinct changes in polarity and spectroscopic properties. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 4 Tab.
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  • 7
    ISSN: 0894-3230
    Keywords: thiapyrylium salt ; photoinduced electron transfer ; laser flash photolysis ; trans-stilbene cation radical ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoinduced electron transfer reactions of trans-stilbene sensitized by 2,4,6-triphenylthiapyrylium tetrafluoroborate (STPP) were carried out by steady-state and laser flash photolysis techniques in the presence and absence of oxygen in dichloromethane. Rapid dimerization of the trans-stilbene cation radical with its neutral species was observed, as previously observed in 2,4,6-triphenylpyrylium tetrafluoroborate (TPP)-sensitized reactions in dichloromethane. Electrochemical and photophysical properties such as fluorescence quantum yield and T-T absorption spectrum of STPP were also studied, and the results were compared with those for TPP. The properties of STPP as an electron transfer sensitizer are discussed. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 8 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 17-22 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mass transfer with chemical reaction by liquid/liquid phase tranfer catalysis (LLPTC) for an isothermal batch reactor was analyzed. The results for the phase transfer catalyzed reaction system can be generally described by a pseudo first-order hypothesis, whereas the reaction system can be controlled by simultaneous mass transfer of the catalysts between two liquid phases and chemical reaction in the organic phase. The mass transfer limitation is mainly from the mass transfer step of QX from the organic phase to the aqueous phase. The concept of catalyst-effectiveness vs. physically meaningful parameters in a liquid/liquid phase transfer catalyzed reaction is introduced. The catalyst effectiveness is increased as the mass transfer factors increase, the ratio of reaction rate coefficients of aqueous forward reaction to organic increases, and the equilibrium constant in the aqueous solution increases.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 40-42 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The use of ozone and hydrogen peroxide for the simultaneous oxidation of nitrogen and sulfur oxides was studied in experiments carried out in a stirred cell. It was found that in a gas mixture, containing both nitrogen and sulfur oxides, only the nitrogen oxides are oxidized by ozone. Contrary to earlier results, sulfur dioxide does not disturb the oxidation of nitrogen oxides under dry conditions. The consumption of ozone in the oxidation of nitric oxide was slightly below the stoichiometric level because the ozone was introduced into the reactor in the oxygen flow. When the molar ratio between ozone and nitric oxide was more than 0.4, some of the nitric oxide was oxidized to higher oxides of nitrogen, the final product being a solid mixture of N2O5 and (NO)2S2O7. Some nitrosyl sulfuric acid was formed in the aqueous solution of hydrogen peroxide in addition to sulfuric acid under wet conditions. Some white solid was found on the walls of the reactor. This solid is said it the literature to consist of H2SO4, HNOSO4 and (NO)2S2O7.
    Additional Material: 4 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 85-89 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A comparative study of reported theoretical and experimental investigations evaluating the numbers and sizes of bubbles emerging from submerged orifices reveals that the lack of consistency can be attributed largely to faulty experimental techniques. Errors are attributed to an inadequate knowledge of the influence of the surface properties of the solid and liquid media on the emission process and to the lack of standardization of the equipment geometries especially regarding the pressure chambers and orifice plates. The analyses provide guidance to designing standardized equipment to produce reproducible bubbles.
    Additional Material: 1 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 429-433 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When in contact with water, organoalkoxysilanes and other alkoxy metal compounds react to organofunctionalized polysiloxanes or heteropolysiloxanes. A new method for the continuous preparation of porous organopolysiloxane spheres was developed. Droplets of the precursor mixture are injected into the vertical reactor column. Movement of the gelating droplets is controlled by flow of the aqueous reaction medium. Advantages are adjustable residence time, minimized coalescence and low reactor height. An example shows typical product characteristics like narrow particle size distribution and macroporosity.
    Additional Material: 8 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 533-537 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Airlift loop reactors are useful in many chemical and biotechnological processes where three phase reaction systems are required. One example is biological waste water treatment. In order to enhance biological reaction rates it is often useful to immobilize the bacteria on carrier particles. Knowledge of solid distribution and local gas holdup in those systems is important for calculation of mass and energy transfer or reaction kinetics. For this reason a method has been developed which enables to measure such local phase holdups. The measuring system consists of a time-domain-reflectometry (TDR)-instrument in combination with a pressure difference meter. The method has successfully been applied to determine local axial gas and solid distribution in internal airlift loop reactors, filled with a three phase system consisting of water, air, and polymer particles.
    Additional Material: 6 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 538-549 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New data of gas-liquid mass transfer for cocurrent downflow through packed beds of porous and non-porous particles are presented. Mass transfer parameters for air/carbon dioxide/water, air/carbon dioxide/carboxymethylcellulose solution and air/carbon dioxide/sodium hydroxide systems were evaluated by least square fit of the calculated CO2 concentration profiles in gas phase to the experimental values. The volumetric liquid-side mass transfer coefficient increases with the increase of the flow consistency index of the liquid. A comparison of the volumetric liquid-side mass transfer coefficient values evaluated with and without taking into account the axial dispersion shows that the influence of the liquid axial dispersion is significant at low liquid velocity and high CMC concentrations, and the influence of the gas axial dispersion is insignificant.
    Additional Material: 14 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 342-347 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two types of solid adsorbents, activated carbon and zeolite 13X, were used at 80°C to remove sulfur compounds from naphtha solutions. Adsorption isotherms have been determined in a pressure vessel. This investigation indicated that activated carbon is superior to zeolite 13X at such high temperatures. A new formula based on the Langmuir model has been found to fit the experimental data satisfactorily. Comparison of the findings of this study with those of a previous one conducted at ambient temperatures in this department indicates that such treatment generally gives better results at low temperature where almost complete recovery of the sulfur compounds can be performed by using zeolite 13X.
    Additional Material: 3 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 371-377 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluctuation solution theory relates thermodynamics partial derivatives to integrals of molecular direct correlation functions from statistical mechanics. This paper describes an application of that theory for correlating and predicting solubilities of light gases in heavy n-paraffins. Two of the solvents are complex waxes. Equations from the theory represent the liquid phase, and additional hypothesis are adopted to build a model for the high pressure vapor-liquid equilibrium. In the correlation mode, the model, based in the fluctuation solution theory, produces a molar fraction of the gas in the liquid phase with an average absolute relative deviation under 3% in a large number of cases. In the prediction mode, when binary parameters are used, errors are on the order of 10%. Overall for n-paraffins solvents, the model presented in this paper shows a good capacity to correlate experimental solubility and an adequate power to extrapolate lower pressure data when a binary parameter value has been chosen.
    Additional Material: 6 Ill.
