The interaction of xenon with cryptophane-A in
1,1,2,2-tetrachloroethane-d
2 is investigated by
129Xe
and 1H NMR spectroscopy. Xenon is reversibly trapped
into the cavity of this host to form a 1 to 1 host−guest complex with an apparent association constant K of the
order of at least 3 × 103 M-1
at 278 K. The
exchange between the free and bound xenon is slow on the
129Xe NMR time scale, and the bound xenon
resonance is shifted by approximately 160 ppm to lower frequencies with
respect to the free xenon resonance.
The xenon complex is at least 4 and 20 times more stable,
respectively, than the corresponding chloroform
and methane complexes under the same conditions. The stability of
this xenon complex appears to be much
greater than that of the previously described xenon complex of
α-cyclodextrin in water. This is probably due
to the combination of three favorable effects: (i) good size matching
between the guest and the cryptophane
cavity in its most relaxed conformation, resulting in the optimization
of the London forces between the highly
polarizable guest and the electron rich aromatic rings of the host
(enthalpic stabilization); (ii) no rotational or
vibrational entropy loss of the monatomic guest in the cryptophane
cavity; and (iii) no (or little) entropy loss
due to reduction of the conformational freedom of the host.
Analysis of the line widths of the signals
corresponding to the free and bound xenon as a function of the relative
xenon/cryptophane ratio suggests that
the incoming xenon atom must displace the departing one to enter the
cryptophane cavity, and that the empty
cryptophane is not involved in the complexation
equilibrium.
Mean acoustic cavitation bubble temperatures have been measured in a series of aqueous solutions containing C(1)-C(5) aliphatic alcohols, at 355 kHz. The method relies on the distribution of hydrocarbon product yields produced from the recombination of methyl radicals generated on the thermal decomposition of the alcohols. The mean bubble temperature was found to decrease with increasing concentration of alcohol with the effect being more pronounced the higher the molecular weight (the lower the vapour pressure) of the alcohol. It is shown that the decrease in the temperatures measured correlates very well with an increase in the surface excess of the alcohol, similar to that previously reported for the quenching of sonoluminescence in aqueous solutions containing alcohols [J. Phys. Chem. B 101 (1997) 10845; J. Phys. Chem. B 103 (1999) 9231]. The measured temperatures ranged from 4600+/-200 K at zero alcohol concentration to 2300+/-200 K at 0.5 M t-butanol. The validity of the method is discussed and it is concluded that even though a number of assumptions need to be applied the results appear to indicate that the method gives an accurate measure of the mean bubble temperature.
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