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  • Titanium
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    HNO 46 (1998), S. 569-578 
    ISSN: 1433-0458
    Keywords: Schlüsselwörter Knochenverankerte Epithese ; Osseointegration ; Chirurgische Epithetik ; Titan ; Extraorales Implantat ; Key words Bone-anchored prostheses ; Osseointegration ; Surgical episthetics ; Titanium ; Extraoral implants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary The prosthetic rehabilitation of cranio-facial defects and malformations has made enormous progress with the development of currently available silicones and the discovery of titanium as an optimally bicompatible implant material. This allows for a reliable, solid fixation of cranio-facial prostheses, which, due to modern production techniques, give outstanding camouflage to defects. To reconstruct such complex aesthetic entities as the ear, nose and orbit, bone-anchored prostheses now represent more than just an alternative to plastic surgery. Their removal also allows early recognition of recurrences following tumor surgery. The principles of implantology and all commercially available systems are presented, as well as indications, contraindications and our personal experience with 120 patients who received bone-anchored prostheses at the ENT Department of the University of Saarland in Homburg, Germany.
    Notes: Zusammenfassung Die Rehabilitation von kraniofazialen Defekten und Deformitäten hat durch die Einführung der modernen Silikone und die Entdeckung von Titan als idealem biokompatiblen Implantationsmaterial einen großen Fortschritt erlebt. Damit gelingt eine zuverlässige solide Fixierung von Gesichtsepithesen, die dank der modernen Herstellungstechniken eine außerordentliche Camouflage des Defektes gestatten. Für die Rekonstruktion komplexer ästhetischer Einheiten wie z.B. Ohr, Nase und Orbita stellen die knochenverankerten Epithesen mehr als lediglich eine Alternative zu plastisch-chirurgischen Verfahren dar. Gerade nach Tumoroperationen bieten sie die Möglichkeit, ein Rezidiv frühzeitig zu entdecken. Die Grundzüge der Implantologie und die verschiedenen, kommerziell erhältlichen Systeme für den extraoralen Bereich werden dargestellt, ebenso Indikationen und Kontraindikationen sowie eigene Erfahrungen bei 120 Patienten, die an der Klinik und Poliklinik für Hals-Nasen-Ohren-Heilkunde der Universität des Saarlandes in Homburg mit knochenverankerten Epithesen versorgt wurden.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    European journal of orthopaedic surgery & traumatology 8 (1998), S. 133-139 
    ISSN: 1432-1068
    Keywords: Total hip replacement ; Results ; Aseptic loosening ; Cemented ; Uncemented ; Titanium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Mid- and long term stability is still the major challenge in total hip replacement (THR). A consecutive series of cemented 250 cases and of uncemented 250 cases was analyzed in a prospective follow-up study. The femoral component of the BiCONTACT hip stem system with the same design for cemented and uncemented implantation was used. While the cemented stems had a smooth surface, the cementless implants were proximally coated with a microporous titanium plasmaspray (Plasmapore®). Follow-up time averaged 7 years for cemented and 6.5 years for uncemented THRs. Follow-up rate was 88.7% in cases treated with cemented stems and 93.1% in cases treated with an uncemented stem. The rate of aseptic loosening was 1.2% for the cemented version and 0.4% for the uncemented one. Radiological loosening could be observed in another 1.2% of the cemented stems but was not found in the uncemented cases. Our data suggest excellent midterm stability of both the cemented and the uncemented version of the BiCONTACT hip stem system. Early aseptic loosening especially of the cemented titanium alloy straight stem has not occurred in our series as reported recently. The prosthesis design and follow-up time may therefore play an important role. The long-term results for both cemented and uncemented BiCONTACT prostheses of our series are still to be evaluated.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2673-2676 
    ISSN: 1434-193X
    Keywords: Aromatic aldehydes ; Pinacol coupling ; Radical reactions ; Reagent control ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel concept for conductingtransition-metal-catalyzed radical reactions that allows highly diastereoselective titanocene-catalyzed pinacol couplings is described.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1434-1948
    Keywords: Alkyne complexes ; Titanium ; Zirconium ; Coordination mode ; Metallacycles ; Cyclopentadienes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of metals, alkyne substituents, Cp substitution and additional ligands on the stability of bridged and unbridged η2-alkyne-titanocene and -zirconocene complexes has been investigated. The reduction of the complex [(η5-C5H4)-SiMe2-(η5-C5H4)]TiCl2 with magnesium in the presence of tolan (PhC2Ph) does not give the expected alkyne-titanocene complex [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-PhC2Ph) but by coupling of two tolan molecules the corresponding titanacyclopentadiene [(η5-C5H4)-SiMe2-(η5-C5H4)]TiC4Ph4 (1) was obtained. In the analogous reaction with Me3SiC2SiMe3 the stable η2-alkyne complex without additional ligands [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-Me3SiC2SiMe3) (2) was formed, due to the sterical influence of the alkyne substituents. The compounds without additional ligands (thi)2Ti(η2-PhC2Ph) (3) and (thi)2Ti(η2- Me3SiC2SiMe3) (5) were isolated from the unbridged titanocene complex (thi)2TiCl2 (thi = tetrahydroindenyl). Two equivalents of complex 3 reacted with one equivalent of water to yield the dimeric alkylidene-μ-oxo complex [(thi)2Ti(CPh=CHPh)]2(μ-O) (6). The reaction of the unbridged zirconocene compound (thi)2ZrCl2 gave the alkyne complex (thi)2Zr(THF)(η2-Me3- SiC2SiMe3) (7) which is stabilized by THF. At higher temperature THF was eliminated from the orange complex 7 forming the green complex (thi)2Zr(η2-Me3SiC2SiMe3). This behaviour was investigated in detail using NMR spectroscopy and compared to similar complexes such as Cp2Zr(η2-Me3SiC2SiMe3) (not stable without THF), (ebthi)2Zr(η2-Me3SiC2SiMe3) (ebthi = ethylenebistetrahydroindenyl; stable without THF) and Cp*2Zr(η2-Me3SiC2SiMe3) (Cp* = pentamethyl-Cp, stable without THF). All complexes were characterized by spectroscopic methods. X-ray structural determinations were conducted for the complexes 1, 3 and 7. Compound 3 is the first example of a structurally characterized tolan-titanocene complex without additional ligands.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1485-1494 
    ISSN: 1434-1948
    Keywords: Titanium ; Vanadium ; Polymerizations ; Diimine ; Dialkylmetal compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Mono-β-diiminato)titanium(III) and -vanadium(III) dichlorides LMCl2 [L = ArNC(R)CHC(R)NAr-] are easily accessible from the metal trichlorides and LLi in THF. The crystal structures of LVCl2 (Ar = 2,6-iPr2C6H3, R = Me) and LTiCl2 (Ar = 2,4,6-Me3C6H2, R = Me and Ar = 2,4,6-Me3C6H2, R = tBu) reveal tetrahedral metal environments. Treatment of LVCl2 with alkyllithium reagents affords surprisingly stable dialkylvanadium(III) compounds; the structure of LV(nBu)2 (Ar = 2,6-iPr2C6H3, R = Me) is similar to that of the dichloride. The corresponding dialkyltitanium(III) compounds are less stable; only the dimethyl derivatives could be obtained in pure form (from LTiCl2 and MeMgI), and only for ligands bearing 2,6-disubstituted aryl groups. The structure of LTiMe2 (Ar = 2,4,6-Me3C6H2, R = Me) is also similar to that of the dichloride. Reaction of LTiMe2 with B(C6F5)3 produces a catalyst for α-olefin polymerization, but the corresponding VIII derivatives are inactive.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 87-91 
    ISSN: 1434-1948
    Keywords: Imido complexes ; Titanium ; Heteroallylic ligands ; Benzamidinate ligands ; Diiminophosphinate ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of Ti(NtBu)Cl2(py)2 (1, py = pyridine) with bulky heteroallylic ligands in a 1:1 molar ratio affords the monosubstituted derivatives [PhC(NSiMe3)2]Ti(NtBu)Cl(py)2 (2), [MeOC6H4C(NSiMe3)2]Ti(NtBu)Cl(py) (3), and [Ph2P(NSiMe3)2]Ti(NtBu)Cl(py) (4). Similarly, 2:1 reactions afforded the disubstitution products [PhC(NiPr)2]2Ti(NtBu)(py) (6) and [Ph2P(NSiMe3)2]2Ti(NtBu) (7). The bis(pyridine) adduct Ph2P(NSiMe3)2Li(py)2 (5) was isolated as a by-product during the preparation of 4. The molecular structures of 7 has been established by X-ray crystallography.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 159-161 
    ISSN: 1434-1948
