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  • Chemistry  (13)
  • Wiley-Blackwell  (13)
  • Washington, DC : United States Gov. Print. Off.
  • American Association of Petroleum Geologists (AAPG)
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Publisher
  • Wiley-Blackwell  (13)
  • Washington, DC : United States Gov. Print. Off.
  • American Association of Petroleum Geologists (AAPG)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1871-1880 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of an adiabatic tubular plant reactor during the startup is demonstrated, together with the impact of a feed-pump failure of one of the reactants. A dynamic model of the reactor system is presented, and the system response is calculated as a function of experimentally-determined, time-dependent, manipulated variables. The values of model parameters are estimated by using the SimuSolv (1991) computer program. The data set collected during the reactor start-up is used for the parameter estimation procedure. An excellent agreement is obtained between the experimental and the calculated system response. Many continuously-operated commercial reactors require a complete conversion of one of the main reactants at the reactor exit. It is shown that for an industrial tubular reactor a much higher initial reactor temperature is required during the startup, compared to the reactor inlet temperature during normal steady-state operation, to ensure a complete reactant conversion. Much more research is necessary to determine whether this is a generally valid rule.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 148-158 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rules are presented for the startup of an adiabatic tubular reactor, based on a qualitative analysis of the dynamic behavior of continuously-operated vapor- and liquid-phase processes. The relationships between the process dynamics, operating criteria, and operating constraints are investigated, since a reactor startup cannot be isolated from an entire plant startup. Composition control of the process material is critical to speed up plant startup operations and to minimize the amount of offgrade materials. The initial reactor conditions are normally critical for a successful startup. For process conditioning, a plant should have an operating mode at which the reactor can be included in a recycle loop together with its feed system and downstream process section. Experimental data of an adiabatic tubular reactor startup and thermal runaway demonstrate some operational problems when such an intermediate operating stage is missing. The derived rules are applied to an industrial, highly heat-integrated reactor section, and the resulting startup strategy is summarized in an elementary-step diagram.
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 503-515 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The safeguarding methodology of chemical plants is usually based on controlling the instantaneous values of process state variables within a certain operating window, the process being brought to shutdown when operating constraints are exceeded. This method does not necessarily prevent chemical reactors suffering from a runaway during dynamic operations because (a) excessive amounts of unreacted chemicals can still accumulate in the process, and (b) no means are provided to the operating personnel to identify hazardous process deviations. A model-based startup and safeguarding procedure is developed for an industrial adiabatic tubular reactor to improve process safety during startup. The trajectories of manipulated variables are calculated by minimizing the amount of one of the main reactants in the reactor effuent. It is concluded that proper control of the initial reactor temperature profile is critical for a safe startup while the impact of other manipulated variables is relatively smaller than that of the initial reactor temperature profile.
    Additional Material: 13 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 82 (1970), S. 138-138 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on equilibrium binding studies, as well as on kinetic investigations, two types of interactions of Cu2+ ions with native DNA at low ionic strength could be characterized, namely, a nondenaturing and a denaturing complex formation. During a fast nondenaturing complex formation at low relative ligand concentrations and at low temperatures, different binding sites at the DNA bases become occupied by the metal ions. This type of interaction includes chelate formation of Cu2+ ions with atoms N(7) of purine bases and the oxygens of the corresponding phosphate groups, chelation between atoms N(7) and O of C(6) of the guanine bases, as well as the formation of specific intestrand crosslink complexes at adjacent G°C pairs of the sequence dGpC. CD spectra of the resulting nondenatured complex (DNA-Cu2+)nat may be interpreted in terms of a conformational change of DNA from the B-form to a C-like form on ligand binding. A slow cooperative denaturing complex formation occurs at increased copper concentrations and/or at increased temperatures. The uv absorption and CD spectra of the resulting complex, (DNA-Cu2+)denat, indicate DNA denaturation during this type of interaction. Such a conclusion is confirmed by microcalorimetric measurements, which show that the reaction consumes nearly the same amount of heat as acid denaturation of DNA.From these and the kinetic results, the following mechanism for the denaturing action of the ligands is suggested: binding of Cu2+ ions to atoms N(3) of the cytosine bases takes place when the cytosines come to the outside of the double helix as a result of statistical fluctuations. After the completion of the binding process, the bases cannot return to their initial positions, and thus local denaturation at the G·C pairs is brought about. The probability of the necessary fluctuations occurring is increased by chelation of Cu2+ ions between atoms N(7) and O of C(6) of the guanine bases during nondenaturing complex formation, which loosens one of the hydrogen bonds within the G·C pairs, as well as by raising the temperature. The implications of the new binding model, which comprises both the sequence-specific interstand crosslinks and the described mechanism of denaturing complex formation, are discussed and some predictions are made. The model is also used to explain the different renaturation properties of the denatured complexes of Cu2+, Cd2+, and Zn2+ ions with DNA.In temperature-jump experiments with the nondenatured complex (DNA-Cu2+)nat, a specific kinetic effect is observed, namely, the appearance of a lag in the response to the perturbation. The resulting sigmoidal shape of the kinetic curves is considered to be a consequence of the necessity of disrupting a certain number of the crosslinks existing in the nondenatured complex before the local unwinding of the binding regions (a main step of denaturing complex formation) may proceed.
