Speed both directions without moving equilibrium
Lower an assigned barrier and distinguish faster equilibration from a changed equilibrium mixture.
Learning outcome: Explain why a catalyst changes the approach to equilibrium while preserving its position at fixed temperature.
Starting recap
For the first-order A ⇌ B model, equilibrium means k_forward[A] = k_reverse[B]. Therefore equilibrium B/A equals the ratio of rate constants.
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Try
A catalyst makes product appear sooner. Must the equilibrium mixture contain a larger product fraction?
Open the experimentPredict
At 300 K, predict what lowering both activation barriers by 20 kJ/mol changes: forward rate, reverse rate, rate-constant ratio or equilibrium composition.
Experiment
At 300 K compare lowering values 0, 10 and 20 kJ/mol. Capture the extremes and compare both rate-constant factors and relaxation times. Then change temperature at fixed lowering and explain why this is a different intervention.
Change temperature and a shared activation barrier
Worked teaching model · synthetic values · Synthetic reversible first-order A ⇌ B with equal fixed Arrhenius prefactors of 10⁸ s⁻¹. Baseline forward/reverse activation energies are 60/70 kJ/mol; a catalyst-like control lowers both by the same amount. Assigned endpoint energies are A = 0 and B = −10 kJ/mol. This effective one-barrier model omits real catalyst mechanisms, changes in prefactors, transport, deactivation and measurement noise. R = 8.314 J/(mol K); temperature is absolute.
Reset keeps your prediction, captures and practice history.
The forward barrier is measured upward from A; the reverse barrier is measured upward from B. Moving the shared peak changes both barriers while their 10 kJ/mol difference remains fixed. The drawing is an assigned energy diagram, not a measured molecular path or an animation.
| Quantity | Baseline | Selected |
|---|---|---|
| Forward barrier | 60 kJ/mol | 60 kJ/mol |
| Reverse barrier | 70 kJ/mol | 70 kJ/mol |
| Forward rate constant | 3.570218e-3 s⁻¹ | 3.570218e-3 s⁻¹ |
| Reverse rate constant | 6.478540e-5 s⁻¹ | 6.478540e-5 s⁻¹ |
| Equilibrium B/A ratio | 55.108368 | 55.108368 |
| Time to halve displacement from equilibrium | 1.906868e+2 s | 1.906868e+2 s |
Equilibrium B fraction for the two-state conserved A+B model: 98.2177%. This is an equilibrium composition, not the product yield at a specified observation time. The rate-constant chart below uses a fixed linear 0–100 s⁻¹ scale; very small nonzero values remain explicit in the scientific-notation ledger above.
| Row | Quantity | Value (s⁻¹) |
|---|---|---|
| 1 | Baseline forward rate constant | 0.0036 |
| 2 | Selected forward rate constant | 0.0036 |
| 3 | Baseline reverse rate constant | 6.478540e-5 |
| 4 | Selected reverse rate constant | 6.478540e-5 |
Both rate constants change by a factor of 1.000 relative to the baseline at 300 K.
Equilibrium B/A ratio = 55.108368, unchanged by the barrier-lowering control at fixed temperature. Time to halve displacement from equilibrium = 1.906868e+2 s. These are rate constants, not concentration-change rates; concentrations are required to obtain rates.
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Understand
Apply
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Explain why lowering only the forward barrier would be inconsistent with the catalyst model. Distinguish a faster fixed-time yield from a changed equilibrium yield and a catalyst from a reagent consumed overall.
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