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  • Chemical Engineering  (17,974)
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  • Biochemistry  (1,822)
  • Theoretical, Physical and Computational Chemistry  (1,576)
  • Wiley-Blackwell  (31,027)
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  • 1
    Electronic Resource
    Electronic Resource
    Unexpected rate enhancement in the intramolecular carboxylic acid-catalyzed cleavage of o-carboxybenzohydroxamic acid (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 216-222 
    Details
    ISSN: 0894-3230
    Keywords: o-carboxybenzohydroxamic acid ; phthalic anhydride ; phthalic acid ; hydrolysis ; intramolecular acid catalysis ; kinetics ; activation parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phthalic anhydride was detected spectrophotometrically in the hydrolysis of o-carboxybenzohydroxamic acid (OCBA) in CH3CN-H2O solvent containing 0.03 mol dm-3 HCl. Pseudo-first-order rate constants (k1) for hydrolysis of OCBA are almost independent of the change in CH3CN content from 10 to 80% (v/v) in mixed aqueous solvents. The rate constants k1 are more than 10-fold larger than the corresponding rate constants for hydrolysis of phthalamic acid. These observations are explained in terms of a mechanism slightly different from the mechanism for hydrolysis of phthalamic acid. The activation parameters, ΔH* and ΔS*, are not affected appreciably by an increase in CH3CN content from 10 to 80% in mixed aqueous solvents. © 1998 John Wiley & Sons, Ltd.
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  • 2
    Electronic Resource
    Electronic Resource
    Solute-solvent and solvent-solvent interactions in binary solvent mixtures. Part 7. Comparison of the enhancement of the water structure in alcohol-water mixtures measured by solvatochromic indicators (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 185-192 
    Details
    ISSN: 0894-3230
    Keywords: solute-solvent interactions ; solvent-solvent interactions ; binary solvents ; alcohol-water mixtures ; water structure ; solvatochromic indicators ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preferential solvation model that takes into account the enhancement of the structure of water when small amounts of alcohol are added was applied to solvatochromic data for binary mixtures of water with 2-methylpropan-2-ol, propan-2-ol, ethanol and methanol. Application of the model allows the calculation of the effect of the enhancement of the water structure on solvatochromic solvent properties. It is demonstrated that the enhancement of water structure increases the solvent dipolarity/polarizability and hydrogen-bond donor acidity and decreases the solvent hydrogen-bond acceptor basicity. The effect decreases in the order 2-methylpropan-2-ol-water, propan-2-ol-water, ethanol-water and methanol-water. © 1998 John Wiley & Sons, Ltd.
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  • 3
    Electronic Resource
    Electronic Resource
    Structural dependence of heterolytic bond dissociation energy of carbon-carbon σ bonds in hydrocarbons (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 157-170 
    Details
    ISSN: 0894-3230
    Keywords: heterolytic bond dissociation energy ; carbon-carbon σ bonds ; hydrocarbons ; structural dependence ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon σ bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pKHA, pKR+ and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis. © 1998 John Wiley & Sons, Ltd.
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  • 4
    Electronic Resource
    Electronic Resource
    Correlation of the rates of solvolysis of the N,N-diphenylcarbamoylpyridinium ion (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 273-276 
    Details
    ISSN: 0894-3230
    Keywords: N,N-diphenylcarbamoylpyridinium ion ; solvolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolyses of the N,N-diphenylcarbamoylpyridinium ion are subject to specific and/or general base catalysis, which can be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalyzed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (l  =  0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. © 1998 John Wiley & Sons, Ltd.
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  • 5
    Electronic Resource
    Electronic Resource
    Effects of ionic and non-ionic micelles on rate of hydroxide ion-catalyzed hydrolysis of securinine (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 209-215 
    Details
    ISSN: 0894-3230
    Keywords: securinine ; cationic micelles ; anionic micelle ; non-ionic micelle ; alkaline hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyltrimethylammonium bromide (TTABr), sodium dodecyl sulfate (SDS) and polyoxyethylene 10 lauryl ether (C12E10) on the rates of alkaline hydrolysis of securinine were studied at a constant [-OH] (0.05 M). An increase in the total concentrations of CTABr, TTABr, SDS and C12E10 from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, 7 and 4, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelle. The binding constants, KS, of securinine with SDS, C12E10, CTABr and TTABr micelles are 32.4, 14.8, 22.1, and 9.1 M-1, respectively. The magnitudes of the second-order rate constants, kM, for the reactions in the micellar pseudophase are negligible compared with the corresponding rate constant, kW, for the reaction occurring in the aqueous pseudophase for CTABr, TTABr, SDS and C12E10. © 1998 John Wiley & Sons, Ltd.
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  • 6
    Electronic Resource
    Electronic Resource
    Colloidal CdS-induced photocatalytic reaction of 2-methylindole - mechanistic analysis of oxidation of indoles (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 277-282 
    Details
    ISSN: 0894-3230
    Keywords: colloidal CdS-induced photochemical reactions ; photocatalytic reactions ; photooxidation ; 2-methylindole ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Methylindole (2-MI) is adsorbed on the surface of colloidal CdS particles with an adsorption intensity of 0.6 × 103 dm3 mol-1. A new emission band at 530 nm is produced by forming an exciplex between excited CdS and 2-MI and the red emission due to CdS is simultaneously quenched. The emission maxima of green bands for different indoles increase in the order indole 〈 tryptophan 〈 2-MI 〈 3-MI and are observed at 508, 520, 530 and 540 nm, respectively. The shift in emission maxima is related to the oxidation potential of these substrates. The irradiation of an aerated reaction mixture containing CdS and 2-MI with visible light induces the oxidation of adsorbed 2-MI by photogenerated holes to produce 2-methyl-3-indolinone and 2-acetamidobenzaldehyde. The latter product is formed due to oxidative C - C bond cleavage of the pyrrole ring. The reactivity of trapped holes towards the adsorbed 2-MI is evidenced by a decrease in the lifetime of the red emission of CdS in the presence of 2-MI. In this reaction the possibility of the participation of singlet oxygen is ruled out. A general mechanism of CdS-induced oxidation of indoles is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 7
    Electronic Resource
    Electronic Resource
    The Menschutkin reaction of benzyl p-toluenesulfonates with N,N-dimethylanilines. Evidence for the duality of SN1 and SN2 mechanisms (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 254-260 
    Details
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
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  • 8
    Electronic Resource
    Electronic Resource
    Editorial (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    Details
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 9
    Electronic Resource
    Electronic Resource
    Solvent effects on infrared spectroscopic and calorimetric characteristics of aliphatic ketones in binary solvent mixtures (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 283-289 
    Details
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 10
    Electronic Resource
    Electronic Resource
    Solvent effects on C=O stretching frequencies of some 1-substituted 2-pyrrolidinones (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    Details
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
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  • 11
    Electronic Resource
    Electronic Resource
    Molecular orbital calculations on the P - S bond cleavage step in the hydroperoxidolysis of nerve agent VX (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    Details
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
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  • 12
    Electronic Resource
    Electronic Resource
    Conformational analysis of a 12-membered crown dithioether in the solid state and in solution (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 241-253 
    Details
    ISSN: 0894-3230
    Keywords: crown dithioether ; conformational analysis ; multicomponent equilibrium ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state molecular structure and the conformational behaviour in solution of the 12-membered crown dithioether 8-methyl-1,4-dioxa-7,10-dithiacyclododecane-5,12-dione were studied by x-ray crystallography, 1H and 13C NMR spectroscopy and molecular mechanics. The conformational rigidity of some constituent structural fragments allowed a detailed analysis of the structure and distribution of the conformers. A protocol for studies of multiconformational equilibrium was developed by means of the combined use of structure calculations and dynamic NMR measurements. © 1998 John Wiley & Sons, Ltd.
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  • 13
    Electronic Resource
    Electronic Resource
    Metal-catalyzed carbenoid reactions with iodonium and sulfonium ylides (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 321-333 
    Details
    ISSN: 0894-3230
    Keywords: metal-catalyzed carbenoid reactions ; iodonium ylides ; sulfonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter- and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst. © 1998 John Wiley & Sons, Ltd.
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  • 14
    Electronic Resource
    Electronic Resource
    In vivo formation of C - S bonds in biotin. An example of radical chemistry under reducing conditions (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 529-535 
    Details
    ISSN: 0894-3230
    Keywords: biotin ; in vivo C - S bond formation ; radical chemistry ; reducing conditions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The last step in the biosynthesis of biotin involves the formation of carbon-sulfur bonds at non-activated carbons catalyzed by biotin synthase. S-Adenosylmethionine (AdoMet) and an electron source are essential for activity in cell-free systems. This important finding connects biotin synthase to a family of enzymes, namely pyruvate-formate lyase, anaerobic ribonucleotide reductase and lysine 2,3-aminomutase, which use the same cofactors. Additional experimental data led to the proposition of the following general mechanism. The carbons to be functionalized are first activated by homolytic cleavage of the C - H bonds, initiated by the deoxyadenosyl radical produced by a monoelectronic reductive cleavage of AdoMet with NADPH as electron source. The electron transfer system involves flavoproteins and very likely the [Fe - S] center of biotin synthase. NADPH and the flavoproteins can be replaced by photoreduced deazaflavin. By using a deuterated substrate, a deuterium transfer into deoxyadenosine has been observed, indicating that biotin synthase should be closely related to lysine 2,3-aminomutase, which uses AdoMet as a surrogate of vitamin B12. The source of sulfur, the nature of the immediate sulfur donor and hence the mechanism of trapping of the intermediate radicals are still unknown. © 1998 John Wiley & Sons, Ltd.
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  • 15
    Electronic Resource
    Electronic Resource
    Ground- and excited-state properties of some 3,4-dihydro-1-(2-p-substituted benzylidene)naphthalenones: substituent and environmental effects (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 687-696 
    Details
    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.
