/*! This file is auto-generated */ .wp-block-button__link{color:#fff;background-color:#32373c;border-radius:9999px;box-shadow:none;text-decoration:none;padding:calc(.667em + 2px) calc(1.333em + 2px);font-size:1.125em}.wp-block-file__button{background:#32373c;color:#fff;text-decoration:none} Problem 63 At temperatures below \(500 \mat... [FREE SOLUTION] | 91Ó°ÊÓ

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At temperatures below \(500 \mathrm{K}\), the reaction between carbon monoxide and nitrogen dioxide $$ \mathrm{CO}(\mathrm{g})+\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{NO}(\mathrm{g}) $$ has the following rate equation: Rate \(=k\left[\mathrm{NO}_{2}\right]^{2}\) Which of the three mechanisms suggested here best agrees with the experimentally observed rate equation? Mechanism 1 \(\quad\) single, elementary step $$ \mathrm{NO}_{2}+\mathrm{CO} \rightarrow \mathrm{CO}_{2}+\mathrm{NO} $$ Mechanism \(2 \quad\) Two steps Slow $$ \mathrm{NO}_{2}+\mathrm{NO}_{2} \rightarrow \mathrm{NO}_{3}+\mathrm{NO} $$ Fast $$ \mathrm{NO}_{3}+\mathrm{CO} \rightarrow \mathrm{NO}_{2}+\mathrm{CO}_{2} $$ Mechanism 3 Two steps Slow $$ \mathrm{NO}_{2} \rightarrow \mathrm{NO}+\mathrm{O} $$ Fast $$ \mathrm{CO}+\mathrm{O} \rightarrow \mathrm{CO}_{2} $$

Short Answer

Expert verified
Mechanism 2 is the correct mechanism.

Step by step solution

01

Identify the given rate equation

The problem states that the rate of the reaction is given by the equation \( \text{Rate} = k[\text{NO}_2]^2 \). This implies that the reaction rate is dependent on the concentration of \( \text{NO}_2 \) squared, suggesting that two molecules of \( \text{NO}_2 \) are involved in the rate-determining step.
02

Analyze Mechanism 1

Mechanism 1 proposes a single, elementary step: \( \text{NO}_2 + \text{CO} \rightarrow \text{CO}_2 + \text{NO} \). In this mechanism, the rate law would be \( \text{Rate} = k[\text{NO}_2][\text{CO}] \), which doesn't match the given rate law of \( \text{Rate} = k[\text{NO}_2]^2 \). Therefore, Mechanism 1 cannot be the correct mechanism.
03

Analyze Mechanism 2

Mechanism 2 consists of two steps:1. Slow: \( \text{NO}_2 + \text{NO}_2 \rightarrow \text{NO}_3 + \text{NO} \)2. Fast: \( \text{NO}_3 + \text{CO} \rightarrow \text{NO}_2 + \text{CO}_2 \)In the slow step, two molecules of \( \text{NO}_2 \) are involved, which aligns with the given rate law \( \text{Rate} = k[\text{NO}_2]^2 \). This mechanism matches the observed rate equation, indicating that the first step is the rate-determining step.
04

Analyze Mechanism 3

Mechanism 3 also consists of two steps:1. Slow: \( \text{NO}_2 \rightarrow \text{NO} + \text{O} \)2. Fast: \( \text{CO} + \text{O} \rightarrow \text{CO}_2 \)The slow step involves only one \( \text{NO}_2 \) molecule, leading to a rate law of \( \text{Rate} = k[\text{NO}_2] \), which does not match the observed rate law \( \text{Rate} = k[\text{NO}_2]^2 \). Thus, Mechanism 3 isn't suitable.
05

Conclusion: Determine the suitable mechanism

Based on the analysis, Mechanism 2 is the only one that matches the experimental rate law \( \text{Rate} = k[\text{NO}_2]^2 \) because the rate-determining step involves two molecules of \( \text{NO}_2 \) reacting.

