Free enthalpy Johnson

The minimization of the free energy in accordance with White-Johnson-Dantzig allows the determination of the composition of the detonation products in equilibrium state. The thermodynamic parameters (enthalpy, entropy, free enthalpy, free energy) of the detonation products can be calculated using functions based on the enthalpy //°-//°. The coefficients c0,. .. c4 can be found in literature J. Chem. Phys 1958, 28, 751 755 Prop., Expl. Pyrotech. 1985,10, 47-52] ... 

The White-Johnson-Dantzig method may be regarded as one of non-linear programming. Dorn" " has shown, that every problem that is based on minimalisation of a convex function has a dual form. Mutual linkage of the two formulations of the dual theorem can only be used to determine the overall free enthalpy in the individual steps, and thus also to establish the accuracy of the solution achieved. When minimalisation is expressed as... 

In addition to the Hopf cydization of 176, there is a second pericydic reaction leading to 162, that is, the dehydro Diels-Alder reaction of butenyne with acetylene (Scheme 6.47). The theoretical treatment of this process by Johnson et al. [59] predicted a free reaction enthalpy and a free activation enthalpy, both at 25 °C, of -13.4and 42.0kcalmol-1, respectively. Ananikov [116] arrived at a similar result for the intramolecular case of non-l-en-3,8-diyne (202) and calculated the same quantities to be -15.3 and 30.9 kcal mol-1 for the formation of the isoindane 203. As already discussed regarding Scheme 6.40, the conversion of 162 into benzene and likewise that of 203 into indane have to be considered as a sequence of two [1,2]-H shifts 116, 117], whose highest transition state has a significantly lower energy than that for the formation of 162 and 203 by the dehydro Diels-Alder reaction. 

Johnson, F.A., Lewis, S.D., Shafer, J.A. (1981). Perturbations in the free energy and enthalpy of ionization of histidine-159 at the active site of papain as determined by fluorescence spectroscopy. Biochemistry 20 52-8. 

A. Cooper, C. M. Johnson, J. H. Lakey, M. Nollmann, Heat does not come in different colours entropy-enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions, in Biophys. Chem., 2001,93, 215-230. 

Frisch, C., Schreiber, G., Johnson, C. M., and Fersht, A. R. (1997). Thermodynamics of the interaction of barnase and barstar Changes in free energy versus changes in enthalpy on... 

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