Why can a thermodynamically favorable reaction still fail to proceed at a noticeable rate?
Topic 9.4 Thermodynamic and Kinetic Control: distinguish thermodynamic favourability (sign of delta G) from kinetic feasibility (rate), and explain why a favorable reaction may be slow.
A focused answer to AP Chemistry Topic 9.4, covering the distinction between thermodynamic favourability and kinetic feasibility, why a favorable reaction can be slow due to a high activation energy, and the role of catalysts, with full worked examples.
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What this topic is asking
The College Board (Topic 9.4) wants you to distinguish thermodynamic favourability (the sign of ) from kinetic feasibility (the rate), and to explain why a favorable reaction may be slow. This resolves the apparent paradox of reactions that should happen but do not, by separating whether a reaction can occur from how fast it occurs.
Two different questions
A negative says the products are lower in free energy than the reactants, so the reaction is downhill and can happen. But whether it actually happens at a useful rate is a separate question, answered by kinetics. A reaction can be favorable and fast, favorable and slow, or unfavorable entirely.
Why a favorable reaction can be slow
This is why many favorable reactions do not visibly occur at room temperature: a fuel and oxygen are thermodynamically poised to react, but the mixture is stable until a spark provides the activation energy. The energy profile of Unit 5 makes this concrete: is the difference between the start and end levels, but the rate depends on the height of the barrier between them.
The role of a catalyst
A catalyst lowers the activation energy, providing a faster pathway, so it can make a kinetically hindered but favorable reaction proceed at a useful rate. Crucially, the catalyst does not change or the favourability, because it does not alter the free energies of the reactants or products. It only changes how fast the system reaches equilibrium. Raising the temperature has a similar kinetic effect (more collisions clear the barrier), though temperature can also change through the term.
Try this
Q1. A reaction has but does not proceed at room temperature. State whether the problem is thermodynamic or kinetic, and explain. [2 points]
- Cue. Kinetic; the reaction is favorable () but has a high activation energy, so the rate is negligible.
Q2. State whether a catalyst changes the favourability of a reaction, and explain. [2 points]
- Cue. No; a catalyst lowers the activation energy and speeds the reaction but does not change or the favourability.
Exam-style practice questions
Practice questions written in the style of College Board exam questions on this dot point, with worked answer explainers. The year tag is the paper they imitate, not the source.
AP 2022 (style)4 marksSection II (long FRQ, part). The reaction has , yet diamonds do not noticeably turn to graphite. (a) State whether the reaction is thermodynamically favorable, and justify. (b) Explain why diamond persists despite this. (c) Explain the role of activation energy in this behavior. (d) Describe how a catalyst would change the rate but not the favourability.Show worked answer →
A 4-point conceptual FRQ on kinetic control.
(a) Favourability (1 point): , so the conversion of diamond to graphite is thermodynamically favorable (spontaneous in the thermodynamic sense).
(b) Persistence (1 point): the reaction is favorable but kinetically hindered; the activation energy is enormous, so the rate is immeasurably slow at room temperature and diamond persists.
(c) Activation energy (1 point): a high activation energy means almost no collisions have enough energy to rearrange the carbon lattice, so even a favorable reaction proceeds at a negligible rate.
(d) Catalyst (1 point): a catalyst would lower the activation energy and speed the reaction, but it would not change or the favourability, only how fast equilibrium is approached.
Markers reward the favorable conclusion, the kinetic-hindrance reasoning, the activation-energy explanation, and the catalyst distinction.
AP 2021 (style)1 marksSection I (multiple choice). A reaction has but proceeds extremely slowly. The most likely reason is (A) is wrong (B) the reaction has a high activation energy (kinetic control) (C) the reaction is endothermic (D) the entropy decreases. Justify your choice.Show worked answer →
A 1-point conceptual MCQ. The answer is (B).
A favorable reaction () can still be slow if it has a high activation energy, so it is kinetically controlled; thermodynamics says it can happen, kinetics says how fast. The trap is (A): a negative is consistent with a slow reaction; the two describe different things.
Related dot points
- Topic 9.3 Gibbs Free Energy and Thermodynamic Favorability: use the equation delta G equals delta H minus T delta S to determine thermodynamic favourability and the temperature dependence of spontaneity.
A focused answer to AP Chemistry Topic 9.3, covering the Gibbs free energy equation, how the signs of enthalpy and entropy determine favourability, the temperature dependence of spontaneity, and the four sign cases, with full worked examples.
- Topic 5.5 Collision Model: use collision theory and the Arrhenius equation to explain how activation energy, temperature, orientation and collision frequency control the rate constant.
A focused answer to AP Chemistry Topic 5.5, covering collision theory, activation energy, the Maxwell-Boltzmann distribution, molecular orientation, and the Arrhenius equation linking rate constant to temperature, with full worked examples.
- Topic 5.11 Catalysis: explain how a catalyst increases the rate by providing an alternative pathway with a lower activation energy, and distinguish homogeneous, heterogeneous and enzyme catalysis.
A focused answer to AP Chemistry Topic 5.11, covering how a catalyst lowers the activation energy by offering an alternative mechanism, the types of catalysis (homogeneous, heterogeneous, enzymatic), and why a catalyst leaves enthalpy and equilibrium unchanged, with full worked examples.
- Topic 5.6 Reaction Energy Profile: interpret a potential-energy diagram to identify the activation energy of the forward and reverse reactions, the transition state and the enthalpy of reaction.
A focused answer to AP Chemistry Topic 5.6, covering the potential-energy diagram, the transition state, the activation energy of the forward and reverse reactions, the relationship to enthalpy of reaction, and the effect of a catalyst, with full worked examples.
- Topic 9.5 Free Energy and Equilibrium: relate the standard free energy change to the equilibrium constant using delta G standard equals minus RT ln K, and use delta G equals delta G standard plus RT ln Q for non-standard conditions.
A focused answer to AP Chemistry Topic 9.5, covering the relationship between the standard free energy change and the equilibrium constant, delta G standard equals minus RT ln K, the non-standard delta G equation, and how the sign of delta G standard relates to the size of K, with full worked examples.
Sources & how we know this
- AP Chemistry Course and Exam Description — College Board (2020)