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  • 1995-1999  (971)
  • 1995  (971)
  • Chemical Engineering  (730)
  • Physical Chemistry  (241)
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. i 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 1-4 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative thermodynamic stabilities of the title compounds were determined by iodine catalyzed chemical equilibration in cyclohexane solution. The main point of interest was a determination of the thermodynamic stability of the —O—C=C—O— moiety found in the exocyclic isomers, i.e. the stabilizing effect of a MeO group on the olefinic linkage of 2-methylenetetrahydrofuran. All three isomeric compounds have essentially similar enthalpy values, which, in comparison with some previous thermodynamic data, shows that the double bond stabilization energy of the MeO group in the exo isomers is only ca 3 kJ mol-1. The entropy difference between the geometrical isomers is negligible, whereas the endo isomer is favoured by an entropy contribution of ca 9 J K-1 mol-1.
    Additional Material: 1 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 5-14 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new approach to the long-standing problem of interrelating meta and para substituent constants is presented. An analysis of the unified σ0-scale shows that the interrelation between σ40 and σ40/σ30 can be modelled by a pair of conjugate rectangular hyperbolae, one for normal (n) and the other for special (s) substituents. The latter are characterized by a lone electron pair in the first atom. The equations σ4n0 (σ4n0 - γ0)/(σ4n0 - 2γ0) = λ0 σ3n0 and σ4s0 = γ0 + λ0 σ3s0 are derived and discussed in terms of Taft's separation of mesomeric and non-mesomeric effects. Asymptotic values λ = 0.960 γ = -0.225 were obtained by non-linear least rectangles fitting. A nonnegligible mesomeric contribution to σ0 constants for normal substituents is predicted by the hyperbolic model. The present results are at variance with Exner's analysis of the meta-para interrelationship in benzene compounds with normal substituents. This divergence is ascribed to opposite views concerning the role of the π-inductive effect.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 31-34 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On irradiation on a dry silica gel surface, 2-(N, N-dialkylamino)ethyl 3-benzoylacrylates undergo selective E-Z isomerization. Competing processes, such as remote-hydrogen abstraction via a charge-transfer state, with the photoisomerization in solution are completely suppressed on the surface. The yield of the Z - from the E- isomer increases with increase in the coverage of the E-isomer on the surface, reaching a limiting value. Thermal isomerization of the Z- to the E- isomer occurs easily on the silica gels surface when the alkyl group on the nitrogen atom is small. Benzoylacrylates without any amino group also undergo selective photoisomerization.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 26-30 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Slight structural moiecular variations are known to affect different properties of compounds. In solution, different solute-solvent interactions are known also to alter the properties of numerous compounds. Quantitative structure-activity relationships (QSAR) are used regularly to analyze and predict the variations of different properties of compounds that are caused by structural variations and significant solute-solvent interactions. The relative basicities of n-propylamine, dipro;ylamine and tripropylamine were determined in nine different solvents from potentiometric titrations. QSAR that were developed from these experimental basicity values were used to evaluate the type and significance of the solute-solvent interactions. The important interactions that influence basicity variations for the propylamines studied are dipolarity-polarizability interaction between the solute and the solvent and hydrogen bonds from the propylammonium ions to basic solvents. The role of hydrogen bonds from the propylamines to acidic solvents is minor.
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  • 7
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpies of formation of the condensed phase and gaseous N,N-dimethyl derivatives of pivalamide, 1-adamantylcarboxamide and benzamide were determined by combustion calorimetry and the associated enthalpies of vaporization and sublimation. The enthalpies of formation of styrene and its α-, trans-β- and β,β-methylated derivatives were determined from measurements of their enthalpies of hydrogenation in dilute hydrocarbon solution. Strain and resonance effects of amides and alkenes are discussed in terms of the exo-/endothermicity of the following reactions: and in terms of the difference of enthalpies of formation of the isomeric (Z)- and E-RCH=CHCH3.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 35-40 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Substituent effects were measured for the reactions of substituted benzaldehydes with allytributylin (1) and allyltriethyllead (2) reagents in the presence of BF3.OEt2 in CH2Cl2. The Hammett p values were small and positive at 25 °C and negative at -78 °C for both 1 and 2. These could be interpreted in terms of the contribution of electrophilic complexation between the aldehyde function and BF3 as a rate-limiting step. A large negative p value was observed for the complex-formation equilibria between substituted benzaldehydes and BF3.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 54-62 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,3-Bis(aminocyclohexyl)-6-methoxy-1,3,5-triazine (1a) forms intermolecular H-bonded complexes with 3,3′-diacetyl-cis-azoenzene (4) and 6,6′-diethoxy-cis-thioindigo (5b), (association constants K = 4.9 × 104 and 3.5 × 105 1 mol-1, respectively). The thermal cis→trans isomerization of 4b and 5b to 3,3′-diacetyl-trans-azobenzene (4a), and 6,6′-diethoxy-trans-thioindigo (5a), is inhibited in the intermolecular complex 1a-4b and 1a-5b. Molecular mechanics calculations support the formation of the intermolecular H-bonded complexes between 1a and 4b or 5b.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 47-53 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The associationof C6H5O with NO was studied with the cavity-ring-down method by directly monitoring the decay of C6H5O in the presence of varying, excess amounts of NO. The biomolecular rate constant determined in the temperature range 297-373 K can be effectively rate constant determined in the temperature range 297-373 K can be effectively represented by k1 = 10- 12 · 12 ± 0.24e (194±185)/r cm3 molecule-1 with a negative activation energy of 0.8 kcal mol-1 (1 kcal = 4.184 kJ). In order to understand better the mechanism of the reaction, ab initio molecular orbital calculations were also carried out at the MP4(SDQ)/6-31G* level of theory using the HF optimized geometries. The molecular structues and energetics of five C6H5N1O2 isomers were calculated. Among them, the most likely and stable association product, phenyl nitrite (C4H5ONO), was found to be 17 kal mol-1 below the reactants, C6H5O + NO. Combining the measured rate constant and the calculated equilibrium constant for the association reaction, C6H5O + NO = C6H5ONO the rate constant for the unimolecular decomposition of C6H5ONO was obtained as k-1 = 4.6 × 1015E-8580/T s-1. The relatively large frequency factor suggests that a loose transition state was involved in the reaction, akin to those of its alkyl analogs (RONO, R = CH3, C2H5, etc.).
    Additional Material: 5 Ill.
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  • 11
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal and molecular structues of six quasi-phosphonium salts containing phosphorus-heteroatom heteroatom=oxygen, sulphur or nitrogen0 bonds were determined. Comparison of the molecular parameters obtained with those available for reference structures demonstrated that the ‘double bond’ character for the P+ — Y bond decreases in the order Y = N ≫ O 〉 S.
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  • 12
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 13
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 63-70 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the Menshutkin reaction between triethylamine and iodoethane was studied at 313 K in seven primary and secondary alkanols. An accurate conductimetric method was employed to obtain second-order rate constants at pressures of 0·1-200 MPa. Volumes and isothermal compressions of activation were calculated by different model-based equations which are compared. Activation volumes at 0·1 MPa are in the range -26 to -33 cm3 mol-1. Procedures for dissecting intra- and intermolecular contributions to the volume of activation are discussed. A clear dependence of model parameters on the solvent volumetric properties was found.
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  • 14
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 71-76 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of 2-(p-nitrophenyl)ethyl bromide with hydroxide ion was studied in oil-in-water (o/w) microemulsions at 50°C. The octane-in-water microemulsion systems were stabilized by chemodegradable cyclic acetal-type cationic surfactants as [(2-alky-1,3-dioxolan-4-yl)methyl]trimethylammonium bromides Ia-c (alkyl: a = n-C9H19; b = C11H23; c = C13H27) and butan-1-ol as co-surfactant. The rate constants were also determined in the corresponding aqueous micelles and in water. The hydrolytic lability of Ia-c in the microemulsion systems was achieved at 50°C by acid hydrolysis of the 1,3-dioxolane ring. Systematic synthetic studies of the dehydrobromination were performed in order to develop a preparative approach for the product separation without unfavourable process such as foaming and emulsification.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 77-83 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrogen bond complexes between metyrapone [methyl-1,2-di(3-pyridyl)propan-1-one] and hydroxylic proton donors (phenols, water) were investigated by infrared spectroscopy. The thermodynamic and spectroscopic data determined in carbon tetrachloride suggest that the nitrogen atom of the pyridine ring A [bonded to the C(CH3)2 group] is the main hydrogen bond interaction site. The data are compared with di-2-pyridylglyoxal complexes where the hydrogen bonds are formed on the oxygen atom of the carbonyl function. In the solid adduct of metyrapone with HCl, protonation takes place on the two nitrogen atoms of the pyridine rings. The data from this work are compared with those from chemical oxidation, which leads predominantly to the formation of mono-N-oxide A and di-N-oxide.