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  • 16
    Electronic Resource
    Electronic Resource
    Chemistry of secologanin. Part 5. Graphical analysis of the acidic deglycosylation of vincoside derivatives (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 622-631 
    Details
    ISSN: 0894-3230
    Keywords: secologanin ; vincoside derivatives ; acidic deglycosylation ; graphical analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidic hydrolysis and cyclization were studied in vincoside glycosides (‘natural’ series) and their dihydro derivatives (‘dihydro’ series) in which either one or both N atoms were free or blocked by an alkyl group. For interpretation of the results, a graph was constructed in which 25 points (actually circles) represent a maximum of 81 aglycone types and 40 arrows indicate 131 possible cyclizations. The reaction matrix of the graph was under thermodynamic control and in most cases afforded the thermodynamically most stable product aglycones. In addition to the deglycosylation, two types of cyclization were observed. In azacyclizations, the preferred nucleophilic site is N-4 over N-1, and the preferred electrophilic site is C-22 in the glycosides, C-21 over C-19 and C-17 in aglycones. In oxacyclizations, the preferred nucleophilic site is O-17 over C-18 and C-21, and the preferred electrophilic site is C-19 over C-21 and C-17 in the ‘natural’ series, C-21 over C-17 in the ‘dihydro’ series. In one case, the kinetically favoured aglycone types which had been generated in the reaction mixture were trapped in a subsequent reaction (outside the graph) before thermodynamic equilibrium was attained. With the help of graphical analysis it was possible to justify the formation of the most favourable and actually isolated products and pathways out of a large number of possibilities. © 1998 John Wiley & Sons, Ltd.
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  • 17
    Electronic Resource
    Electronic Resource
    Reactant-solute encounters in aqueous solutions studied by kinetic methods: hydration cosphere overlap and camouflage effects (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 841-846 
    Details
    ISSN: 0894-3230
    Keywords: reactant-solute encounters ; aqueous solutions ; water ; kinetic methods ; hydration cosphere destructive overlap ; camouflage effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rates of chemical reactions in aqueous solutions are often sensitive to low concentrations of added solutes such as ureas, alcohols, α-amino acids and carbohydrates. In this work, several simple chemical reactions were used to probe this sensitivity, which arises from interactions between added solute and the reacting solute. It was found that derived interaction parameters provide a novel insight into interactions between solute molecules in aqueous solution. For example, it was possible to identify two interesting effects, which are termed (i) ‘destructive overlap’ of hydration cospheres and (ii) ‘camouflage effects’ by water-solute interactions. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 18
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    Absolute proton affinities of some substituted toluenes: the additivity rule of thumb for ipso attack (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 663-669 
    Details
    ISSN: 0894-3230
    Keywords: ipso proton affinities ; additivity ; disubstituted toluenes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of the ipso protonation of toluene and its predominantly disubstituted derivatives was considered by the MP2(fc)/6-31G**//HF/6-31G*+ZPE(HF/6-31G*) theoretical model. The substituents involved covered a wide range of different donor-acceptor capabilities. It is shown that the calculated MP2 ipso proton affinities of substituted toluenes follow mutatis mutandis the same additivity rule which was found earlier to be operative in polysubstituted benzenes, naphthalenes and biphenylenes. The additivity equation is both intuitively appealing and useful, being able to offer quantitative estimates of the proton affinity by very simple calculation. It is based on the concept of the increment, which in turn describes the influence of a single substituent on the proton affinity. Any substituent behaves as a rule as if the other were non-existent, thus giving rise to the independent substituent approximation (ISA). The performance of the additivity rule of thumb is very good, as evidenced by the average absolute deviation of 1 kcal mol-1. Larger deviations are possible, but they rarely occur, being indicative of a difference in interactions between substituents in the initial neutral base and in the final cationic conjugate acid. Finally, it follows as a corollary of the present analysis that protonation ipso to the CH3 group is never thermodynamically the most favourable site of proton attack in the benzene ring, provided that there is a single unsubstituted carbon atom within the aromatic moiety. The relevance of ipso protonation in persubstituted benzenes is briefly discussed. © 1998 John Wiley & Sons, Ltd.
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  • 19
    Electronic Resource
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    Photoinduced electron transfer and strand cleavage in pyrenyl-DNA complexes and adducts (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 561-565 
    Details
    ISSN: 0894-3230
    Keywords: pyrenyl-DNA complexes and adducts ; photoinduced electron transfer ; strand cleavage ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fluorescence of pyrenyl residues in complexes with the nucleic acid bases G, C and T, but not A, is strongly quenched by photoinduced electron transfer mechanisms. Site-specifically modified 11-mer oligonucleotide duplexes containing a single modified guanosyl base G* bearing a covalently attached pyrenyl residue were prepared in order to probe for photochemical damage associated with these photoinduced electron transfer reactions. When the pyrenyl residue positioned at G* is photoexcited with 355 nm light, direct strand cleavage is observed at that site with low quantum yield. Frank strand breaks are also observed up to five base pairs away from G*, suggesting that intrastrand migration of a reactive intermediate from base to base is occurring. © 1998 John Wiley & Sons, Ltd.
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  • 20
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    From olefin cyclopropanation to olefin metathesis through catalyst engineering: recent applications of olefin metathesis to fine organic synthesis and to polymer chemistry (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 602-609 
    Details
    ISSN: 0894-3230
    Keywords: olefin metathesis ; olefin cyclopropanation ; catalyst engineering ; fine organic synthesis ; polymer chemistry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An overview of the recent synthetic breakthroughs brought about by the discovery of new, functional group tolerant late transition metal (Rh and Ru)-based catalysts is proposed. Whereas dirhodium(II)-based complexes promote only carbene transfer reactions to olefins (i.e. olefin cyclopropanation), a few ruthenium-based catalysts can be engineered and fine tuned so as to mediate either carbene-transfer reactions or olefin metathesis. The different outcome of the reactions can be rationalized by the capability of the metal center to coordinate or not both the carbene and the olefin. This quite simple-minded approach indicates that several available coordination sites at the metal center favors metathesis reactions to the prejudice of olefin cyclopropanation. Examples of recent applications in ring opening metathesis polymerizations and copolymerizations include the formation of postpolymers of polydienes, of carbohydrate-substituted polymers and of telechelic oligomers. Application of the same ruthenium-based catalysts in ring-closing metathesis is illustrated by the formation of crown ether analogs, of unsaturated peptides and amino acids, of β-lactams, and of different bicyclic systems.
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    Imperatives for enzymatic catalysis of isomerization of sugars and sugar phosphates (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 512-518 
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    ISSN: 0894-3230
    Keywords: sugar isomerization ; sugar phosphate isomerization ; enzymatic catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative yields of the products of isomerization of D,L-glyceraldehyde in D2O with intramolecular transfer of a hydride ([1-1H]DHA) and with proton transfer ([1-2H]DHA) were determined by high-resolution 1H NMR analyses. A study of the catalysis of this isomerization by deuteroxide ion, buffer anions and Zn2+ established the following: (1) isomerization with proton and hydride transfer occurs at approximately equal rates in dilute solutions of sodium deuteroxide; (2) Brønsted bases catalyze isomerization with proton transfer in a bimolecular reaction; (3) Zn2+ catalyzes isomerization with hydride transfer in a bimolecular reaction; and (4) Zn2+ and acetate ion react in concert to catalyze isomerization with proton transfer in a termolecular reaction. These results show that the various pathways for isomerization with proton and hydride transfer proceed via transition states of similar energies, so that there is no strong imperative for enzymatic catalysis by any particular reaction mechanism. The relevance of these results to the mechanism of action of xylose isomerase is discussed briefly. © 1998 John Wiley & Sons, Ltd.
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    Structural effects of the Grunwald-Winstein correlations in the solvolysis of some simple tertiary alkyl chlorides (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 717-724 
    Details
    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.
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    Kinetics and mechanism of the aminolysis of p-nitrophenyl N-phenylcarbamates (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 725-730 
    Details
    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.
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    Infrared and 1H NMR studies of hydrogen bonding in N-(2-amino-2-deoxy-β-D-glucopyranoside)-N′-carbamoyl-L-amino acid esters (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 747-754 
    Details
    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.
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    Solvent effects on aromatic nucleophilic substitution reactions. Part 7. Determination of the empirical polarity parameter ET(30) for dipolar hydrogen bond acceptor-co-solvent (chloroform or dichloromethane) mixtures. Kinetics of the reactions of halonitrobenzenes with aliphatic amines (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 849-860 
    Details
    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.
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    Solvent effect on polar and spectroscopic properties of 2-N-methylamino-5-nitro-6-methylpyridine and 2-N-methylamino-3-nitro-6-methylpyridine (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 835-840 
    Details
    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.
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    Thiapyrylium salt-sensitized electron transfer reactions of trans-stilbene. Dimerization and oxygenation (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 861-869 
    Details
    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.
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    Selective arylation of exocyclic N-position of 2-pyrimidylnitrenium ion photolytically generated from tetrazolo-[1,5-a]pyrimidine in the presence of trifluoroacetic acid (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 478-484 
    Details
    ISSN: 0894-3230
    Keywords: Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
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    Kinetics of the hydrolysis of cyclic N-substituted sulfamides: 4-amino-2-cyclohexyl- and 4-amino-2-phenethyl-2,3-dihydro-3-oxo-1,2,5-thiadiazole 1,1-dioxides (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 489-494 
    Details
    ISSN: 0894-3230
    Keywords: Cyclic N-substituted sulfonamides ; 1,2,5-thiadiazole 1,1-dioxide derivatives ; hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrolysis reactions of 4-amino-2-phenethyl- and 4-amino-2-cyclohexyl-2,3-dihydro-3-oxo-1,2,5-thiadiazole 1,1-dioxide (Ia and Ib) were investigated in the range 24-73 °C in buffered aqueous solutions. The observed rate constants (kobs) are independent of pH in the range ca 1-4 pH, but increase with increase in pH above ca 4. A linear log kobs vs pH profile with unit slope is observed from pH ca 4 up to the highest experimental pH (ca 10). The products are the corresponding new compounds: 2-amino-2-[(N-substituted-sulfamoyl)imino]acetic acid salts. The C=N bond of these compounds hydrolyses further, in a slow reaction, to the sulfamide and oxalic acid derivatives. The substrates decompose to the final products without accumulation of the acetic acid derivatives under these experimental conditions. A mechanism is proposed. Rate constants and activation parameters are given for the first reaction step. Owing to steric effects, the reaction rate is higher for the N-phenethyl-substituted derivative than for the 2-cyclohexyl-substituted derivative. © 1998 John Wiley & Sons, Ltd.
