Steady-State Approximation

Caleb Thomas
7 min read
Study Guide Overview
This study guide covers reaction mechanisms, including elementary steps, overall reactions, intermediates, and catalysts. It explains the rate-determining step and the steady-state approximation, using the bathtub analogy. The guide also demonstrates how to apply the steady-state approximation when the first step isn't slow, including an example walkthrough. Finally, it provides practice questions and exam tips for AP Chemistry.
AP Chemistry: Reaction Mechanisms & Steady State Approximation ๐
Hey there, future AP Chem master! Let's break down reaction mechanisms and the steady-state approximation. Think of this as your cheat sheet for acing those kinetics questions. You've got this! ๐ช
Reaction Mechanisms: The Step-by-Step Story ๐
What's a Mechanism?
A reaction mechanism is a series of elementary steps that show how a reaction actually occurs at the molecular level. It's like the behind-the-scenes story of a chemical reaction.
- Elementary Step: A single molecular event (e.g., collision, bond breaking/forming).
- Overall Reaction: The sum of all elementary steps. It shows the net change.
Intermediates vs. Catalysts
- Intermediates: Species that are produced in one step and consumed in a later step. They don't appear in the overall reaction.
- Think of them as short-lived actors in the play.
- Catalysts: Species that speed up a reaction but are not consumed in the overall reaction. They appear in the reactants and products.
- They are like stage directors who make the play happen faster.
Intermediates are produced and then consumed, while catalysts are used and then regenerated.
Rate-Determining Step
- The slowest step in a reaction mechanism. It determines the overall rate of the reaction.
- Think of it as the bottleneck in a factory - the slowest process limits the overall production rate.
Steady-State Approximation: The Bathtub Analogy ๐
The Concept
Imagine a bathtub being filled by a faucet and drained by a plug. Initially, the water level changes, but eventually, it reaches a point where the rate of water entering equals the rate of water leaving. This is the steady state.
Bathtub Analogy: Faucet = reactants entering, drain = products leaving, water level = concentration.
In chemical reactions, the steady-state approximation assumes that the concentration of intermediates remains constant over time. This happens when the rate of formation of the intermediate equals its rate of consumption.
Why Use It?
- Simplifies complex rate laws, especially when the first step is not the slow step.
- Allows us to express the rate law in terms of reactants and products, not intermediates.
Applying Steady-State: When the First Step Isn't Slow โก
The Challenge
When the first step is fast and reversible, the slow step's rate law will often include intermediates. We need to get rid of those intermediates!
The Solution: Substitution!
- Identify the Intermediate: Find the species that's formed and then consumed.
- Set Up Equilibrium: For the fast, reversible step, set the forward rate equal to the reverse rate.
- Solve for the Intermediate: Express the concentration of the intermediate in terms of reactants.
- Substitute: Plug the intermediate's expression into the slow step's rate law.
Example Walkthrough
Let's use the example from your notes:
Mechanism:
- Step 1: 2NO โ NโOโ (Fast, Reversible)
- Step 2: NโOโ + Hโ โ HโO + NโO (Slow)
Steps:
- Intermediate: NโOโ
- Equilibrium: rateโ = kโ[NO]ยฒ = rateโ = kโ[NโOโ]
- Solve for [NโOโ]: [NโOโ] = (kโ/kโ)[NO]ยฒ = k'[NO]ยฒ
- Slow Step Rate: rate = k[NโOโ][Hโ]
- Substitute: rate = k * k'[NO]ยฒ[Hโ] = k"[NO]ยฒ[Hโ]
Remember to replace the intermediate in the rate law of the slow step. Don't leave it in the final rate law.
Key Takeaways
- If the first step is fast, use the steady-state approximation.
- Equate forward and reverse rates for the fast step.
- Solve for the intermediate and substitute into the slow step rate law.
Forgetting to substitute the intermediate in the slow step's rate law is a common error. Always ensure your final rate law only includes species from the overall reaction!
Visual Aid
Image courtesy of SDMESA.
Final Exam Focus ๐ฏ
High-Priority Topics
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Reaction Mechanisms: Identifying intermediates, catalysts, and the rate-determining step.
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Steady-State Approximation: Applying it when the first step is not slow.
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Rate Laws: Deriving rate laws from mechanisms.
Reaction mechanisms and rate laws are frequently tested. Master these concepts!
Common Question Types
- Multiple Choice: Identifying intermediates, catalysts, rate-determining steps, and correct rate laws.
- Free Response: Deriving rate laws using the steady-state approximation, proposing mechanisms, and explaining the role of catalysts.
Last-Minute Tips
- Time Management: Don't spend too long on one question. If you're stuck, move on and come back later.
- Check Your Work: Make sure your final rate law only contains reactants from the overall reaction.
- Practice: Work through as many practice problems as you can. It builds confidence!
Always double-check that your final rate law only contains reactants from the overall balanced equation. Intermediates should be eliminated!
Practice Questions
Practice Question
Multiple Choice Questions
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The rate law for the reaction 2A + B โ C is found to be rate = k[A][B]ยฒ. Which of the following mechanisms is consistent with this rate law? (A) A + B โ X (slow), X + B โ C (fast) (B) A + B โ X (fast), X + B โ C (slow) (C) 2A + B โ X (slow), X โ C (fast) (D) A + B โ X (slow), X + A โ C (fast)
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In a multi-step reaction, the rate-determining step is the: (A) fastest step (B) slowest step (C) step with the highest activation energy (D) step with the lowest activation energy
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A reaction mechanism involves the following steps: Step 1: A + B โ C (fast equilibrium) Step 2: C + D โ E (slow) What is the rate law for the overall reaction? (A) rate = k[C][D] (B) rate = k[A][B][D] (C) rate = k[A][B] (D) rate = k[A][B][D]ยฒ
Free Response Question
The following reaction mechanism is proposed for the reaction between nitrogen dioxide and carbon monoxide:
Step 1: NOโ + NOโ โ NOโ + NO (slow) Step 2: NOโ + CO โ NOโ + COโ (fast)
(a) Write the overall balanced equation for the reaction. (b) Identify any intermediates in the mechanism. (c) What is the rate law predicted by this mechanism? (d) If the experimental rate law is found to be rate = k[NOโ]ยฒ, does this mechanism agree with the experimental data? Explain.
Scoring Breakdown:
(a) (1 point) * NOโ + CO โ NO + COโ
(b) (1 point) * NOโ
(c) (1 point) * rate = k[NOโ]ยฒ
(d) (2 points) * Yes, the mechanism agrees with the experimental data because the rate law derived from the slow step matches the experimental rate law.
Combining Units
Consider the following reaction mechanism:
Step 1: A โ B (fast equilibrium) Step 2: B + C โ D (slow)
Given that the equilibrium constant for Step 1 is K = 2.0 and the rate constant for Step 2 is k = 0.50 Mโปยนsโปยน, calculate the rate of formation of D when [A] = 1.0 M and [C] = 2.0 M.
Solution:
- From Step 1: K = [B]/[A] => [B] = K[A] = 2.0 * 1.0 M = 2.0 M
- From Step 2: rate = k[B][C] = 0.50 Mโปยนsโปยน * 2.0 M * 2.0 M = 2.0 M/s
Remember, you've got the tools and the knowledge. Stay calm, stay focused, and you'll nail this exam! ๐

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Question 1 of 12
What is an elementary step in a reaction mechanism? ๐
The overall reaction from reactants to products
A single molecular event involving collision or bond change
A step involving a catalyst
The fastest step in a reaction mechanism