    Keywords: Oxo clusters ; Titanium ; Metal alkoxides ; Sol-gel processes ; Carboxylato complexes ; Solid-state structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ti9O8(OPr)4(methacrylate)16 was obtained by the reaction of Ti(OPr)4 with an excess of methacrylic acid and analyzed by X-ray diffraction. The compound consists of a ring of nine [TiO6] octahedra linked by six μ2- and only two μ3-oxide bridges.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1434-1948
    Keywords: Cyclizations ; Cross-coupling ; Ab initio calculations ; Titanium ; Metallacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Cp2Ti(CO)2 (3) with two equivalents of α,β-unsaturated ketones 4 yield the novel titana-2,9-dioxacyclonona-3,7-dienes 5. Cross-coupling of 3 with two different ketones 4 and 6to give 7 can be achieved under certain reaction conditions. Hydrolysis of 5 or 7 may generate diketones 9, cyclopentanols 10/11, or cyclopentenes 12/13, depending on substituents and conditions. The X-ray crystal structure of 5a, the first nine-membered bis(η5-cyclopentadienyl)-substituted titanaheterocycle containing carbon, is presented. Ab initio calculations were performed for 5a and for titana-2-oxacyclopentene 1, a conceivable intermediate in the coupling reaction.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 253-256 
    ISSN: 1434-1948
    Keywords: Titanium ; Vinylidene complexes ; [2+2] Cycloaddition ; Metallacycles ; Azatitanacyclobutanes ; Clathrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The titanocene vinylidene intermediate [Cp*2Ti=C=CH2] (9) reacted with the carbodiimides R-N=C=N-R [R = p-CH3C6H4 (19a), C6H11 (19b)] to give the N=C-cycloaddition products [Cp*2Ti{-NR-C(=NR)-(C=CH2)-}] [(R = p-CH3C6H4 (20a), C6H11 (20b)]. The X-ray structure of 20a in form of a surprisingly stable n-hexane clathrate is presented. The azatitanacyclobutane [Cp*2Ti{-NPh-C(Ph)(H)-(C=CH2)-}] (22) was formed from the reaction between 9 and benzylidene aniline [PhN=C(Ph)H (21)]. Reactivity studies showed that azatitanacyclobutanes are unreactive upon typical ring-enlargement reactions as observed for other four-membered titanacycles.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1434-1948
    Keywords: Titanium ; C-H activation ; Amido complexes ; Bridging imide ligands ; Bridging imine group ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new organometallic binuclear complexes [{Cp*Ti(NEt2)}2(μ-NEt)2] (1), [(Cp*Ti)2(NMe2)(NHMe2)(μ-NMe)(μ-NCH2)] (2), and [(Cp*TiCl)2(μ-NMe)2] (3) have been obtained by heating the dialkylamido derivatives [Cp*Ti(NR2)nCl3-n] (R = Et, n = 3; R = Me, n = 2, 3) (Cp* = η5-C5Me5) in solution and at different temperatures. The thermal decomposition of [Cp*Ti(NMe2)Cl2] at temperatures above 145 °C caused the activation of the pentamethylcyclopentadienyl ligand to give the new, geometrically constrained, complex [{η5:η1-C5Me4CH2CH2N(Me)}TiCl2] (5). Addition of the isocyanide 2,6-Me2C6H3NC to the solution obtained in this last process led to the isolation of the complex [{η5:η2-C5Me4CH2CH2N(Me)CN(C6H3Me2)}TiCl2] (6) by insertion of one isocyanide molecule into the titanium-nitrogen bond in 5. The structure of 6 has been proved by an X-ray diffraction study which showed the organic ligand, C5Me4CH2CH2N(Me)CN(C6H3Me2), to be coordinated to the titanium atom via the cyclopentadienyl ring and a η2-iminocarbamoyl fragment. Heating of the trinuclear oxo derivative [{Cp*Ti(NMe2)}3(μ-O)3] at 110 °C gave the complex [{Cp*3Ti3(NMe2)(μ-η2-CH2NMe)}(μ-O)3] (4) where an imine ligand bridges two of the three metallic centres.
    Type of Medium: Electronic Resource
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  • 11
    ISSN: 1434-1948
    Keywords: Alkyne complexes ; Titanium ; ansa-Metallocenes ; Carbon dioxide fixation ; C-C coupling ; Metallacycles ; Regioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [meso-(ebthi)TiCl2] [ebthi = 1,2-ethylene-1,1′-bis(η5-tetrahydroindenyl)] with magnesium in the presence of the alkynes Me3SiC≡CSiMe3 and PhC≡CSiMe3 resulted in the formation of the complexes [meso-(ebthi)Ti(η2-Me3SiC2SiMe3)] (1) and [meso-(ebthi)Ti(η2-PhC2SiMe3)] (2a and 2b), which were isolated and then characterized by their NMR spectra. Due to incomplete reduction the TiIII complex [meso-(ebthi)Ti(THF)Cl] (3) was also obtained as a by-product of these reactions. By insertion into the Ti-CPh bond carbon dioxide reacted with the titanacyclopropene structure of the alkyne complex [meso-(ebthi)Ti(η2-PhC2SiMe3)] (2a), with untypical regioselectivity to yield the α-silyl-substituted meso-(ebthi)titanafuranone 6a. In the analogous reactions of the complexes [(thi)2Ti(η2-PhC2SiMe3)] (thi = η5-tetrahydroindenyl), [rac-(ebthi)Ti(η2-PhC2SiMe3)], and [Cp*2Ti(η2-PhC2SiMe3)] with carbon dioxide typical regioselectivity (insertion into the M-CSi bond of the titanacyclopropene) was observed, yielding the β-silyl-substituted titanafuranones 7, 8a, and 9. These results show that insertion of carbon dioxide into the M-C bond of the titanacyclopropene structure of the alkynemetallocene complexes is governed by the substitution pattern of the alkyne and the steric enviroment around the metal center. The complexes 3, 6a, and 7 were investigated by X-ray crystal structure analysis.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 61-67 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Risk assessments have been performed to determine the risk associated with the transportation of hazardous wastes through a city. In the course of these assessments, a number of modeling issues arose relating to transportation accident rates, the characterization of incidents, the effect of thermal radiation, the impact of exposure to toxic chemicals, and the threshold for acceptable risk. This paper discusses these issues.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. S3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 98-103 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper presents the design of ribbon wound pressure vessels useful for Ammonia, Urea and Methanol plants. The design is to create a thin shell of 1/5 the total wall thickness required, weld it to the end pieces, and wind 4 to 8 mm thick ribbons of 80 mm width at an angle of 15 to 30 degrees on the inner shell, using a prestress. The ribbons are welded at the ends and an even number of layers are wound cross-helically on to the shell. With more than 7000 vessels over the pressure range of 50 to 350 atmospheres in use in the various chemical industries in China over the past 30 years, their safety record has been excellent. Of particular interest has been the application of this technology in the Ammonia and Urea plants, where the design allows fabrication of these vessels at substantial reduction in cost, and early delivery, when compared to the mono wall technology.
    Additional Material: 6 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 20-22 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most audits try to look at a representative selection of the plant procedures and equipment. An alternative is a survey, a look in depth at selected procedures (such as those for testing alarms and trips, issuing permits-to-work, controlling modifications, taking samples or testing relief devices) or selected equipment (such as level glasses or equipment for handling LPG). If the procedure or equipment is well-chosen, surveys may make a bigger contribution to safety, per person-hour, than a conventional audit.
    Additional Material: 1 Tab.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 39-42 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Under OSHA 1910.119, all Process Safety Management (PSM) facilities are required to keep their pressure relief system design information current. This article demonstrates why a pressure relief system design verification effort must be based on an equipment list, rather than a relief device list, in order to ensure that every piece of equipment is adequately protected. The formerly common practice of simply checking the design bases of all existing relief devices is deficient is deficient since this technique does not systematically ensure that every piece of equipment is protected.The “Berwanger Method” is a step by step process for designing or analyzing a pressure relief system to meet OSHA 1910.119 Process Safety Information (PSI) and Process Hazard Analysis (PHA) mandates. The method uses a relational database which tracks the relationships between protected equipment, potential overpressure scenarios, and protective devices.The challenge facing an operating company does not end once the design basis has been “verified” - the design basis information must also be maintained and be readily accessible to avoid costly reinvention of the wheel down the road. The “Berwanger Method” also addresses these maintenance issues.