    Additional Material: 19 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 61-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical possibilities for investigation of nucleic acids with high molecular weight are restricted to the determination of the adsorption behavior. According to our experience the alternating current polarography (Breyer-polarography) is mainly appropriate for the characterization of changes in the secondary structure of DNA. The Breyer-polarogram shows the alternating current of the dropping electrode in dependence on their potential which varied from 0-2 v. negative against the normal calomel electrode (NCE). By addition of native DNA to the supporting electrolyte (buffer solution) the current drops down in the range of adsorption between 0 and 1 v. At 1.16 v. against NCE the desorption takes place together with the formation of a rounded desorption peak. The investigation was carried out in phosphate buffer solution 0.1m with 0.075m NaCl or in a phosphate buffer 0.18m with 0.03m NaCl. In the pH range above pH 8 NaOH was added to realize the higher pH values. A calf thymus DNA sample having a mean molecular weight of about 18 million was used. The concentration of DNA was 5 × 10-3-1 × 10-1 wt.-%. The polarographic measurements were performed with an a.c./d.c.-polarograph “GWP 564” from Akademiewerkstätten für Forschungsbedarf der Deutschen Akademie der Wissenschaften zu Berlin (DAW). The denaturation of the double helix causes a sharp desorption peak at negative potentials of the alternating current polarogram. This new criterion for the helix-coil transition is due to formation of unpaired bases. These nearly free bases undergo a specific adsorption and the desorption takes place within a narrow potential range. Nevertheless, at present time an electron transfer to particular bases cannot be excluded at special conditions. The increase of the sharp peak permits to estimate: (a) the melting curve of the double helix in agreement with spectroscopic measurements; (b) the photolysis of the double helix; (c) the strand separation in acid and alkaline solution. In the alkaline range the sharp peak increases and reaches its maximum at pH 〉 12. In the acid range, however, no sharp peak is observed and the rounded desorption peak decreases. Therefore, the best way of following the conformation changes is to measure the current difference between the curves of the solutions with and without DNA at electrocapillary-zero-potential. On the classical d.c.-polarogram one can measure small current steps only, which may be caused mainly by capacity changes. Moreover, the scission of the molecule by ultrasonic action can be followed. In this case the rounded peak of DNA increases but the sharp peak does not appear. Similar alternating current polarograms are obtained with poly-A in the native state, because helical and unordered regions coexist in the same molecule. The very rapid indication of these structure changes allows one to carry out kinetic measurements at a fixed potential with this method.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 319 (1977), S. 848-856 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Physico-chemical Analysis of the Hydrolysis of N-(2-Cyanethylene-)ureaBy means of pulse-polarography, infrared and n.m.r.-spectroscopy and electronattachment-mass-spectroscopy the hydrolysis of N-(2-cyanethylene-)urea (BA 1) under relatively mild conditions has been evidenced (pH 5,6 to 9.0; T = 37° C and 22° C). With rising pH value the rate of hydrolysis increases. At pH 5.6 the hydrolysis is very slow (half life time ca. 6 days), but condensation products are already demonstrable. At pH 9.0 nearly all of BA 1 molecules are hydrolysed within 2 days under splitting of the heterocycle and formation of various hydrolysis products. On the middle pH range from 7.3 to 8.3 the formation of 2-cyanaziridine was followed and after cycle splitting various resultant products were observed. The half life time of BA 1 hydrolysis at pH 7.3 and T = 37° C has been determined to 103 ± 1 hours (0.144 m BA 1, phosphate buffer).
    Notes: Mit Pulspolarographie, Infrarot- und NMR-Spektroskopie sowie Elektronenanlagerungs-Massenspektrographie wurde die Hydrolyse von N-(2-Cyanäthylen-)harnstoff (BA 1) unter noch relativ milden Bedingungen (pH 5,6 bis 9,0; T = 37°C und 22°C) nachgewiesen. Die Hydrolysegeschwindigkeit nimmt mit steigendem pH-Wert zu. Bei pH 5,6 erfolgt die Hydrolyse sehr langsam (Halbwertszeit etwa 6 Tage), wobei auch schon Kondensationsprodukte nachweisbar sind. Bei pH 9,0 ist bereits nach 2 Tagen BA 1 unter Ringspaltung weitgehend hydrolysiert, und eine Reihe Kondensationsprodukte sind entstanden. Im mittleren pH-Bereich von 7,3 bis 8,3 wurde das Auftreten von 2-Cyanaziridin, aber auch schon Ringspaltung und hydrolytische Folgeprodukte beobachtet. Die Halbwertszeit der BA 1-Hydrolyse konnte bei pH 7,3, 37°C für eine 0,144 molare Lösung in Phosphatpuffer zu 103 ± 1 h bestimmt werden.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 319 (1977), S. 522-525 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polarographic Differentiation between 6-Azalumazines and 1,2,4-Triazines
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 320 (1978), S. 270-278 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polarographic Reduction of β-Aminovinylimines of the Indene SeriesThe mechanism of electrolytic reduction of aminovinylimine (AVI) is suggested, based on results of the identification of electrolysis products and on the dependence of polarographic curves. It is shown that this mechanism becomes complicated by the kinetics of hydrolysis of starting substances and intermediates. The determination of complex forming constants for AVI and bovine serum albumine is determined and compared by polarography and spectroscopy.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 75 (1963), S. 868-870 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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