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  • 19
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The following deliberations are concerned with the application of economy criteria to the optimization of process-engineering plants. We are therefore not concerned here with criteria for investment decisions, i.e., decisions on the implementation orabandonment of an investment project, nor with criteria for the selection of the most profitable investment options from a series of alternatives. Instead, we are interested here in the question of how a plant, while at the planning stage, can best be designed, i.e., the most rational method of selecting process parameters, such as throughputs, pressures, temperatures, concentrations, etc. The problem of plant optimization only occurs, however, when there are design parameters which can be selected at will or can, at least, be varied within certain limits. This is however, virtually always the case. There is then a need for an optimization strategy in the form of an objective function which is either reduced to a minimum, where lowest possible production costs are the target, for instance, or advanced to a maximum, where high profitability is the aim. The inclusion of engineering economy functions, in the form, namely, of the net present value function and the internal rate of return function for definition of such objective functions, provides better defined information on the best possible choice of process parameters than was possible with methods previosly used, such as the annuity method, for instance. One obtains different values for the process parameters to be optimized, depending on the objective functionused, and therefore different investment costs and utility consumptions. These differences are delineated and quantified using a process-engineering example in the course of the following discussion. The example selected is a gas scrubber, the function of which is to remove and recover useful components from a flow of gas. The specific problem examined is one of heat recovery.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 90-92 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of sodium lauryl sulphate (anionic) and Triton X-100 (nonionic) on the solid-liquid mass transfer at a gas-sparged fixed bed of copper Raschig rings was studied by measuring the diffusion-controlled dissolution of copper rings in acidified chromate solution. The variables studied were the nitrogen flow rate, the type of surfactant, and the surfactant concentration. It was found that an increase occurs in the solid-liquid mass transfer coefficient with increasing the nitrogen flow rate. Increasing the surfactant concentration was found to decrease the mass transfer coefficient. For a given surfactant concentration, it was found that Triton X-100 reduces the mass transfer coefficient more than sodium lauryl sulphate.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 571-575 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For a specific combustion problem involving calculations of several species at equilibrium, it is much simpler to write a special computer program and calculate the concentrations, rather than to use a generalized computer program. To calculate these concentrations, one must solve a set of non-linear algebraic equations. This work describes a procedure in which the Newton-Raphson method and the successive substitution method are combined. It is was found that for these types of problems the value of unknowns and the nature of the equations are such that by adopting the two procedures simultaneously a much faster and reliable convergence is achieved. This study also shows what possible species should be considered for these calculations.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 582-588 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The shape-selective transalkylation of biphenyl with pentamethylbenzene over ultrastable Y-faujasites to produce para-methylated biphenyls was studied in the liquid slurry phase. The reaction was carried out in a discontinuously operated stainless steel autoclave using n-heptane as the solvent with a temperature range of 513 to 533 K and a pressure of 3 MPa. As for the progress of the reaction the presence of strong Brønsted acid sites was essential, an ultrastable faujasite treated with aqueous hydrochloric acid having a high content of those sites was used as the catalyst. Thus, a yield of the target product 4,4′-dimethylbiphenyl of above 11% referring to biphenyl could be achieved. The effect of the operating conditions on the formation of the target product was investigated. The decisive influence was acted out by the molar ratio of biphenyl to alkylating agent, in so far as a surplus of pentamethylbenzene of 7:1 referring to biphenyl enhanced the yield of the target product to 14%. The kinetics of the reaction could be successfully descibed with a lumped reaction scheme, introducing pseudo components, summarizing structural isomers, and pseudo reactions, such as the formation of coke.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 624-632 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The oxidation of sulfide in oxygen-saturated aqueous solutions is accelerated by dissolved or silica-bonded cobalt phthalocyanines. On the basis of thermodynamical considerations it is postulated that the catalyst enhances the formation of disulfide as the initial elementary reaction step. The following reaction steps are largely unaffected by the catalyst, as indicated by a product ratio sulfate/thiosulfate=0.86, comparable to that of the uncatalyzed autoxidation. A Langmuir-Hinshelwood formalism is developed for the catalytic reaction step and is demonstrated to fit best with the kinetics. In addition, from the kinetic data free enthalpies for the adsorption of HS- (i) at the dissolved phthalocyanine (ΔG = -17.6 kJ/mole) and (ii) at the immobilized complex (ΔG = -20.0 kJ/mole) are calculated.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 641-645 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An In-HZSM 5 honeycomb catalyst is used for the experimental investigations of the NO reduction with methane. The catalyst is prepared by the ion-exchange method. The influence of temperature and concentration of oxygen and methane is studied. In addition to methane, natural gas is used as reductant for the reduction of nitric oxide. The results are compared with those of other authors who use zeolithe pellets.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997), S. 290-294 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A compact and commercial aerosol generator capable of generating narrowly size-distributed aerosols with high mass concentrations was designed, fabricated and tested. The aerosol generator, consisting of a Delavan simplex nozzle (Model 30610-4), an L-shaped settling chamber and a virtual impactor with a clean air core, was modified and improved from Chein and Lundgren's work [20] to be more compact and readily commercial. The performance of the aerosol generator was evaluated using corn-oil, sodium chloride and uranine solutions. The results indicated that the cornoil droplets produced by the generator had a mass medium aerodynamic diameter (MMAD) of 7.20 ± 0.32 μm with a geometric standard deviation (GSD) of 1.48 ± 0.01 and the aerosol generation rate was 13.8 ± 1.3 mg/min. Solid aerosols generated from NaCl solution were found to have an MMAD in the range 1.39-4.88 μm with a GSD of 1.34-1.47 with the volumetric solution concentration varying from 0.1% to 9%. At the same time, the aerosol generation rate varied from 0.27 ± 0.05 to 15.8 ± 1.8 mg/min. depending on the solution concentration and the particle size produced. In addition, a 0.01% uraniane solution was tested to generate a submicron aerosol with an MMAD of 0.93 μm and a GSD of 1.48.
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  • 27
    ISSN: 0894-3230
    Keywords: merocyanines ; solvatochromism ; solvent polarity ; VBHB model ; SA-SAB-SB model ; binary solvent mixtures ; solvation equilibria ; spectra simulation ; pyridinium betaines ; 7H-indolo[1,2-a]quinolinium betaines ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---A quantitative model of solvatochromism in a binary solvent system is presented. Although it is derived for merocyanine and betaine dyes, it explains a majority of known examples of solvatochromism in binary solvents. The model provides an estimation of equilibrium constants between particular types of solvates present therein. UV-VIS absorption spectra of solvated species can be simulated. They perfectly fit the experimental data. The model proposed describes the internal solvent picture from the solute point of view, which differs from other known models and may be useful for studying the structure of liquids © 1997 John Wiley & Sons, Ltd.
    Additional Material: 16 Ill.
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  • 28
    ISSN: 0894-3230
    Keywords: complex stabilities ; alkali metals ; alkaline earth metals ; dibenzo crown ethers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---An experimental method was developed to determine the stability constants with nearly insoluble ligands in homogeneous solution. This method was tested using dibenzo crown ethers, which have a very low solubility in aqueous solution. The stability constants for the complexation of alkali and alkaline earth metal cations with different dibenzo crown ethers were determined in aqueous solution. Owing to the complex formation the total concentration of the ligand in solution increases. Dibenzo crown ethers absorb in the ultraviolet spectral range, hence the increase in the ligand concentration can be easily detected. Without the knowledge of the molar absorptivities of the ligands and of the corresponding complexes and of the solubilities, the stabilities of the complexes formed can be calculated under certain assumptions. To verify these assumptions, the solubilities of the dibenzo crown ethers and the molar absorptivities were determined. The kinetics of the solubilization process of the ligands was followed by spectrophotometric measurements. © 1997 John Wiley & Sons, Ltd.
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  • 29
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    Journal of Physical Organic Chemistry 10 (1997), S. 777-780 
    ISSN: 0894-3230
    Keywords: tandem energy transfer-electron transfer ; photosensitized alkylation ; α,β-Unsaturated ketones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: -α,β-Unsaturated ketones are not conveniently alkylated by radicals generated from tetraalkylstannanes via photoinduced electron transfer (PET), either by direct irradiation or when a singlet sensitizer (an aromatic nitrile, a pyrilium salt) is used. However, the procedure is successful with tetramethyl pyromellitate (TMPM) as the sensitizer. TMPM is promoted to the triplet state by energy transfer from the unsaturated ketones and then sensitizes the cleavage of alkylstannanes by electron transfer. The alkyl radicals thus formed finally add to the unsaturated ketones, giving the β-alkyl derivatives. © 1997 John Wiley & Sons, Ltd.
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  • 30
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    Journal of Physical Organic Chemistry 10 (1997), S. 662-668 
    ISSN: 0894-3230
    Keywords: propan-1-ol oxidation ; alkaline hexacyanoferrate(III) ; ruthenium trichloride catalyst ; kinetic ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The oxidation kinetics of propan-1-ol by alkaline hexacyanoferrate(III) catalyzed by ruthenium trichloride were studied spectrophotometrically. The initial rate method was used for kinetic analysis. The reaction rate shows a fractional order in [oxidant] and [substrate] and a first-order dependence on [RuCl3]. The dependence on [OH-] is complicated. A reaction mechanism involving two active catalytic species is proposed. Each one of these species forms an intermediate complex with the substrate. The attack of these complexes by hexacyanoferrate(III) in rate-determining step produces a radical species which is further oxidized in the subsequent step. © 1997 John Wiley & Sons, Ltd.