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    Rate enhancement of 1,3-dipolar cycloaddition of N-methylindole: the singular role of Grignard reagents (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 455-466 
    Details
    ISSN: 0894-3230
    Keywords: 1,3-dipolar cycloaddition ; N-methylindole ; Grignard reagents ; rate enhancement ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactions of 2-N-methylindolyl and 2- and 3-benzo[b]thiophenyl anions with nitrile oxides and nitrilimines were performed in order to investigate whether the use of anionic dipolarophiles modifies a classical 1,3-dipolar cycloaddition. When lithium compounds were used as bases, the heterocyclic anions invariably acted as nucleophilic species; in contrast, when a Grignard reagent was employed, the N-methylindole gave cycloaddition products with an extraordinary rate enhancement. The hypothesis that N-methylindole and ethylmagnesium bromide give an adduct much more reactive than N-methylindole itself was supported by the results of a theoretical investigation. The structure and electron distribution of the adduct were determined by ab initio calculations and compared with those of known Grignard complexes with nitrogen ligands. The performance of different basis sets was tested. The quantum theory of atoms in molecules was used to determine atomic charges and to describe the nature of bonds in terms of the properties of the electron density at the bond critical points. © 1998 John Wiley & Sons, Ltd.
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    The ring inversion of silacycloheptatriene and cycloheptatriene. Comparison of the ‘aromaticity’ of planar and boat conformers estimated by nucleus-independent chemical shift (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 475-477 
    Details
    ISSN: 0894-3230
    Keywords: cycloheptatriene ; silacycloheptatriene ; ring inversion ; aromaticity ; ab initio calculation ; nucleus-independent chemical shift ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nucleus-independent chemical shifts (NICS) of boat and planar structure of silepins (1) and cycloheptatriene (2) were calculated at the HF/6-31+G* level for the Becke3LYP/6-31G* optimized geometries in order to investigate the correlation between the inversion barrier and aromatic nature in the boat and planar forms of 1 and 2. The NICS of unsubstituted silepin 1a indicated that there is almost no stabilization in the boat form (NICS, -0.5) and that the planar form (NICS, 3.5) is relatively destabilized in comparison with the boat form. On the other hand, the NICS of 2 showed that there is considerable homoconjugative stabilization in the boat form (NICS, -4.2) and destabilization in the planar form (NICS, 8.2). In addition to the geometrical effects resulting from angle strain, these electronic effects are considered to affect the energy barriers for ring inversion, which have been calculated to be 0.9 kcal mol-1 for 1a and 5.2 kcal mol-1 for 2. © 1998 John Wiley & Sons, Ltd.
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    Hydrogen-bonding-based thermochromic phenol-amine complexes (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 737-742 
    Details
    ISSN: 0894-3230
    Keywords: thermochromism ; proton transfer ; hydrogen bond ; phenol ; amine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Variable-temperature UV-vis, 13C NMR and IR studies showed that proton-transferred complexes were formed between phenols and amines in apolar solvents at low temperature. Upon cooling a solution of p-nitrophenol and diisopropylamine in toluene, the colour of the solution changed from colourless to yellow. This thermochromism was ascribed to the proton transfer in the hydrogen-bonding complex. Under UV-vis conditions, butylamine and imidazole also caused similar thermochromism upon complexation with p-nitrophenol, while triethylamine, quinuclidine and pyridine did not. The thermochromic behaviour was particularly dependent on the stoichiometry of the amine and the phenol: a solution of 3,3′-dibromo-5,5′-dinitro-2,2′-biphenyldiol and diisopropylamine with a molar ratio of 1:1 showed no thermochromism, while solutions with 1:2 or higher ratios showed thermochromism, indicating that excess amine is required to obtain the proton-transferred species. These results revealed that the proton-transferred species forms in apolar solvents at low temperature if an appropriate hydrogen-bonding network between the phenol and the amine can stabilize it. © 1998 John Wiley & Sons, Ltd.
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    Double fragmentation in cation radicals. An example in the NADH analogues series (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 774-780 
    Details
    ISSN: 0894-3230
    Keywords: double fragmentation ; cation radicals ; NADH analogues ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cation radical of 9-tert-butyl-N-methylacridan, generated electrochemically or photochemically, offers, in the presence of strong bases, a remarkable example of a double fragmentation. Whereas in acidic or weakly basic media the tert-butyl radical is cleaved with concomitant formation of the methylacridinium cation, the presence of a strong base triggers the cleavage of both the methyl group borne by the nitrogen atom and the tert-butyl group on C-9 leading to acridine, formaldehyde and the tert-butyl anion, even though methylacridinium cation is stable under these conditions. The origin of this unprecedented behavior resides in the prior deprotonation of the methyl group borne by the nitrogen atom which outruns the usual deprotonation at the 9-carbon because this is slowed by the steric hindrance due to the presence of the tert-butyl group. © 1998 John Wiley & Sons, Ltd.
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    Effect of sulfuric acid on reactions of peroxymonosulfate ion with sulfides and thiol esters (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 803-808 
    Details
    ISSN: 0894-3230
    Keywords: peroxymonosulfate ion ; oxidation ; sulfuric acid ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Peroxymonosulfate ion, HSO5-, as Oxone in aqueous H2SO4, oxidizes sulfides [MeSC6H4X(p), X = Me, H, NO2] to sulfoxides and converts aryl thiobenzoates [PhCOSC6H4X(p), X = Me, H] and thiol phosphorus(V) esters [Ph2POSPh, (EtO)2POSPh, Ph2POSEt, Ph(EtO)POSEt] into the acids and sulfonate ions. Second-order rate constants increase with increasing concentration of H2SO4 (10-53 wt%), owing to the high polarity of the medium rather than to acid catalysis. The rate increases fit the Grunwald-Winstein equation based on YOTs solvent parameters derived from rate effects on SN1 solvolyses. © 1998 John Wiley & Sons, Ltd.
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    Cation radical cycloaddition polymerization: Diels-Alder copolymerization (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 825-830 
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    ISSN: 0894-3230
    Keywords: cation radical cycloaddition polymerization ; Diels-Alder copolymerization ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Diels-Alder cycloaddition copolymerization of a bis(diene) with ionizable bis(dienophiles) via a cation radical mechanism has been accomplished using tris(4-bromophenyl)aminium hexachloroantimonate as a catalyst in dichloromethane solvent. The reactions occur at 0°C and yield Diels-Alder polymers of MW up to ca. 10,000 and a polydispersity index ca. 2. © 1998 John Wiley & Sons, Ltd.
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    Masthead (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987) 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    URL: http://dx.doi.org/10.1002/ceat.270100101
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    Liquid channelling on trays and its effect on plate efficiency (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 33-37 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: All the present experiments confirm that there is some liquid channelling on trays. Liquid channelling is extensive on trays of large diameters. It largely depends on the tilting of the plate, modifications of the inlet weirs and on non-uniform bubble cap spacing. Consequences of liquid channelling for plate efficiency are clear; the higher the degree of liquid channelling the lower the plate efficiency. However, own experimental and theoretical investigations indicate that plate efficiency never falls below the value of point efficiency. Therefore, liquid channelling only affects the crossflow on trays. Liquid channelling reduces the mass transfer performance to a similar extent as does the backmixing of liquid. Consequently, plate efficiency is not very sensitive to liquid channelling. Since the liquid is completely mixed in the downcomer, the effects of liquid channelling are restricted to a single tray. The behaviour of tray columns completely differs from that of packed columns, where the effects of liquid channelling are cumulative over the packed height. Consequently, trays represent a suitable design for columns of large diameters.
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    Use of carbon dioxide in industrial organic syntheses (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 16-27 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Although carbon dixoide is important as an abundant carbonaceous raw material, so far, its utilization in chemical processes has been rather limited. This review covers the reactions of CO2 employed in industry, such as the production of urea, the Kolbe-Schmitt reaction, the synthesis of cyclic organic carbonates and the use of CO2 in methanol synthesis. Interesting recent developments in CO2 chemistry, such as the reactions catalyzed by transition metals, are also described. Apart from the synthesis of polymers and hydrocarbons, the production of oxygen-containing substances appears to be very profitable and attractive for future industrial applications. Not only can derivatives of formic and carbonic acids be produced but also longer-chain carboxylic acids and their derivatives by reactions of carbon dioxide with hydrocarbons such as alkynes, alkenes and 1,3-dienes.
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    URL: http://dx.doi.org/10.1002/ceat.270100103
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    The separation of lecithin and soya oil in a countercurrent column by near critical fluid extractionLecture at the “Jahrestreffen der Verfahrens-Ingenieure”, Hamburg 25. to 27. Sept. 1985. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 37-42 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The present contribution illustrates a way of developing a continuous separation process for near critical fluid extraction, on the example of separation of soya oil from lecithin. First, a suitable solvent was selected. Phase equilibria were measured in autoclaves. Operating conditions for a pilot plant were derived from the phase equilibrium data. The pilot plant experiments provided the necessary data for designing a production plant. Computer programs for phase equilibrium, stage to stage and mass and heat balance calculations were used in order to minimize the number of experiments. A production plant with a capacity of 500 t/a of raw lecithin was designed on the basis of experimental and computational results. A cost estimation, based on tenders, showed that it is more economical to produce lecithin by near critical fluid extraction than by conventional acetone extraction.
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    URL: http://dx.doi.org/10.1002/ceat.270100106
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    Local energy dissipation in agitated turbulent fluids and its significance for the design of stirring equipment (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 56-63 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ideal flow conditions are generally assumed for the reactor design. If stoichiometry, reaction mechanism and kinetics are known, the balance equations for the ideal flow tube, the ideal steady-state continuous stirred tank reactor or the ideal, completely mixed stirred batch reactor are often applied. In many cases, formal kinetics, which forms the basis of reaction modelling, is so uncertain that the idealization of the flow field can be accepted. In practice, however, deviations from the ideally calculated conversions, yields and product qualities, often occur. In these cases, it is necessary to consider the real flow conditions. In general, a distinction is made between macroand micromixing processes.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100108
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    Mass transfer area in different gas-liquid reactors as a function of liquid properties (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 1-15 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using pilot-scale test plant, the interfacial area per unit volume was investigated in different gasliquid reactors, i.e. packed column, bubble column and free jet reactor. The interfacial area was studied as a function of liquid viscosity and of operating parameters. As a rule, identical test conditions were maintained in all the measurements, in order to obtain comparable results. The interfacial area was determined by chemical means using the sulphite system (a solution of sodium sulphite in water as model liquid and air as gaseous medium). The viscosity of the solution can be increased by adding carboxymethyl cellulose without significantly affecting the reaction kinetics. The addition of a surfactant to the sulphite system allowed comparative measurements at reduced surface tension. Based on a large number of measurements, the correlations of the interfacial area are expressed as power laws. The inclusion of experiments with a jet tube reactor and a stirring vessel allows an extensive comparison of all reactors. All tests were carried out with the same material system and the same method was used to determine the interfacial area per unit volume. Therefore, a comparison with respect to mass transfer is possible.
