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The decomposition of dinitrogen pentaoxide $$ \mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g}) $$ has the following rate equation: Rate \(=k\left[\mathrm{N}_{2} \mathrm{O}_{5}\right] .\) It has been found experimentally that the decomposition is \(20.5 \%\) complete in 13.0 hours at 298 K. Calculate the rate constant and the half-life at 298 K.

Short Answer

Expert verified
Rate constant: \( k = 0.016 h^{-1} \), half-life: \( t_{1/2} = 43.3 \) hours.

Step by step solution

01

Understand the Problem

We have a first-order decomposition reaction and need to find the rate constant \( k \) and the half-life for the reaction. It is given that the reaction is 20.5% complete in 13.0 hours at 298 K.
02

Use the First-Order Rate Law

For a first-order reaction, we use the rate law: \[ k = \frac{1}{t} \ln \left(\frac{[A]_0}{[A]}\right) \] where \( t \) is time, \( [A]_0 \) is the initial concentration, and \( [A] \) is the concentration at time \( t \). Since 20.5% of the reactant has decomposed, \( [A] = 0.795[A]_0 \).

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Key Concepts

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

First-Order Reaction
In chemical kinetics, a first-order reaction is characterized by its rate being directly proportional to the concentration of a single reactant. This means that as the concentration of the reactant decreases, the rate of reaction decreases at a similar rate. The mathematical representation of a first-order reaction is given by the rate law equation: \[\text{Rate} = k[A] \]Where:
  • \( k \) is the rate constant, a unique value characteristic of the reaction under specific conditions.
  • \([A]\) is the concentration of the reactant.
This representation indicates that if you double the concentration of the reactant, the rate also doubles. Such reactions follow an exponential decay pattern, which is reflected in their calculations.
Rate Constant Calculation
The rate constant \( k \) is a crucial value in the study of reaction kinetics because it provides insight into the speed of the reaction. For first-order reactions, it can be calculated using the integrated rate law:\[ k = \frac{1}{t} \ln \left(\frac{[A]_0}{[A]}\right) \]Where:
  • \( t \) is the given time period, here 13.0 hours.
  • \([A]_0\) is the initial concentration of the reactant.
  • \([A]\) is the concentration of the reactant at time \( t \).
For the exercise, \( [A] = 0.795[A]_0 \) because 20.5% of the reactant is used up. Substitute these values into the rate law to find \( k \). Understanding the behavior of \( k \) helps predict how a reaction progresses under different conditions.
Half-Life Determination
In first-order kinetics, the half-life \( t_{1/2} \) is the time required for the concentration of the reactant to decrease to half of its initial value. One of the interesting properties of a first-order reaction is that its half-life is constant and does not depend on the initial concentration. The equation relating the half-life to the rate constant is:\[t_{1/2} = \frac{0.693}{k}\]This relationship makes calculating half-life straightforward once \( k \) is determined. Since the half-life is constant, it is especially useful in predicting how long a reaction will take to proceed through various stages, regardless of how much of the reactant is present at the start.

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Most popular questions from this chapter

The decomposition of ammonia on a metal surface to form \(\mathrm{N}_{2}\) and \(\mathrm{H}_{2}\) is a zero-order reaction (Figure \(14.7 \mathrm{c}) .\) At \(873^{\circ} \mathrm{C},\) the value of the rate constant is \(1.5 \times 10^{-3} \mathrm{mol} / \mathrm{L} \cdot \mathrm{s}\). How long it will take to completely decompose 0.16 g of \(\mathrm{NH}_{3}\) in a \(1.0-\mathrm{L}\) flask?

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?

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 $$ \mathrm{CO}+\mathrm{O} \rightarrow \mathrm{CO}_{2} $$

The ozone in the Earth's ozone layer 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 equilibrium and a slow step: Step 1: Fast, reversible \(\quad \mathrm{O}_{3}(\mathrm{g}) \rightleftharpoons \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}(\mathrm{g})\) Step 2: Slow \(\quad \mathrm{O}_{3}(\mathrm{g})+\mathrm{O}(\mathrm{g}) \rightarrow 2 \mathrm{O}_{2}(\mathrm{g})\) Show that the mechanism agrees with this experimental rate law: $$ \text { Rate }=-(1 / 2) \Delta\left[\mathrm{O}_{3}\right] / \Delta t=k\left[\mathrm{O}_{3}\right]^{2} /\left[\mathrm{O}_{2}\right] $$.

A proposed mechanism for the reaction of \(\mathrm{NO}_{2}\) and \(\mathrm{CO}\) is Step 1: Slow, endothermic $$ 2 \mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+\mathrm{NO}_{3}(\mathrm{g}) $$ Step 2: Fast, exothermic $$ \mathrm{NO}_{3}(\mathrm{g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{NO}_{2}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g}) $$ Overall Reaction: Exothermic $$ \mathrm{NO}_{2}(\mathrm{g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g}) $$ (a) Identify each of the following as a reactant, product, or intermediate: \(\mathrm{NO}_{2}(\mathrm{g}), \mathrm{CO}(\mathrm{g})\) \(\mathrm{NO}_{3}(\mathrm{g}), \mathrm{CO}_{2}(\mathrm{g}), \mathrm{NO}(\mathrm{g})\) (b) Draw a reaction coordinate diagram for this reaction. Indicate on this drawing the activation energy for each step and the overall enthalpy change.

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