What does reaction exothermicity say about the stability of molecules

Question

If a reaction is exothermic it means that the energy state of the products is lower than that of the reactants so this will be the state that 'nature' will naturally strive for. Often you see that stability of molecules is argued in this way (e.g. in one of the answers here), saying that the higher the exothermicity of the decomposition reaction, the more unstable the molecule and thus the more unlikely that it will exist in nature.

My question is whether this reasoning is correct?

The reason I am doubting this, is that the reaction enthalpy $\Delta H_r$ is not the only parameter of importance in the energetics of chemical reactions: the activation energy $\Delta E_a$ can also play a major role. To clarify my point, take a look at the diagram for 2 hypothetical reactions I have made. Reaction 1 has a low activation energy and a low exothermicity, whereas 2 has a high activation energy and a high exothermicity.

Judging solely by exothermicity you would conclude that the reactants of reaction 2 are more unstable, but if you look at the activation energies for the reactions than I would argue that the reactants of reaction 1 are more unstable because they more easily react to form their products. Of course having a high activation energy would at best make the reactants meta-stable, but metastability could last for decades as well given the right conditions.

So my general question is: can reaction exothermicity be used to say something about the stability of molecules and what is the role of activation energy in this story?

Answer 1

Good question. There exists two types of stability - thermodynamic stability (determined by $\Delta G_{reaction}$, or $\Delta H_{reaction}$ approximately) and kinetic stability (determined by $\Delta G ^{\ddagger}$, or $E_{activation}$ approximately). The reactant compound in your first reaction is thermodynamically more stable than the second, since it sits at a lower potential energy, but it is kinetically less stable, since there is a smaller barrier for decomposition.

Usually context is sufficient to determine what kind of stability is being talked about, though in general I think stability is more often mentioned in the thermodynamic sense than the kinetic, since thermodynamic stability is related to the reaction free energy (a sum of its enthalpy change and a factor containing its entropy change) and is more commonly tabulated and more readily measured than activation free energies.

For example, all explosives are quite thermodynamically unstable (otherwise they wouldn't be very good at exploding!), but we still speak of "stable explosives", such as TNT or RDX and "unstable explosives", such as $\ce{NI_3}$ or $\ce{Hg(CNO)_2}$. Clearly kinetic stability is what is taken into account.

In constrast, when studying acidity and basicity of substances, it's common to justify reactions based on the "stability" of the acids/bases/conjugate species, but in this case, we're talking about thermodynamic stability, as it defines the acidity/basicity constants.