    Additional Material: 21 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100102
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    A new method for measuring local velocities of the continuous liquid phase in strongly aerated gas-liquid multiphase reactors (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 27-32 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new measurement method for determining the local liquid-phase velocities in multiphase flows is presented. It is based on a tracer technique, using heat introduced into the flow, seemingly at random, instead of a material tracer. The input of heat pulses and measurement of temperature at an adjacent point is performed by small probes. As an intermediate result, the flow time distribution of the heat-labelled fluid elements is calculated on-line as a cross-correlation function between the pseudo-random input and the measured output signals. This calculation and the automatic control of measurements is carried out by a simple microprocessor unit. The device produced excellent results in gas-liquid flows at high gas throughputs and high liquid-phase velocities.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100104
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    Kinetics of removal of impurities from gases by high pressure adsorption (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 63-72 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Among other processes, adsorption is used for the removal of hydrogen sulphide from natural gases. Hereby, competitive adsorption of the different gas components plays an important role, e.g., that of carbon dioxide. Data of equilibrium loading and adsorption kinetics are required for the design of adsorbers, filled with molecular sieve. In order to obtain these data under the prevailing operating conditions, hydrogen sulphide was removed from gas mixtures H2S/CH4 and H2S/CO2/CH4, in a pilot plant, by adsorption on molecular sieve 5A. The equilibrium loading, the height of transfer zone, and the length of unused bed were determined from the measured breakthrough curves of H2S. With these data, the breakthrough time and the optimum process conditions were calculated for a practical example.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100109
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    Reaction models for simulation of the oxidation of carbon monoxide in turbulent diffusion flames (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 43-55 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The oxidation of carbon monoxide by air in a turbulent flow was investigated under experimental conditions where the rates of turbulent mixing and of chemical reaction are comparable. For this purpose, carbon monoxide was admixed into the completely burnt gas of a natural gas flame operated with excess of air. Measurements of mean values of axial velocity, temperature and volume fractions of carbon monoxide and oxygen were compared with computational simulations involving the k - ∊ turbulence model and several turbulent reaction models for the oxidation of carbon monoxide. The comparison of measurements and numerical calculations demonstrated that the k - ∊ turbulence model is suitable for prediction of the turbulent flow field in the flow system investigated. Furthermore, it could be shown that one-variable turbulent reaction models, such as the flamesheet or the eddy-break-up model, cannot explain the measured carbon monoxide volume fraction profiles. Two-variable turbulent reaction models with a probability density function closure of the source term of the transport equation for the mass fraction of the chemical species result in a better agreement between the measured and simulated volume fraction profiles, particularly in predicting the clear influence of the initial temperature on carbon monoxide volume fractions. Weighting of the kinetic rate expression for the oxidation of carbon monoxide with different presumed probability density functions yields slightly different predictions of the carbon monoxide volume fractions, reflecting the assumed different character of turbulent fluctuations.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100107
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    Distillation columns with vertical partitions (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 92-98 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Distillation columns with vertical partitions can separate a feed mixture into 3 or 4 pure fractions. Compared to other column arrangements, their investment costs and energy consumption are lower. Production columns show good results and are easily controlled. Conventional distillation columns produce only 2 pure product streams at the top and at the bottom of the column. Side products are contaminated by light or heavy components, depending on the location of the side stream in the rectifying or stripping section. This disadvantage is set aside by using a distillation column with a vertical partition. The internal separation wall prevents lateral mixing of liquid and vapour in the central part of the column, forming there separate feed and outlet sections. In the presence of a vertical partition, 3 or 4 pure fractions can be obtained in a single distillation step. This is particularly advantageous when heat sensitive components are to be separated. On account of good thermodynamic properties, the energy consumption is 20 to 35% lower than that of other distillation arrangements. The control behaviour is similar or better than that of conventional distillation columns.
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    URL: http://dx.doi.org/10.1002/ceat.270100112
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    Advances in gas permeability measurements (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 86-92 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Carman-Arnell equation relates the rate of flow of a fluid through a packed bed to the pressure drop across the bed. This equation is the basis for surface area determination by permeametry. It is found that the surface area measured at sub-atmospheric pressure varies with the bed porosity, so a porosity was selected where the rate of change was at a minimum. The study suggests that, at reduced pressures, the gas flow rate is a linear function of the mean pressure.
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    URL: http://dx.doi.org/10.1002/ceat.270100111
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    Tentative modelling of spray-dry scrubbing of SO2 (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 104-112 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A 0.5 MW spray-dry scrubbing FGD pilot plant was used in the study of spray dryer performance over a wide range of operating conditions. Experimental findings were compared with a spray dryer model. During operation with large excesses of lime, the SO2 absorption was limited by gas phase diffusion. At operation with a shortage of lime, the rate limiting step was the dissolution rate of lime. In addition, the flow regime in a spray dryer can be best described as well mixed. The SO2 level in the flue gas was found to exert no direct effect on the efficiency of SO2 removal. The observed effects are attributed solely to the changes in the drying process, due to the inter-dependence of slurry composition and SO2 concentration.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100114
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    A new method for the prediction of liquid pulsed sieve-tray extractorsLecture at the Annual Meeting of Chemical Engineers, September 19th to 21st 1984 in Munich. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 73-86 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As a part of a research project on the mass transfer in liquid pulsed sieve-tray extraction columns (PSE), the diameters and hold-ups of the drops were measured: the drop size using a suction technique, with photoelectric detection, which was adapted to the special boundary conditions of the PSE; the integral hold-up by the pressure difference between the lower and upper parts of the column. Since experimental results cannot be described by known calculation formulae for the Sauter mean diameter and the hold-up, a new method of calculation was developed. It is phenomenologically based on high-speed photographs of the drop motion on a sieve tray. The mathematical-physical model allows the prediction of drop size and hold-up within certain limits, while the possible different operating regimes of the PSE, i.e. the mixer-settler and dispersion regimes can also be estimated.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100110
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    Continuous deasphalting of heavy petroleum residues with ethyl acetate (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 125-131 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When crude oil is vacuum distilled, about 30% of the feed remain as low value residue. Hydrocracking can upgrade this residue into valuable light hydrocarbons. The hydrocracking could be optimized catalytically, if the residue were not to contain the metals vanadium and nickel that poison the catalyst. This contribution shows that continuous extraction of the residue with ethyl acetate yields a fraction with low metal content, while an asphaltene fraction with the remaining metal content is filtered off.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100116
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    Calculation of primary bubble volume in gravitational and centrifugal fieldsModified version of a paper presented at the meeting of “GVC Subject group: Mehrphasenströmung”, Kaiserslautern, February 20th, 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 99-103 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A one-stage model of the formation of primary bubbles is presented in which the bubble volume is deduced from an equilibrium of buoyancy, viscosity, inertia and surface tension forces. In contrast to the two-stage model, presented by Kumar and Kuloor, it was not assumed that the drag coefficient in bubble expansion can be described by the same constants as in the steady-state bubble ascent. The constants were adapted in such a way that the introduction of an additional bubble volume was not necessary. It was demonstrated that this model describes the bubble formation in gravitational and centrifugal fields equally well and, furthermore, is also applicable to structurally viscous liquids, provided that the effective shear gradient \documentclass{article}\pagestyle{empty}\begin{document}$$ \mathop {\rm \gamma }\limits^. = \frac{1}{6}({\rm \Delta \rho }gzd_{\rm B} /{\rm \eta }) $$\end{document} is calculated from the equilibrium of shearing and buoyancy forces. The model is based on the assumption of a constant volumetric flow rate during bubble formation and, for this reason, a minimum Froude number is necessary in analogy to the weeping limit for sieve plates. The normalized presentation permits simple operation. The possibility of applying the model to drop formation was confirmed by comparison of experimental values with those, predicted by the model.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100113
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    New equipment for the determination of virial coefficients of pure substances and binary mixturesDedicated to Professor Dr. Kurt Hedden on the occasion of his sixtieth birthday (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 143-150 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new equipment for the measurement of virial coefficients of pure substances and binary mixtures is described. It consists of an improved modification of the set-up proposed by Eucken and Meyer in 1929. The development is based on a critical review of the existing methods particularly with respect to adsorption effects. In order to reduce the influence of adsorption on the accuracy of virial coefficients, an optimum range for gas density is recommended. The accuracy of the virial coefficients is better than 20 cm3 mol-1. The set-up was employed for the measurement of virial coefficients of acetone and hexane in the range from 352.95 to 393.85 K. The results are in excellent agreement with data published in literature. Furthermore, cross-virial coefficients of the binary system acetone/hexane were measured and interpreted.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100118
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    Fouling of heat transfer surfaces (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 113-125 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fouling and/or scaling of heat transfer surfaces causes serious problems in industry. Prevention of fouling is therefore essential for technical (considerable deterioration of heat transfer) and also economic reasons (increased costs). In order to provide successful countermeasures, it is, however, necessary to obtain more detailed information on the physical, chemical and biological processes which produce fouling. Based on the already known fouling mechanisms, it is shown that a satisfactory prediction of fouling behaviour of heat exchangers is not yet possible. This contribution presents a physical model for the description of fouling, caused by sedimentation and crystallization. It is assumed that, during fouling, deposition and removal processes overlap. In order to verify the theoretical considerations, experiments were carried out on a test rig, which could also be used for field experiments. Aqueous CaSO4 solutions served as experimental liquids. A comparison of experimental and calculated fouling factors shows a satisfactory agreement.
