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Ozone, \(\mathrm{O}_{3,}\) in the Earth's upper atmosphere decomposes according to the equation $$ 2 \mathrm{O}_{3}(\mathrm{g}) \rightarrow 3 \mathrm{O}_{2}(\mathrm{g}) $$ The mechanism of the reaction is thought to proceed through an initial fast, reversible step followed by a slow, second step. Step 1: Fast, reversible $$ \mathrm{O}_{3}(\mathrm{g}) \rightleftarrows \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}(\mathrm{g}) $$ Step 2: Slow $$ \mathrm{O}_{3}(\mathrm{g})+\mathrm{O}(\mathrm{g}) \rightarrow 2 \mathrm{O}_{2}(\mathrm{g}) $$ (a) Which of the steps is rate-determining? (b) Write the rate equation for the rate-determining step.

Short Answer

Expert verified
Step 2 is the rate-determining step; rate equation: \(\text{Rate} = k[\mathrm{O}_{3}][\mathrm{O}]\).

Step by step solution

01

Identify the Rate-Determining Step

The rate-determining step is usually the slowest step in a reaction mechanism. Here, Step 2 is labeled as 'Slow.' Therefore, Step 2 is the rate-determining step.
02

Write the Rate Equation for the Slow Step

The rate equation can be derived from the rate-determining step. In Step 2, the reactants are \(\mathrm{O}_{3}(\mathrm{g})\) and \(\mathrm{O}(\mathrm{g})\). The rate law is based on these reactants, thus the rate equation is: \(\text{Rate} = k[\mathrm{O}_{3}][\mathrm{O}]\), where \(k\) is the rate constant.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Reaction Mechanism
A reaction mechanism is a sequence of elementary steps that leads to the overall chemical reaction. Each step represents a single transformation where bonds are broken and formed, involving a few molecules at a time. Understanding the mechanism helps us predict the rate of reaction and describe how the reactants transform into products.
In the exercise about ozone decomposition, the reaction mechanism consists of two steps:
  • Step 1: Fast and reversible; \(\mathrm{O}_{3}(g) \rightleftharpoons \mathrm{O}_{2}(g) + \mathrm{O}(g)\)
  • Step 2: Slow and irreversible; \(\mathrm{O}_{3}(g) + \mathrm{O}(g) \rightarrow 2\mathrm{O}_{2}(g)\)
The first step involves the formation of \(\mathrm{O}(g)\) and is quickly reversible, reaching a temporary equilibrium. In contrast, the second step consumes \(\mathrm{O}(g)\), producing oxygen molecules. Together, these steps describe how ozone decomposes in the upper atmosphere.
Rate-determining Step
In a multistep reaction, one step typically controls the reaction speed, called the rate-determining step. It's often the slowest step because it forms a bottleneck that dictates how quickly the overall reaction can proceed.
From the given reaction mechanism of ozone decomposition, the second step (\(\mathrm{O}_{3}(g) + \mathrm{O}(g) \rightarrow 2\mathrm{O}_{2}(g)\)) is labeled as 'Slow.' This indicates that it is the rate-determining step. Since it's the slowest step, it limits the speed at which the ozone decomposes into oxygen molecules.
Understanding which step is rate-determining allows chemists to focus on that part to control or optimize the reaction rate. If this step can be sped up, the entire reaction could potentially proceed faster.
Rate Equation
The rate equation quantifies the speed of a reaction, expressed usually in terms of the concentration of reactants for the rate-determining step. This mathematical representation allows us to calculate the reaction rate and understand how changes in concentration affect it.
For the ozone decomposition mechanism, the rate-determining step involves \(\mathrm{O}_{3}(g)\) and \(\mathrm{O}(g)\). Therefore, its rate equation is: \[\text{Rate} = k[\mathrm{O}_{3}][\mathrm{O}]\] Here:
  • \(k\) is the rate constant, a factor that includes the reaction's temperature sensitivity and other conditions.
  • The concentration terms \([\mathrm{O}_{3}]\) and \([\mathrm{O}]\) indicate that the rate depends on both ozone and atomic oxygen concentrations.
This equation is crucial for calculating the reaction rate and performing experiments that can validate the proposed mechanism or help discover unknown components affecting the reaction.

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Most popular questions from this chapter

Identify which of the following statements are incorrect. If the statement is incorrect, rewrite it to be correct. (a) Reactions are faster at a higher temperature because activation energies are lower. (b) Rates increase with increasing concentration of reactants because there are more collisions between reactant molecules. (c) At higher temperatures, a larger fraction of molecules have enough energy to get over the activation energy barrier. (d) Catalyzed and uncatalyzed reactions have identical mechanisms.

A reaction that occurs in our atmosphere is the oxidation of NO to the brown gas \(\mathrm{NO}_{2}\) $$ 2 \mathrm{NO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g}) $$ The mechanism of the reaction is thought to be Step \(1: \quad 2 \mathrm{NO}(\mathrm{g}) \rightleftharpoons \mathrm{N}_{2} \mathrm{O}_{2}(\mathrm{g})\) rapidly established equilibrium Step \(2: \quad \mathrm{N}_{2} \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g}) \quad\) slow Which is the rate determining step? Is there an intermediate in the reaction? If this is the correct mechanism for this reaction, what is the experimentally determined rate law?

The decomposition of phosphine, \(\mathrm{PH}_{3}\), proceeds according to the equation $$ \mathrm{PH}_{3}(\mathrm{g}) \rightarrow^{1 / 4} \mathrm{P}_{4}(\mathrm{g})+3 / 2 \mathrm{H}_{2}(\mathrm{g}) $$ It is found that the reaction has the following rate equation: Rate \(=k\left[\mathrm{PH}_{3}\right] .\) The half-life of \(\mathrm{PH}_{3}\) is 37.9 seconds at \(120^{\circ} \mathrm{C}\) (a) How much time is required for three fourths of the \(\mathrm{PH}_{3}\) to decompose? (b) What fraction of the original sample of \(\mathrm{PH}_{3}\) remains after 1.00 minute?

Hypofluorous acid, HOF, is very unstable, decomposing in a first-order reaction to give HF and \(\mathrm{O}_{2},\) with a half-life of \(30 .\) minutes at room temperature: $$ \mathrm{HOF}(\mathrm{g}) \rightarrow \mathrm{HF}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g}) $$ If the partial pressure of HOF in a 1.00-L flask is initially \(1.00 \times 10^{2} \mathrm{mm}\) Hg at \(25^{\circ} \mathrm{C},\) what are the total pressure in the flask and the partial pressure of HOF after exactly 30 minutes? After 45 minutes?

The decomposition of \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\) is a first-order reaction: $$ \mathrm{SO}_{2} \mathrm{Cl}_{2}(\mathrm{g}) \rightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g}) $$ The rate constant for the reaction is \(2.8 \times\) \(10^{-3} \min ^{-1}\) at \(600 \mathrm{K} .\) If the initial concentration of \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\) is \(1.24 \times 10^{-3} \mathrm{mol} / \mathrm{L},\) how long will it take for the concentration to drop to \(0.31 \times\) \(10^{-3} \mathrm{mol} / \mathrm{L} ?\)

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