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.
Let be Gibbs free energy, enthalpy and thermodynamic temperature for a fixed amount and composition of material, with the derivative taken at constant pressure. Apply the Gibbs–Helmholtz equation to the standard molar reaction quantities, obtained by summing product minus reactant contributions with their stoichiometric coefficients:
Define as the dimensionless thermodynamic equilibrium constant expressed using activities in specified standard states. Since , where is the molar gas constant,
If the reaction enthalpy is constant over the interval, integration gives
This is the requested Van't Hoff equation. For an exothermic reaction, increasing temperature decreases . Although the name “isochore” is often used in this context, the displayed enthalpy form follows from standard Gibbs energies and the stated constant-pressure Gibbs–Helmholtz identity; the analogous ideal-gas concentration form involves internal energy when the temperature dependence of standard concentration is retained.