Van’t Hoff Analysis and Hidden Thermodynamic Variables
Van’t Hoff analysis is a procedure in classical chemical thermodynamics that may be used to estimate the apparent enthalpy (ΔHvH) of a process from the temperature dependence of its equilibrium constant (Keq), usually determined from the slope of a (linear) van’t Hoff plot of ln Keq vs 1/T.
For any thermodynamic equilibrium process that proceeds with non-zero enthalpy (heat of reaction), the equilibrium will be perturbed by change in temperature (Le Chatelier principle). This is the basis for van’t Hoff analysis that has previously been used extensively as a way to characterize the temperature dependence of thermodynamic equilibrium processes and is often applied in biophysical and biochemical investigations as an indirect method for estimating standard enthalpy changes. Although now largely superseded by more direct calorimetric methods, careful application of this kind of analysis can yield useful additional...
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