    Additional Material: 6 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 49-60 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper reports on a comprehensive literature search and small scale experimental work on the reaction characteristics of phosphorous trichloride and water. More than 30 tests were conducted, including both closed and open test cells. The water to phosphorus trichloride molar ratio was varied from 1 to 25. When in contact, water and phosphorus trichloride will form two liquid layers with a reaction starting at the interface. The impact of variables on reaction rates including the interface surface area, layer depth, and stirring were investigated experimentally. A reaction rate model that fits all the measured data is presented. Case studies illustrating the use of this data for emergency relief systems and vent containment design are presented in reference. [1].
    Additional Material: 10 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 68-73 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two major accidents in the 80's: the summit Tunnel Fire, England and Piper Alpha disaster, an offshore platform in the North Sea; and very recently, possible explosion of the Boeing, TWA flight 800 at New York, makes it imperative that further research into the mechonisms of the ignition of flammable vapor/air mixture in contact with hot surfaces needs to be done. There have been a number of studies of ignition by hot surfaces, but in all these studies the ignition sources were wire, sphere or strip, i.e., most of them were flat surfaces. But to the authors' knowledge, other variables which affect the ignition mechanism such as irregular geometrical shapes have not been studied. The purpose of this paper is to examine how the degree of confinement (or, configuration), size and orientation, of the heated surface affects the ignition temperature of the flammable vapors. The results were obtained by experimentnal and by computational fluid dynamics.
    Additional Material: 13 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. S3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 9-15 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design and deflagration pressure relief vents is based on correlations developed for various types of combustible materials and for enclosures of different strengths. The primary guideline for deflagration vent design in the US is NFPA 68 Guide for Venting of Deflagrations [5]. That document gives guidance for the design of vents for enclosures containing flammable gases, specifically hydrogen, coke oven gas, propane, and methane. Application of the guide to other gases is achieved using the KG value. Values of KG are published for a relatively small number of gases, as seen in Table D-1 of NFPA 68. This work present KG data on several additional gases obtained in a laboratory scale test vessel along with analysis of the results with respect to published values of fundamental burning velocity.
    Additional Material: 9 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 23-31 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In May 1996, the Flammable and Combustible Liquids Code Committee of the National Fire Protection Association (NFPA) proposed for adoption by the Association a new edition of NFPA 30, Flammable and Combustible Liquids Code. This new edition was the culmination of two and one-half years' work by the Committee and included one of the most significant changes to that document in some twenty years: the incorporation of mandatory fire protection criteria for warehouses and other inside areas that store flammable and combustible liquids in containers and portable tanks.
    Additional Material: 2 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 32-38 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes the development of a risk ranked Inspection Recommendation procedure that is used by one of Exxon's chemical plants to prioritize repairs that have been identified during equipment inspection.As part of the Company's Safety Management Practices initiative in the late 1980's a procedure was put into place to ensure that an Inspector's repair recommendations were properly addressed by the organization. The initial procedures were successful at “systematizing” the documentation and stewardship-to-completion of the Inspector's recommendation, however, there were complications with the original process: (1)The Inspector made a simple High, Medium or Low assessment of the priority/criticality of the recommendation. Frequently, this resulted in disagreements with Operations about the true priority of the recommendation.(2)If there was agreement on the priority of the recommendation, there was still disagreement on the relative rank within the priority-which high priority was the highest priority?(3)With limited funds to spend on repairs, it was (and is) important to make sure that the money was being spent on the highest risk items that had the greatest risk reduction/cost benefit ratio.To address these concerns, the procedure was modified to incorporate a risk assessment of the recommendation by both the Inspector and Operations. In the new procedure, the Inspector describes the deficiency that he/she finds and assesses the probability of failure within a certain time-frame. Operations must assess the consequences, from an environmental, safety and economics standpoint, were the failure to occur. These assessments are combined in the typical risk equation (risk = probability × consequences) to arrive at a severity index which serves to rank the recommendation relative to the other recommendations. Because Operations participates in the assessment there is very little disagreement about the priority of the recommendation. The severity index puts the recommendations in order so it is quite clear which are the highest priority recommendations. This process has helped to focus the entire organization on those deficiencies that represent the greatest risk with the result that less time and money is spent correcting items that have a low risk/cost benefit ratio, allowing these savings to be used to reduce the higher risks in the plant.
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  • 23
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    Process Safety Progress 17 (1998), S. 124-126 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A simple analytical method is presented for estimating the hybrid minimum ignition energy (HMIE) of dust-gas mixtures, based on the assumed generality of Bartknecht's well-known test data for mixtures of propane with a series of dusts in air. Since the HMIE equation requires input data which might be unavailable, the use of conservative default methods is discussed.
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  • 24
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    Process Safety Progress 17 (1998), S. 138-148 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A large and potentially hazardous decrease in aldehyde autoignition temperature (AIT) occurs with increased pressure. The AIT-pressure curve determined in a 5 L stainless steel sphere was similar for propionaldehyde and butyraldehyde in air, falling from about 185°C at atmospheric pressure to 90°C at 140 psia. Reduction of oxygen concentration had little effect on propionaldehyde AIT. At 100°C and 140 psia, autoignitions accompanied by at least a doubling of pressure were observed above 4% oxygen. In the presence of a few grams of free liquid, propionaldehyde vapor ignited in air at initial conditions significantly below the AIT. The mechanism appears to involve rapid Fe-catalyzed exothermic liquid-phase oxidation leading to autoignition of the adjacent heated gas layer. An acetaldehyde vapor-air mixture in the presence of free liquid and rust exploded at room temperature when air pressure was increased to 95 psia; this result is discussed with reference to a cylinder overpressurization that occurred while making up an ostensibly sub-LFL calibration mixture with compressed air. Propionaldehyde's limiting oxygen concentration (LOC) was investigated in the near-autoignition region using the same 5L apparatus; the findings are discussed with reference to an overpressurization incident in an air-liquid partial oxidation reactor. The general results are used to illustrate the application of LOC in partial oxidation processes subject to autoignition and to discuss elements of the current ASTM draft test method for LOC, which does not address test difficulties associated with condensable and/or reactive gas systems.
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  • 25
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    Process Safety Progress 17 (1998), S. F3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 26
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    Process Safety Progress 17 (1998), S. 157-170 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Risk analysis in chemical process industries is an elaborate exercise involving several steps from preliminary hazard identification to development of credible accident scenarios, to preparation of strategies for prevention or control of damage.All this requires substantial inputs of time and money. In order to get an approximate yet workable assessment of risk at much lesser costs, indices have been developed which link typical findings of elaborate risk analysis to scales of risk. The scales, in turn, provide workable measures of hazards/risks/safety.In the past, indices have been reported for swift risk assessment - the noteworthy among them include Dow fire and explosion index, Mond fire, explosion and toxicity index, IFAL index, and mortality index. A few rapid ranking techniques have also been proposed.This paper presents a new system of methodologies for Hazard Identification and Ranking (HIRA). The system consists of two indices: one for fire and explosion hazards and another for the hazard due to likely release of toxic chemical. The magnitudes of these indices indicate the severity of the likely accident; in terms of the size of the impacted area.HIRA has been applied to a typical chemical process industry - a sulfolane plant - and its performance has been compared with that of the Dow's and the Mond's indices. The study reveals that HIRA is more sensitive and accurate than the other indices.
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  • 27
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    Process Safety Progress 17 (1998), S. 200-208 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 14 Ill.
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  • 28
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    Process Safety Progress 17 (1998), S. 213-218 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: On October 31, 1987 a crane lifting a heat exchanger convection section failed and severed a 4″ loading line and a 2″ pressure relief line to an HF alkylation reactor settler drum at a petroleum refinery in Texas City, Texas. Vapors were emitted under pressure for about two hours and the vessel was plugged and drained aproximately 44 hours later. A plume from this accidental release passed through residential areas, damaging some vegetation (brown lawns), and spawning a class action law suit. An extensive analysis was conducted to determine the total inventory loss and to model the blowdown process and the concentrations of HF in the plume. Since the discharge rate was decreasing with time, a peak concentration of HF in the emitted vapors occurred just before the water spray mitigation system became fully operative. Consequently, the mitigation efforts were more effective late in the response when concentrations were already low. The predicted plume concentrations are consistent with observed vegetation damage effects, with concentrations below Emergency Response Planning Guideline Level 3 past 3/4 mile from the source. These results support a policy of sheltering in place during such an event.
