MCGRAW: CHEMISTRY THE MOLECULAR NATURE
MCGRAW: CHEMISTRY THE MOLECULAR NATURE
8th Edition
ISBN: 9781264330430
Author: VALUE EDITION
Publisher: MCG
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Chapter 16, Problem 16.75P

(a)

Interpretation Introduction

Interpretation:

An overall equation for the given reaction has to be written.

Concept introduction:

Reaction: Substances which are mutually involved each other in a chemical process and changed into different substances.

Mechanism of a reaction: The representation of step by step process involved in the chemical process is said to be mechanism of a chemical reaction.

Elementary step: The first step in a reaction mechanism is said to be elementary step.

Intermediate: Sometimes, in between the reaction some separable amount and useful amount of substances are formed during the reaction and which are said to be intermediates

(a)

Expert Solution
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Explanation of Solution

The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,

ClO+H2OHClO+OH[fast]I+HClOHIO+Cl[slow]OH+HIOH2O+IO[fast]_ClO+ICl+IOOverallreaction_

In the reaction, the slow step is the rate determining step; and its rate law is the overall rate law. The overall equation becomes,

ClO+ICl+IO

(b)

Interpretation Introduction

Interpretation:

The intermediate has to be identified.

Concept introduction:

Rate law or rate equation: The relationship between the reactant concentrations and reaction rate is expressed by an equation.

aA + bBxXRate of reaction = k [A]m[B]nTotalorderof reaction = (m + n).

Reaction Rate = k [A]m[B]n[C]p,where 'm, n and p' are orders of the reactants.

Order of a reaction: The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression, and the overall reaction order is the sum of the exponents on all concentration terms.

Rate constant, k: It is a proportionality constant that relates rate and concentration at a given temperature.

(b)

Expert Solution
Check Mark

Explanation of Solution

The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,

ClO+H2OHClO+OH[fast]I+HClOHIO+Cl[slow]OH+HIOH2O+IO[fast]_ClO+ICl+IOOverallreaction_

The intermediates are not involved in the overall reaction; thus, the components ‘HClO, HIO, OH’ are intermediates that are produced and consumed in the reaction.

(c)

Interpretation Introduction

Interpretation:

The molecularity and the rate law for each step have to be identified.

Concept introduction:

Rate law or rate equation: The relationship between the reactant concentrations and reaction rate is expressed by an equation.

aA + bBxXRate of reaction = k [A]m[B]nTotalorderof reaction = (m + n).

Reaction Rate = k [A]m[B]n[C]p,where 'm, n and p' are orders of the reactants.

Order of a reaction: The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression, and the overall reaction order is the sum of the exponents on all concentration terms.

Rate constant, k: It is a proportionality constant that relates rate and concentration at a given temperature.

(c)

Expert Solution
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Explanation of Solution

Step 1: ClO+H2OHClO+OH[fast]

Molecularity (collision) of a reaction step (1) is the number of reactant involved in that elementary step. Here, two molecules ClO- and H2O are involved; thus, molecularity is BIMOLECULAR. The rate law of this step is Rate1 = k [ClO-][H2O].

Step 2: I+HClOHIO+Cl[slow]

Molecularity (collision) of a reaction step is the number of reactant involved in that elementary step. Here, two molecules I- and HClO are involved; thus, molecularity is BIMOLECULAR. The rate law of this step is Rate2 = k [I-][HClO].

Step 3: OH+HIOH2O+IO[fast]

Molecularity (collision) of a reaction step is the number of reactant involved in that elementary step. Here, two molecules OH- and HIO are involved; thus, molecularity is BIMOLECULAR. The rate law of this step is Rate3 = k [OH-][HIO].

(d)

Interpretation Introduction

Interpretation:

The mechanism whether consistent with the given rate law has to be predicted.

Concept introduction:

Rate law or rate equation: The relationship between the reactant concentrations and reaction rate is expressed by an equation.

aA + bBxXRate of reaction = k [A]m[B]nTotalorderof reaction = (m + n).

Reaction Rate = k [A]m[B]n[C]p,where 'm, n and p' are orders of the reactants.

Order of a reaction: The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression, and the overall reaction order is the sum of the exponents on all concentration terms.

