Thermodynamic modeling reveals accuracy limits of Gibbs free energy during PI-controlled heating, highlighting high sensitivity to perturbations despite heat capacity estimation constraints.
Challenges in chemical lab experiments often differ from industrial flow process control. Small inaccuracies can become major cost factors, often ignored in lab tests. The present work connects limits of test accuracy and calculated non‐equilibrium entropy, enthalpy, and Gibbs free energy for PI‐controlled heating. While using thermodynamic models, approaches for entropy by J. W. Gibbs and L. Boltzmann as well as enthalpy show comparable trends. Another entropy by E. C. Shannon gives an impression of the instability of PI‐control. Finally, interpretation of Gibbs free energy (Gibbs–Helmholtz) for process description is possible but limited. An impact assessment reveals major limits in reliability, for example, accuracy of heat capacity, but also promising good sensitivity to external perturbation.
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Dutschke et al. (2026) studied this question.
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