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  • 16
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 84-88 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of the amount of water bound to human serum albumin (HSA) suspended in water-dioxane mixtures vs the equilibrium water concentration in the liquid phase was determined by the Fisher method at 298 K. The Langmuir model was used in order to describe the isotherm of the sorption of water by HSA at low water concentrations in the solvent. The calculated equilibrium constant of water adsorption (3.8 ± 0.6 l mol-1) is in good agreement with the adsorption constant obtained earlier from calorimetric data. The comparison of the determined isotherm of water sorption by HSA with the reported enthalpies of suspension formation showed that at low water concentrations in the solvent, water sorption is the only process contributing to the heat effects of the formation of the ‘protein + liquid’ heterogeneous system. From this comparison, the enthalpy of water adsorption by HSA was evaluated as -11.9 ± 1.7 kJ mol-1. At higher water concentrations in the solvent the amount of water adsorbed by HSA increased considerably. This increase in the amount of water on HSA at water activities above 0.5 is assumed to be due to the enlargement of the protein surface area.
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  • 17
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 89-93 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conformational preferences have been measured for 4-X-cyclohexenes (X = Br, Cl, CHO, COOH) in a series of solvents with increasing polarity. The conformational equilibrium exhibits a very weak solvent dependence. ΔG varies at most by 0·25 kcal mol-1 (1 kcal = 4·184 kJ) shifting from a non-polar mixture (CS2-CDCI3) to highly polar (CD3)2SO. The reaction field theory was used to calculate the variation of ΔG with solvent polarity. The calculated solvent shifts δΔG are small and in agreement with the values determined experimentally.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 94-96 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray data on the crystal and molecular structure of bis(biphenyl-2,2′-diyl)allene, reveal a remarkably strong deviation from linearity (170·1°) of the allene unit of the molecule. Ab initio calculations involving dimers of molecules yield good correlation with this geometry, showing that the non-linearity is due to packing effects in the crystal.
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  • 19
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 97-102 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the reaction of 1,1,1-trichloro-4-methoxy-3-penten-2-one with various aliphatic and aromatic amines was studied at 25°C in water, dimethyl sulphoxide, methanol, ethanol, chloroform, toluene and hexane. The formation of the corresponding 1,1,1-trichloro-4-amino-3-penten-2-one is explained in terms of an addition-elimination mechanism.
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  • 20
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 103-107 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The superaromaticity concept is examined and developed, taking into account what is known about aromaticity. Three new hardness indices indices are defined, and shown to be excellent parameters for characterizing superaromaticity. High superaromaticity indicates significant global annulenoid conjugation relative to local benzenoid conjugation in circularly annealed benzenoid molecules. Kekulene, coronene and corannulene tetraanion all are predicted to be superaromatic. The prediction for the corannulene tetraanion strongly supports the “annulene-within-an-annulene” structure derived from NMR data.
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  • 21
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Titration calorimetric data show a dramatic change from endo- to exothermic deaggregation when pentanol-hexadecyltrimethylammonium bromide (CTAB) mixed solutions are injected into an aqueous solution containing pentanol. The results are interpreted in terms of a change in the structures of the aggregates in solution from simple CTAB micelles to mixed amphiphilic microheterogeneities when pentanol is added.
    Additional Material: 5 Ill.
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  • 22
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetic study of the reaction of 1-pyrrolidino-2,4-dinitrobenzene, 1-piperidino-2,4-dinitrobenzene and 1-morpholino-2,4-dinitrobenzene with NaOH in the presence and absence of the amine leaving group was carried out in aqueous solutions at 25°C, giving 2,4-dinitrophenol as the only product. A mechanism involving the formation of σ complexes by addition of HO- or the amine to the unsubstituted positions of the aromatic ring is proposed. These complexes were found to react faster than the original substrates.
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  • 23
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 24
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reactions of diazomethane with butanol, allyl alcohol and β- and γ-halo alcohols led to efficient methylation (giving the corresponding methyl ethers) with the use of a proton-exchanged X-type zeolite compared with H2SO4. The reactions with propylene and isobutylene glycols using the zeolite provided regioselective methylation of the primary OH rather than the secondary or tertiary OH, whereas regioselectivity was not observed in the reactions using H2SO4. The reactions with 2-aminoethanol and 2-mercaptoethanol showed high chemoselective S-methylation and N-monomethylation, respectively, in the presence of the zeolite instead of H2SO4. The mechanism for the reactions is proposed to involve acid-base bifunctional catalysis of the zeolite in which the acidic site reacts with diazomethane to form its conjugate acid, and the nucleophilicity of OH and SH groups is enhanced by the interaction of the basic site with the proton of the groups.
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  • 25
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical studies on the acid-catalysed dehydration of 15-substituted dihydrodiols were carried out using the AM1 method. In agreement with the experimental results, the rate-limiting step is dehydration of the protonated diols, R+, and the o-phenol-forming pathway (path 1) is favoured both kinetically and thermodynamically over m-phenol product formation. The transition state for path 1 (TS 1) is found to be at an early position (ca 23% progress) along the reaction coordinate and a better correlation of the rate constant is obtained with σ+. Three resonance forms can exist for the benzenonium intermediate but the contribution of one form is dominant in the later TS, which resembles the cationic intermediate. The contribution of the other two, however, weakens the σ+ effect of +M subsituents. The σP correlation of the rate constant in acid solution is therefore suggestive of a later TS resembling the cationic intermediate which is stabilized by solution.
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  • 26
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 133-138 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the gas-phase pyrolysis of ω-chlorocarboxylic acids were examined in a seasoned static reaction vessel and in the presence of at least twice the amount of the free radical inhibitor cyclohexene or toluene. In conformity with the available experimental data on rate determination, these reactions proved to be unimolecular and obeyed a first-order rate law. The presence of the primary chlorine leaving group in Cl(CH2)nCOOH (n = 1-4) showed a change in mechanism from intramolecular displacement of the Cl leaving group by the acidic hydrogen of the COOH to anchimeric assistance of the carbonyl COOH to the C—Cl bond polarization in the transition state. This mechanistic consideration is nearly the same for the series of 2-, 3-, and 4-chlorobutyric acids. The chlorine atom at the 2-position of acetic, propionic and butyric acids is dehydrochlorinated through a prevailing reaction path involving a polar five-membered cyclic transition state.
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  • 27
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 143-148 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: UV spectra of 17 para-Y-substituted styrenes, 8 para-Y-substituted α-methylstyrenes and 20 para-Y-substituted α,β,β-trifluorostyrenes were measured and correlated against spin-delocalization substituent constants (σ.) with confidence levels above 99·9%.
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  • 28
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 139-142 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic studies were carried out on the thermal epimerization by pyramidal inversion of optically active (S)-(-)Se- and (R)-(+)Se-4-[(-)-menthyloxycarbonyl]phenyl(2′,4′,6′-triisopropylphenyl)selenonium-N-toluene-4″-sulphonimides (1). The first-order rate constants for the pyramidal inversion of (S)-(-)Se-1 and (R)-(+)Se-1 were determined and the activation enthalpies and entropies were calculated. A fairly large difference was found in the activation parameters between optically active (S)-(-)Se-1 and (R)-(+)Se-1, i.e. a large negative activation entropy was obtained in the case of (R)-(+)Se-1.
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  • 29
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 149-158 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoelectron spectra of trans-bicyclo[4.1.0]hept-3-ene and two methyl derivatives, 1-3, and cis-bicyclo[4.1.0]hept-3-ene and three of its derivatives, 4-7, were measured. Ab initio molecular orbital (MO) and density functional theory (DFT) calculations were performed on these compounds. By combining the results of the experimental and computational trends, it was established that the highest occupied molecular orbitals (HOMOs) of 1-3 are the ‘twist’ bent σ bond at the fusion between the two rings whereas for 4-7 the HOMOs are the π orbital in the six-membered ring. The DFT ordering is the same as that suggested by the photoelectron spectra whereas at the MO level the HOMO always corresponds to the π orbital. The intensities of the photoelectron spectra were calculated at the DFT level and good qualitative agreement with experiment was found.
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  • 30
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 171-174 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semi-empirical AM1 theoretical calculations were carried out on the pentaphenylethyl and 9-trityfluorenyl free radicals, related radicals and their precursor hydrocarbons. Previous reports of the preparation of the former radical have been questioned, although the existence of the second is on secure ground. Based on simple energy considerations, it is concluded that pentaphenylethyl should be as readily prepared. However, the acidity of the precursor hydrocarbon is considerably less than that of 9-tritylfluorene, and possible radical decomposition via dissociation to triphenylmethyl and diphenylcarbene is calculated to be more facile than the corresponding decomposition of 9-tritylfluorenyl. A previous postulation of a rapid phenyl equilibration of the pentaphenylethyl radical is shown to be untenable.