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  • 31
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    Journal of Physical Organic Chemistry 10 (1997), S. 731-736 
    ISSN: 0894-3230
    Keywords: solvatochromism ; preferential solvation ; aryliminomethylpyridinium iodides ; binary mixtures ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Studies on the solvatochromic behaviour of N-methyl-4- and N-methyl-2-[(4-dimethylaminophenyl)iminomethyl]pyridinium iodide dyes in a variety of solvents and the preferential solvation of the former dye in binary mixtures of protic and non-protic solvents are presented and interpreted in terms of solute-solvent and solvent-solvent interactions. © 1997 John Wiley & Sons, Ltd.
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  • 32
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    Journal of Physical Organic Chemistry 10 (1997), S. 787-796 
    ISSN: 0894-3230
    Keywords: carbonyl oxide ; ozone ; structure and reactivity ; oxygen atom transfer ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and chemical properties of 1,3-dipolar peroxidic species (X - O - O) such as ozone (X=O) and carbonyl oxides (X=R2C) depend significantly on the nature of X. Although cyclic O3 is thermodynamically unstable, dioxiranes, cyclic isomers of carbonyl oxides, are isolable and have been fully characterized. In contrast to the well known electrophilic nature of ozone, carbonyl oxides usually act as a nucleophilic oxygen transfer agent, but their reactivity could be altered by substituents. It is expected that the chemistry of R2C - O2 species will provide a good starting point for a better understanding of dioxygen complexes (X - O2) with various Xs. Interesting aspects of carbonyl oxide chemistry are discussed, including methods of generation, cyclization to dioxiranes and the nature of their oxygen transfer activities. © 1997 John Wiley & Sons, Ltd.
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  • 33
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    Journal of Physical Organic Chemistry 10 (1997), S. 825-834 
    ISSN: 0894-3230
    Keywords: N-tert-butoxycarbonyl-L-phenlylalanine-pyridine complex ; isotope effect ; x-ray structure ; vibrational spectroscopy ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The x-ray structure of the complex between N-tert-butoxycarbonyl-L-phenylalanine and pyridine shows that the crystals are held together by short hydrogen bonds between the OH group and the N atom of the pyridine ring [RO(H)· · ·N=2·574(3) Å]. Deuteration of the OH and NH groups results in a small expansion of the unit cell associated with an elongation of the O· · ·N distance [RO(D)· · ·N=2·610(3) Å]. The infrared spectra show very broad stretching protonic bands in the range 2750-600 cm-1. The isotopic ratio ν(OH· · ·H)/ν(OD· · ·N) of nearly unity suggests a double minimum potential with a low barrier for the hydrogen bridge. The Raman and near-infrared spectra are discussed. The perturbation of the fundamental modes and of the overtones of pyridine suggests that the complex is not of the proton transfer type. The broad absorptions of the hydrogen bridge disappear in the near-infrared region. The perturbation of the pyridine overtones is discussed. © 1997 John Wiley & Sons, Ltd.
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  • 34
    ISSN: 0894-3230
    Keywords: 13C and 1H magic angle spinning NMR ; x-ray diffraction ; 1,8-bis(dimethylamino)naphthalene ; picrolonic acid ; multicentre hydrogen bonding ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An ionic complex of 1,8-bis(dimethylamino)naphthalene with picrolonic acid was studied by 13C and 1H magic angle spinning and x-ray diffraction. Structural and spectroscopic features of this compound were investigated. The detailed x-ray structure of this complex is described. A multicentre model of hydrogen bonding in proton sponges {[Me2N - H· · ·NMe2]+· · ·Xδ-} is proposed and the influence of weak intermolecular intractions with the nearest electronegative atom in crystal lattice of a proton sponge on the strong intramolecular [N - H· · ·N]+ hydrogen bonding is demonstrated. It appears that weak interactions of electronegative atoms with the nearest methyl hydrogen atoms can influence the localization of the proton in the intramolecular [N - H· · ·N]+ hydrogen bridge. © 1997 John Wiley & Sons, Ltd.
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  • 35
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    Journal of Physical Organic Chemistry 10 (1997), S. 797-813 
    ISSN: 0894-3230
    Keywords: statistics ; regression ; correlation analysis ; incorrect data processing ; least-squares method ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Examples are given from older and more recent literature (kinetics, ionization equilibria, complex formation in solution, dipole moment determination, thermochemistry, resonance energies, NMR shifts, photoelectron spectroscopy) where experimental data were processed in an incorrect way from the point of view of statistics. The results were more or less biased, sometimes completely wrong. Corrected procedures, based entirely on the least-squares method, are reported; in several cases methods are proposed. Some hints are given as to how these mistakes can be avoided, how they can be revealed in the literature and how the literature data can be recalculated: the last task is the most difficult. © 1997 John Wiley & Sons, Ltd.
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  • 36
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    Journal of Physical Organic Chemistry 10 (1997), S. 879-884 
    ISSN: 0894-3230
    Keywords: solvolysis ; correlation analysis ; azide salt effect ; β-deuterium kinetic isotope effect ; YBnCl ; 1-alkyl-1-chloro-1-(4-methyl)phenylmethanes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solvolysis of 1-alkyl-1-chloro-1-(4-methyl)phenylmethanes (4a-d) in aqueous acetone, aqueous ethanol, aqueous methanol and ethanol-trifluoroethanol was studied. Grunwald-Winstein-type correlation analysis using the YBnCl scale suggests significant nucleophilic solvent intervention in the case of 1-chloro-1-(4-methyl)phenylethane (4a). Increasing bulkiness of the 1-alkyl substituent from methyl (4a) to ethyl (4b), to isopropyl (4c) and to tert-butyl (4d) resulted in a gradual change to limiting SN1 mechanisms. The observed excellent linear correlations with YBnCl and the good solubility in high-water-containing binary solvents made 4d a suitable reference standard for deriving more YBnCl values. A positive azide salt effect was realized in the solvolysis of 4a but not 4d. A small decrease in the β-deuterium kinetic isotope effect from 4a to 1-chloro-1-(4-methoxyphenyl)propane (5) suggested the presence of additional stabilization of the benzylic cationic transition state. Howver, no relationship between k(CH3)/k(CD3) and the solvent effect was found. The superiority of employing the YBnCl scale over the combination of YCl and I scales in the mehanistic study was observed. © 1997 John Wiley & Sons, Ltd.
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  • 37
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The oxidative coupling of methane (OCM) was carried out in a polytropic fixed-bed reactor applying a Zr/La/Sr catalyst developed by the Neste company. Over this catalyst the OCM reaction follows a complex reaction scheme which includes primary parallel reaction steps to CO, CO2 and C2H6 and consecutive reactions of ethane to ethylene or COx. Yield of higher hydrocarbons C2+ obtained with this catalyst strongly depended on reaction conditions, i.e. low partial pressures of methane and oxygen obtained by diluting the feed gas with nitrogen and high reaction temperatures promoted C2+ selectivity and yield. The maximum yield amounted to 21.4% (20 Vol.-% CH4, 9 Vol.-% O2, 71 Vol.-% N2, T = 860°C; XCH4 = 41.8%, SC2+ = 52.5%). This result belongs to the highest yields reported in the open literature.
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  • 38
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    Chemical Engineering & Technology - CET 20 (1997), S. 47-52 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An ultrasonic transmission technique is under development to determine the concentration of solids in a three-phase slurry reactor by measuring the velocity of ultrasound in slurries. Preliminary measurements have been made on slurries consisting of water, glass beads, and air bubbles. The data show that both the sound speed and attenuation are well-defined functions of both the solid and gas concentrations in the slurries. A simple model is proposed to correlate the concentration of solids with the measured ultrasonic signals.
    Additional Material: 5 Ill.
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  • 39
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Chemical engineering is taught at German universities in three different types of curricula: chemical engineering proper, process engineering (“Verfahrenstechnik”), and industrial chemistry (“Technische Chemie”). Independent departments resp. faculties of chemical engineering exist at four universities. At other universities process engineering is offered as a complete curriculum with a smaller amount of chemistry than chemical engineering curricula, mostly by the departments of mechanical engineering. Industrial chemistry is an essential component of chemistry courses at most technical universities and optional subject at several classical universities. The cause of this diversity of approaches to chemical engineering can be traced back to the beginning of the production of high-value organics (dyes, pharmaceuticals) in Germany in the second half of the 19th century.
