Delayed coefficient

In contrast to the cell experiments of Gibilaro et al., it is now seen from equation (10.45) that measurement of the delay time gives no information about diffusion within the pellets this can be obtained only through equation (10.46) from measurements of the second moment. As in the case of the cell experiment, the results can also be Interpreted in terms of an "effective diffusion coefficient" associated with a Fick equation for the... 

Between about Rop = 350,000 and 1 X 10 , the drag coefficient drops dramatically in a drag crisis owing to the transition to turbulent flow in the boundary layer around the particle, which delays aft separation, resulting in a smaller wake and less drag. Beyond Re = 1 X 10 , the drag coefficient may be estimated from (Clift, Grace, and Weber) ... 

The delay, t0, preceding the onset of the main reaction may include contributions from (i) the time required for the sample to attain reaction temperature, h, (ii) additions to fh resulting from changes within the reaction sample, e.g. water removal (endothermic) from a hydrate, td, phase transitions, etc. and (iii) slow processes preceeding establishment of the main reaction, which are to be regarded as the true induction period, The effective values of th, td and may show different temperature coefficients so that the magnitude of t0(=th + ta + i) may vary with temperature in a complex manner, perhaps differently from that of the subsequent rate process. 

The based PSRE was carried out by taking linear combinations of the spectra at zero and 12 ms delay with the coefficients calculated to make the mean spectral intensity equal to zero between 83 and 85 ppm. The T-i -based PSRE was done in the same way using the spectra at zero and 8 fi% delay. 

In pure crystals, singlet excitons can be created by mutual annihilation of triplet excitons. The intensity of the singlet exciton fluorescence depends quadratically on the triplet exciton concentration and is therefore proportional to the square of the singlet-triplet extinction coefficient. It is interesting to compare such a delayed fluorescence excitation spectrum, observed by Avakian et cd. 52) on naphthalene, with a corresponding phosphorescence excitation spectrum (Fig. 22). 

Fig. 22 B. Exeitation spectrum at room temperature showing the intensity of delayed fluorescence of a naphthalene crystal as a function of the wavelength of the exciting light. The ordinate is proportional to the square of the singlet-triplet absorption coefficient. (From Avakian and Abramson, Ref.52))...

Four highly fluorinated ethers with low boiling points are currently used in anesthesia enflurane, isoflurane, sevoflumne, and desflurane (Figure 8.89). Des-flurane and sevoflurane are now the most used (sevoflurane is especially used in pediatrics). They exhibit the lowest blood-gas partition coefficients, the lowest ratio of toxic metabolites, and the lowest solubilities in lipids. These features limit the retention and, consequently, the metabolism is delayed (Table 8.2). 

Using time-resolved crystallographic experiments, molecular structure is eventually linked to kinetics in an elegant fashion. The experiments are of the pump-probe type. Preferentially, the reaction is initiated by an intense laser flash impinging on the crystal and the structure is probed a time delay. At, later by the x-ray pulse. Time-dependent data sets need to be measured at increasing time delays to probe the entire reaction. A time series of structure factor amplitudes, IF, , is obtained, where the measured amplitudes correspond to a vectorial sum of structure factors of all intermediate states, with time-dependent fractional occupancies of these states as coefficients in the summation. Difference electron densities are typically obtained from the time series of structure factor amplitudes using the difference Fourier approximation (Henderson and Moffatt 1971). Difference maps are correct representations of the electron density distribution. The linear relation to concentration of states is restored in these maps. To calculate difference maps, a data set is also collected in the dark as a reference. Structure factor amplitudes from the dark data set, IFqI, are subtracted from those of the time-dependent data sets, IF,I, to get difference structure factor amplitudes, AF,. Using phases from the known, precise reference model (i.e., the structure in the absence of the photoreaction, which may be determined from... 

See also Delay to Ignition and Its Temperature Coefficient in Vol 3 of Encycl, pp D53-D54 and Notes 1 2, which are given after the Refs... 

The transient absorption spectra of duplexes with [2AP]A4GGAs are depicted in Fig. 5. At a delay time of 100 ns, the transient absorption spectrum is attributed to the superposition of the spectra of the 2AP(-H) and G /G (-H) radical products and the hydrated electrons. The structureless tail of the eh absorption in the 350-600 nm region decays completely within At<500 ns. The formation of G VG(-H) radicals monitored by the rise of the 310-nm absorption band and associated with the decay of the 2AP V 2AP(-H) transient absorption bands at 365 and 510 nm (Fig. 5) occurs in at least three well-separated time domains (Fig. 6). The prompt (<100 ns) rise of the transient absorption at 312 nm due to guanine oxidation by 2AP was not resolved in our experiments. However, the ampHtude, A((=ioo), related to the prompt formation of the G /G(-H) radicals (Fig. 6a) can be estimated using the extinction coefficients of the radical species at 312 and 330 nm (isosbestic point) [11]. The kinetics of the G VG(-H) formation in the yits and ms time intervals were time-resolved and characterized by two well-defined components shown in Fig. 6a (0.5 /zs) and Fig. 6b (60 /zs). 

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