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  • 31
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline host compounds consisting of a roof-shaped dicarboxinide framework and pendant diarylethanol analogous subunits were synthesized and shown to form inclusion complexes with small organic molecules such as alcohols, amines, ketones or polar and apolar organic solvents. Clathrate efficiency and selectivity depend on the particular host structure. The crystal and molecular structures of a free host compound (2a) and inclusion compounds [2a·3-methylcyclohexanone (1 : 1), 1a·3-methylcyclopentanone (1 : 1), 1a·2-methylcyclohexanone (1 : 1), 1b·butyronitrile (1 : 1), 1b·propan-1-ol (2 : 1) and 1b·(-)-fenchone (1 : 1)] were determined by x-ray diffraction analysis. In all the structures, the hydroxyl group is involved in intramolecular hydrogen bonds and the host and guest molecules are held by lattice forces only. The channels and cavities left in the host matrix are large enough to allow disorder or high thermal displacement parameters of the guest molecules. The local packing coefficients for all guests are 0·42 on average.
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  • 32
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The oxidation of 1-phenyl-2,2,2-trifluoroethanol (ROH) with potassium permanganate in 0.2 M aqueous sodium hydroxide solution at 25 °C provides 2,2,2-trifluoroacetophenone as the sole product. The reaction rate constant, which was measured under pseudo-first order conditions by following the decrease in substrate concentration as a function of time, was found to be substantially smaller than previously reported. The primary kinetic deuterium isotope effect was measured as k2H/k2D = 14·7 ± 1·0. A hydrogen-transfer mechanism involving significant tunnelling is proposed. The oxidation of 1-phenylethanol under similar reaction conditions yields acetophenone as the initial product. The kinetic deuterium isotope effect was found to be k2H/k2D = 5·2 ± 0·8.
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  • 33
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    Journal of Physical Organic Chemistry 8 (1995), S. 191-194 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of bis-silylated ynamines with different nitrosyl reagents affords products derived from an electrophilic attack at the β-carbon atom and not the expected alkynyldiazonium salts.
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  • 34
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 35
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    Journal of Physical Organic Chemistry 8 (1995), S. 195-195 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 36
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    Journal of Physical Organic Chemistry 8 (1995), S. 197-207 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of various imperfections such as slow initiation, termination, transfer and slow exchange on kinetics, molecular weights and polydispersities in chain growth polymerizations are simulated. The simukations demonstrate that well defined polymers polymers can be prepared in systems with chain-breaking reactions. Thus, under carefully selected conditions, non-living polyumerizations may provide controlled polymers. On the other hand, polymers with unpredictable molecular weights and broad and even polymodal molecular weight distributions can be formed in living systems without irreversible transfer and termination. In some living systems molecular weights may stay constant or even decrease with conversion. Therefore, a clear distrinction should be made between living and polymerizations.
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  • 37
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    Journal of Physical Organic Chemistry 8 (1995), S. 258-272 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isobutylene (IB)-p-methylstyrene (pMeSt) monomer pair readily produces by living copolymerization nearly random copolymers with up to M̄n ≈ 50,000 g mol-1 and M̄w/M̄n ≈ 1·4. The livingness of the copolymerization process and the compositional homogeneity of the copolymers have been demonstrated by the following four diagnostic plots: (A) M̄n (number-average molecular weight) and corresponding N (number of moles of copolymer formed) vs Wp (weight of copolymer formed) for the diagnosis of chaintransfer; (B) -ln (1 - C) (C = conversion of monomers) vs time for the diagnosis of termination; (C) copolymer composition vs molecular weight; and (D) cumulative copolymer composition vs conversion for the diagnosis of true homogeneous copolymers. The theory for the use of the -ln(1 - C) vs time plot for the quantitation of irreversible termination in copolymerization has been developed. The exact conditions (i.e. nature of reagents, reagent concentrations, temperature, etc.) which lead to desirable products in terms of conversion, molecular weight, molecular weight distribution (MWD) and copolymer composition, were developed systematically by analyzing the results of a large number of experiments. The following combination of chemicals was found to lead to living copolymerization, and uniform high molecular weight, narrow MWD copolymers: IB-pMeSt 97 : 3 mol/mol with 5-tert-butyl-1,3-dicumyl methyl ether (5-tBu-1,3-DiCumOMe) initiator, TiCl4 coinitiator, ethyl chloride (EtCl) solvent, triethylamine (TEA) electron pair donor (ED) and 2,6-di-tert-butylpyridine (DtBP) proton trap at -52, -65 and -85°C.
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  • 38
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    Journal of Physical Organic Chemistry 8 (1995), S. 273-281 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel method was developed for the quantitative description of copolymerization behavior, specifically for the derivation of reactivity ratios and micro- and macro-compositions of monomer pairs with significantly different reactivities. The novelty of the method lies in the manner of generating instantaneous feed and copolymer composition data from experimentally readily obtainable cumulative copolymer compositions, although the latter drifts with progressing copolymerization. It is demonstrated that such copolymer systems can be described by two reactivity ratios, albeit the values are valid only over the narrow feed composition range within which they were determined. The great advantage of this method is that whereas the differential copolymer composition equation is strictly valid only at 0% conversion, the method produces corresponding instantaneous feed and copolymer compositions at any conversion. Assumptions or approximations are unnecessary to calculate reactivity ratios. Subsequently the procedure was applied to obtain reliable monomer reactivity ratios of isobutylene (IB)-p-methylstyrene (pMeSt) copolymers, rIB and rpMest, prepared by living carbocationic copolymerizations with [IB]/[pMeSt] feeds compositions of 90:10 and 97:3 mol/mol, i.e., with feed compositions of industrial importance. According to our procedure, rIB = 0·74±0·11 and rpMeSt = 7·99±3·34. These reactivity ratios were then used to calculate overall IB-pMeSt copolymer compositions over the entire comonomer conversion range and to compare calculated with experimental compositions. The good quantitative agreement between calculated and experimental compositions indicates that the description of both macro- and micro-compositions of IB-pMeSt copolymers obtained in the 90:10 and to 97:3 mol/mol feed composition range is satisfactory.
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  • 39
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    Journal of Physical Organic Chemistry 8 (1995), S. 301-305 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The autopolymerization of styrene in the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), with and without organic acids, such as benzoic acid and camphorsulfonic acid, was studied. Broad polydispersities are obtained in the absence of acid, whereas narrower polydispersities are obtained in their presence. The significance of these results for the synthesis of narrow polydispersity polystyrene by the TEMPO-mediated living polymerization process is discussed.
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  • 40
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photostimulated reaction of N,N-dibutyl-p-toluenesulfonamide with diphenylphosphide ions in liquid ammonia leads to the corresponding phosphinic amides after oxidation Inhibition experiments with p-dinitrobenzene and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) and the fact that the reaction is retarded in the dark suggest that it proceeds by the SRN1 mechanism.
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  • 41
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    Journal of Physical Organic Chemistry 8 (1995), S. 377-384 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular complex formation of six macrocyclic and six acyclic polyethers with tropylium and 4-methoxyphenyltropylium tetrafluoroborates was observed and characterized in the gas phase by fast atom bombardment mass spectrometry (FABMS), to obtain information on intrinsic molecular interactions in the absence of the complicating effect of solvation. The stoichiometry of the complexes was assessed on the basis of corresponding peaks in FAB mass spectra. In addition to the expected 1 : 1 complexes between polyether and tropylium ion, some 2 : 1 complexes were also formed. The stability order of selected complexes was studied in competition experiments. The complexation equilibrium constant and thermodynamic parameters for the interaction of dibenzo-18-crown-6 with tropylium ion were determined in 1,2-dichloroethane solution by UV-visible spectrophotometry. Complexation of polyethers with tropylium salts has not been reported previously.
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  • 42
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    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 43
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    Journal of Physical Organic Chemistry 8 (1995), S. 395-399 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free energies of solvation were calculated for the four most stable gas-phase tautomeric forms of 2-thiocytosine (TC) using a local field SCF procedure with the solvation model SM2. The calculated changes in the free energies for each pair of tautomers reveal that all six possible equilibria tend to produce the thione-amino TC(1, 8, 8) and TC(3, 8, 8) species. This is in agreement with UV and ionization constant data.
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  • 44
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    Journal of Physical Organic Chemistry 8 (1995), S. 587-596 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reductive cyclization of several 2-nitroarylamides was studied by radiolytic reduction, examining the effects of substituents on the nitrophenyl ring and on the leaving aniline and variations in the nature of the link between the nitrophenyl ring and the leaving aniline. The stoichiometry of the reduction and the identification of N-hydroxylactam and aniline products suggest that the major initial products of such a reduction of the nitroamides are the corresponding hydroxylamines. Under anaerobic conditions, cyclization via the hydroxylamines was considerably faster (up to 160-fold) than via the corresponding amines under comparable conditions, but was similarly influenced by changes in geometry. Unlike cyclization via the amines, rates of cyclization via the hydroxylamines were sensitive to substitution on the leaving aniline, being accelerated by electron-withdrawing groups. The rate-determining step in the cyclization of the hydroxylamines is proposed to be breakdown of the tetrahedral intermediate.