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  • 40
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    Chemical Engineering & Technology - CET 20 (1997), S. 485-490 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic model of the liquid fluidized bed containing two or more solid particle species of different size and density is presented. The model incorporates the particle mass transport mechanisms of the convection and the dispersion. The movement of the upper interface of the bed subject to a change in the liquid velocity is specified using the mass balance constraint. The particle velocities and dispersion coefficients are evaluated using correlations. The model is capable of describing the bed expansion, concentration profiles of the individual particle species, the bulk density profile, and the occurrence of layer inversion.
    Additional Material: 7 Ill.
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  • 41
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    Chemical Engineering & Technology - CET 20 (1997), S. 495-501 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An algorithm for the computation of design variables in layer crystallisation processes is presented, based on an algebraic solution of the moving boundary equation for heat transfer, as well as on an expression for the concentration profile. The algorithm was applied to the discontinuous crystallisation of a NaCl-H2O solution around the wall of an internally cooled cylindrical tube. Good agreement between simulation results and laboratory experiments was observed. After input of experimentally measurable values of the distribution coefficient, the algorithm enables the prediction of the following process variables along the crystallisation time: layer thickness, temperature, and composition profiles across the layer, as well as the end-values of solid and liquid mass and concentrations. Multistage processes can be studied by the series association of crystallisation cycles, enabling the determination of the optimal number of stages that meets a specific design criterion.
    Additional Material: 9 Ill.
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  • 42
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    Chemical Engineering & Technology - CET 20 (1997), S. 522-532 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The intermixing of fluidizing gas between the compartments of a compartmented circulating gas fluidized bed fitted with a V-valve and riser combination has been experimentally studied. The intermixing of fluidizing gas that flows co-current (cross flow) as well as counter-current (back flow) to the circulating solids has been investigated. At low aerations, gas cross flow increased proportionally with the increase in solid circulation rate. But at high aerations, gas cross flow increased with aeration even when solid circulation decreased. Studies on back flow of gas revealed some interesting observations. At high fluidizing bed height on upstream side back flow of V-valve, gas has been negligible. But at low upstream bed heights and low aeration in V-valve and riser back flow of V-valve, gas has been substantial.
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  • 43
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    Chemical Engineering & Technology - CET 20 (1997), S. 511-521 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When working with disperse solid matter systems, one uses the effect of vibration in numerous processes. Solid matter mixing with vibration has only occurred in very simple units up to now. By means of the 3D-vibrational mixer from the company Kuston, Kleve, the influence of vibration on bulk materials and new mixing techniques are demonstrated. The 3D-vibrational mixer is suitable for liquids and solids, does not require mixing tools that need to be cleaned, and does not carry out rotary motions which would hinder incoming lines. It is used for mixing small amounts, where the mixing tank can be used simultaneously as the transportation container, so that a transfer is unnecessary.With the aid of 4 linear motors, the vibrational amplitudes and the frequencies can be varied within wide boundaries in all three spatial directions. By analyzing the vibrational system by means of Lissajous figures, it can be demonstrated that the optimal mixing effect occurs in the case of small frequency differences between the three axes. For freeflowing bulk materials, the best possible mixing state, the uniform coincidence mixing, is achieved after 2 min.
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  • 44
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    Chemical Engineering & Technology - CET 20 (1997), S. 23-28 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the present study, a mass transfer model for Type-1 facilitated transport in liquid surfactant membrane is developed by taking into consideration a size distribution of emulsion drops, and analytical solution of the model equations has been presented. The model takes into account the continuous phase and outer liquid membrane phase resistances along with diffusion through composite emulsion drop. Effort has been made to highlight the effect of the various system parameters on the extraction rate including computation of reaction front position. The results of this work are found to be in good agreement with the published experimental results on batch extraction of phenol using NaOH as internal reagent. The model would thus provide an insight of the separation mechanism involved in the mass transfer processes in this type of system.
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  • 45
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    Chemical Engineering & Technology - CET 20 (1997), S. 419-423 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By applying the macroscopic conservation laws to a simplified jet downstream from a sudden enlargement, a new correlation of the two-phase subcritical pressure recovery is obtained. Comparisons with the set of existing data (air-water and steam-water subcritical flows) show that the predictions obtained by means of this formula are more accurate than the ones given by available analytical models. The proposed correlation presents an important improvement of the pressure recovery predictions in the case of small mass velocities. However, it can not be applied in the conditions of quality too close to one.
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  • 46
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    Chemical Engineering & Technology - CET 20 (1997), S. 435-444 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes how gain scheduling control is applied to a continuous stirred tank reactor model. The CSTR process, equipped with a cooling system, is modelled. Based on the resulting nonlinear model, a gain scheduling controller is designed. The gain scheduling follows a scheme denoted bias compensation. Compared to earlier reported gain scheduling schemes, the proposed scheme results in a controller that is less complex, which is advantageous in the controller implementation stage. Numerous simulations are performed, using the gain scheduling controller and two choices of control input to the reactor model. The simulation results indicate that a gain scheduling controller performs better than a linear controller. Simulations using different choices of control input to the reactor model indicate that proper process design is crucial for the controlled process performance.
    Additional Material: 9 Ill.
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  • 47
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    Chemical Engineering & Technology - CET 20 (1997), S. 475-477 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple and new model for the prediction of drop velocity as a function of dispersed phase volume fraction has been proposed on the basis of experimental knowledge of onset time of complete separation between two phases as function of the initial hold-up.
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  • 48
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    Chemical Engineering & Technology - CET 20 (1997), S. 478-484 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two important structural factors that affect distillation efficiencies, the outlet weir heigh and the liquid flowpath length, are investigated. Performance and efficiency data of an industrial scale i-butane/n-butane distillation column equipped with two-pass trays are used as a basis for the calculations. A mathematical development for a new method for predicting the numbers of vapor and liquid phase transfer units is given. This method together with some other NTU calculation methods is used to assess the effect of the outlet weir height on efficiencies. The effect of outlet weir height on the Murphree tray efficiencies is investigated using the observed point efficiencies and different point efficiency to the Murphree tray efficiency relation methods. The effect of varying liquid flowpath lengths on efficiencies is studied by calculating the Murphree tray efficiencies for one-pass and two-pass trays. The results obtained using the NTU calculation method presented in this study show that a certain outlet weir height point efficiency reaches its maximum. Most of the other methods give opposite results giving a minimum for point efficiency at a certain outlet weir length. The results also show that the Murphree tray efficiencies for one-pass trays are higher than for two-pass trays. Obviously, this is caused by the longer liquid flowpath length of one-pass trays. The Murphree tray efficiencies are also calculated for an industrial-scale MTBE purification column. The column is equipped with two-pass trays in the stripping section and with one-pass trays in the rectifying section. The Murphree tray efficiencies of one-pass trays are considerably higher than the two-pass tray Murphree tray efficiencies.
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  • 49
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    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 50
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    Chemical Engineering & Technology - CET 20 (1997), S. 118-130 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic model is developed for a fluid catalytic cracking (FCC) unit to describe the dynamic behavior of both the riser and the regenerator reactors and their interactions. The cracking reactions are simulated by the four-lumped kinetic model [1]. The reactions in the riser occur in a transported bed with the fluid and the solids in ideal plug flow. The two-phase nature of the regenerator-fluidized bed is considered and the kinetic model for the coke combustion on the cracking catalyst [2,3] is incorporated. The proposed model is validated using steady-state plant data from an industrial unit and the results are found to be in good agreement. One of the main advantages of the model is that it does not include any partial differential equations. This facilitates the solution of the equations and makes the model particularly suitable for control studies. Simulation studies are performed to investigate the effect of changing various process variables, such as catalyst circulation rate, gas oil feed rate, and oxygen feed concentration.