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    URL: http://dx.doi.org/10.1002/ceat.270100115
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    Computer-aided design of tube-bundle heat exchangers (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 157-164 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on a paper by Hein, a dimensioning program for tube-bundle heat exchangers with straight tubes and fixed tube sheets has been developed. The equipment to be dimensioned is tested at 14 critical points, with regard to permissible stresses. The optimum thickness of the tube sheet, the shell and channel are subsequently selected on the basis of economic criteria. Compared to dimensioning according to AD-data sheet, it is possible to save between 10 and 25% of production costs. With the aid of a finite-element (FE) program, complex structures such as heat exchangers can be calculated accurately. Several mesh-generation programs were written for the data input. The structure of a tube-bundle heat exchanger with straight tubes is generated with 3/D elements with only some geometrical data. An FE-calculation of a heat exchanger is explained with the aid of an example and stress analysis is presented.
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    URL: http://dx.doi.org/10.1002/ceat.270100120
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    Simulation of fluid dynamics in a pulsed sieve plate columnLecture at the “Jahrestreffen der Verfahrensingenieure”, 17. to 19. September 1986 in Strasbourg. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 151-157 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The present contribution reports on a new method for the simulation of the dispersed phase behaviour in liquid-liquid extraction columns. The fluid dynamic description is based on a mathematical model which explicitly takes into account drop transport, break-up and coalescence mechanisms, via a drop population balance along the column. Application of the model requires some simple measurements on single drops in order to determine transport and break-up laws, which are required by the model, and possibly also coalescence parameters. In this study the model is applied to pulsed sieve plate columns. The specific example considered here is based on systematic studies on the determination of break-up rates from the corresponding probabilities of break-up and the generated daughter drop size distributions by means of high-speed photography. The validity of the model was subsequently tested by comparison with some experimental results from studies on two different pulsed columns 80 and 225 mm in diameter for the water/toluene system without mass transfer. The satisfactory agreement between the results justifies the use of such a method for the description of the behaviour of liquid-liquid extraction columns in a wide range of operating conditions. Furthermore, application of the model may help to dispense with long and expensive pilot tests.
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    URL: http://dx.doi.org/10.1002/ceat.270100119
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    Microbial desulphurization of coal - development and application of a slurry reactorPaper presented at the “Jahrestreffen der Verfahrensingenieure”, 17. to 19. September 1986 in Strasbourg (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 173-179 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microbial desulphurization of coal by pyrite oxidizing enrichment cultures containing predominantly Thiobacillus ferrooxidans was performed in an air-agitated slurry reactor, 20 l in volume. A model of microbiological and chemical reactions, occurring at various points within the coal, was set up taking into account the pore structure of the coal. The influence of parameters relevant to industrial processes, such as superficial gas velocity, particle size, initial pyrite concentration, and slurry density of the coal, on the conversion of pyrite was examined. Variation of the superficial gas velocity in the range of 0.01 to 0.04 m/s confirmed that the reaction is not controlled by oxygen transfer from gaseous to liquid phase. The rate of pyrite oxidation depends mainly on the accessibility of pyrite to micro-organisms which is determined by the particle size of the coal as well as the distribution of pyrite crystals in the coal matrix. The accessibility of pyrite to the micro-organisms is described by the ratio of effective to maximum microbial activity, measured as oxygen consumption. Starting with higher initial concentration of pyrite in the coal increases the oxidation rate, according to first order kinetics. Enhanced slurry densities lead to a decrease of pyrite conversion, in spite of higher pyrite concentration. The maximum pyrite oxidation rate was measured at 15% (v/v) slurry density and 25°C as 1800 mg Spyr/kg coal per day, or 360 mg Spyr/l reactor volume per day.
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    URL: http://dx.doi.org/10.1002/ceat.270100122
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    Influence of electrolytes on the absorption of nitrogen oxide components N2O4 and N2O3 in aqueous absorbents (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 131-142 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of electrolytes, which are dissolved in the aqueous absorbent and do not react with nitrogen oxides, on the absorption kinetics of both these components was investigated experimentally. In addition to demineralized water, various salt solutions of different concentrations as well as sodium hydroxide solution were used as absorbents. The term H \documentclass{article}\pagestyle{empty}\begin{document}$ H\sqrt {k_1 D} $\end{document} for N2O4 and N2O3, which is important for the design of industrial absorbers, was determined as a function of composition and concentration of the absorbents. In the case of N2O4, the chosen measuring and evaluation methods permitted a separate determination of the rate constant k of the pseudo first order reaction and of the solubility H. The diffusion coefficient D of the gas in the absorbent can be obtained only by calculation. Experimental results showed that \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document} decreases with increasing ionic strength I, however, without a clear indication of any ion-specific effects. This decrease does not appear to be caused simply by a reduction in solubility (salting out effect), or in diffusion coefficient, but at least, to the same extent, through a decrease of the rate constant k with increasing electrolyte content in the absorbent. The measurements permitted the determination of the gas-based salting out parameter for N2O4. The investigations on the absorption of N2O3 in water and in an Na2SO4 solution showed no experimentally detectable influence of dissolved salts on \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document}. The numerical value of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document} is six times that of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document}.
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    Fluid dynamics and mass transfer in a bubble column with suspended particlesPaper presented at the Annual Meeting of German Chemical and Process Engineers (GVC, VDI) 1986, September 17 to 19 Strasbourg. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 180-189 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Slurry bubble columns are widely used in biotechnology. Therefore, the effects of solid particles on fluidization characteristics, gas hold-up and volumetric liquid-side mass transfer coefficient were measured in a slurry bubble column (i.d. 0.14 m). The density and diameter of the suspended particles were similar to those applied in biotechnology with immobilized bacteria. Based on models of turbulence and of liquid circulation induced by rising gas bubbles, equations for critical gas velocity, gas hold-up and volumetric liquid-side mass transfer coefficient were obtained by dimensional analysis.
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    URL: http://dx.doi.org/10.1002/ceat.270100123
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    DIVA - a flow-sheet oriented dynamic process simulatorExtended version of a lecture presented by W. Marquardt at Jahrestreffen 1986 der Verfahrensingenieure, Strasbourg, 17. to 19. September 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 164-173 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The detailed dynamic simulation of coupled process units in chemical plants is gaining an increasing importance as a useful tool in plant engineering and operation. The outline of the program package DIVA (Dynamische Simulation verfahrenstechnischer Anlagen) which is currently under development is presented in the following. The dynamic plant equations and the corresponding Jacobian matrix are generated automatically. The full exploitation of sparse matrix techniques in combination with stiff ODE (ordinary differential equation) solvers allows an efficient solution of all the equations simultaneously. The possibilities offered by the simulator are demonstrated by the simulation of two laboratory plants.
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    URL: http://dx.doi.org/10.1002/ceat.270100121
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    Contact-free measurements of oxygen concentration in industrial flames by raman scattering (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 190-203 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Spatially resolved oxygen concentration measurements were performed in premixed hydrocarbon flames by using laser induced spontaneous Raman scattering. The measurements demonstrate the performance of a relatively simple pulsed laser Raman probe for fundamental combustion studies and also for the control of the equivalence ratio in flames (best spatial resolution: 0.2 mm3; theoretical detection limit: 0.8% of O2). Comparison of the results with those obtained by a mechanical suction probe (Magnos 2 T) confirmed a good agreement. At present, control of different stoichiometric conditions is possible at a minimum O2 concentration of 1.3%.
    Additional Material: 25 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100124
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    Desorption delay in gas/liquid systems during vessel top ventingLecture at the European Two-Phase Flow Group Meeting, München, June 10 to 13, 1986.Dedicated to Prof. Dr. rer. nat. Heinz Harnisch on occasion of his 60th birthday (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 217-224 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During the sudden unheated vessel top venting of initially saturated two-component gas/liquid mixtures, in which the gas is also extensively dissolved in the non-evaporating liquid phase, a solubility inequilibrium develops between the phases; re-equilibration can set in only after a so-called desorption delay time. Laboratory measurements of this delay time were under-taken with model mixtures of CO2 and water and viscous aqueous (Newtonian) solutions by high speed cinematography. The parameters of the experiments are relief cross-section, initial liquid level, pressure, temperature, and concentration. The shortest deley time obtained lasts approximately 75 ms. It differs substantially from the minimum boiling delay time previously measured with various refrigerants in the same test facility. The experimental results are correlated by a semi-empirical dimensionless power relationship, which includes all independent primary design variables generally availble in a physically consistent interrelationship. Reasonable extrapolations to other test conditions and aqueous two-component systems with an acceptable accuracy systems can therefore be expected.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100126
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    Pressure drop and flooding in packed columns operating at high pressuresPresented at the joint session of the GVC Subject Group for “Thermal Separation of Gas and Liquid Mixtures” on 9th to 10th May 1985 in Bergheim/Austria. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 231-242 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Correlations for pressure drop and upper capacity limit (flooding) are useful for the design of packed columns. Available correlations are based on the results of measurements made at atmospheric pressure. Extrapolation to higher pressures is not recommended. Therefore, systematic experimental investigations were carried out in a pilot plant at pressures of up to 100 bar. The experimental equipment and techniques, evaluation methods, and some characteristic experimental results are presented.
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    URL: http://dx.doi.org/10.1002/ceat.270100128
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    Investigation of entrainment in tray columns (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 224-230 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes a pilot plant for entrainment measurements on various types of column trays. The data obtained from different trays differ by up to a factor of 10. The measurements were compared with the theoretical model of Stichlmair. The Stichlmair entrainment diagram permits a fairly accurate prediction for most types of trays if the height of the two-phase layer is known. Prediction of the height and relative liquid hold-up in this two-phase system should be modified by a term reflecting the vapour flow profile, which requires further testing. These tests should examine the effect of tray spacing, fractional free area and, in particular, the influence of different media.
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    URL: http://dx.doi.org/10.1002/ceat.270100127
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    Gas/liquid interfacial area per unit volume and volumetric mass transfer coefficient in stirred slurry reactors (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 204-215 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In three-phase systems, where the liquid constitutes the continuous phase, solid is the catalyst and gas represents the dispersed phase, there are decisive criteria which have to be observed in reactor design. These are e.g. the interfacial area per unit volume between gas and liquid, the volumetric mass transfer coefficient and the mass transfer coefficient. The basic aim of the present work was therefore the investigation of these parameters in relation to the main influencing parameters. Process parameters stirrer speed and superficial gas velocity were varied as well as the physical properties such as liquid viscosity, solids concentration, particle diameter and a geometrical parameter, i.e. reactor diameter. The sulphite method was employed for the determination of these values. The test results confirmed the known relationships of power consumption and superficial gas velocity. An increase in the liquid viscosity leads to a decrease in all the tested values. In most cases, suspended solid particles lead to a lowering of the test values. The influence of the tank diameter on the plots of the test values against specific power consumption turned out to be invariant so that a scale-up of geometrically similar systems can be carried out at constant power consumption, superficial gas velocity and liquid viscosity.