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  • 29
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fifty-five gallon steel drum of a liquid organic peroxide pressurized and ruptured in the mix room of a manufacturing plant. The head of the drum blew off and the ejected material ignited. The resulting fire was extinguished by the building sprinkler system and operating personnel. Although there were no injuries, the fire caused significant damage in the mix room. The investigation of this incident, its likely cause, and the corrective actions will be discussed.
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  • 30
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    Process Safety Progress 17 (1998), S. 238-242 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Brazoria County Petrochemical Council, 13 companies that are working together to enhance relations between industry and the community, united in a joint effort at complying with the EPA's Risk Management Program. One of the significant issues the group had to address was the need to develop meaningful hazard assessment for presentation to the public. The EPA's “Table Look-Up Approach” found in the Offsite Consequence Analysis Guidance document is certainly a good tool; however, the built-in conservatism results in over-estimates of potential hazard areas. Much more meaningful results are shown to be obtained using one of the hazard release models.The value of using a credible scenario with realistic meteorological data is demonstrated through the consistently smaller areas predicted by the PHAST Model for planning purposes. Realistic scenarios/failure modes and realistic model parameters are important so that the risk to the public is not overstated. Proprietary models such as PHAST are invaluable in providing more meaningful consequences for planning purposes.
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  • 31
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    Process Safety Progress 17 (1998), S. 263-271 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some of the hazards encountered by process plant operators involve the operation of in-line valves to control, start, and to stop flow. Torque required to operate valves may vary according to valve wheel size, in-line pressure, and valve flange position (open/closed). This study determined how valve wheel size, in-line pressure and valve position (open/closed) affect torque required to actuate a valve. Data were gathered with each combination of size, pressure and position for 336 valves in an operating petrochemical process facility. The results indicate that the main effects of valve wheel size, the in-line pressure, and open/closed valve position significantly affect operational torque requirements. In addition, the interaction between position and pressure was significant for operational torque. The implication of these results is that operators are exposed to operational torque requirements that exceed maximum acceptable capabilities that have been determined in previous studies.
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  • 32
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    Process Safety Progress 17 (1998), S. 288-296 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An ammonia storage tank was built at the BASF Antwerp site in 1969 on land reclaimed from the sea. After several years of operation uneven foundation settlement, of up 2, occurred. In order to assure stability of this area for the next operation period (at least 10 years) measures were taken to ensure continued safe operation. One key measure was strain gauge monitoring at the location of maximum stress.
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  • 33
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    Process Safety Progress 17 (1998), S. 297-301 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Baker-Strehlow methodology was developed to provide an objective approach to prediction of blast pressures from vapor cloud explosions. The complete methodology was first published in 1994 [1]. Since then, it has evolved through ongoing research and use in VCE hazard analyses, facility siting studies and accident investigations. This article gives a brief overview of a paper on recent developments in the Baker-Strehlow methodology presented at the 31st Loss Prevention Symposium in Houston on March 9-13, 1997. Because the entire paper is too lengthy to be presented here, the following discussions may be lacking in some details. A copy of the complete paper can be obtained from the American Institute of Chemical Engineers (AIChE).Since the Baker-Strehlow method was first published, it has been used extensively in VCE hazard assessments in refineries and chemical plants. As expected, many practical lessons have been learned during the course of the hazard assessments, and the Baker-Strehlow method has evolved as a result. The changes have been evolutionary, not revolutionary. In keeping with the goals of the original study in which the methodology was developed, all changes have been incorporated with the intent of achieving an objective methodology to provide consistent prediction of VCE blast effects.The revisions to the Baker-Strehlow method resulting from experience gained during plant walk-downs and hazard assessments include: Systematic identification of “potential explosion sites” or “PESs,”Selection of the level of confinement for mixed zones of 2D and 3D confinement,Deciding on flame expansion when confinement is elevated above the vapor cloud,Selecting the reactivity for a fuel that is a mixture of fuels with differing reactivities,Predicting blast loads when there are multiple PES's within a vapor cloud considering different ignition source locations.
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  • 34
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    Process Safety Progress 17 (1998), S. 83-85 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Safety, health and loss prevention are major areas of interst for the American Institute of Chemical Engineers (AIChE). There has been an evolution of these concerns over the years in the Institute just as it has in industry. This article chronicles this evolution.
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  • 35
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    Process Safety Progress 17 (1998) 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 36
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    Process Safety Progress 17 (1998), S. 1-8 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recent guidelines released by the U.S. EPA define a worst-case scenario as a release under stable atmospheric conditions defined as Pasquil-Gifford stability class F. Unfortunately, very few tests at F stability have been available heretofore to provide a basis for models. Recent test data with propane releases by the German research organization TUV provide a set of 60 experiments conducted specifically to define the effects of atmospheric stability class on dispersion. Of these, 25 tests were at F stability. A comparable number were at each other stability class A through E. In addition 23 tests were at wind speeds under 1.5 m/s in stable atmospheres. This paper reports on adjustments made to our models based on these new data by reducing the originally-postulated sensitivity to stability class. In spite of considerable scatter in the TUV data, particularly between two different types of propane analyzers, the model allows us to extract information by averaging over the tests.
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  • 37
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    Process Safety Progress 17 (1998), S. 16-19 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A multi-disciplinary team developed a guideline for determining access restriction zones around vented solids handling equipment. The guideline provides a method for ensuring the discharge from a vented explosion will not cause injury to personnel. The steps in this method include: calculating the extent of external hazards from vented explosions; identifying potential areas where personnel could be exposed to a hazard; identifying ways to eliminate or reduce the hazard area; and establishing and documenting any access restrictions needed. Hazard zone calculations use the latest knowledge from research into fireball size, flame length and external pressure equations in VDI 3673. The guideline provides guidance for using this information. Options for mitigating or reducing external hazards from vented explosions are also described. As part of the project, the team audited several solids handling systems to look for potential oversights in existing restricted access areas. Some of the team's learnings from these audits are reviewed.
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  • 38
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    Process Safety Progress 17 (1998), S. 43-48 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper defines situation awareness (SA) and discusses its importance to operator-machine system safety and functioning in the context of process control activities. Specifically, identified are relationships of human detection of critical process cues converying the status of automated control systems and operator interpretation of the meaning and relevance of such information to the potential for negative incidents in chemical processing. Beyond individual operator SA in interacting with control systems, intra- and inter- work team SA are discussed for supporting individual attainment of process control responsibilities. Factors critical to team SA are discussed. “Road blocks” to team SA are also analytically examined. Lastly, methods for assessing individual and team SA are reviewed and vehicles for relating outcomes of these methods to changes in process control operator and team behavior to improve human-machine system safety and performance are relayed.
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  • 39
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    Process Safety Progress 17 (1998) 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 40
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    Process Safety Progress 17 (1998), S. 74-81 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The knowledge of the ingition behavior of dust-air mixtures due to electrical sparks (MIE, Minimum Ignition Energy) and hot surfaces (MIT, Minimum Ignition Temperature) is important for risk assessments in chemical production plants. The ignition behavior determines the extent and hence the cost of preventive protection measures.This paper describes the use of the minimum ignition energy and minimum ignition temperature as very important safety indexes in practice.Based on the latest results from large scale experiments on pneumatic filling of silos with polymeric materials and new results of full scale filling tests using Flexible Intermediate Bulk Containers (FIBC) manufactured from a variety of materials, guidance can be given to ensure safe operation in different situations such as filling, emptying operations, type of powder handled.The aim of this paper is to assist people dealing with product. It reflects the present state of the art and current knowledge of the assessment and measures associated with powder handling.
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  • 41
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    Process Safety Progress 17 (1998), S. 104-106 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In mid-1997, an Advanced Process Control (APC) scheme was implemented at a resins manufacturing complex with the goal of minimizing flare fuel gas usage while maintaining sufficient energy (BTU/SCF flare gas) to be in environmental regulatory compliance. Prior to APC implementation, the flare system was manually controlled by plant operators with minor attention paid to the minimization of fuel gas usage. Since implementation, APC has saved the plant thousands of dollars in fuel gas costs and reduced unnecessary combusted fuel gas emissions.Hazard analysis techniques were used in the development of the control scheme. An overview of the APC used, the economic evaluation, and the hazard analysis techniques used in the project are presented here.
