JentooChemistry

AP® Chemistry · Unit 9 · Topic 9.4

Thermodynamic and Kinetic Control

A reaction can be thermodynamically favored (negative delta G) and still not happen on any observable timescale if it faces a huge activation energy barrier. Favorability and speed are separate questions, answered by thermodynamics and kinetics respectively.

Delta G tells you whether a reaction is downhill overall, comparing the energy of reactants to products. It says nothing about the path between them. That path has its own obstacle: the activation energy, the energy needed to break old bonds and distort molecules into the transition state before new bonds can form. A reaction can have a very negative delta G and still face a towering activation barrier, which makes it kinetically trapped. The reaction is thermodynamically favored but frozen in practice, sometimes for a million years, sometimes forever on a human timescale.

Picture an energy profile: reactants sit high, products sit much lower, so the overall drop is large and favorable. But between them the curve spikes upward into a tall hump before it drops down to the product. That hump is the activation energy. The system has to climb it before it can fall into the lower, more stable valley. A big hump means almost no molecules at room temperature have enough energy to get over it, so the reaction crawls or simply does not proceed, regardless of how favorable the end state is.

This is why thermodynamics and kinetics are separate stories about the same reaction. Delta G, built from enthalpy and entropy, predicts the destination. Activation energy and rate constants predict how fast, or whether, you arrive. A catalyst changes the kinetic story only: it lowers the activation barrier by offering a different pathway, so a previously frozen but favorable reaction can suddenly proceed, while delta G and the final equilibrium stay exactly the same.

Key terms

Thermodynamic control
A reaction's outcome determined by which product is most stable, regardless of how long it takes to get there.
Kinetic control
A reaction's observed behavior dominated by activation energy and rate rather than final stability.
Activation energy
The minimum energy needed to reach the transition state and convert reactants into products.
Metastable state
A state that is not the most stable possible but is trapped there by a high activation barrier.
Catalyst
A substance that speeds up a reaction by lowering its activation energy without changing delta G or the equilibrium.

Watch it explained

  1. How it worksHow can a reaction be thermodynamically favored and still take a million years?
  2. How it worksDraw an energy profile where the favored product is trapped behind a huge activation barrier.
  3. Common mistakeWhy isn't a negative delta G a prediction about the speed of a reaction?
  4. Going furtherWhat changes when a catalyst is added to a thermodynamically favored but frozen reaction?

Check yourself

Your turn1 of 2
Graphite is more thermodynamically stable than diamond, yet diamond doesn't spontaneously turn into graphite at room temperature. Why?

End of topic.