Gibbs free energy intramolecular

The quantity of primary interest in our thermodynamic construction is the partial molar Gibbs free energy or chemical potential of the solute in solution. This chemical potential reflects the conformational degrees of freedom of the solute and the solution conditions (temperature, pressure, and solvent composition) and provides the driving force for solute conformational transitions in solution. For a simple solute with no internal structure (i.e., no intramolecular degrees of freedom), this chemical potential can be expressed as... 

The Gibbs free energy reaction profiles in Fig. 16 have been calculated from the results in Table 16 and the mechanism in (30) and refer to reaction in a 1 1 2-methylphenol buffer at buffer concentrations of 0.001 and 0.1 moldm" (Fig. 16(a) and (b), respectively). TS(1) is the transition state for opening of the intramolecular hydrogen bond and TS(2) is the transition... 

Ptitsyn et al. (1968) argued that the collapse process was a first order transition (i.e. the first derivatives of the Gibbs free energy with respect to both the temperature and pressure are discontinuous at the transition). They used the terms coil and globule for the two different states and likened the transition to the first order condensation of a real vapour into liquid droplets when the forces of attraction are increased sufficiently. They were led to believe that experimental observation of the transition would be very difficult, if not impossible, because intermolecular condensation would overwhelm the intramolecular contraction, leading to phase separation. Until quite recently this pessimism seemed fully justified. 

Additionally, the determined values for the initial reaction rate constants (Arj j,) and the Gibbs free activation energies indicated that the accessibility of the catalysts is improved by reduced intramolecular interactions and the greater flexibility ofthe spacer. 

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