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  • 51
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    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 52
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    Chemical Engineering & Technology - CET 20 (1997), S. 182-191 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The uncatalyzed esterification of acetic acid is described in the literature as a typical example of reactive distillation. Many rigorous models were validated using this esterification as an example. Process proposals for the production of pure ethyl acetate from ethanol and acetic acid have been determined using short-cut methods with the assumption of chemical equilibrium only. In this publication, the limitations of this esterification are clarified, using a rigorous model that was developed. The reasons why reactive distillation appears to be unfavorable for this esterification are explained. It is, however, theoretically possible to obtain ethyl acetate in high purity with different variants of the process. Different process variants are examined in this work. Construction variables that are important for the design of reactive columns, such as the number of reactive separation stages and the holdup in the column, are analyzed. Furthermore, the influence of variables dependent on the component system, such as the phase equilibrium of the reactive system and the reaction kinetics on the conversion in the column, are described. It can be shown that the short-cut methods published so far for reactive distillation, which assume chemical equilibrium, are inadequate.
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  • 53
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    Chemical Engineering & Technology - CET 20 (1997), S. 203-207 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transient heat transfer in a mechanically agitated vessel is studied in the case of an anchor and an helical ribbon impeller using Newtonian and shear thinning fluids. Temperature stratification is found more pronounced with the anchor, making this impeller clearly inadequate for heat transfer. The impact of natural convection is evaluated first using the classical Gr/Re2 ratio. It is shown that the use of this criterion in viscous mixing is somewhat misleading. A new Grashof number is then proposed to assess the significance of the viscous and buoyancy effects in non-isothermal, non-Newtonian mixing applications. It is shown that the interpretation of this new number is strongly related to the concept of process viscosity.
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  • 54
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    Chemical Engineering & Technology - CET 20 (1997), S. 240-246 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rate of the homogenous exothermic hydrolysis reaction of acetic anhydride catalyzed by sulfric acid in solvent acetic acid was estimated from nonisothermal experimental batch reactor transient temperature data. Rate equations based on three different reaction mechanisms of hydrolysis published in the literature were fitted to the experimental rate data. The experimental results on runaway and limit cycle behavior obtained with this reaction were explained by using the mechanism-based rate equations for hydrolysis in the reactor dynamic models, and good agreement was obtained between the predicted and the experimental dynamic data.
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  • 55
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    Chemical Engineering & Technology - CET 20 (1997), S. 282-284 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 56
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    Chemical Engineering & Technology - CET 20 (1997), S. 268-276 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As an alternative to the existing bioheat transfer models a new system of two energy equations is proposed by considering the human body as a deformable porous medium. One equation is developed for the blood and the other for the peripheral skeletal tissue. It includes such significant factors as the vascular geometry and size, the blood flow and direction, thermal diffusion and the local thermal nonequilibrium between the blood and peripheral tissue. Discussion and application of both equations are given.
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  • 57
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    Chemical Engineering & Technology - CET 20 (1997), S. 285-286 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An ortho-experiment design and the analysis method of mathematical statistics are adopted to study the conversion of gypsum and potassium chloride to potassium sulfate in the system of K+, Ca2+, NH4+ ‖ Cl-, SO42- in H2O. Optimal reaction parameters and engineering mean are acquired to attain a conversion yield of potassium chloride of 94.52%.
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  • 58
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    Chemical Engineering & Technology - CET 20 (1997), S. 297-303 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electrochemical gas absorption or biotechnical purification processes using structured packing as electrode or as biological support, respectively, may operate in bubble columns in presence of suspended solids. In both systems the knowledge of mass transfer rates from the liquid to the packing is important for the design of equipment. In the present investigation, the fluid dynamic behavior of a simple bubble column and a bubble column containing small size particles, both in presence of structured packing, was studied. Furthermore, mass transfer coefficients between the liquid and the structured packing were obtained by the electrochemical method. The influence of physical properties of the liquid phase, gas flow rate, kind and concentration of the suspended particles on both gas holdup and mass transfer was investigated. Correlations of the experimental data of mass transfer using dimensionless groups were derived and compared to previous correlations. Similarity with a heat transfer expression already used in two-phase systems was found.
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  • 59
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    Chemical Engineering & Technology - CET 20 (1997), S. 333-337 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The reaction of anisole hydroxylation with hydrogen peroxide to form methoxyphenols over TS-1 was studied. Four C1-C3 alcohols and the two aprotonic solvents acetone and acetonitrile were used. Product conversion was almost proportional to the titanium content of the catalyst sample. The highest conversion and p-selectivity were observed in ethanol. Some speculations, based on the formation of substrate-solvent or titanium-solvent-oxidant complexes, about the role of the solvent are presented. It was found that in all the solvents studied the p/o ratio increased with time.
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  • 60
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    Chemical Engineering & Technology - CET 20 (1997), S. 445-454 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two different layouts for the liquid-liquid extraction section of an industrial caprolactam process are evaluated. Laboratory mass transfer measurements on streams obtained from an industrial and a demonstration plant with different extraction sections are interpreted by a model describing the effect of surface contaminants on mass transfer coefficients. Indications of the impact of these layouts on the complexity of the extraction section, quality of products and efficiency of the extraction processes are given.
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  • 61
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    Chemical Engineering & Technology - CET 20 (1997), S. 469-474 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bubble columns are commonly used in industry for polluted gas treatment. Based on the same principle, the droplet column which is not widely known in the literature, uses much higher gas velocities, up to 14 m/s. This study concerns the hydrodynamics and mass transfer in this apparatus, in presence or absence of solid particles. Our results have demonstrated the impact of dusts on mass transfer performance giving rise to an increase in the kL aL coefficient with decreasing particle size. However, no influence of dust on the hydrodynamics of the column has been demonstrated within the studied particle size range.A study of liquid holdups obtained by three different methods is also carried out. Our results are comparable, thus validating the methods used.
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  • 62
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    Chemical Engineering & Technology - CET 20 (1997), S. 491-494 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiments were carried out in a conventional circulating fluidised bed to measure the axial pressure profile and total pressure drop, which covered a wide range of operating conditions. Material belonging to the Geldart A (fine material) as well as the Geldart B (course material) categories have been used in the present work. Slip velocity is determined from the total pressure drop and noticed that the slip velocity is much higher than the free fall velocity of single particle for Geldart A type material, while it is approximately equal to the free fall velocity of single particle for the Geldart B type materials.A model is developed for slip velocity taking into account all the hindrance effects: particle-particle, and particle-wall, and particle agglomeration. Predictions of the present model are validated with the data due to present study and the data reported in the literature.
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  • 63
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    Chemical Engineering & Technology - CET 20 (1997), S. 502-509 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dust explosion hazard exists in plants and facilities wherever combustible dusts are hardled. Minimum explosible concentration of dust clouds is an important factor requiring special attention for hazard evaluation if any technological equipment is to be protected by inertisation. The mathematical models available for prediction of this parameter have been analysed for their application to organic dust clouds. Solution of the most general mode for determination of minimum explosible concentration of dust clouds proposed by Mitsui and Tanaka is presented, together with the comparison with experimental data. It has been found that the model is not successful in predicting the minimum explosible concentration for organic dusts. Recommendations on requirement of development of a new model for prediction of minimum explosible concentration of an organic dust such as polyethylen have been given.
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  • 64
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    Chemical Engineering & Technology - CET 20 (1997), S. 557-563 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Capillary viscometry is used to characterize viscosity, entrance pressure loss and apparent wall slip of paper coating colors at high shear rates. Special emphasis is laid on the dependence of these phenomena on solids content in order to account for changes in the rheology due to the dewatering of the color during the coating process. Coating colors with substantially different runnability have been investigated. Differences in apparent wall slip and high shear viscoelasticity (manifesting itself in extremely high entrance pressure losses) are observed at increased concentration, even if these phenomena do not show up at the initial solids content. Poor runnability is observed when viscosity, entrance pressure loss and wall slip increase strongly with increasing solids content. But all rheological features change simultaneously with the coating color recipe and it is not possible to separate out the contribution of the particular rheological features on the runnability of the coating colors or to correlate the runnability to a single rheological prorameter. Future work will have to focus on a numerical analysis of the blade coating process taking into account all the rheological features described here. First simulations including slip at the color/blade interface indicate that wall slip may cause severe runnability problems, at least when the apparent slip velocity exceeds the web velocity.