Rate constant, k: It is a proportionality constant that relates rate and concentration at a given temperature.

(d)

Expert Solution
Check Mark

Explanation of Solution

In the reaction, the slow step is the rate determining step; and its rate law is the overall rate law. The overall equation becomes,

ClO+ICl+IO

The overall reaction rate is same as the rate of slowest reaction step.

The slowest step is, I+HClOHIO+Cl[slow]

The rate law for the above reaction is, Rate = k'[I-][HClO]        (1)

The concentration [HClO] is the intermediate that cannot be involved in the overall rate law. Hence, substitution is needed for the [HClO][X] intermediate.

The rate law for the given mechanism steps are,

The rate of mechanism (1), Rate1 = k1 [ClO-][H2O]andRate1 = k-1 [HClO][OH], thus the step is in equilibrium, the rate of forward and backward reaction rate are equal,

 k1 [ClO-][H2O] = k-1 [HClO][OH-][HClO]=k1  k-1[ClO-][H2O][OH]-----------------------(2)

Thus, by substituting above relation into the equation (1), the rate law becomes,

Rate = k'[I-][HClO]= k'k1  k1[ClO-][OH][I-]=k[ClO-][OH][I-] ,where k' k1  k1=kRate=k[ClO-][OH-][I-]

Therefore, the given rate law is consistent with the rate law of overall reaction Rate=k[ClO-][OH-][I-].

