Combining with the equilibrium relation gives
If reaction enthalpy and reaction entropy are approximately constant over the measurement interval, a plot of against is straight, with slope and intercept . An exothermic reaction therefore has a positive slope. In the more general local form, the Gibbs–Helmholtz equation gives
which is the Van't Hoff equation without assuming a constant enthalpy.
Use a dimensionless equilibrium constant built from thermodynamic activities. Measure sufficiently separated temperatures after verifying true equilibrium, and avoid phase changes or a changing chemical reaction. Temperature-dependent heat capacities cause curvature: the fitted straight-line slope then estimates an interval-dependent enthalpy. Small errors in the equilibrium measurements can produce large slope errors over a narrow range. The entropy intercept is particularly sensitive because requires distant extrapolation, and slope/intercept errors are correlated. A numerical line through a few points is not, by itself, evidence that all these assumptions hold.
Figure 1.
Original schematic van't Hoff plot showing how slope and intercept encode enthalpy and entropy
. Details.
Integrating the Van't Hoff equation with approximately constant reaction enthalpy gives
Using the full calculated yields
The negative sign agrees with the decrease of on heating. This is the two-temperature estimate from the supplied equilibrium data. It is not exactly the implied by treating equal prefactors and a fixed activation-energy difference as exact throughout the interval: that stricter model predicts rather than . The data and idealizations are therefore only approximately mutually consistent; no rounding of intermediate calculations can make both numerical enthalpy estimates identical.