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Key Concepts

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

Rate-Determining Step
In a multi-step chemical reaction, not all steps occur at the same speed. The rate-determining step is the slowest step in the sequence and effectively limits the rate at which the overall reaction proceeds. When analyzing reaction mechanisms, identifying the rate-determining step is crucial because it controls the kinetics of the reaction.

Consider the reaction between carbon monoxide and nitrogen dioxide where we have to choose from three proposed mechanisms. Each mechanism offers a different pathway for the reaction, and the rate-determining step would dictate which mechanism matches the observed rate law. A slow step involving two NO₂ molecules aligns with the experimental observation, as it matches the rate law of Rate = k[NO₂]², indicating that two molecules must collide in the rate-determining step. Therefore, Mechanism 2, with a slow step involving NO₂ + NO₂, is consistent with the given data.
Rate Law
The rate law for a chemical reaction expresses the relationship between the reaction rate and the concentration of its reactants. It takes the form Rate = k[ ext{Reactant1}][ ext{Reactant2}], where k is the rate constant, reflecting factors like temperature and catalyst presence.

For understanding our reaction, we consider the given rate law Rate = k[NO₂]². This indicates that the rate is second-order with respect to NO₂ and independent of CO concentration under the conditions specified. Such a rate law implies that any plausible mechanism must involve two NO₂ molecules in the rate-determining step. When comparing the potential mechanisms, the rate law points us towards Mechanism 2, which involves two NO₂ molecules in its slow step, conforming to the experimentally determined rate expression.
Chemical Kinetics
Chemical kinetics is the study of reaction rates and the steps by which they occur. It helps us understand how different variables such as concentration, temperature, and catalysts affect reaction progress. This vital area of chemistry extends beyond merely predicting how fast a reaction will occur by dissecting the mechanism—or the series of steps—leading to the product formation.

Examining the reaction of CO with NOâ‚‚ offers a classic application of principles from chemical kinetics. The process involves analyzing each proposed mechanism step-by-step, considering the slowest (rate-determining) step's contribution to the reaction kinetics. Mechanism 2 contains a slow initial step involving two NOâ‚‚ molecules, which chemically validates the observed rate law according to theories of chemical kinetics, making it the most suitable mechanism for explaining the reaction's behavior at temperatures below 500 K.

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Most popular questions from this chapter

Many biochemical reactions are catalyzed by acids. A typical mechanism consistent with the experimental results (in which HA is the acid and X is the reactant) is Step \(1: \quad\) Fast, reversible: \(\quad \mathrm{HA} \rightleftarrows \mathrm{H}^{+}+\mathrm{A}^{-}\) Step \(2: \quad\) Fast, reversible: \(\quad \mathrm{X}+\mathrm{H}^{+} \rightleftharpoons \mathrm{XH}^{+}\) Step 3: Slow \(\mathrm{XH}^{+} \rightarrow\) products What rate law is derived from this mechanism? What is the order of the reaction with respect to HA? How would doubling the concentration of HA affect the reaction?

Draw a reaction coordinate diagram for an exothermic reaction that occurs in a single step. Identify the activation energy and the net energy change for the reaction on this diagram. Draw a second diagram that represents the same reaction in the presence of a catalyst, assuming a single-step reaction is involved here also. Identify the activation energy of this reaction and the energy change. Is the activation energy in the two drawings different? Does the energy evolved in the two reactions differ?

Isotopes are often used as "tracers" to follow an atom through a chemical reaction, and the following is an example. Acetic acid reacts with methanol. Explain how you could use the isotope \(^{18} \mathrm{O}\) to show whether the oxygen atom in the water comes from the \(-\) OH of \(\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\) or the \(-\mathrm{OH}\) of \(\mathrm{CH}_{3} \mathrm{OH}\).

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?

Using the rate equation Rate \(=k[\mathrm{A}]^{2}[\mathrm{B}],\) define the order of the reaction with respect to A and B. What is the total order of the reaction?

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