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  • 45
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of mono-, bis- and tetra-acridine ligands were prepared and their effects on the higher order structure of DNA were studied by dynamic fluorescence microscopy. The single-crystal structure of the bis-acridine derivative N-[2-(dimethylamino) ethyl]-4-[2-(9-acridinylamino)benzamido]-2-(9-acridinylamino)benzamide trihydrochloride (4) was determined, and shows that the molecule is sufficiently flexible to fold into an intramolecular stacking interaction in the crystal, supporting earlier hydrodynamic evidence that this compound can bis-intercalate into DNA forming a single base pair (bp) sandwich complex. The corresponding tetra-acridine analogue 1,11-bis[4-[2-(9-acridinylamino)benzamido]-2-(9-acridinylamino)phenyl]-1,11-dioxo-6-methyl-2,6,10-triazaundecane pentahydrochloride (6) was synthesized, and dynamic fluorescence microscopy was used to study the effects of 4 and 6 on the higher order structure of large T4 DNA molecules (166 kbp), by measuring the average long-axis legth (persistence length, l) of the complexes. The mono-intercalating ligand acridine orange (5) increase l, whereas the bisintercalating diacridine 4 has no apparent effect and the putative multi-intercalating tetracridine derivative 6 decreases l by compacting the higher order DNA structure. These results demonstrate the usefulness of the technique for directly observing ligand-DNA complexes, and show that ligands with suitably positioned multiple binding sites can influence the higher order structure of DNA (and thus possibly gene expression).
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  • 46
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    Journal of Physical Organic Chemistry 8 (1995), S. 605-609 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interactions between compounds containing phosphoryl, carbonyl, or hydroxyl groups (or combinations of these groups) with metal ions (Na+, Mg2+) were probed in CD3CN solutions by 17O NMR spectroscopy. For all phosphoryl and carbonyl substrates a strong high - field shift of the P=O and C=O signals was observed on the addition of a salt; no shift was observed, however, for the OH group signal, indicating that no chelation takes place in the hydroxyphosphoryl (or hydroxycarbonyl) derivatives. For 2-hydroxy-3-benzoylpropylphosphonic diester the 17O NMR studies, together with conformational analysis based on the 1H spectroscopy, demonstrated the chelation of a metal ion by the P=O and C=O functions (fermation of an eight-membered cyclic structure) with the OH group involved in the intramolecular hydrogen bonding, but not in the complexation to the metal ion.
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  • 47
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    Journal of Physical Organic Chemistry 8 (1995), S. 610-616 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The aminolysis and hydrolysis of several sulphamate esters, RNHSO2ONp (R = PhCH2, Ph, 4-MeC6H44, 3-MeC6H4, 4-FC6H4, 4-ClC6H4, 3-ClC6H4, H; Np = 4-NO2C6H4) were been studied in 50% (v/v) aqueous acetonitrile at various temperatures. Reaction of the esters with an amine (R1NH2) gives -ONp and both sulphamide, (RNHSO2NHR1) and sulphamate (RNHSO2O-R1NH3+) products. First-order rates were determined by the appearance of -ONp and sometimes also by the disapperance of ester. The reaction was found to be independent of amine type and concentration and at the high pHs that obtain the substrate esters are fully ionized. A Hammett ρacyl of -;1·8 was obtained for the decomposition of the sulphamate anions and this is consistent with substantial N=S bonding in the transition state leading to N-sulphonylamine, RN=SO2. This intermediate then partitions very rapidly, reacting with R1NH2 and H2O respectively. ΔH
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  • 48
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    Journal of Physical Organic Chemistry 8 (1995), S. 175-185 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between acridine orange hydrochloride [3,6-bis(dimethylamino)acridine hydrochloride] and potassium bromate in dilute sulphuric acid was studied by monitoring the absorbance change at 492 nm. The reaction exhibited complex kinetic behaviour. In excess bromate the reaction had an induction period with slow depletion of acridine orange (AC) followed by a fast depletion step. The initial reaction step was found to be first order with respect to both AC and bromate and second order with respect to H+. The stoichiometric ratio of AC to bromate was 3 : 2. At the end of the induction period, the redox potential of the reaction mixture has shown a distinct rise, while the Br- concentration dropped sharply. The dual role of bromide ion both as an inhibitor and autocatalyst is discussed. A 16-step reaction mechanism is proposed and the simulated curves agreed well with the kinetic curves.
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  • 49
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct 1H, 13C and 19F NMR spectroscopic analysis was carried out on the carbocationic intermediate generated in the interaction of tin(IV) chloride (SnCl4) with the adduct [4, CH3CH(OiBu)OCOCF3] of isobutyl vinyl ether (IBVE) and trifluoroacetic acid (CF3CO2H), either in the presence or in the absence of tetrabutylammonium chloride. The reactions were to mimic the living cationic polymerization of IBVE by the 4-SnCl4 initiating system (with added nBu4NCl) that was also found in this study. In CD2Cl2 solvent at -78°C, the 1H and 13C NMR analysis revealed the formation of a carbocationic intermediate [CH3C+H(OiBu)] that is in a rapid exchange equilibrium with the covalent counterpart 4. For the first time, the cation formation was further supported by 19F NMR analysis on the counteranionic part (CF3COO-) in 4, where, with SnCl4, the CF3 group gave a broadened signal that appeared clearly downfield relative to that in the covalent form. These and other results, which are in close correlation with the corresponding polymerizations, demonstrated the following: (i) the SnCl4-assisted generation of carbocationic species from the covalent ester 4; (ii) a rapid exchange between the cation and its covalent precursor 4; (iii) the relatively high cationic concentration in the salt-free system, where no living polymerization occurs; and (iv) the effective suppression of the cationic species in the presence of the salt, which proved to be the prime key factor for living polymerization.
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  • 50
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    Journal of Physical Organic Chemistry 8 (1995), S. 293-300 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Kinetics of the polymerization of isopropyl vinyl ether, isobutyl vinyl ether (IBVE) and chloroethyl vinyl ether initiated by HI in CH2Cl2, in the presence and in the absence of tetrabutylammonium iodide as common anion salt, were investigated. The polymerizations proceed directly through the carbon-iodide termini without any necessary electrophilic activator. As previously observed with cyclohexyl vinyl ether, it was found that the addition of small amounts of salt, (0·5-10% with respect to initial [HI], depending on the monomer) drastically reduces the polymerization rate and leads to living-type polymerizations. Higher amounts of salt have no influence on the polymerization rate which remains constant over a broad range of [NBu4I]/[HI] ratios. This general behaviour, observed for the all vinyl ethers, suggests a common ion salt effect and therefore an ionic polymerization mechanism involving ion pairs and free ions. In the absence of salt, both ion pairs and free ions of higher reactivity participate in the propagation, whereas only ion pairs contribute to the propagation in the presence of a common ion salt. According to this scheme, the living character of the polymerization is assumed to result from a propagation reaction governed by undissociated ionic species. The validity and the implications of this reaction scheme, in terms of active centre concentrations, are also discussed.
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  • 51
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    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 52
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    Journal of Physical Organic Chemistry 8 (1995), S. 316-324 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various N-alkoxyphthalimides were prepared and tested as initiators for polymerization of a variety of monomers. Acrylates and methacrylates polymerized at 40-50°C. Vinyl acetate and styrene were moderately reactive at 60-65°C. Rates of reaction were sensitive to the choice of solvent. THF generally gave the highest conversions, with much reduced reactivities in solvents of higher polarity, such as acetonitrile, acetone, DMSO or DMF. In aliphatic hydrocarbon solvents or di-n-butyl ether no polymers were obtained. Bulk polymerizations proceeded well, depending on the monomer. Rates of polymerization were sensitive to the structure of the group attached to nitrogen. OR groups, where R contained α-electron-withdrawing esters, benzylic or allylic groups, were more reactive than when R was an aliphatic group. A-B block copolymers were readily prepared, starting with PMA, PBA or PMMA. However, because the rates of initiation were slow, relative to rates of propagation, N-alkoxyphthalimide initiators survived mostly intact. Consequently, final A-B block copolymers were invariably contaminated with indeterminate amounts of homopolymer from polymerization of the second monomer.