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  • 65
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    Chemical Engineering & Technology - CET 20 (1997), S. 581-581 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 66
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    Chemical Engineering & Technology - CET 20 (1997), S. 10-16 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The performance of an upflow packed-bed biofilm reactor has been analyzed under dual substrate limitation conditions. The numerical solution of the proposed equations defining the system has been obtained for a wide range of operating conditions for a case of practical significance involving glucose and oxygen as dual substrates. The results show that the inlet glucose concentration defines the limiting substrate at a position near the inlet of the reactor. For inlet glucose concentrations up to 300 mg/l, glucose acts as the limiting substrate. However, for inlet concentrations of 400 mg/l of glucose or higher, oxygen assumes the role of the limiting substrate at that position. For all other positions in the reactor, glucose acts as the limiting substrate, irrespective of its inlet concentration. Extensive computations were performed in order to define regions where glucose, oxygen or both are limiting. The predicted results have been found to be in agreement with the theoretical criteria, proposed in the literature, of determining the limiting substrate.
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  • 67
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    Chemical Engineering & Technology - CET 20 (1997), S. 36-39 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to reduce the B2O3 content in sintered magnesium oxide as much as possible, in precipitation with 80% of the stoichiometric quantity of dolomite lime, the effect of the pH of the agent used for rinsing the magnesium hydroxide precipitate was examined, as well as the effect of mannitol in sea water before precipitation. Mannitol binds orthoboric acid present in sea water into a weakly dissociated complex acid HB(OC)4. Experiments have shown that the B2O3 content in the sintered magnesium oxide samples is satisfactorily low. The lowest B2O3 content is obtained when mannitol is added; no B2O3 was found in these samples after sintering. Magnesium oxide samples were sintered at 1500°C; duration of isothemal sintering was one hour. Values for density and porosity of individually sintered samples are listed. The ratio CaO/SiO2 indicates that forsterite (Mg2SiO4), monticellite (CaMgSiO4) and mervinite (Ca3MgSi2O8) are formed during sintering of the samples.
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  • 68
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    Chemical Engineering & Technology - CET 20 (1997), S. 53-62 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The minimum ignition temperature of dust clouds is one of the important factors required for the design of preventive measures against dust explosion. The mathematical models available to predict this parameter have been analyzed for thier application to organic dust clouds. A solution of the most general model proposed by Mitsui and Tanaka is presented, together with its comparision with experimental data. It has been found to be quite successful in predicting the minimum ignition temperature for metal dusts but not for organic dusts. Recommendations for the development of a new model to predict the minimum ignition temperature of an organic dust, such as polyethylene, have been given.
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  • 69
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    Chemical Engineering & Technology - CET 20 (1997), S. 76-84 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During recent years in chemical engineering processes for instance with aerated stirred tanks containing surface-active components foams and their mechanical control have become very important. However, there are still no rules for calculating mechanical foam breakers. As a contribution to foam control the present paper discusses the fundamentals of foam breaking by means of foam densities and gives a physical model for the mechanisms of a mechanical foam breaker when the main breaking effect is based on impact. The mechanisms were proved by measuring pressures in a foam breaker box. Diameters of secondary foam bubbles produced by foam breakers are calculated and discussed. Experimental investigations were made with different surfactants in aqueous solutions. The paper points out their influence on the process of foam breaking.
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  • 70
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    Chemical Engineering & Technology - CET 20 (1997), S. 101-107 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A vapor pressure calculation procedure based on a lattice equation is applied to several compounds. Originally, the method was used to predict low vapor pressures of heavy hydrocarbons. In this work, the method is used at low vapor pressure for nonhydrocarbons, and a modified version is employed at high vapor pressure for n-alkanes. As the procedures require the knowledge of one vapor pressure datum only, they work in a predictive mode. Prediction for hydrocarbons is good and for nonhydrocarbons is poor. Prediction of n-alkanes high vapor pressure is good with an overall average relative absolute deviation under 6 percent.
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  • 71
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    Chemical Engineering & Technology - CET 20 (1997), S. 144-148 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of the liquid phase hydrogenation of 4-tert-butylphenol to form cis- and trans- 4-tert-butylcyclohexanol at 1.0-10.0 MPa and 40°C in isopropanol over a Rh catalyst has been studied. The kinetic behavior of this parallel system is described by a proposed reaction network. Keto-enol tautomeric transformation of adsorbed 4-tert-butyltetrahydrophenol and 4-tert-butylcyclohexanone is thought to be a key step, which governs the stereoselectivity of the overall complex reaction of alkylphenol hydrogenation.
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  • 72
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    Chemical Engineering & Technology - CET 20 (1997), S. 162-170 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The performance of an upflow packed-bed biofilm reactor has been analyzed under multisubstrate limitation by considering simultaneous carbon oxidation and nitrification reactions. The fasting shock load of inlet methanol concentration has a much more pronounced effect on the response of the system compared to that of inlet NH4+ -nitrogen concentration. The exit concentration of NH4+ -nitrogen drops very close to zero, thereby showing essentially complete nitrification during methanol fasting condition. Further, the concentration profiles of oxygen within the biofilm show significant variation during methanol fasting and nonfasting conditions whereas during NH4+ -nitrogen fasting conditions the oxygen concentration profile in the biofilm remains essentially unaffected.
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  • 73
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    Chemical Engineering & Technology - CET 20 (1997), S. 199-202 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An electrochemical technique which involved measuring the limiting current of the cathodic reduction of potassium ferricyanide was used to study the rate of mass transfer inside a cubical cavity machined in the wall of a vertical rectangular duct. Variables studied were side length, physical properties of the solution and flow rate of the solution. The mass transfer coefficient was found to decrease with increasing cavity size; in all cases, the mass transfer coefficient inside the cavity was less than that at the duct wall. Mass transfer data inside the cavity were correlated by the equation Shc = 0.525 (Sc Re de/L)0.33. Comparison of the present results with the results obtained using other cavity geometries shows that cavity geometry plays an important role in determining the rate of mass transfer inside the cavity.
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  • 74
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    Chemical Engineering & Technology - CET 20 (1997), S. 212-219 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Subnetwork Corollary provides some sufficient conditions for which a complex reaction network could be determined to have capacity of admitting multiple positive steady-states, if it contains a subnetwork that also admit multiple positive steady-states. A family of reaction networks, involving catalytic reactions in an isothermal continuous flow stirred tank reactor (CFSTR), is determined to have the capacity to exhibit steady-state multiplicity by implementation of the Deficiency One Algorithm and the Subnetwork Corollary. A set of rate constants and two corresponding positive steady-states are constructed for several cases.
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  • 75
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    Chemical Engineering & Technology - CET 20 (1997), S. 247-258 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: New uses of artificial selective membranes, particularly ion-exchange membranes, improve on traditional methods of treating liquid mixtures before, during or after chemical or biochemical reactions. With the correct choice of ion-exchange membrane in a membrane reactor, reactions can be performed in such a way that the main product is not contaminated by undesired byproducts. Recent examples, mainly in organic chemistry, are given for eight typical ion-exchange membrane reactors: electrodialysis (ED), electrometathesis (EMT), electro-ion substitution (EIS), electro-ion injection-extraction (EIIE), coupled counter-transport (CCT), electro-electrodialysis (EED), electrohydrolysis with bipolar membranes (EHBM), and catalysis with ion-exchange membrane (IEMC).
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  • 76
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    Chemical Engineering & Technology - CET 20 (1997), S. 277-281 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new method for cleaning inner surfaces of pipes was studied both theoretically and experimentally. The method is based on the phenomenon of a sphere rotating in a pipe (levitation), when the translational movement of the sphere is restricted and the sphere is subjected to fluid flow in the pipe. The high rotation velocity causes a vibration process, which may be exploited for cleaning sediments or rust from the inner surfaces of pipes. A simplified theoretical model for the determination of the relationships among the dimensionless parameters governing the rotation phenomenon was developed. The model was validated with experimental data and found to be appropriate for engineering design of the system. Application of the cleaning method was demonstrated by cleaning the sediments and rust off the inner surface of a one-inch nominal diameter pipe.
