Temperature dependence of ratio

Fig. 15 Temperature dependence of ratio of average radius of gyration i g)) to average hydrodynamic radius () of copolymer PNIPAM-g-PEO chains in water during heating and cooling. The weight-average molar mass (Mw) is 7.2 x 106 g/mol, the molar number ratio of NIPAM monomers to PEO macromonomers is 111, and there are 392 short PEO chains grafted on each PNIPAM chain [69]...

Fig. 39 Aggregation temperature dependence of ratio of average radius of gyration to average hydrodynamic radius ((i g)/) of resultant stable mesoglobules made of different copolymers [141]...

Seeley J V, Morris R A, Viggiano A A, Wang FI and Flase W L 1997 Temperature dependencies of the rate constants and branching ratios for the reactions of Cr(Fl20)g 3 with CFIjBr and thermal dissociation rates for CI (CFl3Br) J. Am. Chem. Soc. 119 577-84... 

The temperature dependence of the reactivity ratio rj also involves the Ell Ej2 difference through the Arrhenius equation hence... 

Fig. 102. Temperature dependence of unit cell parameters a and c ratio of parameters - c/a volume - V. Figure (a) - KsNb3OFi8, figure (b) -RbsNb3OFi8 (after Agulyansky and Ravez [438]).

The dependence of birefringence on the temperature seems to be correlated to the temperature dependence of the lattice parameters ratio c/a shown in Fig. 102. 

Such considerations appear to be very relevant to the deformation of polymethylmethacrylate (PMMA) in the glassy state. At first sight, the development of P200 with draw ratio appears to follow the pseudo-affine deformation scheme rather than the rubber network model. It is, however, not possible to reconcile this conclusion with the temperature dependence of the behaviour where the development of orientation reduces in absolute magnitude with increasing temperature of deformation. It was proposed by Raha and Bowden 25) that an alternative deformation scheme, which fits the data well, is to assume that the deformation is akin to a rubber network, where the number of cross-links systematically reduces as the draw ratio is increased. It is assumed that the reduction in the number of cross-links per unit volume N i.e. molecular entanglements is proportional to the degree of deformation. 

Fig. 4. Top Theoretical temperature dependence of the hyperfine shift of the H/3 protons of reduced spinach [Fe2S2] ferredoxin 151). The solid line corresponds to the situation where only one species exists in solution, whereas the dashed line corresponds to a situation where there is fast equilibrium between two species (in a 20/80 ratio) differing for the location of the extra electron 151). Bottom.-. Experimental temperature dependence of the H NMR shifts. The signals are labeled as in Fig. 2B.

Lithium triflate was the most used salt and the temperature dependence of the electrical conductivity of a series of (LiS03CF3)x/MEEP complexes with a ratio metal cation/MEEP repeat unit 0.125[Pg.203]

The model [39] was developed using three assumptions the conformers are in thermodynamic equilibrium, the peak intensities of the T-shaped and linear features are proportional to the populations of the T-shaped and linear ground-state conformers, and the internal energy of the complexes is adequately represented by the monomer rotational temperature. By using these assumptions, the temperature dependence of the ratio of the intensities of the features were equated to the ratio of the quantum mechanical partition functions for the T-shaped and linear conformers (Eq. (7) of Ref. [39]). The ratio of the He l Cl T-shaped linear intensity ratios were observed to decay single exponentially. Fits of the decays yielded an approximate ground-state binding... 

Fig. 2.11. The temperature dependence of cation/proton activity ratios of geothermal well discharges in Japan. The lines in the figure are recalculated temperature dependences of cation/proton ratios in Icelandic geothermal waters. The dashed curve in B represents the reaction 1.5 K-feldspar + H+ = 0.5 K-mica + 3 quartz (or chalcedony) + K+ (Chiba, 1991). Open circle Takigami, open triangle Kakkonda, open square Okuaizu, solid circle Kirishima, solid triangle Sumikawa, solid square Nigoiikawa.

Figure 6.13 shows the Mossbauer spectra of ferritin [51], which is an iron-storage protein consisting of an iron-rich core with a diameter around 8 nm with a structure similar to that of ferrihydrite and which is surrounded by a shell of organic material. At 4.2 K essentially all particles contribute to a magnetically split component, but at higher temperatures the spectra show the typical superposition of a doublet and a sextet with a temperature dependent area ratio. At 70 K the sextet has disappeared since all particles have fast superparamagnetic relaxation at this temperature. 

Based on C-H versus C-D zero point vibrational differences, the authors estimated maximum classical kinetic isotope effects of 17, 53, and 260 for h/ d at -30, -100, and -150°C, respectively. In contrast, ratios of 80,1400, and 13,000 were measured experimentally at those temperatures. Based on the temperature dependence of the atom transfers, the difference in activation energies for H- versus D-abstraction was found to be significantly greater than the theoretical difference of 1.3kcal/mol. These results clearly reflected the smaller tunneling probability of the heavier deuterium atom. 

Interestingly, in a comparison of the CD3 and CHj carbenes, an unusual temperature dependence of the kinetic isotope effect was observed. In contrast to typical reactions, the ratio of rates of H versus D shift, k /ko, actually increased as temperature was raised. In fact, k was measured to be larger than k at 248 K. It was suggested that these results required a normal temperature dependence of the isotope effect for the classical component of the reaction, but an unusual diminished isotope effect for the QMT reaction. 

---