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  • Analytical Chemistry and Spectroscopy  (99)
  • Physics  (74)
  • 1980-1984  (173)
  • 1980  (173)
  • 1
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatographic mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined.
    Additional Material: 8 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 9 (1980), S. 230-238 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The IR spectra (1400 cm-1 to 160 cm-1) of the gases at ambient temperature and the Raman spectra (below 1400 cm-1) of the liquids near -196°C are reported for CF3OF and CF3OCl. All fundamentals are assigned under Cs symmetry and the results of a normal coordinate analysis are presented. The assignments of Smardzewski and Fox are adopted with one exception for both CF3OF and CF3OCl: the CF3 rock of A″ symmetry is assigned near 430 cm-1 and the two bands between 200 cm-1 and 300 cm-1 are assigned to an A′ fundamental, involving CF3 rocking and COX bending and a Δν=2 transition in the CF3 torsion. An extra band at 548 cm-1 in the Raman spectrum of liquid CF3 COl near -196°C is assigned to a CF3OCl⃛Cl2 complex. The values of the force constants d(OX) for CF3OX molecules are suggested to be near those for X2O molecules. More than half the normal modes of A′ symmetry show extensive mixing of symmetry coordinates. In some of these cases the symmetry coordinate for which the normal mode is named is the largest but not the dominant contributor to the potential energy distribution, while in others this symmetry coordinate is not even the largest contributor to the potential energy distribution. No normal modes of A′ symmetry are present in which ν(CO), δs(CF3), δ(COX), or δ(CF3) symmetry coordinates are dominant, and the mode conventionally labeled as v(CO) should be labeled as νs(CF3). For the remaining A′ normal modes and all the A″ normal modes, the symmetry coordinate for which the normal mode is named is dominant in the potential energy distribution.
    Additional Material: 3 Ill.
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  • 3
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The plasma polymers formed in glow and nonglow regions of an inductively coupled RF plasma with perfluorobenzene and perfluorocyclohexane are discussed as a function of operating conditions of the plasma by means of ESCA. The core levels of the plasma polymers are shown to be strikingly different but characteristic of a well-defined but complex polymerization scheme. For the nonglow regions fluorine incorporation is shown to be greater than for polymers prepared in the glow regions and a preponderance of CF2 features is apparent. Perfluorobenzene deposits polymer faster than perfluorocyclohexane and changes in component composition of the C1s profile are studied as a function of operating conditions of the gas plasma.
    Additional Material: 13 Ill.
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  • 4
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The plasma polymers prepared from perfluorocyclohexa-1,3-diene, perfluorocyclohexa-1,4-diene, and perfluorocyclohexene have been investigated by ESCA. The carbon-to-fluorine stoichiometries of the diene-derived polymers are similar and close to that of the starting material. The polymer prepared from perfluorocyclohexene is depleted in fluorine compared to the fluorine content of the “monomer.” The polymers prepared in nonglow regions are also studied and shown to be high in CF2 derived species. The results are compared with those for perfluorobenzene and perfluorocyclohexane, and the polymerization rates are in the order C6F6 〉 C6F8 1,3 ∼ 1,4 〉 C6F10 ∼ C6F12. The variations in composition of the plasma polymer as revealed by ESCA as a function of the polymerization conditions are discussed.
