Pseudoration

In the same paper, Limbach et al. (87AGE934) reported the study of the compound related to porphyrins, porphycene 79. Porphycene behaves very differently from FI2P in CPMAS DNMR experiments. Its behavior was explained assuming that the four porphycene tautomers (two cis and two trails) are present in the crystal and interconverting very rapidly due to short N-H...N distances in the seven-membered pseudorings. 

Partitioning of carbocations between addition of nucleophiles and deprotonation, 35, 67 Perchloro-organic chemistry structure, spectroscopy and reaction pathways, 25, 267 Permutational isomerization of pentavalent phosphorus compounds, 9, 25 Phase-transfer catalysis by quaternary ammonium salts, 15, 267 Phosphate esters, mechanism and catalysis of nucleophilic substitution in, 25, 99 Phosphorus compounds, pentavalent, turnstile rearrangement and pseudoration in permutational isomerization, 9, 25... 

Pseudoreduced compressibility is a function of z-factor and pseudore-duced pressure. Thus, a graph relating z-factor to pseudoreduced pressure, Figure 3-7, Figure 3-8, or Figure 3-9, can be used with Equation 6-14 to calculate values of Cpr. 

Note that an alternative formulation, when the Z concentrations in Eq. (171) are kept constant, consists of including their contribution into the rate constant, which amounts to defining a pseudorate constant = kj H [Zi]. Thus Eq. (171) is rewritten as... 

In the analysis of our data to test rate laws and to calculate pseudorate constants, the value of (a02)qo is needed. We used the experimental value of the SF since it does not vary significantly from run to run. 

Here subscript f refers to the fasf mode the other mode is the slow mode. 6 and Of are relaxation pseudorates p and pf are stretching exponents Af is the amplitude fraction of the fast mode. In some systems, pr <0.5 the Laplace transform of the fast mode then contains a wide range of decay times, including very short times, justifying the appellation fast for this mode. Hie breadth of the fast mode is such that it may finish decaying only at times later than the times at which the slow mode decays. 

Figure 1 shows how the slow relaxation pseudorate depends on i obe diameter. Each point style corresponds to a different polymer concentration. 6 falls with increasing d. From this Figure, 0 of probes smaller than 60 nm is approximately independent of c. Probes larger than 100 nm have 0 that decreases markedly with... 

The fast relaxation pseudorate 6f also shows 1,2) a crossover between small- and large-particle behaviors. The crossover diameter for 9f is the same as the crossover diameter for 0. For small (d < R,) probes, 0f is nearly independent of d for large d >Rj) probes, 0f falls as d is increased. For all probes, large and small, 0f is nearly independent of c. 

Figure 3. Relaxation pseudorates (1,17) 0 and Of (eg. 5) against c for PSL probes (legend. Figure 3b). a) Slow-mode relaxation pseudorate and fits to 0jexp(-ac ). Dashed lines fit to all measurements. Solid lines separate fits for c < c and c > c. b) Fast mode relaxation pseudorate. Dashed lines are simple exponentials. Solid lines are 1) pure exponentials (50. 87nm probes) or 2) a power law (189nm probes). Units of 0 are (pS). ...

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