    Additional Material: 27 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100125
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    Heat transfer in boiling of multicomponent mixturesPaper presented at GVC-Conference bAden-Baden (FRG) 25./26. April 1985. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 242-248 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pool boiling data of multicomponent mixtures show that the heat transfer coefficients can be considerably lower than those of a corresponding pure fluid with the same physical properties as the mixture. The proposed model, which assumes maximum mass transfer resistance in the liquid boundary layer, is confirmed by the comparison between calculated and experimental data. The model allows the prediction of heat transfer coefficients in pool boiling of mixtures using only single component properties and vapour-liquid equilibrium data. Judging by experience with a number of different systems, the method should be sufficiently accurate for most practical applications.
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    URL: http://dx.doi.org/10.1002/ceat.270100129
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    Steam reforming of natural gas with intergrated hydrogen separation for hydrogen production (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 248-255 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The development of heat resistant permeation membranes has opened up new possibilities for the conversion of fossil energy resources. In steam reforming of natural gas, such membranes even permit a direct production of hydrogen at high temperatures during the conversion of feed hydrocarbons. Further gas processing, such as required for reformer gas in existing hydrogen production processes, is not necessary. Due to continuous hydrogen discharge directly in the reformer tube, the chemical equilibrium of the occurring reactions becomes displaced towards the products, resulting in more favourable process conditions and, consequently, in improved by 36% utilization of the feed hydrocarbons. At the same time, the hydrogen yield increases by 44%. The heat required, which is provided by a high temperature reactor, is 17% in excess of that in conventional plants. It can be expected that the simplified process design will produce substantial cost advantages over the existing processes for the production of hydrogen.
    Additional Material: 14 Ill.
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    Influence of temperature and properties of solids on the size and growth of bubbles in gas fluidized bedsPaper presented at the annual GVC meeting, Spetember 17-19, 1986, Strasbourg/France. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 272-280 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the present paper, models are developed for the description of coalescence and splitting of bubbles in gas fluidized beds. The distinction between slow and fast bubbles, which originates from the Davidson model of gas flow in and around a rising bubble, was found to be decisive for the modelling of coalescence processes. On the basis of the respective models, it is shown that a change in bed temperature does influence the mechanisms of both bubble coalescence and splitting. In cases of both slow and fast bubbles undergoing splitting, the theory predicts a decrease of bubble size with temperature whereas in the case of a non-splitting system with fast bubbles, typically encountered with Geldart type B particles, no significant temperature effect on bubble size is expected. The theoretical predictions are shown to be in agreement with own measurements as well as with the results of other workers.
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    URL: http://dx.doi.org/10.1002/ceat.270100133
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    Pressure pulsations in the piping of reciprocating pumps (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 262-271 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure pulsations in hydraulic systems, generated by reciprocating pumps, can cause serious problems with regard to plant safety and reliability. In particular, fatigue problems arise in high-pressure piping systems. The available knowledge is not sufficient for an accurate computation of pressure peaks in the piping of reciprocating pumps. A number of calculation models are available which, however, neglect both fluid compressibility and friction. This contribution presents a calculation method which allows a precise modelling of various pump installations. Comparison of calculated and experimental data shows a good agreement and provides a validation of the computational model.
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    URL: http://dx.doi.org/10.1002/ceat.270100132
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    Oxygen and methane enrichment  -  a comprison of module arrangements in gas permeation (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 256-261 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the separation of gaseous mixtures by gas permeation, it is in some cases impossible to achieve the desired product quality in a single stage and, therefore, several stages may be necessary. Multistage processes can be implemented by membrane modules arranged in the form of a cascade or by a membrane column design. On the basis of an economic analysis, this paper discusses different possible module arrangements for 2 cases, i.e. the enrichment of oxygen from air and the separation of methane from biogas. Present calculations indicate that, in the first case, two-stage cascades with or without recycle and, in the second case, one-stage cascade without recycle constitute the optimum module arrangements. However, depending on the selling price of the methane enriched gas, one- or two-stage cascades with recycle have to be considered. Finally, It was shown that, in the permeation of non-ideal gases, the Joule-Thomson effect has to be taken into account.
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    URL: http://dx.doi.org/10.1002/ceat.270100131
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    Particle velocity in a stratified two-phase flow between inclined parallel plates (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 281-289 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fundamental investigations of coalescence processes in settlers with plate packages for the separation of liquid-liquid dispersions prompted an analysis of the drop motion on the interface of a stratified two-phase flow. Therefore, a physical model was developed, which permits the calculation of drop velocity along the interface of an inclined trickling film. Starting from a balance of forces around a single particle, the model provides the equation of motion for a steady motion of single particles in a stratified two-phase flow. Several assumptions and considerations were necessary to solve this equation, such as taking into account the influence of the wall and of flow resistance. The model calculation assumes Newtonian liquids and laminar, smooth trickling films. A comparison with experimental results confirms that the drop motion behaviour is well reproduced.
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    URL: http://dx.doi.org/10.1002/ceat.270100134
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    Calculation of reactive extraction in countercurrent columns (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 291-296 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of extraction processes with chemical reaction was studied experimentally on the system copper/Acorga PT 5050 and quantified according to meaningful kinetic models. These were coupled with other models describing the behaviour of dispersions in columns in order to permit a computer aided simultation of reactive extraction. Thus, a better prediction of column performance is achieved.
    Additional Material: 8 Ill.
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    Flow-induced vibrations of tube arrays in cross-flow (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 312-322 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Existing heat exchanger design criteria do not satisfy the continually increasing requirements for greater efficiency or mass flux and energy throughput. Occasionally, failures appear even after only a few hours of operation, as shown in section 3. A long series of experiments, often carried out on original scale, did lead to the derivation of a large number of empirical expressions; however, physical explanations of the complex tube-failure interactions could not as yet be found. In contrast, experiments with a well defined simple model, whereby the tube deflections were recorded digitally and, at the same time, tube-fluid interactions were registered on a high-speed film, show that elementary “fluid transport mechanisms” control the stability behaviour of the heat exchanger tubes. Vibration excitation mechanisms such as “galloping”, “jet switching” and “whirling” (fluid elastic coupling) proved, with their characteristics, as typical for the vibration behaviour of single rows within the tube array, but not for the vibration phenomena of tube bundles.
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    URL: http://dx.doi.org/10.1002/ceat.270100138
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    Chemical technology of natural gas - its present state and prospects (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 297-305 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Against the background of long-term availability of natural gas, its present technology and future prospects are described. Particular emphasis is put on the oxidative coupling of methane to C2+ hydrocarbons: (1) Catalyst development, activity, selectivity and deactivation as well as reactor operation are discussed; (2) a tentative process scheme is put forward and its economics evaluated with respect to ethylene production.
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    Conversion of organic oxygen compounds and their mixtures on H-ZSM-5 (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 323-329 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of a number of alcohols, ethers, ketones, aldehydes, carboxylic acids, esters, and cyclic compounds and their mixtures on H-ZSM-5 at 673 K was investigated. These compounds can be easily converted to aromatic hydrocarbons if the C/H ratio of the molecule fragment, remaining after elimination of oxygen as water, is less than 0.62. At higher C/H ratios, coking of the catalyst increases, thus reducing its lifetime, a difficulty which can be overcome by hydrogenation of these compounds prior to their conversion over H-ZSM-5. A procedure is proposed for converting at least a part of organic waste chemicals to valuable products instead of burning them.
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    URL: http://dx.doi.org/10.1002/ceat.270100139
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    Rheology and flow of phosphate slurries (mine tailings) in pipesPresented by O. Scrivener at the “Jahrestreffen der Verfahrens-Ingenieure”, Strasbourg, September 17 to 19, 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 305-311 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study of the flow of phosphate mine tailings was carried out in order to characterize these suspensions of fine particles for pipeline transport. Rheological measurements with a rotating cylinder viscometer indicate a viscoplastic behaviour which can be represented by a Herschell-Bulkley or by a Casson model. The variation of the parameters of these models with solids concentration reveals a change in the behaviour at a concentration of 10 to 15%. The pressure drops were measured during flow in capillary tubes, in both laminar and turbulent regimes. The variation of the pressure drop coefficient (Fanning friction factor) as a function of the generalized Reynolds number confirms the validity of the employed rheological models. The results are in good agreement with measurements made in pipes of industrial size. The velocity profiles measured with a novel ultrasonic velocimeter demonstrate the influence of the rheological behaviour on the yield and wall stresses.
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    Rear surface deposition of fine particles on spheres  -  eddy deposition or electrostatic effects? (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 330-337 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The aim of this investigation is to show the demarcation of two possible mechanisms for surface deposition of fine particles on the rear surface of single spheres. By means of single particle trajectory computation, based on numerically determined flow fields (Remax = 103), it is shown that the mere existence of a wake is not in itself sufficient to produce eddy deposition. In addition, the particle's motion must undergo a lateral transfer promoted by fluid trubulence, in order to effect eddy deposition commencing at a Reynolds number of about 100. On the other hand, rear deposition, influenced by electrostatic forces, especially by the Coulomb force, is possible at any Reynolds number. Consequently, for Reynolds numbers of less than 100, only electrostatic effects can produce rear surface deposition. In the range of high Reynolds numbers, the coexistence of both mechanisms is possible. Very high Reynolds numbers (Re 〉 103) and low Stokes numbers indicated the predominance of the electrostatic effect over eddy deposition, whereas at very high Reynolds numbers and medium to high Stokes numbers the electrostatic effect is only predominant in presence of high electrostatic charges.
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    Comparison of performance of an industrial VGO-treater with reactor model predictions (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 349-352 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simplified reactor model can be used for predicting the performance of an industrial VGO-treater. Laboratory-scale experiments performed on the same feed and catalyst as those in the industrial unit lead to a reactor simulation which agrees well with the data from this unit. In the laboratory experiments, it is possible to overcome the specific hydrodynamic problems of tricklebed reactors by appllying the catalyst dilution technique. Results obtained by this technique allowed the development of a reactor model which enables the user to simulate the adiabatic behaviour of the industrial reactor. In this way, the significant gap between the reaction temperature in the isothermal laboratory reactor and the WABT of the industrial adiabatic reactor can be bridged.