    Additional Material: 14 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 3245-3251 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypropylene (PP) and polyethylene (PE) peroxy radicals undergo photoreactions, but under commonly encountered photodegradation conditions these reaction rates are much lower than those of conventional radical reactions; for example, for PP peroxy radicals in noon summer sunlight at 25°C their rate of photolysis to alkyl radicals is less than one-tenth of their rate of hydrogen abstraction from the polymer. At lower temperatures( 〈 -10°C) or when more intense radiation is used, however, peroxy radical photolysis becomes a proportionately more important source of alkyl radicals. In addition, occurrence of photoinduced radical combination is confirmed but is shown to be important only when photolysis generates an alkyl radical sufficiently close to a peroxy radical that termination can occur before oxygen reconverts the alkyl radical to a peroxy radical. This termination mechanism therefore becomes more important for radicals generated at lower temperatures when the average separation of a radical pair is lower.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 903-911 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental investigation was conducted to relate the average number of radicals per particle, n̄ to the dimensionless parameter α, as suggested by Stockmayer. Seed emulsion polymerizations of polystyrene were run over a wide range of particle sizes and initiator levels in the 50-70°C temperature range. The seed polymerization technique removed the question of particle formation behavior and allowed a straightforward determination of n̄. Alpha was varied more than three orders of magnitude and resulted in measured values of n̄ in the range 0.5-1.3. These data are in good agreement with Stockmayer's relationship as long as the value of the termination rate constant is taken at the monomer/polymer ratios found in emulsion polymerization. For polystyrene at a monomer/polymer ratio of 60/40 this value is an order of magnitude lower than that found for infinitely dilute polystyrene solutions.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 13 (1980), S. 143-147 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two resonance lines were observed in 2,6-dichlorobenzamide, both in liquid nitrogen and at room temperatures, using a self quenched super-regenerative NQR spectrometer. Analysis of the Zeeman effect on the two lines using an uncut crystal grown from solution reveals: (1) the crystal belongs to the orthorhombic system; (2) there are two crystallographically equivalent but physically non-equivalent directions for the principal field gradient making an angle of 71° for the low frequency line, and four such directions for the high frequency line; (3) the directions of the crystalline axes a, b and c are tentatively fixed as (90°, 90°), (90°, 90°) and (0°, - ); (4) from morphological studies a: b: c are estimated as 0.959 ± 0.005: 1:1,402 ± 0.005 and, from the estimated density (1.440 gms/cc) of the crystal, the absolute values a, b, c are calculated, on the basis of four molecules per unit cell, as a = 8.33 Å, b = 8.68 Å and c = 12.18 Å; (5) there are a mininium of four molecules per unit cell; the four molecules lie in four different planes which are, however, connected by symmetry operations. There is an inplane bending by 6.5° between the two C—Cl bonds away from one another and (6) the ionic, single bond and double bond characters for both chlorines are almost equal and are in the ratio 25:72:3.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 14 (1980), S. 192-197 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton spectra of exo- and endo-3-thiatricyclo[4.2.1.02,5]non-7-ene 3,3-dioxide have been analysed and completely assigned. Considerations of coupling constants indicate that the thietane ring is nonplanar and that the norbornene residue is significantly distorted from the geometry of norbornene itself. The sulfone group induces significant changes in the shielding of the proximate olefinic proton in the endo isomer and the bridge protons in the exo isomer. These shifts appear to be the result of the electrostatic effects and effects associated with the diagmagnetic anisotropy of the sulfone group.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 71-82 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In light of novel and problematic diffraction patterns arising through the thermoreversible gelation of isotactic polystyrene, the conformational possibilities were examined with particular reference to other conformational works published recently on this polymer. The specific objective was to ascertain whether highly extended, helical backbone geometries such as are required by the new x-ray patterns are possible or not with a purely isotactic arrangement of side groups. The first realization was that the recently announced low-energy, near-trans conformations are not relevant to the present issue as they do not provide the required extended geometry. Further, specific sampling of the conformational energy map revealed that the required high chain extension may be energetically feasible, contrary to traditional conceptions and to recent conformational calculations elsewhere. The divergences as regards the latter were traced to the specific choice of nonbonded atomic radii - all within generally accepted limits - which accordingly has a crucial effect even to the extent whether specific conformation types are forbidden or energetically stable. The implications this has for conformational analysis in general are being pointed out. While the novel crystal structure has not been solved, the present study at least eliminates the previously believed categoric objections to it being associated with isotactic chains and, beyond this, opens up new perspectives as regards conformational possibilities in polyolefins. The more general problems concerning the nature and origin of the gelation phenomenon nevertheless remain.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 779-791 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman spectra of 1,6-di-p-methoxybenzene-sulfonyloxy-2,4-hexadiyne (MBS) have been recorded during thermal polymerization. The spectra are similar to those of the related p-toluene-sulfonyloxy monomer but indicate a higher strain in the initially formed MBS polymer chains. Despite this similarity, the polymerization kinetics for the two monomers are markedly different. The polymerization behavior of MBS shows that the polymer chain initiation and propagation are practically independent of lattice strain. Possible causes for this independence are discussed.
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