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  • 53
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical MO (PM3) studies are reported on the reactions of 18 substituted phenolate anions with m-(MNPF), p-(PNPF) and 3,4-dinitrophenyl formates (DNPF). The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate (T-) can occur in the gas phase, especially for MNPF, at approximately an equal proton affinity (PA) of the nucleophile and leaving group phenolates, i.e. ΔPA = 0 as the PA of the phenolate anion is decreased. In solution, however, owing to the low stability of T and a greater stabilization by solvation of the transition state for the breakdown step (TS2), all three formate esters are predicted to proceed by a concerted mechanism, which is in agreement with the experimental results. The low stability of T can be ascribed to the relatively high electron affinity of the phenolate anions.
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  • 54
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    Journal of Physical Organic Chemistry 8 (1995), S. 341-343 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oscillations of electrical potential differences across the liquid-liquid interface in phase-transfer catalyst systems are reported. The occurrence of the oscillations is consistent with the Starks' shuttling mechanism.
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  • 55
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    Journal of Physical Organic Chemistry 8 (1995), S. 335-340 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal isomerizations of 1′,3′,3′-trimethyl-spiro[2H-1-benzopyran-2,2′-indoline]-6-sulphonic acid (6-SO3--SP) between its spiro (SP) and merocyanine (MC) forms were followed spectrophotometrically in the presence of cyclodextrins (β- and γ-CDs) at various pressures. From the pressure dependence of the isomerization rate, the activation volumes for the thermal isomerization of 6-SO3--SP were estimated to be 17·1 cm3 mol-1 for MC → SP and 8·5 cm3 mol-1 for SP → MC. The equilibrium constants (K) for the inclusion complex formation of CDs with 6-SO3--SP were determined at various pressures. It was found that the stability of the 1:1 inclusion complex between 6-SO3--SP and CDs decreases in the order β- 〉 γ- 〉 α-CD. From the pressure dependence of K, the reaction volumes were estimated to be -0·9 cm3 mol-1 for the 6-SO3--SP-β-CD system and 4·0 cm3 mol-1 for the 6-SO3--SP-γ-CD system. Based on the activation volumes, the structure of the transition state for the thermal isomerization is discussed and an explanation for the effect of CDs on the reaction rate is given. The difference in the reaction volumes for the inclusion complex formation of β- and γ-CDs is explained in terms of the difference in the number of water molecules excluded from the CD cavity.
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  • 56
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    Journal of Physical Organic Chemistry 8 (1995), S. 344-350 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction in acetonitrile solution of (Z)-O-methylbenzohydroximol chlorides [ArC (Cl)=NOCH3] with morpholine, pyrrolidine and azetidine gives the corresponding (Z)-amidoximes [ArC(NR1R2)=NOCH3] in acetonitrile. The rates of these reactions were measured under pseudo-first-order conditions (excess amine). The reactions were found to follow overall second-order kinetics (first order in amine). The Hammett ρ-value (with σ) for the reaction with pyrrolidine is +0·92. The reaction of the p-nitro compound with pyrrolidine gives a significant element effect [k(p-nitrobenzohydroximoyl bromide)/k(p)-nitrobenzohydroximoyl chloride = 10]. A Brφonsted β-value of 0·38 was estimated from the reactions of morpholine and piperidine with the p-nitrohydroximoyl chloride. The slower reaction of (E)-O-methyl-p-nitrobenzohydroximoyl chloride with azetidine gives primarily the (E)-amidoxime (E:Z ≈ 98:2) This reaction also follows second-order kinetics. The kinetic observations made in this study are compared with the corresponding results obtained in earlier work in benzene solution. It is suggested that in acetonitrile solution the reactions proceed by an addition-elimination mechanism with rate-determining loss of chloride ion (AN + DN#). It is further suggested that acetonitrile is assisting in the breakdown of the tetrahedral intermediates formed in these reactions.
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  • 57
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    Journal of Physical Organic Chemistry 8 (1995), S. 371-376 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: EPR techniques, including spectral double integration, were utilized to measure the equilibrium contants in dimethoxyethane at 195 K for electron transfer between perdeuteriated p-xylene and xylene, α-d3-p-xylene and α,α′-d6-p-xylene. The results, coupled with the law of Hess, yield all the relative solution electron affinities (EA). It was found that methyl deuteriation lowers the solution EA by 160 J l mol-1 per deuterium, whereas ring deuteriation in these systems lowers the solution EA by about 370 J l mol-1 per deuterium, which is about the same effect as is observed in the benzene system. The results are discussed in terms of hyperconjugative, inductive and solvation effects.
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  • 58
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    Journal of Physical Organic Chemistry 8 (1995), S. 385-385 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 59
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of proton/deuteron transfer reactions of 2,4,6-trinitrotoluene (TNT), 2,2′4,4′6,6′-hexanitrobibenzyl (HNBB) and 2,4,6-trinitrobenzyl chlorides (TNB) with tertiary amines was followed spectrophotometrically. The rate constants obtained under various conditions were interpreted in terms of isotope, solvent and steric effects. The Arrhenius plots curved upward at low temperatures for TNT and TNB, indicating clearly the intervention of tunnelling. The tunnelling parameteres were calculated semi-empirically on the basis of Bell's theory. The observed rate constants at low temperatures agreed well with the predicted values. In the present systems, some side and consecutive reactions involving the formation of 2,2′,4,4′6,6′-hexanitrostilbene took place, and in some cases interrupted the rate measurements in the proton/deuteron transfer steps.
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  • 60
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    Journal of Physical Organic Chemistry 8 (1995), S. 421-428 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measured molecular dipole moments and theoretical percentages of mesomeric zwitterionic forms were used to calculate the attractive electrostatic potentials at short, V(s), medium, V(m), and long, V(I), distances. Values of an attraction power function Φ (H) = A + BV (s) V(m) V(I) was then deduced for 18 nitriles and cyanamide vinylogues or iminologues along the C≡N direction. The satisfactory agreement observed between Φ (H) and the hydrogen bond basicity scale pKHB indicates that the method can be a useful tool for the prediction of hydrogen bonding, needing only simple calculations and allowing easy interpretation.
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  • 61
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    Journal of Physical Organic Chemistry 8 (1995), S. 429-434 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oxidation of several monosubstituted (phenylthio)acetic acids (PTAA) by pyridinium hydrobromide perbromide (PHPB) was studied in aqueous acetic acid. The reaction is first order with respect to PHPB. Michaelis-Menten type kinetics are observed with respect to (arylthio)acetic acid. The effect of solvent composition indicates that the transition state is more polar than the reactants. The formation constants of the intermediate substrate-PHPB complexes and the rates of their decomposition were determined at different temperatures. The rates of oxidation of para and meta-substituted (phenylthio)acetic acids were correlated with Hammett's substituent constants. The ρ value is -1·60 at 35°C. The rates of oxidation of ortho substituted compounds are correlated with Charton's triparametric equation. A mechanism involving the decomposition of the intermediate complex in the slow rate-determining step affording a sulphonium ion which hydrolyses in a subsequent fast step to the sulphoxide is proposed.
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  • 62
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    Journal of Physical Organic Chemistry 8 (1995), S. 407-420 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An ab initio molecular orbital study of the potential energy surface of the C6H5O + O reaction was performed at the (PUMP3/6-31G*//UHF/6-31G*) level of theory. Various reaction channels were considered. The most favorable mechanism, la and Ib, start from the attachment of the oxygen atom to the carbon atom of the C6 ring in the ortho- or para position with respect to CO, taking place without activation energy. Then, either hydrogen elimination by mechanism Ia or 1,2-H shift from the C(H)(O) group takes place; the latter process leads to the formation of the very stable C6H4(O)(OH) radical, which can also eliminate H by mechanism Ib. Thus, the main products of the C6H5O (2B1) + O(3P) reaction are o/p-benzoquinones and the hydrogen atom. At low temperatures, however, the system may be trapped in the potential well of the C6H4(O)(OH) intermediate. At high temperatures, the reaction may proceed by the formation and decomposition of o/p-benzoquinones. Because of their higher activation energies, the reaction mechanisms giving rise to other products-the attachment of the oxygen atom to the bridging position to form an epoxy intermediate, followed by insertion of O into the CC bond and dissociation to give C5H5 and CO2 (channel IIc), in addition to the attachment of oxygen to the terminal O atom of C6H5O followed by elimination of O2 (channel III) - cannot compete with channel Ia or Ib. RRKM calculation was carried out for the total and individual rate constants for channels Ia and Ib. The three-parameter expression for the total rate constant, fitted by the least-squares method for the temperature range of 300-3000 K, is given as ktot = 5·52×10-17 T1·38 e+148/T cm3 mol-1 s-1.
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  • 63
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    Journal of Physical Organic Chemistry 8 (1995), S. 463-467 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H and 13C NMR data for 2-diethylaminomethyl-3,4,6-tri- and -tetrachlorophenols in CH2Cl2 solutions at a variety of temperatures are reported. The results are consistent with intramolecular hydrogen bonding and proton transfer as shown in the structure 3. Concentration dependence of the NMR data for the perchloro compound shows an additional hydrogen bonding process attributed to the solute self-association. The 1H, 13C and 15N NMR data support the proposed proton transfer structure.
