Fig. 3. Linear free energy scaling relationships amongst intermediates for the thermodynamic steps of olefin hydroformylation without consideration of different ligand size. The free energies are relative to a reference state, defined in eqn (2)–(6). The mathematical equations that define the linear scaling relationships are used to create the simulated reaction profile and, ultimately, the final volcano plot (vide infra). The zero slope observed between intermediates 5 and 4 indicates that the binding energy is independent of the choice of catalyst.