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Ch.14 - Chemical Kinetics
Chapter 14, Problem 128

Assume that you are studying the first-order conversion of a reactant X to products in a reaction vessel with a constant volume of 1.000 L. At 1 p.m., you start the reaction at 25 °C with 1.000 mol of X. At 2 p.m., you find that 0.600 mol of X remains, and you immediately increase the temperature of the reaction mixture to 35 °C. At 3 p.m., you discover that 0.200 mol of X is still present. You want to finish the reaction by 4 p.m. but need to continue it until only 0.010 mol of X remains, so you decide to increase the temperature once again. What is the minimum temperature required to convert all but 0.010 mol of X to products by 4 p.m.?

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<insert step 1> Determine the rate constant (k) for the reaction at 25 °C using the first-order rate equation: \( k = \frac{1}{t} \ln \frac{[X]_0}{[X]} \), where \([X]_0\) is the initial concentration and \([X]\) is the concentration at time t.>
<insert step 2> Calculate the rate constant (k) for the reaction at 35 °C using the same first-order rate equation, with the concentrations and time interval from 2 p.m. to 3 p.m.>
<insert step 3> Use the Arrhenius equation \( k = A e^{-\frac{E_a}{RT}} \) to determine the activation energy (E_a) of the reaction, using the rate constants from steps 1 and 2 and the corresponding temperatures.>
<insert step 4> Calculate the rate constant (k) required to achieve the desired concentration of 0.010 mol of X by 4 p.m. using the first-order rate equation, with the concentration at 3 p.m. and the desired concentration at 4 p.m.>
<insert step 5> Use the Arrhenius equation again to find the minimum temperature required to achieve the rate constant calculated in step 4, using the activation energy determined in step 3.>

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

First-Order Kinetics

First-order kinetics describes a reaction where the rate is directly proportional to the concentration of one reactant. The rate law can be expressed as rate = k[X], where k is the rate constant. The integrated rate law for a first-order reaction allows us to calculate the concentration of the reactant at any time, which is essential for determining how much reactant remains at specific intervals.
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Arrhenius Equation

The Arrhenius equation relates the rate constant of a reaction to temperature, expressed as k = A * e^(-Ea/RT), where A is the pre-exponential factor, Ea is the activation energy, R is the gas constant, and T is the temperature in Kelvin. This equation indicates that increasing the temperature generally increases the rate constant, thereby accelerating the reaction. Understanding this relationship is crucial for determining the minimum temperature needed to achieve the desired conversion by a specific time.
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Reaction Completion and Time Management

In chemical kinetics, managing the time required for a reaction to reach completion is vital, especially when aiming for a specific concentration of reactants. By analyzing the remaining concentration of reactant X at different times and applying the first-order kinetics and Arrhenius equation, one can estimate the necessary conditions to achieve the target concentration within the desired timeframe. This involves calculating the required rate constant and subsequently the temperature needed to meet the reaction completion goal.
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Related Practice
Textbook Question

Consider the reversible, first-order interconversion of two molecules A and B: where kf = 3.0⨉10-3 s-1 is the rate constant for the forward reaction and kr = 1.0⨉10-3 s-1 is the rate constant for the reverse reaction. We'll see in Chapter 15 that a reaction does not go to completion but instead reaches a state of equilibrium with comparable concentrations of reactants and products if the rate constants kf and kr have comparable values.

(a) What are the rate laws for the forward and reverse reactions?

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Textbook Question

Consider the reversible, first-order interconversion of two molecules A and B: where kf = 3.0⨉10-3 s-1 is the rate constant for the forward reaction and kr = 1.0⨉10-3 s-1 is the rate constant for the reverse reaction. We'll see in Chapter 15 that a reaction does not go to completion but instead reaches a state of equilibrium with comparable concentrations of reactants and products if the rate constants kf and kr have comparable values.

(b) Draw a qualitative graph that shows how the rates of the forward and reverse reactions vary with time.

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Textbook Question

Consider the reversible, first-order interconversion of two molecules A and B: where kf = 3.0⨉10-3 s-1 is the rate constant for the forward reaction and kr = 1.0⨉10-3 s-1 is the rate constant for the reverse reaction. We'll see in Chapter 15 that a reaction does not go to completion but instead reaches a state of equilibrium with comparable concentrations of reactants and products if the rate constants kf and kr have comparable values.

(c) What are the relative concentrations of B and A when the rates of the forward and reverse reactions become equal?

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Textbook Question
The half-life for the first-order decomposition of N2O4 is 1.3 * 10-5 s. N2O41g2S 2 NO21g2 If N2O4 is introduced into an evacuated flask at a pressure of 17.0 mm Hg, how many seconds are required for the pressure of NO2 to reach 1.3 mm Hg?
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Textbook Question

Some reactions are so rapid that they are said to be diffusion-controlled; that is, the reactants react as quickly as they can collide. An example is the neutralization of H3O+ by OH-, which has a second-order rate constant of 1.3⨉1011 M-1 s-1 at 25 °C. (a) If equal volumes of 2.0 M HCl and 2.0 M NaOH are mixed instantaneously, how much time is required for 99.999% of the acid to be neutralized?

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Textbook Question

Some reactions are so rapid that they are said to be diffusion-controlled; that is, the reactants react as quickly as they can collide. An example is the neutralization of H3O+ by OH-, which has a second-order rate constant of 1.3⨉1011 M-1 s-1 at 25 °C. (b) Under normal laboratory conditions, would you expect the rate of the acid–base neutralization to be limited by the rate of the reaction or by the speed of mixing?

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