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  • 42
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    Process Safety Progress 17 (1998), S. 107-123 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the risk assessment parlance, especially with reference to chemical process industries, the term “domino effect” is used to denote “chain of accidents,” or situations when a fire/explosion/missile/toxic load generated by an accident in one unit in an industry causes secondary and higher order accidents in other units. The multi-accident catastrophe which occurred in a refinery at Vishakhapatnam, India, on September 14, 1997, claiming 60 lives and causing damages to property worth over Rs 600 million, is the most recent example of the damage potential of domino effect.But, even as the domino effect has been documented since 1947, very little attention has been paid towards modeling this phenomena. In this paper we have provided a conceptual framework based on sets of appropriate models to forecast domino effects, and assess their likely magnitudes and adverse impacts, while conducting risk assessment in a chemical process industry. The utilizability of the framework has been illustrated with a case study.
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  • 43
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    Process Safety Progress 17 (1998) 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 44
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    Process Safety Progress 17 (1998), S. 149-154 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article deals with fire protection for water miscible flammable liquids stored in plastic containers packaged in boxes located on pallets. A series of fire tests was conducted with palletized rack storage arrangements using in-rack sprinkler protection at various levels. The intent of the paper is to present data from this test series for these types of commodities. The paper will identify various existing water miscible flammable liquid products stored in this fashion and provide background information for protecting this type of storage as it relates to NFPA 30 Flammable and Combustible Liquids Code. The test data indicates that further research work is needed in the area of plastic containers for use with the storage of combustible and flammable liquids. Included in the paper are discussions concerning possible protection strategies and suggestions for future research which would benefit those involved in risk management of this type of commodity.
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  • 45
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    Process Safety Progress 17 (1998), S. 176-183 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The safest method to prevent fires and explosions of flammable mixtures in the first place. This method requires detailed knowledge of the flammability region as a function of the fuel, oxygen, and nitrogen concentrations. A triangular flammability diagram is the most useful tool to display the flammability region, and to determine if a flammable mixture is present during plant operations.This paper describes how to draw and use a flammability diagram. A procedure to estimate the flammability region using the available and sometimes limited data is discussed. The paper also shows how to use the flammability diagram with plant operations involving inerting and purging, and from bringing vessels into and out of service. A compilation of flammability diagrams for 30 materials, based on previously published data is provided.An automated apparatus for acquiring data for a flammability diagram is described. The apparatus consists of a 20-L sphere with an automated gas mixing system, a fuse-wire ignition system, and a high speed pressure measurement and data acquisition system. Data derived from the apparatus includes flammability limits, maximum pressure during combustion, and the maximum pressure rate. The effect of fuse-wire ignitor dynamics on the results is studied. A flammability diagram for methane drawn from data obtained from the apparatus, is presented.
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  • 46
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    Liebigs Annalen 1998 (1998), S. 1063-1070 
    ISSN: 1434-193X
    Keywords: 2-Amino-1,1,2-triphenylethanol ; Bridging ligands ; Crystal structure ; Diastereoselectivity ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The imines 4 containing a diphenylcarbinol moiety serve as chiral ligands in novel enantiomerically pure imine-alkoxytitanium(IV) complexes. Depending on the molar ratio of the starting materials, imines 4 and titanium tetraisopropoxide, mono-chelated complexes 5 or bis-chelated complexes 6/7 result. The latter are formed diastereoselectively and the isomers 6 are main or exclusive products. Their (A) configuration is determined by a crystal-structure analysis of 6b. The bis-ligand complexes 6 or mixtures of 6/7, which are found to be remarkably stable, are used as precursors not only for the reactive dihalo complexes 8a/8b but also for the preparation of the mixed chloroisopropoxytitanium complex 8c.
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  • 47
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    Process Safety Progress 17 (1998), S. 86-97 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Regulatory issues related to material safety have made the accurate measurement and/or prediction of flash points essential. The flash point is one of the major physical properties used to determine the fire and explosion hazards of a liquid. Flash points are used by virtually all governmental entities worldwide to define “flammable” and “combustible” materials for shipping and safety regulations.A model is described here for the calculation of closed cup flash points for multicomponent, single liquid phase, mixtures. The model is based upon rigorous vapor/liquid equilibrium calculations supplemented with information about the lower flammable limits (LFL's) and heats of combustion (ΔHc's) for the mixture's constituent components. The closed cup flash points predicted with this model are typically within ± 5°C of the experimentally reported values. Such a model is useful as a means of verifying experimental data and as a tool for screening product formulations prior to experimental flash point determination. The model should considerably enhance the safety evaluation portion of the product development cycle, thus leading to shortened product time-to-market cycles. While flash points calculated with this model are in excellent agreement with experiment, experimental determination is still encouraged for critìcal safety applications.
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    Process Safety Progress 17 (1998), S. 134-137 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: National Advisory Committee's Acute Exposure Guideline Levels (AEGLs) for ammonia are critically evaluated. The technical bases for concern about AEGL-2 and AEGL-3 values derived by the committee are summarized recommendations made.
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    Process Safety Progress 17 (1998), S. 127-133 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An explosion and flash fire in a fixed bed reactor occurred at a municipal wastewater treatment plant (WWTP). Two employees were injured in the accident. The accident occurred in an ozone treatment building where ozone was used to treat odors from the offgas of the sludge concentration units. Excess ozone manually was routed to the fixed bed reactor (ozone destruct unit) where the ozone is catalytically transformed into oxygen before being discharged to the atmosphere.An investigation of the accident was conducted to determine the root cause of the explosion and flash fire and identify corrective actions which the WWTP management could undertake to prevent a recurrence. This investigation included site inspections, interview with the injured employees, sampling and analysis of various materials, an explosion dynamics analysis, and a root cause analysis.It was concluded that cooling oil from one of the ozone generation units entered the main ozone gas line due to a crack in one of the reactor's dielectric tubes. The cooling oil was vented into the ozone destruct unit when an employee opened a ball valve on the main ozone gas line. The cooling oil, essentially a saturated hydrocarbon mixture, reacted exothermically when it contacted the manganese dioxide catalyst. The exothermic reaction resulted in an explosion which propelled the access panel outwards and dispersed the catalyst pellets. A flash fire followed the explosion. The flash fire burned two employees and caused thermal damage to a nearby control panel.Although this accident was the first of its kind at this facility, this was not the first time that the ozone generator had experienced a failure of a dielectric tube. Thus, there was a significant probability that a dielectric tube failure could leak cooling oil into the main ozone gas line. This failure event could, in turn, result in another explosion and flash fire. The WWTP staff neither designed nor fabricated the ozone generator-destructor system. Therefore, it did not seem appropriate for the WWTP staff to modify the ozone system. Instead, it was recommended that the ozone destruct unit be taken out of service. The WWTP management acted on this recommendation.
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    Process Safety Progress 17 (1998), S. 171-175 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An explosion occurred in a petroleum product storage tank at a refinery. The liquid petroleum product was a heavy oil used as an asphalt extender. There were no injuries, but the cleanup was costly. The storage tank was one of several which received the product stream from a dehydration unit. The accident occurred shortly after the refinery was brought back on-line following a shutdown for schduled maintenance.This was the first incident of this kind to occur at this facility. Analysis of the process data and eyewitness observations indicated that the dehydration tower, which was supposed to be maintained at a minimum of 100°C during the shutdown, was allowed to drift below 100°C for an unknown period of time. This deviation enabled liquid water to enter the storage tank. Three operational factors contributed to the accident. Corrective actions were recommended to prevent a recurrence of a similar incident.
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    Process Safety Progress 17 (1998), S. 184-189 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dust explosions have been with us for a long time. The first record of a dust explosion occurred in Turin, Italy, on December 14, 1785 [1]. The detailed record of this event is left to us by Count Morozzo. The event took place in Mr. Giacomelli's bakery. We know from his account that the weather was unseasonably dry, that a boy who worked in the bakery was using a shovel to stir and transfer the flour to a chute from a store room to the bakery and he had a lighted lamp to work by. The rest, as the saying goes, is history. No one was killed, and the building was saved by the sagacious fact of having plenty of windows. Since that first record, of course, there have been many explosions with much loss of life and significant economic consequences.
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    Process Safety Progress 17 (1998), S. 190-195 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The RSST DIERS vent sizing methodology is revised to provide realistic design equations for reactive systems consistent with available large-scale experience. Using easy to obtain RSST data such as rate of temperature rise and rate of pressure rise excellent agreement is illustrated for hybrid, vapor and gassy reactive systems.