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  • 64
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    Journal of Physical Organic Chemistry 8 (1995), S. 484-489 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fluorescence of some aliphatic diamines was studied in the gas phase and in some solvents at several temperatures. It was found that N,N,N′,N′-tetramethylpropane-1,3-diamine (TMPD) and N,N,N′,N′-tetramethylbutane-1,4-diamine (TMBD) have two emission bands in the gas phase. TMBD also shows two bands in solution. These bands were assigned previously to an excited monomer and an intramolecular excimer. From the temperature dependence of the intensity ratio of the two bands, the enthalpy changes for the excimer formation were evaluated. The stability of the cyclic excimer is discussed in terms of the ring size effect and the solvent effect on the band positions.
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  • 65
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    Journal of Physical Organic Chemistry 8 (1995), S. 490-495 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pKBH+ values of the conjugate acids of N-phenylhydroxylamines change drastically when the pKBH+ values are determined in dimethyl sulfoxide (DMSO) rather than methanol. The Hammett ρ values change from -5·69 to -1·20 on going from methanol to DMSO for protonated N-phenylhydroxylamines, in contrast to a shift of -4·70 to -4·83 for protonated N-methylanilines in the same two solvents. This large change in susceptibility indicates that the species from which the proton departs is not the same for protonated N-phenylhydroxylamines in the two solvents. Experimental and computational evidence supports ionization of the H+ from the O atom for the protonated N-phenylhydroxylamines in DMSO.
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  • 66
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    Journal of Physical Organic Chemistry 8 (1995), S. 496-505 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular reactivity parameters based on the concept of an effective electronic potential and defined as a simple function of the molecular charge distribution were applied in a study of various aspects of the chemical reactivity of azabenzenes and azanaphthalenes. Excellent linear correlations were obtained for proton affinities, pKa values, H-D exchange rate exponents and 13C shifts induced by the paramagnetic shift reagent TEMPO. In the last case, the predictions for quinazoline prompted a reinvestigation of the 13C NMR spectrum of this compound, resulting in a reassignment of the spectrum relative to the assignment assumed by Grant and co-workers.
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  • 67
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    Journal of Physical Organic Chemistry 8 (1995), S. 545-551 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-solid chemical reaction of benzopinacol (1) with p-toluenesulphonic acid monohydrate (2) to give a quantitatively proton-catalysed pinacol rearrangement with formation of triphenylacetophenone (3) in the absence of a solvent was studied preparatively and mechanistically using atomic force microscopy (AFM) measurements and known crystal structure data. The reaction rate is dramatically enhanced if the water of reaction is continuously removed. AFM reveals that no reaction occurs on (001) of 1 whereas (100) exhibits distance dependent craters and volcano-like mounds over areas extending to 1·5 mm from the contact edge of the crystals with 1 undergoing phase rebuilding while reacting. A mechanism resembling the formation of membrane potentials is seen for the first time in crystals. Thus it appears that catalytic protons migrate without their counterions from one molecular compartment to the next by proton consumption at its inside and proton liberation at its outside, which is the inside of the next compartment. The uppermost molecular layer determines reactivity or non-reactivity. On (001) of 1 the hydroxyl groups occur with their hydrogens up. Hence no AFM features are found and crystals of 2 do not become adhered to 1. However, on (100) the hydroxyl hydrogens point down (free electron pair up). Protonation is possible, chemical reaction is indicated by the formation of the AFM features and crystals of 2 adhere firmly to the surface of 1 after reaction.
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  • 68
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium constant, Kan(H2CO), for the formation of α-aminoacetonitrile from formaldehyde, ammonia and hydrogen cyanide was evaluated at 25°C. A first estimation of Kan(H2CO) was obtained from extrathermodynamic relationships of the type log K′ vs ∑σ*. The final value was then obtained from a comparison of the experimental and calculated pH dependences of α-hydroxy- and α-aminoacetonitrile concentrations. From these results, it appears that, after equilibrium, the ratio between the concentrations of the two precursors glycine and hydroxyethanoic acid, is a linear function of the concentration of free ammonia, i.e. [CH2(OH)CN] [CH2(NH2)CN] = 21 [NH3] at 25°C.
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  • 69
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    Journal of Physical Organic Chemistry 8 (1995), S. 753-760 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The utility of thiophene as a diene for Diels-Alder reactions was studied by ab initio methods. The reactivity was evaluated with three dienophiles, vinyl alcohol, ethylene and acrylonitrile. Qualitatively the reactivity was determined by comparison of the reactant's frontier orbital energies, bond orders and charge transfer in the transition states. Quantitatively the reactivity was determined by estimation of activation energy with RHF/6-31G*, MP2/6-31G*, MP3/6-31G*//MP2/6-31G*, and MP4/6-31G//MP2/6-31G* ab initio calculations. The results of the calculations predicts that the reactivity of thiophene with acrylonitrile is similar to butadiene and ethylene with a preferred formation of the endo isomer.
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  • 70
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    Journal of Physical Organic Chemistry 8 (1995) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 71
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    Journal of Physical Organic Chemistry 8 (1995), S. 761-773 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chiral polymethine dyes constitute a particular class of conjugated π systems. Artificial chiral polymethine dyes were first synthesized by König and Langbein in 1928 in order to clarify the electronic structure of cyanine dyes; some natural dyes such as musca-aurin I (from the toadstool fly agaric) and betanin (from the vegetable red beets) are known to be chiral pentamethinium cyanine dyes, the chirality of which stems from L-α-amino acids as end-groups. The reasons why chiral polymethine dyes are not only of historical interest but once again the subject of research are explained.
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  • 72
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Peroxidation of linoleic acid was initiated by azobis(isobutyronitrile) in tert-butyl alcohol and inhibited by α-tocopherol, β-carotene and retinal, either alone or in combination. Significant antioxidant synergism and a novel mutual protection of α-tocopherol and β-carotene were found and the possible involvement of retinal in the process is discussed.
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  • 73
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    Polymer Engineering and Science 35 (1995), S. 18-27 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Solid-catalyzed copolymerization reactions of ethylene and α-olefins can produce complex mixtures generally regarded as “polyethylenes” (including linear low-density polyethylene). The selective nature of those catalysts can lead to block-like character in segments of polymer molecules, and these segments are sufficiently dissimilar (from a thermodynamic viewpoint) to allow for the possibility of microphase separation in the melt. Such a molecular-level phase separation would substantially alter the melt rheology, the crystallization process, and hence the mechanical and optical properties of the resulting product. It would, in principle, be identical to those occurring in conventional well-defined block copolymers, allowing the thermodynamic models developed for those systems to be extended to block-like polyolefins.
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  • 74
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    Polymer Engineering and Science 35 (1995), S. 52-63 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Relationships between the rheological, morphological, and tensile properties of an immiscible blend of 25 wt% of a thermotropic liquid crystalline polymer (LCP) with polycarbonate are presented. The shear viscosity of the blend is intermediate between the two constituent materials, and indicates immiscibility in the melt. Extrudate swell behavior is examined and found to be closely related to that of polycarbonate. The morphology of the dispersed LCP phase varies between droplets and oriented fibrils, and is highly correlated with changes in tensile properties. Fibrils are associated with increased tensile modulus, and their development is favored in the elongation flow fields present in the spinline and in the die convergence section. In all cases, blend stiffness is less than that predicted for a continuous fiber-reinforced composite. Enhanced tensile modulus is associated with both extrusion from shorter length dies and increases in spinline draw ratio, with the latter proving the most important in fibril formation.
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  • 75
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    Polymer Engineering and Science 35 (1995), S. 79-91 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: During the last few years, improvements in control strategies became a necessity, with controls being targeted on material properties. The ever-increasing demand for polymer blends spells the need for in-line instrumentation capable of monitoring blend properties such as morphology. Since ultrasonics have proved to be sensitive to properties of multiphase materials, their performance for discriminating blend morphology was explored here. In-line and off-line (static, with no flow) ultrasonic measurements were made on different blends of polystyrene (PS), polyethylene (PE), and polypropylene (PP) for various viscosity ratios, and over the entire range of composition. Blends were compounded on a ZSK-30 Werner & Pfleiderer intermeshing co-rotating twin-screw extruder. In-line ultrasonic measurements were performed on both single-screw and twin-screw extruders. Ultrasonic properties (velocity and attenuation) were found to vary approximately linearly with composition. Mixing rules were evaluated for the description of ultrasonic behavior. For the attenuation measurements, the positive deviations from these rules were found significant. The additional attenuation was attributed to scattering generated by the presence of the minor phase inclusions.
