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Understand activation energy, collision theory, the Arrhenius equation, and how temperature affects reaction rates.
Learn step-by-step with practice exercises built right in.
For reaction to occur, particles must:
Not all collisions lead to reaction:
Activation energy: Minimum energy needed for reaction
Energy diagram:
Key points:
A reaction has Ea = 75 kJ/mol. At 300 K, k = 2.0 ร 10โปยณ sโปยน. What is k at 350 K?
Given:
Use two-point Arrhenius:
| Section | Format | Questions | Time | Weight | Calculator |
|---|---|---|---|---|---|
| Multiple Choice | MCQ | 60 | 90 min | 50% | โ |
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| Free Response (Short) | FRQ | 4 | 36 min | 20% | โ |
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Temperature dependence of k:
Where:
Linear form:
Plot ln(k) vs 1/T: Straight line, slope = -Ea/R
Compare k at two temperatures:
Useful for:
General rule: Rate roughly doubles for every 10ยฐC increase
Why higher T increases rate:
Exponential dependence: Small T change โ large k change
Exothermic reaction:
Endothermic reaction:
Both have Ea barrier:
Catalyst: Substance that increases rate without being consumed
How catalysts work:
Types:
Example: Decomposition of HโOโ
Calculate 1/Tโ - 1/Tโ:
Calculate Ea/R:
Calculate ln(kโ/kโ):
Solve for kโ:
Answer: kโ = 0.15 sโปยน
Interpretation: 50ยฐC increase โ rate constant increased 73-fold!
For a reaction, k = 3.2 ร 10โปโด sโปยน at 500 K and k = 1.5 ร 10โปยฒ sโปยน at 600 K. Calculate (a) Ea and (b) the frequency factor A.
Given:
(a) Calculate Ea
Use two-point form:
Calculate ln(kโ/kโ):
Calculate 1/Tโ - 1/Tโ:
Solve for Ea:
Answer (a): Ea = 96 kJ/mol
(b) Calculate A
Use Arrhenius equation at either temperature (use Tโ = 500 K):
Calculate Ea/(RTโ):
Calculate A:
Answer (b): A = 3.5 ร 10โถ sโปยน
Check with Tโ: kโ = (3.5 ร 10โถ)e^(-96100/(8.314ร600)) = (3.5 ร 10โถ)e^(-19.25) = (3.5 ร 10โถ)(4.3 ร 10โปโน) = 1.5 ร 10โปยฒ โ
Draw and label an energy diagram for an exothermic reaction with Ea = 80 kJ/mol and ฮH = -50 kJ/mol. What is the activation energy for the reverse reaction?
Given:
Energy Diagram:
Energy
โ
| Transition State
| โ โ
| โ โ Ea(reverse) = 130 kJ
| โ โ
| โ Ea(fwd) โ
| โ 80 kJ โ
Reactants Products
| โ ฮH = -50 kJ
|___________________
|__________________|
Reaction Progress โ
Key points:
Calculate Ea(reverse):
Relationship for exothermic:
But ฮH = -50 kJ (negative), so:
Or think of it as:
Answer: Ea(reverse) = 130 kJ/mol
General relationships:
Exothermic (ฮH < 0):
Endothermic (ฮH > 0):
Always:
If catalyst added:
From an Arrhenius plot, ln(k) = โ9500(1/T) + 18.2. Find (a) Ea and (b) A.
Slope m = โ9500 โ Ea = โmR = 9500ร8.314 = 7.90ร10^4 J/mol = 79.0 kJ/mol. Intercept b = 18.2 โ A = e^{18.2} โ 9.91ร10^7 (units of sโปยน for first-order).
Two reactions: (I) Aโ = 2.0ร10^12 sโปยน, Eaโ = 85 kJ/mol; (II) Aโ = 4.0ร10^10 sโปยน, Eaโ = 65 kJ/mol. At 298 K, which is faster and by what factor?
Compute k = A e^{โEa/RT}. Use R = 8.314 J/(molยทK). Convert Ea to J/mol. For I: exponent = โ85000/(8.314ร298) = โ34.3 โ kโ โ 2.0ร10^12 ร e^{โ34.3} = 2.0ร10^12 ร 1.2ร10^{โ15} โ 2.4ร10^{โ3} sโปยน. For II: exponent = โ65000/(8.314ร298) = โ26.2 โ kโ โ 4.0ร10^10 ร e^{โ26.2} = 4.0ร10^10 ร 4.3ร10^{โ12} โ 0.172 sโปยน. Reaction II is faster by factor โ kโ/kโ โ 0.172 / 2.4ร10^{โ3} โ 71.
By what temperature increase ฮT (ยฐC) will a reaction with Ea = 95 kJ/mol approximately double its rate near 300 K?
Use two-point form with kโ/kโ = 2 and Tโ = 300 K, Tโ = 300 + ฮT. ln(2) = (Ea/R)(1/Tโ โ 1/Tโ). Solve approximately with Tโ โ Tโ + ฮT and small ฮT: 1/Tโ โ 1/Tโ โ ฮT/Tโ^2. Thus ln(2) โ (Ea/R)(ฮT/Tโ^2) โ ฮT โ ln(2)ยทRยทTโ^2 / Ea. Plug in: ฮT โ 0.693ร8.314ร(300)^2 / 95000 โ (0.693ร8.314ร90000)/95000 โ (5187)/95000 โ 0.0546ร10^2 โ 5.46 ยฐC. So roughly a 5โ6 ยฐC increase doubles the rate (depends on Ea and starting T).
A catalyst lowers Ea from 120 kJ/mol to 80 kJ/mol. At 350 K, by what factor does the rate constant increase (assume A unchanged)?
Factor = k_cat/k_uncat = e^{โEa_cat/RT} / e^{โEa_uncat/RT} = e^{(Ea_uncat โ Ea_cat)/(RT)}. ฮEa = 40 kJ/mol = 4.0ร10^4 J/mol; RT = 8.314ร350 โ 2910 J/mol. Factor โ e^{40000/2910} = e^{13.7} โ 9.0ร10^5. So k increases by ~9ร10^5.