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  • 77
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    Chemical Engineering & Technology - CET 20 (1997), S. 287-292 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The development and optimization of the synthesis of an analogue of sperm whale oil have been carried out. The product is an ester with characteristics similar to those of natural sperm whale oil. A central composite design was applied in the synthesis of this fine chemical. The variables selected for the present study are reaction temperature, initial concentration of catalyst and working pressure. Temperature is the most significant factor in the esterification process, and its influence is positive. Pressure influence can be neglected, and the catalyst concentration has a positive influence on the process. Depending on the temperature value, the influence of the interactions can be more important than that of the other two main effects, pressure and catalyst concentration. Response surface models have been found adequate to represent the yield of ester. The commercial quality of the synthesized product is very similar to that of natural spermaceti. Because of its low cost, this synthesis process is considered, from an economical point of view, very attractive.
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  • 78
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    Chemical Engineering & Technology - CET 20 (1997), S. 313-316 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: From the group statistical theory, a new universal equation is proposed for calculating the surface tension of solution with surface thermodynamics of solution. The simple form of the equation makes it convenient to use and its parameters have obvious physical meanings. With this model, we have explained the experimental phenomenan and empirical rules in cited works. Tested for 302 kinds of binary system, the overall absolute average deviation for 3230 data sets is 0.49%, making the model more accurate than those found in the literature. It also accounts for systems unsuitable for reference models because the phase states of the pure components are different under solution condition.
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  • 79
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The catalytic properties of extra-large pore aluminosilicate MCM-41, silicon containing VPI-5 and aluminium containing ETS-10 were investigated by MAT (Micro Activity Test) using n-hexadecane and 1,3,5-triisopropylbenzene as the model feeds and were then compared with the results obtained from Y zeolite in the H-form and a commercial FCC (Fluid Catalytic Cracking) catalyst. It could be demonstrated that not only the acidic properties of the investigated materials, but also the accessibility to the internal active sites of the investigated materials have a significant influence on activity and selectivity. It can be assumed that, by optimising structural and chemical properties, the mesoporously organised MCM-41 and related materials are suitable as active components in cracking catalysts for “deeper” cracking of high boiling hydrocarbons.
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  • 80
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two new constructed strains of X. campestris XLM1521 and XMT1, either alone or in mixed cultures were used for the production of xanthan gum in batch fermentations from whey. Fermentations were carried out at three different pH levels of 6.0, 7.0 and 8.0 and the results were compared with those previously reported for fermentations in Erlenmeyer flasks without controlling the pH. The kinetics of cultures of the strain X. campestris XLM1521 were studied in a batch reactor at constant pH values. A mathematical model, based on the Luedeking-Piret equation, was used and experimental design was employed in order to correlate model's parameters with pH variation. The highest xanthan gum concentration, 17.3 g/l, was observed at pH 8.0. This is the largest amount of xanthan gum reported so far.
    Additional Material: 5 Ill.
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  • 81
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 384-390 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The heterogeneously catalyzed oxidative dehydrogenation of isobutyric acid in a fixed bed reactor using molybdenum (Mo) heteropoly acids as catalysts shows a loss of Mo into the gas phase due to the formation of volatile Mo-complexes under reaction conditions. To avoid this loss of catalyst and to keep the catalytic material in the fixed bed and thus increase the catalyst's lifetime, the process has been performed under periodic flow reversal within the reactor. In this work, periodic flow reversal is tried in a semi-pilot test reactor as a method to fix the Mo-compounds in the catalyst bed. The influence of this mode of operation on the temperature profile in the reactor, on conversion, selectivity and yield of the product methacrylic acid is investigated in comparison with the process without periodic flow reversal.
    Additional Material: 11 Ill.
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  • 82
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 83
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 455-461 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A time- and space-dependent model based on the piston-dispersion-exchange model for liquid flow was developed to analyze the performance of two-phase upflow and downflow fixed bed reactors and was applied to the catalytic SO2 oxidation. The hydrodynamic parameters were determined from residence time distribution measurements, using an imperfect pulse method for time-domain analysis of nonideal pulse tracer response. A transient diffusion model of the tracer in the porous particle coupled with the PDE model was used to interpret the obtained RTD curves. Gas-liquid mass transfer parameters were determined by a stationary method based on the least square fit of the calculated concentration profiles in gas phase to the experimental values. It is shown that two-phase downflow fixed bed reactor performs better at low liquid flow rates, while two-phase downflow fixed bed reactor performs better at low liquid flow rates, while two-phase upflow performs better at high liquid flow rates.
    Additional Material: 7 Ill.
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  • 84
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    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997) 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 85
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    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997), S. 272-277 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two descriptors based on mathematical morphology are described which permit discrimination between convex and concave polygonal shapes which often characterize crystalline particles. Their computation is based on the comparison between the silhouette of the particle and a reference shape. Three reference shapes are discussed: the convex hull, the circle circumscribed to the particle and the equivalent circle.
    Additional Material: 5 Ill.
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  • 86
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    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997), S. 267-271 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method called “image-sedimentation”, based on the application of Stokes' law to suspension and image techniques, is proposed for the rapid analysis of particle size distributions. A parallel beam of optical light, after passing through a cell containing particles, is measured with a linear image sensor with 2048 photodetectors to determine the attenuated light intensity displayed on a monitor screen. The settling height between any given point and the liquid surface can be measured accurately by use of this image technique without any additional mechanical device to move either the light beam or the glass cell containing the suspension. Consequently, the total time required for the determination of the particle size distribution, typically of a carborundum powder having a median diameter of 5 μm, takes only 5 min as compared with more than 20 min by using other instruments based on the sedimentation principle.
    Additional Material: 8 Ill.
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  • 87
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    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997), S. 278-282 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In previous work, the relative performance of various methods used to characterize the particle size distribution of powders composed of fine irregularly shaped particles was assessed. It was found that methods employing Fraunhofer diffraction theory were inferior with respect to particle counting methods. Furthermore, calculated particle size distributions varied considerably between manufactures of Fraunhofer devices. It is well known that the Mie optical model can also be used to analyze the data collected by laser diffraction instruments. Here, we have compared particle size distributions collected using two Laser diffraction instruments to those determined by the Aerosizer. In our earlier work the Aerosizer was shown to produce results nearly identical to those determined by image analysis. The results of this study indicate that the use of the Mie optical model does not correct for deficiencies previously noted for laser diffraction methods. Considerable variation exists between the results obtained on laser diffraction instruments manufactured by different companies. Our earlier recommendation to use extreme caution when employing laser diffraction instruments to characterize fine powders continues to be supported in the present work.
    Additional Material: 10 Ill.
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  • 88
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    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 14 (1997), S. 283-289 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of the surface roughness of solid conducting spheres on the response of a phase-Doppler anemometer (PDA) is described by using a ray theory model. A rough particle surface is modeled as an ensemble of distorted spheres. First- and second-order reflection and diffraction are considered for far-field calculations of the PDA phase difference. The numerical simulations are accompanied and supported by experimental results. Single rough Sn spheres are captured inside an electro-dynamic trap and investigated with a standard phase-Doppler system.
    Additional Material: 11 Ill.
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  • 89
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    Particle and Particle Systems Characterization 14 (1997), S. 295-303 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new method is introduced to analyze the accuracy of phase-Doppler anemometry (PDA) for sizing large particles in two-phase flows. The method is based on Fourier optics theory (FOT) and geometrical optics theory (GOT) to calculate the intensity ratio of refractive and reflective light scattered by a sphere under a slit constraint. To examine the accuracy in calculating the light intensity, the results from the GOT method were compared with those of the direct simulation based on the generalized Lorenz-Mie theory (GLMT). This newly developed FOT/GOT method also predicts the results of phase jump due to the slit constraint. The performance of dual-mode phase-Doppler anemometry can also be simulated by this method.
    Additional Material: 17 Ill.