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    Process Safety Progress 17 (1998), S. 196-199 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: From the 1960s onwards, the chemical and oil industries developed and used a number of new safety techniques which, in time, became second nature to those who applied them. They included the use of QRA for deciding priorities, Hazop and audits for identifying problems, inherently safer design for avoiding hazards, and more thorough investigation of incidents for identifying underlying causes. However, it has not yet become second nature to remember the accidents of the past and the actions needed to prevent them happening again.I joined industry in 1944 and moved to production in 1952. Then, and for at least 15 years afterwards, safety was a non-technical subject that could be left to arts graduates and elderly foremen. There was concern that people should not be hurt - great attention was paid to the lost-time accident rate - but there was no realization, that it was a subject worthy of systematic study by experienced technologists.This view changed at the end of the 1960s. A new generation of plants had been built, operating at higher temperatures and pressures and containing larger inventories of hazardous chemicals; the result was a series of fires and explosions and a worsening fatal accident rate. Figure 1 shows the situation in ICI, at the time the UK, s largest chemical company. Other companies experienced a similar state of affairs.As a result in 1968, I was appointed one of the company's first technical safety advisers, an unusual appointment at the time for someone with my experience, and if the reason for my appointment had not been so obvious I would have wondered what I had done wrong. I and my colleagues tried to apply the same sort of systematic thinking to safety that we applied in our other professional work. We developed some new concepts and techniques and adopted others. A common feature of our ides, realized only in restrospect, was that they consisted of more than mere problem-solving techniques. Once people had got used to these new concepts and used them a few times, they began to look at a whole range of problems in a different way.
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    Process Safety Progress 17 (1998), S. W3 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 55
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    Process Safety Progress 17 (1998), S. 259-262 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Case histories of 65 incidents in runaway reactions and emergency relief in Taiwan were analyzed and classified into several categories according to their causes, materials involved, equipment types, reaction types, and ignition sources. The cases in reactors and storage tanks were examined in more detail owing to the higher probability or larger potential hazard in these two types of equipments. The most common consequence of the incidents are explosions, fires, and atmospheric release of toxic chemicals. The most severe case was a thermal explosion from an organic peroxide storage area which caused the death of 33 persons. Popping and direct releasing of process chemicals to the atmosphere from relieving devices cause the greatest environmental concerns to the community close to the plants. Runaway reactions in batch type reactors occur frequently due to various operational mistakes. Heat of reaction is the most frequent ignition source of runaway reactions and emergency relief.
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    Process Safety Progress 17 (1998), S. 272-277 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: EPA's Risk Management Program regulation, promulgated in June 1996 as 40 CFR Part 68 requires subject industries to submit Risk Management Plans by June 1999. This plan requires hazard assessment of the operations of a facility using worst case scenarios and alternative releases. EPA has provided an Off-site Consequence Analysis (OCA) guidance to help facilities in their hazard assessment.OxyChem will be significantly impacted by the RMP rule. This paper outlines OxyChem's general experience and its strategy in planning to comply with this rule. OxyChem's approach in the development of the scenarios required by the rule is described in this paper. Limitations involved in the use of EPA's look-up tables or a single modeling solution for conducting all of the OCA are discussed. A three tiered OCA approach is presented as a possible alternative.
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    Process Safety Progress 17 (1998), S. 209-212 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: HFC-227ea (CF3CHFCF3;1, 1, 1, 2, 3, 3, 3-heptafluoropropane) is an effective replacement for Halon 1301 in fire suppression systems, providing rapid extinguishment of flames through a combination of physical and chemical mechanisms. The vast majority of applications for HFC-227ea involve the protection of Class A hazards, which are characterized by low fuel loadings and low energy output, with fire sizes often in the range of 5-10 kW. Mid- and large-scale testing has demonstrated that HFC-227ea, at its minimum design concentration of 7.0% v/v, is effective at extinguishing fires typical of those expected to occur in electronic data processing (EDP) facilities, telecommunication facilities and anechoic chambers. The levels of HF produced following extinguishment of typical Class a fires with HFC-227ea were well below the estimated mammalian LC50 and the human Dangerous Toxic Load (DTL), and do not appear to present a threat to electronic equipment.
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    Process Safety Progress 17 (1998), S. 219-224 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sandia National Laboratories (Sandia) has refined a process for developing inherently safer system designs based on methods used by Sandia to design detonation safety into nuclear weapons. The process was created when Sandia realized that standard engineering practices did not provide the level of safety assurance necessary for nuclear weapon operations, with their potential for catastrophic accidents. A systematic approach, which relies on mutually supportive design principles integrated through fundamental physical principles, was developed to ensure a predictably safe system response under a variety of operational and accident-based stesses. Robust, safe system designs result from this thematic approach to safety, minimizing the number of safety critical features. This safety assurance process has two profound benefits: the process avoids the need to understand or limit the ultimate intensity of off-normal environments and it avoids the requirement to analyze and test a large array of accident environment scenarios (e.g., directional threats, sequencing of environments, time races, etc) to demonstrate conformance to all safety requirements.
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    Process Safety Progress 17 (1998) 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Process Safety Progress 17 (1998), S. 233-237 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new method is described to enhance the management of process safety risks such that the number and type of safety systems protecting against any hazard are consistently predicated upon risk. Further, that such an assignment of safety systems can be made consistent throughout an organization. This consistency is gained through standardization of qualitative risk ranking and by setting company guidelines.
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    Process Safety Progress 17 (1998), S. 243-258 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Research was carried out to develop improved protection guidelines for silane handling systems through enhanced understanding of the behavior of releases of this pyrophoric gas. The approach involved addressing three aspects of the problem: the prompt ignition behavior of silane; the reactivity characteristics of quiescent silane/air mixtures; and the rates of reaction of silane leaked into enclosures with and without explosion venting, in the presence of ventilation air flow. A first conclusion, reached from tests in a ventilated cabinet, was that, contrary to prevailing belief, the ventilation flow has no measurable effect on the prompt ignition of the release. From experiments in a 5.1-liter (311-in.3) sphere it was found that silane/air mixtures of concentrations between 1.4 and 4.1% (by volume) are explosive but stable. In this case, piloted ignition tests yielded laminar burning velocities up to 5 m/s (1000 ft/min). Mixtures between 4.5 and 38% (the maximum reached in the tests) were found to be metastable, and would undergo spontaneous ignition after a delay ranging from 15 to 120 seconds, with the shorter values corresponding to higher silane concentrations. Experiments were also performed in a 0.645-m3 (22.8-ft3) vessel both with and without explosion venting, to measure the rates of energy release associated with impulsively-started silane leaks from 1/8 and 1/4-in. (3.2 and 6.4-mm) lines. A method for the prediction of the venting requirements of partial-volume deflagrations (PVD) was evolved into a tool to quantify the pressure rise from ignition of silane leaks in enclosures. These results represent a significant step toward updating existing design recommendations which prescribe ventilation requirements that are based on outdated and, in some instances, misinterpreted data.
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    Process Safety Progress 17 (1998), S. 278-287 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas explosion simulators are often used as tools in process plant design. This article presents some properties of gas explosions found using the EXSIM simulation software on three offshore modules with a total of nearly 10,000 simulations. The selected results are chosen for their supposed applicability to structural design in the process industries.Generalized data are presented for the effect of gas cloud size, explosion impulse vs. explosion pressure, pressure and impulse vs. duration, the probability of a “short” explosion, loading rate, pressure-time “shape” function, and the effect of introducing louvers.
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    AIChE Journal 16 (1970), S. 134-138 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An analysis of the two-dimensional temperature field of a square column embedding a heating cylinder is presented. The analysis leads to a solution in finite series which gives rise to rapidly converging numerical results. The series coefficients computed for the extreme case of the cylinder being a line find a way of parametrization, which then furnishes the solutions for finite cylinders up to the case of the cylinder diameter being half of the column thickness. Results in five-digit accuracy are presented. The method is simple and direct. In addition, it retains the same concise formal solution for a variety of boundary conditions.
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    AIChE Journal 16 (1970), S. 147-148 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 16 (1970), S. 151-153 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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    AIChE Journal 16 (1970), S. 249-254 
    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 hydrolysis of acetyl chloride was studied in a laboratory reactor designed to act as a chemical oscillator. The observed oscillating outputs are in fairly good agreement with the numerical solutions of the stirred tank reactor equations and the approximate analytical solutions published previously.