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Chapter 16 Solutions

MCGRAW: CHEMISTRY THE MOLECULAR NATURE

Ch. 16.4 - Substance X (black) changes to substance Y (red)...Ch. 16.4 - Prob. 16.6BFPCh. 16.4 - Prob. 16.7AFPCh. 16.4 - Prob. 16.7BFPCh. 16.5 - Prob. 16.8AFPCh. 16.5 - Prob. 16.8BFPCh. 16.5 - Prob. 16.9AFPCh. 16.5 - Prob. 16.9BFPCh. 16.6 - The mechanism below is proposed for the...Ch. 16.6 - Prob. 16.10BFPCh. 16.6 - Prob. 16.11AFPCh. 16.6 - Prob. 16.11BFPCh. 16.7 - Prob. B16.1PCh. 16.7 - Aircraft in the stratosphere release NO, which...Ch. 16.7 - Prob. B16.3PCh. 16 - Prob. 16.1PCh. 16 - Prob. 16.2PCh. 16 - A reaction is carried out with water as the...Ch. 16 - Prob. 16.4PCh. 16 - Prob. 16.5PCh. 16 - Prob. 16.6PCh. 16 - Prob. 16.7PCh. 16 - Prob. 16.8PCh. 16 - Prob. 16.9PCh. 16 - Prob. 16.10PCh. 16 - Prob. 16.11PCh. 16 - Prob. 16.12PCh. 16 - Prob. 16.13PCh. 16 - Prob. 16.14PCh. 16 - Prob. 16.15PCh. 16 - Prob. 16.16PCh. 16 - Prob. 16.17PCh. 16 - Prob. 16.18PCh. 16 - Prob. 16.19PCh. 16 - Prob. 16.20PCh. 16 - Prob. 16.21PCh. 16 - Prob. 16.22PCh. 16 - Prob. 16.23PCh. 16 - Prob. 16.24PCh. 16 - Prob. 16.25PCh. 16 - Prob. 16.26PCh. 16 - Prob. 16.27PCh. 16 - Prob. 16.28PCh. 16 - By what factor does the rate in Problem 16.27...Ch. 16 - Prob. 16.30PCh. 16 - Prob. 16.31PCh. 16 - Prob. 16.32PCh. 16 - Prob. 16.33PCh. 16 - Prob. 16.34PCh. 16 - Prob. 16.35PCh. 16 - Prob. 16.36PCh. 16 - Give the overall reaction order that corresponds...Ch. 16 - Phosgene is a toxic gas prepared by the reaction...Ch. 16 - How are integrated rate laws used to determine...Ch. 16 - Define the half-life of a reaction. Explain on the...Ch. 16 - For the simple decomposition reaction AB(g) ⟶A(g)...Ch. 16 - For the reaction in Problem 16.41, what is [AB]...Ch. 16 - The first-order rate constant for the reaction A...Ch. 16 - The molecular scenes below represent the...Ch. 16 - In a first-order decomposition reaction, 50.0% of...Ch. 16 - A decomposition reaction has a rate constant of...Ch. 16 - In a study of ammonia production, an industrial...Ch. 16 - Prob. 16.48PCh. 16 - Prob. 16.49PCh. 16 - Prob. 16.50PCh. 16 - Prob. 16.51PCh. 16 - Prob. 16.52PCh. 16 - Prob. 16.53PCh. 16 - Prob. 16.54PCh. 16 - Prob. 16.55PCh. 16 - Assuming the activation energies are equal, which...Ch. 16 - For the reaction A(g) + B(g) ⟶AB(g), how many...Ch. 16 - Prob. 16.58PCh. 16 - Prob. 16.59PCh. 16 - Prob. 16.60PCh. 16 - The rate constant of a reaction is 4.7×10−3 s−1 at...Ch. 16 - The rate constant of a reaction is 4.50×10−5...Ch. 16 - Prob. 16.63PCh. 16 - For the reaction A2 + B2 → 2AB, Ea(fwd) = 125...Ch. 16 - Prob. 16.65PCh. 16 - Prob. 16.66PCh. 16 - Prob. 16.67PCh. 16 - Explain why the coefficients of an elementary step...Ch. 16 - Is it possible for more than one mechanism to be...Ch. 16 - What is the difference between a reaction...Ch. 16 - Why is a bimolecular step more reasonable...Ch. 16 - Prob. 16.72PCh. 16 - If a fast step precedes a slow step in a two-step...Ch. 16 - Prob. 16.74PCh. 16 - Prob. 16.75PCh. 16 - In a study of nitrosyl halides, a chemist proposes...Ch. 16 - Prob. 16.77PCh. 16 - Consider the reaction . Does the gold catalyst...Ch. 16 - Does a catalyst increase reaction rate by the same...Ch. 16 - In a classroom demonstration, hydrogen gas and...Ch. 16 - Prob. 16.81PCh. 16 - Prob. 16.82PCh. 16 - Prob. 16.83PCh. 16 - Consider the following reaction energy...Ch. 16 - Prob. 16.85PCh. 16 - Prob. 16.86PCh. 16 - A slightly bruised apple will rot extensively in...Ch. 16 - Prob. 16.88PCh. 16 - Prob. 16.89PCh. 16 - Prob. 16.90PCh. 16 - Prob. 16.91PCh. 16 - The citric acid cycle is the central reaction...Ch. 16 - Prob. 16.93PCh. 16 - Prob. 16.94PCh. 16 - Prob. 16.95PCh. 16 - Prob. 16.96PCh. 16 - For the reaction A(g) + B(g) ⟶ AB(g), the rate is...Ch. 16 - The acid-catalyzed hydrolysis of sucrose occurs by...Ch. 16 - At body temperature (37°C), the rate constant of...Ch. 16 - Is each of these statements true? If not, explain...Ch. 16 - For the decomposition of gaseous dinitrogen...Ch. 16 - Prob. 16.102PCh. 16 - Suggest an experimental method for measuring the...Ch. 16 - Prob. 16.104PCh. 16 - Many drugs decompose in blood by a first-order...Ch. 16 - Prob. 16.106PCh. 16 - Prob. 16.107PCh. 16 - Prob. 16.108PCh. 16 - Prob. 16.109PCh. 16 - Prob. 16.110PCh. 16 - Prob. 16.111PCh. 16 - Prob. 16.112PCh. 16 - Prob. 16.113PCh. 16 - Prob. 16.114PCh. 16 - Prob. 16.115PCh. 16 - Prob. 16.116PCh. 16 - Prob. 16.117PCh. 16 - The growth of Pseudomonas bacteria is modeled as a...Ch. 16 - Prob. 16.119PCh. 16 - Prob. 16.120PCh. 16 - Prob. 16.121PCh. 16 - Prob. 16.122PCh. 16 - Prob. 16.123PCh. 16 - Prob. 16.124PCh. 16 - Human liver enzymes catalyze the degradation of...Ch. 16 - Prob. 16.126PCh. 16 - Prob. 16.127P
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