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  • 76
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    Polymer Engineering and Science 35 (1995), S. 92-99 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The phase behavior of polymer blends under simple shear flow has been studied using a custom-designed rheo-optical system consisting of a two-dimensional small-angle light scattering (SALS) device incorporated into a conventional rheometer. Two-dimensional SALS images were gathered for model polymer blend systems with different quiescent phase behavior: polystyrene/polyisobutylene (PS/PIB) that exhibits upper critical solution temperature phase behavior and polystyrene/poly(vinyl methyl ether) (PS/PVME) that shows lower critical solution temperature phase behavior. For the PS/PIB blend, shear-induced phase mixing occurred at a critical shear rate. Below that critical shear rate, the dispersed phase was highly elongated parallel to the flow direction. For PS/PVME blends, a streak scattering pattern was observed even though the sample became optically clear after shearing. We observed, apparently for the first time, the development of a bright-streak pattern from a transient dark-streak pattern for a polymer blend system under shear. Rheo-microscopy studies revealed an intriguing wave pattern that developed coincident with the observation of a streak pattern by SALS. The relationship between the two phenomena has not yet been established.
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  • 77
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dispersions of both reactive and nonreactive polymer-polymer blend systems achieved in three different mixers are compared. The dispersions are prepared using an industrial scale twin-screw extruder, a laboratory internal mixer, and a miniature cup and rotor mixer. The morphology development in the three mixers is remarkably similar: The dispersed phase is stretched into sheets and ribbons; these sheets and ribbons then break into cylinders, which subsequently break into droplets via Rayleigh-type instabilities. Drop size distributions can be accurately predicted if we know the size of cylinders formed in the high shear fields of the mixer. There is a significant effect of quenching time on blend morphology - i.e, to properly evaluate mixing, blends must be quenched extremely quickly (well within a minute). Otherwise, we need to consider the morphology development during the quenching time, which may not be relevant to the mixing. There is a uniform shear stress in the miniature mixer, unlike the other mixers, which have varying stress levels. It is shown that a high stress level followed by a lower stress level is required in polymer blending to achieve efficient mixing. In the high stress level, the dispersed phase is stretched into extended shapes, which undergo instabilities and break up upon entering the low stress level. In the miniature mixer, the dispersed phase sees only one stress level, and thus very extended shapes persist at the end of mixing. The final dispersions in the twinscrew extruder and internal mixer at matched maximum shear rates are almost identical. For similar shear rates in the miniature mixer, the final dispersion of reactive blends is comparable to the other mixers. However, the miniature mixer does a poor job in dispersing high viscosity uncompatibilized blends, and the mixing conditions must be altered to obtain efficient mixing.
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  • 78
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    Polymer Engineering and Science 35 (1995), S. 129-136 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Instrumented impact testing and analysis were performed on an interlaminartoughened carbon fiber epoxy composite (Toray 3900-2/T800H) and a conventional (untoughened) epoxy composite (Fiberite 934/T300). Severity of impact was varied by using a wide range of impact energy. The effect of difference in the tup of the impact instrument was discussed. The residual compressive strengths after compact (CAI's) were measured by using a universal mechanical tester. The impact damage and delamination resistance of the toughened and conventional composites were quantitatively compared. At the same impact energy, the extent of damage was much less severe and the CAI was higher for the toughened composite. Relationships between the CAI's, the state of impact damage, and impact energy were investigated. Impact damage mechanisms for these two composites were not exactly the same. The impact damage of the conventional composite exhibited much greater extents of delamination. By contrast, interlaminar delamination in the toughened composite was found to be significantly suppressed, and the impact damage was more dominated by controlled matrix cracking/fiber damage, instead of catastrophic delamination. As a result, the CAI's of the toughened composite exhibited a monotonous decrease with increase in the impact energy and in the linear dimension of extents of damage.
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  • 79
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    Polymer Engineering and Science 35 (1995), S. 151-156 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thermal diffusivity of high density polyethylene (HDPE) was studied over a wide range of temperatures (25 to 200°C) by melting powdered HDPE in a cylindrical mold at several pressures (101.3 to 5065 KPa gage) and recording the temperature profiles at several radial positions. The energy equation was solved numerically for cylindrical geometry. The thermal diffusivity of HDPE was fit as a function of temperature, porosity, and pressure.
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  • 80
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    Polymer Engineering and Science 35 (1995), S. 170-172 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This communication is a theoretical re-examination of the model proposed by Choe and Lee for the nonisothermal crystallization kinetics of semicrystalline polymers.
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  • 81
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    Polymer Engineering and Science 35 (1995), S. 180-183 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Halogenophenol novolac (HPN)-based negative resists exhibit excellent sensitivity and pattern resolution properties. The HPNs act as synergists for crosslinking with other irradiation labile compounds such as naphthoquinone diazide and bisazide vs. hydrogen halide (HX) elimination reaction, resulting in additional crosslinking, probably by aryl radical recombination and/or addition. We describe a new resist formulation based on HPN binder and melamine crosslinker (Cymel 303). In this case the irradiation induced HX elimination additionally catalyzes the melamine crosslinking.
    Additional Material: 2 Ill.
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  • 82
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The orientational drawing of films from different thermoplastics has been studied. The value of the activation energy of drawing in the regions of forced elasticity (necking), high elasticity, and viscous flow (ΔE1, ΔE2, ΔE3) has been found to vary directly with the activation energy for viscous flow of the melt (ΔEη). Here ΔE1 〈 ΔE2 〈 ΔE3 = ΔEη. Thus Δ Eη characterizes the potential of thermoplastics for orientational drawing under different deformation conditions, since it reflects simultaneously both the intermolecular interaction level and chain flexibility. For maximum chain orientation, the calculated values for the change in the entropy are close to that of the entropy change during crystallization (melting) of the same polymer. The deformation of polymer may be described as a deformation of an entanglement network from the standpoint of classic elasticity theory. Some parameters for an entanglement network were calculated from the results of the drawing experiments. The density of the entanglement network (DEN) depend on the polymer composition: For flexible-chain polymers the DEN is less, for rigid-chain polymers (with coiled chains) it is higher. The DEN affects the maximum (prebreak) drawing ratio: The greater the DEN, the smaller the ratio to which a film can be drawn. At high orientation, the tensile strength of different polymer films tend to be similar, if drawing is not accompanied by crazing.
    Additional Material: 8 Ill.
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  • 83
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 190-194 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The block copolyetheresters with hard segments of poly(butylene terephthalate) and soft segments of poly(tetramethylene ether) were prepared by a terephthalic acid (TPA) process in the presence of some salts. The preparations of a block copolyetherester under various conditions were first studied in a 1 L stainless steel reactor to find the best method. Then, the preparations of four block copolyetheresters were run in a pilot plant comprising a 200 L polyesterification reactor and a 200 L polymerization reactor under the suitable condition. The presence of some salts reduced the formation of tetrahydrofuran (THF), and also reduced the total reaction time in the pilot plant. The thermal properties and various mechanical properties of the block copolytheresters prepared by the pilot plant were investigated to evaluate the feasibility of this method.
    Additional Material: 4 Ill.
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  • 84
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 144-150 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The objective of the current paper was to extend the relationships between complex polymer structures and microwave absorptivity that were formulated in the first three papers of this series (1-3). The microwave processing of composite and polymeric blends via a cylindrical resonance wave cavity and a rectangular standing wave applicator is described. These polymeric materials were irradiated in a low power (〈 100W) electric field at 2.45 GHz. Graphite-epoxy laminates were processed in both standing and traveling wave applicators. Rapid heating and curing were achieved in both cases. An observation of significance was that, with proper tuning of the traveling wave device (the precursor of a protable repair tool), it proved to be highly effective in processing. Additionally, a compatible blend of poly(methyl methacrylate) and poly(vinylidene fluoride) was heated in and applicator and the rates of temperature rise were demonstrated to depend upon morphology.
    Additional Material: 8 Ill.
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  • 85
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Mechanical properties of polymers can be described by their stress/strain curves and by their behavior under dynamic mechanical thermal analysis (DMTA). The purpose of this paper is to report such mechanical properties for two unsaturated polycarbosilanes: poly(1, 1-dimethyl-1-sila-cis-pent-3-ene) (I) and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) (II). Tensile strength, elongation at break, modulus, bending modulus, Tg, and tan δ for I, II and for sulfur crosslinked I and II have been measured. The influence of polymer molecular weight, quantity of crosslinking agent, cure time, presence of carbon black filler, the effect of crosshead speed, and frequency on these properties was investigated.
    Additional Material: 11 Ill.