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    AIChE Journal 16 (1970), S. 233-240 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is shown that existing methods for design of optimal regulators by the Wiener-Hopf procedure must be modified in order to be applicable to unstable and/or nonminimum phase plant or disturbance transfer functions, such as are frequently encountered in the chemical industry. Solutions are developed for three cases: I. stable, but possibly nonminimum phase, plant and disturbance transfer functions; II. minimum phase, but possibly unstable, plant with no restrictions on the disturbance transfer functions; and III. prestabilized, with a proper modification to retain the original control effort inequality constraints, but possibly nonminimum phase plant and disturbance transfer functions. Case III gives the general solution for regulation of linear, time-invariant, lumped-parameter systems. When prestabilization is not necessary, it reduces to case I. Where applicable, solutions by the method of case II frequently involve less algebra than in case III.
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    AIChE Journal 16 (1970), S. 240-248 
    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 Wiener-Hopf procedure for synthesis of optimum constrained linear feedback regulators has been extended in part I to all linear time-invariant lumped parameter systems. The solution is here applied to the control of the output concentration of an exothermic, stirred tank reactor operating close to an unstable steady state, by constrained manipulation of a cooling water flow rate, in the presence of a randomly fluctuating inlet concentration.When the spectral density of disturbance is given (for example, white noise through a first-order time delay, or a series of randomly alternating steps), the optimum controller has three modes: proportional, derivative, and integral with minor feedback. The responses of the nonlinear reactor and the linearized reactor control systems to a series of alternating deterministic step inputs and Gaussian distributed inputs are simulated, and a sensitivity study of the linearized system with respect to variations in process, controller, and disturbance parameters is made in order to demonstrate the feasibility of the method.
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    AIChE Journal 16 (1970), S. 23-31 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this paper, mathematical models for a single adsorbate component present in a gas phase have been developed for isothermal and adiabatic dynamic adsorption-desorption processes with special emphasis on adsorption drying by supported hygroscopic salts. The proposed generalized models are applicable to both an unsupported absorbent bed and a fixed bed of adsorbents impregnated on a supporter which may have nonlinear equilibrium relationships. The partial differential equations governing the dynamic adsorption-desorption processes and the nonlinear equilibrium relations were solved numerically on the digital computer.An experimental study was conducted to measure the adsorption and desorption rates of water vapor by lithium chloride impregnated on a solid supporter, Torvex.The proposed adiabatic adsorption-desorption model has been verified for unsupported adsorbent beds in the cases of water vapor adsorption from air by silica gel and of methane adsorption from a helium-methane mixture by activated carbon. The validity of the generalized adiabatic model for supported adsorbent beds with nonlinear equilibrium relationships was established by a direct comparison of experimental data obtained in this study with the predicted values.
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    AIChE Journal 16 (1970), S. 32-37 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Measurements of the effective self-diffusion coefficients for carbon dioxide and methane were performed in the transition pressure range. The experiments utilized carbon-14 tagged gases and semiconductor radiation detectors in a transient type of experiment. A detailed analysis of the errors associated with the experiments indicated that the accuracy of the measurements was near 5%. The results verify that the additive resistance law is valid for the representation in the transition range. The unknown effects of surface diffusion make the values to be employed in this law subject to review. As an example one surface diffusion model is considered.
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    AIChE Journal 16 (1970), S. 318-320 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    AIChE Journal 16 (1970), S. 329-331 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 16 (1970), S. 76-82 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental results have been obtained for heat transfer to melting ice spheres by measuring the rate of change of apparent weight. It is found that the traditional correlation format of Nusselt number against Rayleigh number is satisfactory only for bulk temperatures above 7°C. Average Nusselt numbers obtained from the sphere experiments are closely related to previous theoretical work with vertical flat plates.
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    AIChE Journal 16 (1970), S. 69-75 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An approach has been developed for predicting rates of interphase mass transfer under conditions of high flux and high concentration level. A rectangular channel device has been used to measure rates of evaporation of four solutes, carbon disulfide, n-pentane, cyclopentane, and ethyl ether, from n-tridecane into flowing nitrogen. The evaporation rate of carbon disulfide agreed with the prediction of the interphase theory up to a carbon disulfide mole fraction of 0.30 in the bulk liquid. For the other three systems, a concentration gradient induced, surface tension driven cellular convection served to increase liquid-phase coefficients substantially. A correlation was obtained for the effect of this cellular motion on the liquid-phase mass transfer coefficient.
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    AIChE Journal 16 (1970), S. 108-111 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Tray efficiencies were measured for desorbing ammonia from water by air in a small sieve-tray column operated in the cycling mode, that is, with alternate flow of vapor and liquid. The actual efficiency improvement obtained was compared with that theoretically possible assuming the liquid flows without mixing when dropped. A mixing model was proposed and the mixing parameter evaluated from the experimental data.
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    AIChE Journal 16 (1970), S. 120-130 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As a step toward a unified treatment of particulately fluidized beds, a statistical-thermodynamic approach has been investigated, with the smoothed potential cell theory of pure liquids used to establish an equation of state and a collisional-viscosity relation. This treatment has correlated well with experimental data on liquid-fluidized beds, and the same method gives reasonable predictions for gas-fluidized beds. A parameter equivalent to thermodynamic temperature has been identified for fluidized beds, which depends solely upon fluid properties and includes the three-halves power of superficial velocity. This approach should be of value for interpreting other liquidlike properties of fluidized systems.
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    AIChE Journal 16 (1970), S. 150-150 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970), S. 177-184 
    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 efficiency of process optimization by mathematical programming can be increased by tearing, that is, rearranging the design equations so as to reduce the number of equality constraints. The structure of a system of equations may be depicted as an undirected bipartite graph; algorithm I-T utilizes this graph to determine an order of solution for the equations which requires no tears. If this is impossible, then algorithm II-T uses indexing in conjunction with algorithm I-T to produce an order which minimizes the number of torn equations. This procedure is extended to the problem of minimum recycle parameters, and the two-way interaction between tearing and algebraic simplification is illustrated.
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  • 81
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    AIChE Journal 16 (1970), S. 499-501 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 82
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    AIChE Journal 16 (1970), S. 501-501 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 83
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    AIChE Journal 16 (1970), S. 512-702 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 84
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970), S. 513-519 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental gas absorption studies for bubbles transported in turbulent pipe flow of water strongly indicate that liquid phase controlled mass transfer is due to surface renewal by turbulent eddies. Predictions of transport behavior from the conditions of turbulent flow cannot be made in support of this mechanism because no satisfactory theory of turbulent transport near a gas-liquid interface is available. This work considers a model of the hydrodynamic behavior near the surface which provides a link between the observed mass transfer behavior and the state of the turbulent field.In this model, the very small scales of turbulent motion are considered to be controlling. These motions are idealized, and their flow and mass transfer behavior are solved analytically. The overall result for eddies of various sizes is related to the turbulent energy spectrum by using only the easily accessible parameter ∊, the energy dissipation rate. This model gives quantitative agreement to within a factor of 2 for three widely different experimental situations including gas-liquid and liquid-solid interfaces. However, the predicted Reynolds number dependence is somewhat higher than the experimental result.The model attempts to clearly define the basic physical process at the interface. Therefore, it indicates the direction for further experimentation needed to clarify the basic relationship between the mass transfer rates in the liquid phase and the hydrodynamic behavior of the turbulent liquid.
    Additional Material: 7 Ill.
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  • 85
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970), S. 553-559 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study of the photochlorination of propane was undertaken to assess the significance of heterogeneous termination steps (wall reactions). Data were obtained in 2- and 10-mm. I.D. tubular flow reactors with varying oxygen concentrations. The results indicated that homogeneous terminations were dominant in the large reactor, and heterogeneous ones were dominant in the small unit. A kinetic scheme which explained the data was proposed. It included two parallel termination steps: a second-order homogeneous reaction between C3H7. and oxygen and a first-order heterogeneous reaction between C3H7. and the reactor wall.Even though the data were taken in the laminar flow regime, the rate of reaction was a function of Reynolds number for the 10-mm. reactor. Kinetic factors may explain these results, but the reasons are not clear. More research in this area is needed.Data taken in the 10-mm. reactor packed with quartz cylinders gave results similar to those for the 2-mm. reactor. This provided confirming evidence for the proposed scheme of parallel, heterogeneous and homogeneous termination steps.
