Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2017 / Paper 1 / Section A(iii) / 6 / ii / Solution

Approximate the reaction enthalpy and entropy as constant over the measured interval, so ${\Delta }_r{G}^{\circ }={\Delta }_r{H}^{\circ }-T{\Delta }_r{S}^{\circ }$. A linear least squares fit of all three free energies against temperature givesand henceThe negative entropy change is reasonable because oxygen gas is incorporated into solids. The fit residuals are $+0.129,-0.257,+0.129\mathrm{kJ}\mathrm{mo}{\mathrm{l}}_{{\mathrm{O}}_2}^{-1}$, so the data support this approximate straight-line description. Extrapolating its intercept to zero temperature is a way of estimating a constant local enthalpy, not evidence that the heat capacities vanish or that the same phases persist to zero temperature. More temperatures and repeated heating/cooling measurements would test curvature and equilibration.