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  • 86
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 165-169 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of physical aging on the failure behavior of a typical brittle polymer, polystyrene, have been studied. Properties examined were creep rupture lifetimes, fatigue lifetimes, and environmental stress cracking in ethanol. Fractured samples were examined both optically and by scanning electron microscopy to determine the degree of crazing. It was found that a longer physical aging time produced shorter lifetimes in all cases. The main reason for this is the reduction in craze strength caused by a reduced toughness due to physical aging. A long aging time was found to delay craze formation, but once formed, these crazes were much less stable than those formed with a short aging time. The effects of aging are important on failure prediction criteria and on testing methodologies, and the implications are discussed.
    Additional Material: 6 Ill.
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  • 87
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 184-189 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dielectric and rheological measurements are reported for the cure in a series of mixtures of an epoxy-acrylate with n-butyl methacrylate. The level of the initiator and properties of the epoxy acrylate and n-butyl methacrylate influence the cure characteristics and morphology of the film formed. Analysis of the rheological data indicates that during the curing process, microphase separation occurs within the mixture. The changes in the dielectric relaxation behavior with composition of the completely cured material is also consistent with microphase separation occurring in these resins while they are cured.
    Additional Material: 7 Ill.
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  • 88
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 195-201 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Using low conversion bulk copolymerization experimental data and the apparent rate constant model, the monomer chain cross-transfer rate constants and the cross-termination coefficient were evaluated. It was found that the dependence of the cross-termination coefficient on composition is a function of initiator efficiency and that monomer chain cross-transfer rate constant are relevant for the theoretical estimation of the molecular weights and molecular weight distributions.
    Additional Material: 5 Ill.
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  • 89
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 202-210 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The melt viscosity of thermoplastic starch has been investigated as a function of temperature, moisture content, and processing conditions. The effects of various low molecular weight additives have also been studied. Starch melts exhibit power law behavior over the range of shear rates studied. Melt viscosity decreased with increasing temperature and moisture content (MC). The power law index m increased with increasing temperature. The consistency K decreased with increasing temperature and increasing moisture content. Moisture content during the pelletizing step influenced melt viscosities measured after equilibration to different MCs. All additives studied except glycerol monostearate (GMS) significantly lowered the melt viscosity of starch, some more effectively than water relative to starch with 15% MC. Starch with GMS had viscosities essentially the same as, or slightly higher than, starch/water. This behavior may be due to the presence of unmelted helical inclusion complexes of starch and GMS. Starch formulations at 160°C exhibited melt visocosities similar to an LDPE of melt index 1.8.
    Additional Material: 16 Ill.
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  • 90
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 289-290 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 91
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 291-303 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The phenomenology of yield in bisphenol-A polycarbonate is explored through tensile tests on thin rectangular specimens and through pressure-induced bulging of thin, clamped circular disks. In a tensile test, while the nominal critical stress at which yield initiates and the nominal draw stress at which a stable neck propagates along a specimen depend on the temperature and the strain rate, the ratio of the draw stress to the critical stress is shown to be approximately 0.75 over a temperature range of 22 to 65°C and strain-rates in the range of 10-4 to 100 s-1. Specimens subjected to constant tensile loads between the draw and critical stresses are shown first to creep till stretches on the order of 1.06 are attained and then are shown to undergo stable necking. Tensile tests on thin, wide rectangular specimens show that yielding initiates through shear bands that broaden and intersect to generate necks, which subsequently propagate along the specimen. In pressure-induced bulging of clamped disks, biaxial stretching progresses monotonically under increasing pressures; strain localization does occur near the outer edges of the specimens, however. Heating of a specimen with a substantial stably necked region shows that the temperature-induced recovery of the specimen from its deformed state begins well below the transition temperature Tg of the material, although most of the recovery occurs at Tg.
    Additional Material: 19 Ill.
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  • 92
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 317-330 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of poly(etherether ketone) (PEEK) were subjected to large plastic deformations under uniaxial tension and simple shear by means of a new video-controlled testing method at constant true strain rate. The “equivalent” stress-strain curves obtained under the two loading modes are close at the yield point, but diverge drastically at large strains, with a rapidly increasing hardening in tension and a moderate hardening under simple shear. X-ray diffraction goniometry shows that these contrasting behaviors are associated with the different textures developed in the crystallite orientations. Under tension, the PEEK lamellae are progressively tilted in such a way that the chain axis becomes oriented parallel to the tensile axis; in the other mode, the final chain orientation is near to the shear axis. DSC analyses of deformed samples in both modes are carried out. The results show that the tension loading induces a fragmentation of the thin lamellae, while the shear mode generates less fragmentation. A quantitative model is presented that involves a composite approach: (i) the viscoplastic deformation of the crystalline lamellae, which is controlled by chain slip and transverse slip systems on planes parallel to the c axis, and (ii) the hyperelastic deformation of the amorphous phase, which depends on the affine unfolding of statistically distributed subchains. A discussion of the influence of the CRSS values on the stress-strain curves and textures is developed by means of this model.
    Additional Material: 19 Ill.
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  • 93
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 345-350 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A constitutive equation for nonlinear viscoelasticity is used to model the mechanical response of solid polymers such as polycarbonate. The nonlinearity arises from a reduced time which causes stress relaxation to accelerate with increasing strain. The constitutive equation can account for the occurrence of yield in a homogeneous uniaxial constant strain rate test. The constitutive equation is used in a study of the pure bending of beams. It is assumed that the classical assumption of beam theory is valid, i.e., plane sections remains plane. At each fixed time, the strains vary linearly through the depth of the beam. At a fixed material element the strain varies in time with the curvature. This spatial variation of the strains combined with the nonlinear dependence of the reduced time on strain leads to a significantly different response from that given by traditional beam theory. The implications of this for the bending moment history, stress distributions, and other factors that relate to beam design are discussed.
    Additional Material: 8 Ill.
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  • 94
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 95
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 385-386 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 96
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 403-410 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Aging experiments using the NIST (National Institute of Standards and Technology) torsional dilatometer have been performed in which the temperature of an isothermally equilibrated epoxy glass was abruptly changed to a new temperature T0 and the evolution of the volume and torsional relaxation responses recorded. The results of down-jump and up-jump experiments were found to differ dramatically. Not only is the normal asymmetry of volume approach to equilibrium found, but the mechanical responses are found to evolve differently from the volume response, contrary to simple free volume models of the physical aging process. It is found that the torsional modulus changes with increasing time after the T-jump. In the case of the down-jump the evolution of the modulus ceases prior to that of the volume of the sample. In the up-jump experiment, the contrary is true, viz., the modulus continues to evolve after the volume has attained its equilibrium value. The implications of this for the description of material behavior are discussed.
    Additional Material: 11 Ill.
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  • 97
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 395-402 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The statistical theory of the birefringence of an individual non-Gaussian elastomer chain is used together with a chain network description of rubber elasticity to develop a relationship among the strain, birefringence, and stress in elastomers, valid for large deformations under generalized strain states. The result is a fully three-dimensional internal variable based constitutive model of rubber elasticity in which measurement of the elastomeric birefringence during straining in one deformation state characterizes the optically anisotropic response of the elastomer. Simultaneous measurement of the stress vs. strain response provides the rubbery modulus and limiting network extensibility properties needed to completely characterize the mechanical anisotropy of the material. Once characterized using the single, large deformation experiment, the birefringence and stress responses of the elastomer in other deformation states may then be predicted without adjusting any model parameters. The theory is compared to experimental studies from the literature of large strain deformations of elastomers in uniaxial tension and compression for which the exhibited birefringence and stress responses of deforming elastomers have been simultaneously recorded.
    Additional Material: 6 Ill.
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  • 98
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 387-394 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rigid, closed-cell, polyurethane foam consists of interconnected polyurethane plates that form cells. When this foam is compressed, it exhibits an initial elastic regime, which is followed by a plateau regime in which the load required to compress the foam remains nearly constant. In the plateau regime, cell walls are damaged and large permanent volume changes are generated. As additional load is applied, cell walls are compressed against neighboring cell walls, and the stiffness of the foam increases and approaches a value equal to that of solid poyurethane. When the foam is loaded in tension, the cell walls are damaged and the foam fractures. A constitutive theory for rigid polyurethane foam has been developed. This theory is based on a decomposition of the foam in two parts: a skeleton and a nonlinear elastic continuum in parallel. The skeleton accounts for the foam behavior in the elastic and plateau regimes and is described using a coupled plasticity with continuum damage theory. The nonlinear elastic continuum accounts for the lock-up of the foam due to internal gas pressure and cell wall interactions. This new constitutive theory has been implemented in both static and dynamic finite element codes. Numerical simulations performed using the new constitutive theory are presented.
    Additional Material: 12 Ill.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 426-431 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The nonlinear fracture behavior of polycarbonate is investigated. The feasibility of measurement of the J integral through the optical method of reflected caustics is demonstrated. Significant increase in the crack growth resistance during small amounts of crack extension is observed.
    Additional Material: 8 Ill.
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  • 100
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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