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    Kinetic studies on catalytic methanation by means of a concentration-controlled recycle reactor (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 361-367 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rate behaviour of multi-step reaction systems is difficult to model. Concentration-controlled investigations in a recycle reactor provide new tools for this purpose, e.g. the possibility to decompose a network into single reaction steps. Methanation of carbon monoxide over a supported Ni catalyst could be shown to be accompanied to a considerable extent by the shift reaction, and to a lesser extent by direct hydrogenation of carbon dioxide. Deactivation of the catalyst was measured at definite gas compositions. The two main steps show different responses to deactivation: Separable kinetics was found only for the methanation step. Power law rate equations were fitted to the rate data of the individual reaction steps to represent the main features of their kinetic behaviour. Some aspects of deactivation kinetics are also discussed.
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    URL: http://dx.doi.org/10.1002/ceat.270100144
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    Bubble flow in pressurized gas/solid fluidized beds (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 368-375 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution presents the measurements of bubble behaviour in presence of A, B and D powders in a semi-industrial scale pressurized fluidized bed. Local measurements were taken at static pressures of 0.2, 1.0 and 2.5 MPa, using capacitance probes. Quartz sand with mean particle diameter of 157 μm was fluidized in small “two-dimensional” transparent equipment with Frigen R 115. In addition, pressure fluctuations in the bulk of the fluidized bed with inner diameter of 0.4 m were studied experimentally.
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    URL: http://dx.doi.org/10.1002/ceat.270100145
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    Theory and application of an alternative correlation flowmeter (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 353-360 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Correlation flowmeters have been used in the scientific field for many years and are actually gaining greater commercial importance due to an increasing number of applications in industrial plants. The importance of the correlation method is based on the fact that essentially no alternatives exist for measuring velocity and mass flow rate in pneumatic conveyors. However, the hitherto employed transit time correlation method leads to results which are clouded by uncertainties. The commonly used theoretical model of the measurement process does not explain these effects satisfactorily. Therefore, the theory of non-intrusive flow sensors is reinvestigated from a physical standpoint. The derived model permits a discussion of the transit time correlation method in some detail. Furthermore, this model leads to an alternative sensor arrangement and signal processing scheme which makes it possible to measure the true mean velocities. Examples of experimental results are given.
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    URL: http://dx.doi.org/10.1002/ceat.270100143
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    Dynamics of distillation with high product puritiesExtended version of a paper presented by Dr. G. Wozny at the internal group meeting of the GVC Technical Committee on “Mass Transfer Processes” and “High-Pressure Process Engineering”, April 10 to 11, 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 338-348 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For the simulation of steady- and non-steady-state behaiour of separation columns, a simulation program was developed and employed for the calculation and optimization of methanol-water separation. The demand for increasingly higher purities and energy-saving optimization of plants results in complex column configurations and thus in complex control schemes. The number of possible control schemes was reduced on the basis of heuristic rules. By simulating the process, the optimum control and manipulative variables and measuring points were determined from the reduced number of control concepts. A control scheme was introduced. The model was verified by simulation of the dynamic behaviour of the process. The investigation included the effects of computing technique, time interval, model reduction and tray hold-up on the results. Thus, various effects and interactions were verified theoretically with respect to the robustness of the model. This was followed by a simulation of the non-ontrolled and controlled column. By implementing the controllers in the existing column program, the computer can predict the control parameters. These parameters were checked and corrected when the metahnol-ater column was put in operation. In the start-up phase, major problems were caused by the sensitivity and failure rate of density, throughput and pump measuring sensors. Feed impurities were another source of problems. Operation with high product purities is possible, with a side stream to discharge impurities.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ceat.270100141
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    Vapour-liquid and vapour-liquid-liquid equilibria in ternary and quaternary systems of n-hexadecane, benzene, water and hydrogen, at elevated temperatures and pressures (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 382-389 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phase equilibria in the n-hexadecane-water-hydrogen and n-hexadecane-benzene-water-hydrogen systems were determined experimentally at temperatures between 200 and 350°C and pressures between 100 and 300 bar. At high water concentrations, three-phase equilibria were observed. Two-phase regions could be correlated with a modified Redlich-Kwong equation of state. The influence of interaction parameters on the calculated miscibility gaps was investigated. On application of mean interaction parameters, it is possible to calculate phase equilibria at different pressures or temperatures with the same set of parameters. In the ternary system, the three-phase regions could be calculated from the correlated binodal curves of two-phase regions. In the quaternary system, cross-sections through the vapour-liquid miscibility gap could be successfully correlated.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ceat.270100147
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  • 82
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    A differential model for a countercurrent extractor column with non-constant flow rates, interfacial area per unit volume and axial dispersion coefficients (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 375-382 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the extraction literature, no attention has been given so far to differential calculation models for countercurrent extraction columns which take into account the changes in flow rates of the phases as a result of transferred mass, and which also reflect the variations in interfacial area per unit volume and in axial dispersion coefficients since these depend on the flow rates. The present contribution puts forward a formulation of such a model; this results in a set of non-linear differential equations with separated boundary conditions, representing the feeds at either side of the extraction column. This set of differential equations must be solved numerically. The model is illustrated by a sample calculation on the extraction of benzene with furfural. In this (realistic) example, the interfacial area per unit volume varies from bottom to top by a factor of 3. Ignoring this effect would obviously result in serious under- or overdesign.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100146
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  • 83
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    Density of desublimed layers (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 405-410 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Starting from the assumption that the growth of desublimed layers is governed mainly by heat and mass transfer, the authors present a model based on conditions in the diffusion boundary layer and suggest that the “hoarfrost”Hereafter the term frost will be used instead of hoarfrost. density depends on only one parameter. The discussion accounts for the process determining factors, i.e. the growth rate, mass transfer and gas concentration. The theoretical relationship is confirmed by the authors' own experiments on two systems and data from literature. The relationship can be established by a few laboratory experiments and permits the calculation of frost density and of associated variables, thus facilitating the optimization of desublimator design.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100150
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    Progress in the kinetics of coal and char gasificationDedicated to Professor Dr. Kurt Hedden on the occasion of his sixtieth birthday (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 411-419 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution reviews the work performed mainly at Bergbau-Forschung during the past few years. First, it deals with the quantitative description of gasification kinetics, taking into account the pressure of the gasifying agent and partial pressures of product gases. Thereby, a method and quantitative data are provided for the calculation of reaction rates for uncatalyzed and potassium-catalyzed gasification, on the example of chars from high volatile bituminous coals. In addition, a method for characterization of internal surface area by oxygen chemisorption with respect to char reactivity has been improved. Progress has also been achieved in the assessment of the impact of pyrolysis conditions, especially the time-temperature profile during char formation, on its chemical activity during subsequent use.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100151
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  • 85
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    Scale-up of power consumption in agitated ball millsLecture at the “Jahrestreffen der Verfahrens-Ingenieure”, Strasbourg, September 17 to 19, 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 398-404 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Previous investigations have shown that the specific energy input is the overall parameter of influence on product size during communition in agitated ball mills, from laboratory up to industrial scale. The specific energy input is the introduced energy related to the amount of comminuted material. This parameter can be used for mill scale-up. Consequently, a method had to be found of introducing power into the mill so as to obtain a given specific energy input. For this purpose, stirring tests with purely Newtonian liquids were carried out in absence of solids and hence, without comminution. Mathematical models are presented which describe the power consumption in agitated ball mills in absence of grinding beads. In addition, tests with grinding beads filling were also performed, leading to scale-up guidelines with respect to power consumption. Finally, the influence of size and material of grinding beads was investigated.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100149
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  • 86
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    Masthead (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988) 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ceat.270110101
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    Modelling of adsorption in cyclic operation of a PSA plant for H2 recoveryLecture by H. Brüggendick at the “Jahrestreffen der Verfahrensingenieure”, 17. to 19. September 1986 in Strasbourg. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 390-398 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A pressure swing adsorption process for hydrogen recovery from coke oven gases comprises the steps of adsorption at pressures above 6 bar, cocurrent and countercurrent depressurization, purging with hydrogen at ambient pressure and repressurization. The process was investigated in the cyclic mode, on a laboratory scale, using an adsorber filled with 1.3 litres of carbon molecular sieve. Based on the test results of concentrations and pressures within the adsorber during complete cycles, a pseudo-homogeneous model was developed for the adsorption step. Adsorption equilibrium parameters were determined by separate measurements, while the transport parameters were evaluated by fitting the experiments of the fixed bed adsorber. It was possible to consider the residual load, resulting from an incomplete regeneration, by the assumption of a load distribution in the inlet region of the adsorber.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100148
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    Homogeneous non-equilibrium two-phase critical flow modelPresented by J.J. Schröder at the “Jahrestreffen der Verfahrens-Ingenieure”, Strasbourg, September 17 to 19, 1986. (1987)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 10 (1987), S. 420-426 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An important aspect of nuclear and chemical reactor safety is the ability to predict the maximum or critical mass flow rate from a break or leak in a pipe system. At the beginning of such a blowdown, if the stagnation condition of the fluid is subcooled or slightly saturated thermodynamic non-equilibrium exists in the downstream, e.g. the fluid becomes superheated to a degree determined by the liquid pressure. A simplified non-equilibrium model, explained in this report, is valid for rapidly decreasing pressure along the flow path. It presumes that fluid has to be superheated by an amount governed by physical principles before it starts to flash into steam. The flow is assumed to be homogeneous, i.e. the steam and liquid velocities are equal. An adiabatic flow calculation mode (Fanno lines) is employed to evaluate the critical flow rate for long pipes. The model is found to satisfactorily describe critical flow tests. Good agreement is obtained with the large scale Marviken tests as well as with small scale experiments.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270100152
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  • 89