    Additional Material: 8 Ill.
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  • 86
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970), S. 588-594 
    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 heat and mass transfer processes in a binary mixture flowing in a parallel plate channel with mass addition at the bounding surfaces are investigated analytically. The rate of mass addition, the temperature, and the mass fraction are arbitrarily prescribed at each of the bounding walls. Similarity solutions are evaluated numerically to yield pressure gradient, Nusselt number, and Sherwood number results for a wide range of each of three governing parameters. It is found that increasingly strong surface mass addition markedly increases the magnitude of the axial pressure gradient. Mass addition decreases the Nusselt and Sherwood numbers at the channel wall at which the injection is strongest but may actually increase these moduli at the opposite wall. A generalizing analysis is performed to accommodate phase change processes as well as to accommodate the specification of plenum conditions rather than wall surface conditions. Application is made to the evaporation of liquid water by an air stream. It is shown that the rate of evaporation is augmented as the rate of air injection increases, but the extent of the augmentation is less than the causative increase in the air flow rate.
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  • 87
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    AIChE Journal 16 (1970), S. 633-638 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A previous report (1) has presented the derivation of new filter cake washing equations. This report presents the procedure for their application and contains an example of application to a specific batch washing system. It also presents the adaption of the equations to permit their use in predicting the performance of a continuous rotary-drum filter.
    Additional Material: 10 Ill.
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  • 88
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 89
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    AIChE Journal 16 (1970), S. 528-535 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical analysis of the laminar-turbulent transition phenomenon is presented for the case of steady, isothermal, fully developed flow of Newtonian fluids in straight ducts of constant isosceles triangular cross section. As a result of this analysis, the simultaneous existence of macroscopically large stable regions of laminar and turbulent flow are predicted to occur during the transition phenomenon. The existence of this special type of flow field, which has not been previously predicted theoretically, is shown to be a consequence of the presence of an asymmetric shear stress distribution. The results of an experimental study are also presented. These data verify the predictions made by the theoretical analysis.
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  • 90
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    AIChE Journal 16 (1970), S. 762-766 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure drops were measured for the high velocity isothermal viscous flow of steam in circular tubes. For the velocities tested, up to 0.48 times the isothermal sonic velocity, these flows obeyed the following equation with an average deviation of 2.4%. \documentclass{article}\pagestyle{empty}\begin{document}$$ P_1 2 - P_2 2 = \frac{{8\mu RTG}}{{DM}}\left[{\frac{{8L}}{D} + \frac{{N_{{\mathop{\rm Re}\nolimits} } }}{3}In\left({\frac{{P_1 }}{{P_2 }}} \right)} \right] $$\end{document}This equation differs from the Poiseuille-Meyer equation commonly used to correlate isothermal viscous flow in that it includes the term (NRe/3) In (P1/P2) which accounts for the change in momentum caused by expansion. In deriving this equation, the mean velocity, mean squared velocity, and wall shear stress were obtained from the parabolic velocity distribution for normal viscous flow. The velocity profile should flatten as the isothermal Mach number increases, and it is therefore anticipated that somewhere above the range tested the equation will no longer prove applicable. Variants of the equation, which take into account the flattening of the velocity profile in the range tested, did not fit the experimental data quite as well.
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  • 91
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    AIChE Journal 16 (1970), S. 766-770 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Information about the transition state of a chemical reaction is quite useful for the determination of mechanisms and for design of solvents for the reaction. High pressure kinetic studies, if sufficiently accurate, provide the required data. This work reports a new technique developed for measuring rates of chemical reactions in solution at high pressure. This method involves in situ mixing of reactants under pressure and direct sampling for analysis, eliminating large errors of temperature equilibration and time measurement inherent in existing techniques, and thus yielding more accurate results. Experimental results for the Diels-Alder reaction of isoprene and maleic anhydride are reported at pressures up to more than 6,000 atm.
    Additional Material: 7 Ill.
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  • 92
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    AIChE Journal 16 (1970), S. 793-802 
    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 problem of mass transfer with nonequilibrium at, and significant convection across, the interface has been studied by the method of matched asymptotic expansions. The inner solution for small values of t or z/Um was found in terms of fk functions which were obtained in closed analytical form. The outer solution for large values of t or z/Um was found in terms of gk functions which had to be determined numerically. With these solutions, calculation of concentratration distributions or instantaneous rates of mass transfer is straightforward, but determination of the total amount of mass transfer as a function of time is complicated by the lack of an intersection wherein the inner and outer solutions overlap and converge. To avoid the need for graphical interpolation and integration of the interfacial concentration as a function of time to obtain the total mass transferred, the constant of integration M1 is found to be (-kγ\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt \pi $\end{document}/2h) by assuming that the ratio of mass transferred with an equilibrium interface to that with a nonequilibrium interface is independent of whether or not Vy convection is negligible in the system as t → ∞.The effect of a nonequilibrium interface is greatest for small t in unsteady systems and z/Um in steady state systems. This occurs because the departure from their equilibrium values of the interfacial concentrations of the phases in contact is greatest when they are first brought into contact. The larger the interfacial mass transfer coefficient α, the smaller is the time required for the interfacial concentrations to achieve their equilibrium values.Other things being equal, the rate of mass transfer is greatest when the driving force xA*-xA0 is greatest. Since the departure from equilibrium at the interface is greatest for small values of time, it follows that nonequilibrium interfacial phenomena can be observed most easily in systems where the rate of mass transfer is high. This is also the case when one cannot neglect the effect of finite velocity at the interface which is shown in the present work to be a significant effect.The method of analysis can be used to study a variety of problems in addition to the specific system considered here. In particular, both batch and flow reverse osmosis problems can be attacked by the present approach.
    Additional Material: 10 Ill.
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  • 93
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    AIChE Journal 16 (1970), S. 832-837 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ternary diffusion coefficients at 25°C. of the system 0.5 g./cc. d-tartaric acid - 0.5 g./cc. l-tartaric acid-water are reported. The results allow experimental verification of the theory for the diffusion of two indistinguishable solutes and clearly illustrate the difference between mutual and tracer diffusion. Moreover, the results allow calculation of ternary mass transfer coefficients and ternary tray efficiencies for the case of two similar species dissolved in a third.
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    AIChE Journal 16 (1970), S. 876-877 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 95
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    AIChE Journal 16 (1970), S. 882-884 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 96
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 16 (1970) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 97
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    AIChE Journal 16 (1970), S. 1117-1117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 98
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    AIChE Journal 16 (1970), S. 999-1004 
    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 mechanism of diffusion in an absorbent pore was studied by applying adsorption rate data to the Damköhler equation. Most of the data were taken in the multimolecular region of the nitrogen-silica gel adsorption isotherm. Vapor-phase and adsorbed-phase contributions to the total transport were separated. Vapor-phase transport increased with temperature and was most dominant at relative pressures of 0.4 to 0.6. Adsorbed-phase diffusivities were of the order of 10-2  -  10-3 sq. cm./sec. and showed some dependence on the amount adsorbed at surface coverages greater than 1.5 molecular layers.
    Additional Material: 7 Ill.
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  • 99
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    AIChE Journal 16 (1970), S. 1047-1054 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A Burnett type of apparatus was built for 12,000 lb./sq.in. pressure and temperatures of 25° to 100°C. Isothermal expansions were run on methane, ethylene, and four binary mixtures at 25°, 50°, and 75°C., and compressibility factors were derived from the pressure ratio observations.From the experimental data, second and third virial coefficients were derived by two techniques, that is, the slope-intercept and the multiple regressions curve-fit of the data by the density-series virial equation. A comparison of these virial coefficients with those from the different empirical equations of state indicates areas of needed improvements in these equations. Second virial cross coefficients were also obtained.
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  • 100
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    AIChE Journal 16 (1970), S. 787-792 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By expressing the meniscus height and the sine of the angle between the horizontal and a tangent to the meniscus curve as simple exponential functions of radial position, a new calculational procedure for determining surface tensions from menisci has been developed. These simple functions, when combined with the Laplace-Young equation, generated three useful equations for calculating surface tensions as a function of radial positions. The overall procedure by using the three equations and five smoothing methods was tested on both experimental and calculated menisci. The results from the procedure for the calculated menisci agreed within 1.5% with the original surface tensions used to generate the meniscus. The agreement of values generated with the method and the comparison method previously reported for experimental menisci was within ±8% in general and within ±2% for the best formed menisci.
    Additional Material: 5 Ill.
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