Hydrogen-bonding liquids, scaling

Two unusual features can be observed in these plots (and, at least for the self-diffusion coefficient, this behaviour is common to all hydrogen-bonded liquids). This ratio is a function of temperature. At constant temperature and pressure, rotation and translation reveal the same isotope effect. From simple sphere dynamics one would expect the rotation to scale as the square root of the ratio of the moments of inertia (=1.38) while for translational mobility the square root of the ratio of the molecular masses ( = 1.05) should be found. This is clearly not the case, indicating that the dynamics of liquid water are really the dynamics of the hydrogen-bond network. The hydrogen bonds in D2O are stronger than those in H2O and thus the mobility in the D2O network decreases more rapidly as the temperature decreases. 

Temperature dependence of pion capture probability in water (Kachalkin et al. 1979] and ammonia (Horvath et al. 1982). The probability is normalized to that measured at room temperature. The temperature is expressed as = (T-Tm)/(Tc-Tm), where T, T, and Tc are the temperatures of measurement, melting point, and critical point, respectively. Ordinary temperature scales are also shown above the boxes. The curves represent fits using the bondbreaking (mixture) model of hydrogen-bonded liquids (Haggis et al. 1952 Luck 1979)... 

Attempts have also been made to separate non-specific effects of the local electrical field from hydrogen-bonding effects for a small group of ionic liquids through the use of the k scale of dipolarity/polarizability, the a scale of hydrogen bond donor acidity, and the (i scale of hydrogen bond basicity (see Table 3.5-1) [13, 16]. 

Solvatochromic pareuaeters, so called because they were Initially derived from solvent effects on UV/visible spectra, have been applied subsequently with success to a wide variety of solvent-dependent phenomena and have demonstrated good predictive ability. The B jo) scale of solvent polarity is based on the position of the intermolecular charge transfer absorption band of Reichardt s betaine dye [506]. Et(io> values are available for over 200 common solvents and have been used by Dorsey and co-%rarkers to study solvent interactions in reversed-phase liquid chromatography (section 4.5.4) [305,306]. For hydrogen-bonding solvents the... 

IPEC or hydrogen-bonded complexes may form not only between mutually interacting polymer blocks but also between a polymer block and low-MW molecules. Complexes between surfactants and block copolymers have been investigated for the formation of micelles. As illustrated by the work of Ikkala and coworkers [313], one of the major interests of these systems is that they combine two different-length scales of supramolecular organizations, i.e., the nanometer-scale organization of the (liquid) crystalline surfactant molecules and the ten-nanometer scale relative to block copolymers. This gives rise to the so-called hierarchical systems. The field of (block)... 

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