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    Axial pressure profile in circulating fluidized beds (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 11-17 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Design and operation of a circulating fluidized bed requires the knowledge of fluid mechanics. According to heat and mass transfer as well as chemical reactions, the effect of the set superficial gas velocity on the axial pressure profile is of particular interest. The axial pressure profile was measured for a variety of solids, as a function of the superficial gas velocity, in a cylindrical circulating fluidized bed with an inner diameter of 0.19 m and an overall height of 11.5 m. Depending on the solids content and superficial gas velocity, two or one sections can be observed in the plant where the pressure gradient is constant. A pressure profile with one pressure gradient exists only at high gas velocities, so long as the acceleration pressure drop immediately above the gas distributor is negligible. Comparison of measured pressure drops in circulating fluidized beds with those measured in vertical pneumatic conveying led to a state diagram for vertical gas-solid flows. The operation behaviour of different types of circulating fluidized bed plants can be explained with the aid of this diagram.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270110103
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  • 90
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    Engineering aspects and applications of crossflow microfiltration (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 17-25 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Crossflow microfiltration (CMF) is a pressure driven membrane process for the separation of suspended microparticles, bacteria and emulsion droplets. The fluid to be filtered flows in parallel to the membrane surface and restricts the formation of a filter cake. This contribution explains the basic process characteristics and the combination of the crossflow technique with other membrane cleaning methods (periodic backflushing, chemical cleaning). Special attention is paid to the influence of different process parameters on the flux through the membrane. The principle of plant design and different operation modes are described. Engineering aspects such as hydrodynamics, energy requirement and selection of construction materials are discussed in some detail.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270110104
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    Mass transfer contributions of solid particles to gas permeation in viscous laminar tube flow (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 25-31 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: While two- and multiphase flows find more and more application in chemical engineering practice, and the demand for theoretical information about mass and heat transfer processes in such systems is increasing, such data or at least experimental results which could be generalized are still lacking. The following pages are concerned with mass transfer in laminar suspension tube flows normal to the main direction of flow due to the individual motions of small, inert spherical particles. On the basis of a large number of experimental data, an interpretation is attempted of the role of nearly neutrally-buoyant particles in mass transfer enhancement, and a model for a semi-empirical description is suggested. The experimental arrangement uses the mass transfer of carbon dioxide in laminar flow of salt water during the process of gas permeation through a permeable membrane tube wall.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270110105
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    Sensitivity analysis of catalytic conversion of n-C6 (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 277-288 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The present paper is a case study of an application of sensitivity analysis in chemical kinetics. Emphasis is laid upon chemical interpretation of sensitivity information and on identification of the most important model important model parameters. The kinetic model for reforming of C6 hydrocarbons proposed by Mobil [14] is extended to the analysis of the behavior of n-hexane conversion in an adiabatic reactor. The importance of six initial conditions (feed composition and initial temperature) is analyzed by the computation of normalized first order sensitivity gradients (y1o/y) (δyi/δy1o). The relative importance of 21 model parameters αj is estimated by the computation of normalized sensitivity gradients of the type (αj/yi) (δyi/δαj). The influence of the decisive model parameters ΔH6o and ΔH3o (activation enthalpies of benzene hydrogenation and methyl cyclopentane isomerization, respectively) as well as operating parameters is presented. The problem of uncertainly in the value of ΔH6o and its influence on the model solution is also sown. Finally, some advantages of the application of normalized gradients of the explanation of process behavior are discussed.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130138
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    Modeling and simulation of reactions involving bifunctional catalysts (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 319-322 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model based on experimental results is set up for a typical model reaction of hydrocarbon reforming, namely the dehydroisomerization of methyl cyclopentane. Computer simulations shows that the existing theory about the reaction path of hydrocracking reactions involving bifunctional catalysts may be only partly valid.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130143
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    Inertial deposition on front and rear sides of ribbons at intermediate and high reynolds numbers (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 322-327 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Deposition of particles from gas flows on ribbons in normally expected on the front side. Collision efficiencies of ribbons are presented for this case, obtained by means of single particle trajectory computation, which is based on numerically determined flow fields in the Reynolds number range between 2 and 50 and on the potential flow model. Further, it is shown, that deposition of particles on the rear side can be caused by eddylike motion of the fluid in the wake of the ribbon. For this to occur, two conditions must be fulfilled: the free shear layer between the wake and the outer flow must be turbulent to cause lateral transfer of particles into the wake and the Stokes number may not exceed 0.5.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130144
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    Mixing in continuous DTB and FC crystallizers (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 349-356 
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Owing to imperfect mixing, the theoretical prediction of CSD for an MSMPR crystallizer deviates from the experimental results. In the present work, different modelling approaches were adopted to account for incomplete mixing in DTB and FC crystallizers. For DTB crystallizers, compartmental model, based on an earlier work of Nyvlt et al. has been proposed. For FC crystallizers, a mixed model comprising perfectly mixed and plug flow regimes has been put forward. This is based on the tracer response studies reported by de Jong. Predicted results were compared with experimental data of Bennett and van Buren for continuous urea crystallizers.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130148
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    Selection and design of aerobic bioreactorsModified version of a paper presented by A. Mersmann at the “Jahrestreffen der Verfahrens-Ingenieure”, Berlin, September 27 to 29, 1989.Dedicated to Professor Kurt Dialer on the occasion of his 70th birthday (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 357-370 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Compared to chemical reactors, there are additional requirements to be considered when selecting and designing a bioreactor. The cultivated organisms and most of the desired products are to a greater or lesser extent sensitive to temperature, pH and Shear stress. Furthermore, sterilization often plays an important role in maintaining a monoseptic process. Many design procedures for chemical reactors can be applied but requirements which are relevant to the biological system are sometimes decisive. Consequently, it is useful to first consider the essential features of the organisms with respect to the selection and design of bioreactors. Attention must be paid to the fermentation medium because its flow behaviour can range from slightly viscous and Newtonian to highly viscous, non-Newtonian. Many papers deal with low viscosity fermentation broths [1-5]. However, little is known about the design of bioreactors for highly viscous non-Newtonian liquids. Fundamentals for the design of bioreactors are presented. It has been attempted to apply theoretical equations suitable for both, low viscosity Newtonian and high viscosity non-Newtonian fermentation broths. Apart from the calculation procedure for the OTR-values, the difference between global and local values within bioreactor is demonstrated by means of velocity and shear stress profiles. Special requirements for bioreactors such as prevention of excessive foaming, shear sensitivity of micro-organisms and cell-lines and effective sterilization are also discussed.
    Additional Material: 15 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130149
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    Monte carlo simulation of transient CSD in a continuous crystallizer (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 392-397 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A Monte Carlo simulation scheme is proposed for transient crystal size distribution in a continuous crystallizer. The suggested scheme can taken into account dispersion effects of growth rate, shape factor and birth size on crystal size distribution. This method is simple and more versatile than solution of the number balance equation or the finite-state Markov chain model. The proposed algorithm of the process has a very simple structure and can be easily implemented on a personal computer. The present contribution is extension of an earlier work of Sen Gupta and Dutta.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130153
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    Fluid dynamics of pulsed sieve plate extraction columnsPaper presented by M. Lorenz at the “Jahrestreffen der Verfahrens-In-genieure”, Berlin, September 27 to 29, 1989. (1990)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 411-422 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The presented contribution reports on comprehensive hydrodynamic investigations in two pulsed sieve-plate extraction columns (PSE) on a pilot scale. The experiments were conducted with three different sieve plate geometries employing test systems recommended by EFCE, under varying pulsation conditions and throughputs. The results of the investigation add to the existing knowledge of relationships between hydrodynamic parameters, drop size, hold-up, flooding throughput and mixing and operating parameters. They also provide useful information for scale up, selection of sieve-plate geometry, most favorable operating range, and constructive design of equipment. On the basis of measurements, analytical methods are recommended for prediction of PSE hydrodynamics.
    Additional Material: 15 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270130156
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    Heat transfer between particle beds and submerged surfacesPaper presented by O. Molerus at the “Jahrestreffen der Verfahrens-Ingenierue”, Freiburg, September 30 to October 2, 1987. (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 126-138 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical modelling of heat transfer to particle beds comprises two sequential steps: transfer from the heating surface to contacting particles followed by transfer to the interior of the bed. Two different limiting case can be formulated for the second step: unmixed and homogeneously mixed bed. In the case, heat is transferred gradually via a repeated sequence of heat transfer in the gap between adjacent particles and conduction in the particulate material. In the second case, heat is transferred to the interior of the bed by mixing of particles which have previously attained the temperature of the heating surface. On the other hand, the mixing motion maintains a homogeneous lower temperature throughout the bed. Theory predicts a significant and easily measurable difference in the behaviour of heat transfer coefficients for the two regimes at long contact times t: unmixed beds ∝ \documentclass{article}\pagestyle{empty}\begin{document}$$ \sqrt t $$\end{document} and homogeneously mixed beds ∝ 1/t. For short times t, both regimes show the same behaviour, namely of t.From a theoretical standpoint, it makes sense to differentiate further between the behaviour patterns of unmixed beds: at long times t, instantaneous heat transfer coefficients are independent of heat transfer form the heating surface to adjacent particles. Comparison with experimental result from literature shows that the derived models, which are consistent, are suitable for describing the heat transfer from submerged surfaces to unmixed and mixed beds of particles.
    Additional Material: 24 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270110118
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    Scale-up of bioreactors for fermentation of mammalian cell cultures with special reference to oxygen supply and microcarrier mixingPaper presentet by J. Vorlop at the “Jahrestreffen der Verfahrensingenieure”, September 17 to 19, 1986 in Strasbourg (1988)
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 171-178 
    Details
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The increasing demand for products from mammalian cells has prompted the authors to develop a new type of bioreactor. Its significant features include the supply of oxygen, homogeneous distribution of microcarrier suspensions and process control. Media with high protein contents, required for mammalian cell cultures tend to generate foam. This causes the flotation of solid particles. The reactor was equipped with a system of porous hydrophobic Accurel hollow fibre membranes in order to prevent the formation of bubbles. The membrane is coiled in the form of a basket, or fixed on several carriers. If the liquid pressure is higher than that of the gas phase inside the membrane, a bubble - free oxygen supply to the culture broth can be achieved. The problem of axial mixing of microcarier suspensions was solved by the use of a spiral agitator, attached underneath the aeration system at the bottom of the reactor. The combined aeration and mixing system, which is driven by an eccentric motor, undergoes a tumbling motion. Sufficiently homogeneous suspensions are produced in this system at low membrane velocities, i.e. in presence of low shear forces.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/ceat.270110123
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