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  • Physical Chemistry  (2)
  • Constant-composition solid-solid phase transformations: polymorphic  (1)
  • 1
    ISSN: 0392-6737
    Keywords: Surface energy (surface tension, interface tension, angle of contact, etc.) ; Phase transitions and critical phenomena ; Constant-composition solid-solid phase transformations: polymorphic ; massive, and order-disorder ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary 1,2-sn-diglyceride monolayers exhibit unique and complex phase transitions as a function of surface pressure. The dynamical response of the layer on expanding the film has been investigated by computer simulations, (π-A) isotherms and grazing-incidence X-ray diffraction. Good agreement is found between the simulations and experiments. The Langmuir film undergoes two phase transitions occurring at 38.3 and 39.8 Å2/molecule. The transition at low surface density is associated with a tilt of ≈14° in the direction close to nearest neighbour. The first transition is unique for the diglyceride molecules and has not been observed for other amphiphilic molecules. It is driven by a competition of hydrophobic/hydrophilic and intra/intermolecular forces and can be pictured as a «seesaw» mechanism. Due to the close packing of the chains at high surface pressure, thesn-1 ester group aligns with the alkyl chain, and only thesn-2 ester group is favoured to lay at the aqueous interface. Hydrophilic forces attract thesn-1 ester group, but its motion towards the aqueous subphase is hindered by intra- and intermolecular chain interactions. On expansion, the intermolecular interaction decreases, and at the first transition, the intramolecular interaction between the two chains is strong enough to cause a «swelling» of the molecules. The diffraction pattern determined in the different mesophases reveals that the layer maintains its hexagonal structure up to the second phase. Concomitant with the tilt, the structure relaxed from a hexagonal to a distorted hexagonal lattice.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 745-753 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the rate constant for the exchange reaction between oxygen atoms and dioxygen molecules has been studied using the oxygen isotopes 16O and 18O. The reaction was studied by VIS-photolysis of ozone in the presence of isotopic dioxygen and with nitrogen as a bath gas at five different temperatures, 143 K, 173 K, 203 K, 253 K, and 295 K. High-resolution microwave spectroscopy was used to measure the composition of the ozone isotopomer mixtures and mass-spectrometry was used to determine the abundances of the isotopomeric dioxygen species formed during the reaction. The rate constant was determined to be kexchange=(2.66±0.78)×10-12 (T/300 K)-(0.88±0.26) cm3s-1 (±2σ) or as the ratio between rate constants for exchange and for ozone formation, (4.67±1.3)×1021 (T/300 K)(1.74±0.19) cm-3 (±2σ). © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 331-343 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of ozone formation has been studied using 16O and 18O2. High-resolution microwave spectroscopy was used to measure the amounts of the isotopomeric ozone species formed. The study is hampered by the very rapid exchange process between the reactants, that tends to scramble the isotopes and hence give a 2:1 statistical ratio between the two possible isotopomers. We have found a strategy to come around this difficulty and conclude that the mechanism is a simple end-on-addition.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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