Free energy of activation AGj

Formation of a relatively stable carbocation is important in an SnI reaction => low free energy of activation (AGJ) for the slow step of the reaction. 

This figure illustrates schematically the relationship between the free energy of formation of clusters (AGj) and the free energies of activation AG of the elementary reactions Xj + X Xj+i,... 

The potential-dependent part of the activation energy AGp can be estimated by introduction of the transfer coefficient a, which was introduced in 1930 by Erdey-Gruz and Volmer (3). The potential-dependent contribution AgJ to the free energy of activation... 

In Eq. (7-21), AGj is the intrinsic barrier, the free energy of activation of the (hypothetical) member of the reaction series having AG = 0. It is evident that the Marcus equation predicts a nonlinear free energy relationship, although if a limited... 

Fig. 6.2. (a) Free-energy profile for a reaction with an intermediate AGj and AG are the free energy of activation for the first and second stages, respectively, (b) Free-energy profile for a reaction with an intermediate in which the first peak is higher than the second. 

The value of kr/k is determined by the difference AAC 1 in the free energies of activation between the syndiotactic AG and isotactic AGj, placements... 

The distribution function of the activation free energy of relaxation /(AGJ can be calculated using Equation 10.25 as the kernel of Fredholm integral equation of the first kind ... 

AGj p) Free energy of binding of a substrate from water to the activating binding region of the transporter... 

Figure 18.6 Correlation between the logarithm of the maximum P-gp activity (In fi) obtained from phosphate release measurements at pH 7.0 (37 °C) and the free energy of drug binding from water to transporter (AGj jj). The maximum activity of P-gp ( fi) is expressed as a percentage of the basal rates taken as 100%. Data are presented as average of two to 15 measurements. The solid line is a linear...

Equation (3.5) also shows that the activation free energy at the peak, AGj, is an increasing function of temperature, taking into account the explicit presence of T and also the variation of k, [equation (1.34)] and Dh. Thus, increasing scan rate and decreasing temperature favor the transition between concerted and stepwise mechanisms, and vice versa. 

---