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  • 90
    ISSN: 0894-3230
    Keywords: N-1-adamantyl-N-p-tolylcarbamoyl chloride ; solvolysis ; decompositions ; hydroxylic solvent ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride undergoes a facile rate-determing ionization with very little assistance from nucleophilic solvation (very low sensitivity to changes in solvent nucleophilicity). In the relatively nucleophilic aqueous ethanol or aqueous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effective competition from a pathway involving disproportionation to the 1-adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization. Grunwald-Winstein plots against YC1 values show for different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term governed by the aromatic ring parameter (I). © 1997 John Wiley & Sons, Ltd.
    Additional Material: 3 Ill.
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  • 91
    ISSN: 0894-3230
    Keywords: Electron transfer properties ; substituted flouranthene derivatives ; redox potentials ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The oxidation and reduction potentials of a series of related even non-alternant derivatives of 7,14-disubstituted acenaphth[1,2-k] fluoranthenes, and also fluoranthene, 7,10-diphenylfluoranthene and 8,9-dihydrodiindeno[1,2-j;2′,1′-] fluoranthene, were determined in organic solvents by cyclic voltammetry. The effects of steric hindrance on conjugation of the substituents with the central polycyclic aromatic hydrocarbon nucleus were evaluated. The semi-empirical molecular orbital calculation programs OMEGAMO, Extended Hückel, AM1 and PM3 were used to obtain optimal geometries and calculated HOMO and LUMO energies. As a further refinement, COSMO solvation was included in the AM1 calculations. The redox properties were correlated with data derived from the various semi-empirical calculations and the quality of these correlations is discussed. Inclusion of solvation energies in the computed molecular orbital energies results in a significant improvement in the correlation between observed and calculated oxidation potentials. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 92
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 697-715 
    ISSN: 0894-3230
    Keywords: silanes ; polysilanes ; molecular mechanics calculations ; MM3 ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: -Molecular structures, conformational energies, heats of formation and vibrational spectra have all been fit using the MM3 force field for a group of 48 silanes and polysilanes for which experimental data are available. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 12 Tab.
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  • 93
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 680-686 
    ISSN: 0894-3230
    Keywords: 8-aminoquinoline ; x-ray structure ; vibrational spectra ; three-center hydrogen bond ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: -The x-ray structure of 8-aminoquinoline indicates that one of the NH bonds of the NH2 group forms a three-center hydrogen bond, the major component being the intramolecular hydrogen bond and the minor component the intermolecular hydrogen bond. The IR and Raman spectra of 8-aminoquinoline and of its N-deuterated counterpart reflect the non-equivalence of the two NH(D) bonds and the weakness of the hydrogen bridge. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 4 Ill.
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  • 94
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 675-679 
    ISSN: 0894-3230
    Keywords: chemical contrast ; scanning near-field optical microscopy ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Repeatable and stable scanning near-field optical microscopy (SNOM) images are obtained under shear-force control if uncoated, i.e. cold and sharp, tapered fiber tips are used. True chemical contrast is seen for the first time on organic crystals due to the different near-field reflectivities of different chemical species on partly oxidized anthracene. The topography spans a Z-range of 500 nm. The surface roughness is tolerable and the sites of reaction can be related to crystal structure data. A submicroscopic local resolution of 18 nm has been obtained for chemical contrast, discriminating different chemical species even with poorly reflecting organics on rough crystal surfaces. Thus, reflection-back-to-the-fiber SNOM will find wide applications for both transparent and opaque samples. All drawbacks with blunt and hot metal-coated tips at a 〈10 nm distance from the surface in previous SNOM setups are overcome. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 6 Ill.
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  • 95
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 607-611 
    ISSN: 0894-3230
    Keywords: electron transfer photochemistry ; 7-(spirocyclopropane)quadricyclane ; cyclopropylcarbinyl rearrangements ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The electron transfer photo-sensitized reaction of 7-(spirocyclopropane)quadricyclane (1) with methanol produces two rearranged mono-methanol adducts, 2 and 3, and a bis-methanol adduct, 4. The products reveal that 1·+ reacts by stereo- and regiospecific attack of methanol on one trisubstituted cyclopropane ring. The resulting free radical rapidly undergoes one or two (consecutive) cyclopropylcarbinyl to butenyl rearrangements. The mono-adducts are formed by net hydrogen abstraction, the di-adduct via a (secondary) electron transfer reaction of 3. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
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  • 96
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; substituted isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of γ-lactones, i.e. 39 substituted 3-(aryl- and alkylmethylene)-(Z)-1(3H)-isobenzofuranones (3-aryl- and alkylmethylenephthalides) in 70% (v/v) aqueous dioxane at 30·0 °C. A Hammett reaction constant for the 3- or 4-substituted phenyl series is ca 1·5, whereas those for the 2-substituted phenyl and 4-substituted 1-naphthyl series, using para-σ values, are ca 1·0 and 1·9. These results are related to an electrostatic field effect model. A very successful correlation between the rates of alkaline hydrolysis of all 39 phthalides and the carbonyl stretching frequencies in chloroform was found. Substituent effects in widely different environments give linearly related effects on both reactivity and physical properties. Computational studies using the semi-empirical AM1 method correctly modelled both the details of the mechanistic pathway and the substituent effects. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 6 Ill.
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  • 97
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 1-9 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this paper enzymatic hydrolysis reactions have been considered as integration-limited reactions analogous to crystal growth. Based on the mathematical formulation of diffusion of polysaccharide substrate molecules to binding sites of the enzyme, integration kinetics were derived and compared to measured data. Significant is the measured and calculated decrease of the ratio of the specific activity and the Michaelis-Menten parameter with increasing molar mass of the enzymes with an exponent more than unity.
    Additional Material: 3 Ill.
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  • 98
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 138-143 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The gas-phase hydrogenation of buta-1,3-diene to but-1-ene, trans- and cis-but-2-ene and butane has been performed over 0.5% Pd/γ-Al2O3 catalyst. The reaction has been investigated at atmospheric pressure and 0°C over a wide range of conversions. The kinetic model based on the present day knowledge of reaction mechanism has been advanced. The parameters of the kinetic model have been estimated through statistical data fitting. The kinetic model provides a fairly good description of selectivity in the whole range of conversions.
    Additional Material: 4 Ill.
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  • 99
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    Chemical Engineering & Technology - CET 20 (1997), S. 149-161 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The following article concerns emulsification reaction in a continuous screw loop reactor. The influence of hydrodynamics on the emulsification process as well as the influence of some specific substances were examined. We produced oil/water model emulsions under different test conditions and we determined the correlations between the mixing behavior of the reactor and the characteristic features of the obtained emulsion. Special consideration was given to the droplet size and its distribution. Variable operating conditions of the reactor are the residence time and the rotational speed of the screw, both of which have a decisive influence on the recycle factor and the number of passages through the rotor/stator system. In addition we determined the dependence of the obtained droplet size distribution on the viscosity of the continuous and dispersed phase, on the interfacial surface tension and on the phase proportions. The influence of the specific type of emulsifying agent and its concentration has been examined as well. The positive effect of the mixing and of the recirculation on the emulsification in the screw loop reactor was particularly evident with low emulsifier concentrations and with emulsifiers with slow adsorption kinetics. The established theories for emulsion formation (Kolmogoroff, Taylor) were used for a quantitative description of the experimental results. The screw loop reactor was compared to an agitated tank reactor and a toothed-ring dispersing machine (Ultra Turrax) based on the comminution energy which is produced per unit volume of emulsion. The agitated tank reactor produced only coarsely dispersed emulsions through the entire rotational speed range, wheras the screw loop reactor and the Ultra Turrax, particularly at high rotational speeds and, therefore, high power densities, showed a similar emulsification and produced much finer dispersed emulsions.
    Additional Material: 18 Ill.
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  • 100
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 208-211 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The results of a process analysis and an experimental exploratory study of supercritical water oxidation (SCWO) show that elements of combustion technology are suitable to overcome the technical problems of SCWO. The Film Cooled Hydrothermal Burner (FCHB) which operates at 25 MPa up to 2000 K in the reaction zone keeping wall temperature under stress at 300 to 400 K shows further development potential of the Wallcooled Hydrothermal Burner (WHB) concept for SCWO, a still promising waste treatment process.
    Additional Material: 6 Ill.
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