Chemistry: The Molecular Science
Chemistry: The Molecular Science
5th Edition
ISBN: 9781285199047
Author: John W. Moore, Conrad L. Stanitski
Publisher: Cengage Learning
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Chapter 11, Problem 71QRT

(a)

Interpretation Introduction

Interpretation:

The rate law for the given mechanism has to be determined.

The reaction:

  2NO(g)+Cl2(g)2NOCl(g)

The accepted mechanism:

  NO+Cl2NOCl2fastNOCl2+NO2NOClslow

Concept Introduction:

Steady-state approximation:

Once the steady state condition is reached, the rate of formation of the intermediate is equal to the rate of destruction of the intermediate.

(a)

Expert Solution
Check Mark

Explanation of Solution

The reaction:

  2NO(g)+Cl2(g)2NOCl(g)

The accepted mechanism:

  NO+Cl2k1k1NOCl2fastNOCl2+NOk22NOClslow

The rate determining step is the slowest step in the mechanism.  Thus, the rate of the reaction is given below.

  Rate=k2[NOCl2][NO]

Applying the steady-state approximation on the intermediate (NOCl2), the concentration of the intermediate can be obtained in terms of reactants.

At steady state condition, the rate of formation of the intermediate is equal to the rate of destruction of the intermediate.

NOCl2 is created in the forward reaction of step 1 and destroyed in the reverse reaction of step 1 and step 2.  Thus,

  Rateforwardreaction1=k1[NO][Cl2]Ratereversereaction1=k1[NOCl2]Ratereaction2=k2[NOCl2][NO]

Now,

  Rateforwardreaction1=Ratereversereaction1+Ratereaction2k1[NO][Cl2]=k1[NOCl2]+k2[NOCl2][NO]

Because the rate of step 2 is presumed to be much smaller than the rate of step 1, the second term is presumed to be negligibly small compared to the first term.

  Rateforwardreaction1Ratereversereaction1k1[NO][Cl2]=k1[NOCl2][NOCl2]=k1k1[NO][Cl2]

Now, the rate law can be modified as given below.

  Rate=k2(k1k1[NO][Cl2])[NO]Rate=k'[NO]2[Cl2][k'=k2k1k1]

Therefore, the rate law of the reaction is Rate=k'[NO]2[Cl2].

(b)

Interpretation Introduction

Interpretation:

Another mechanism that agrees with the same rate law has to be suggested.

Concept Introduction:

Refer to part (a).

(b)

Expert Solution
Check Mark

Explanation of Solution

Another mechanism that agrees with the same rate law is given below.

The imaginary mechanism:

  2NO2k1k1N2O2FastN2O2+Cl2k22NOCl2Slow

The rate determining step is the slowest step in the mechanism.  Thus, the rate of the reaction is given below.

  Rate=k2[N2O2][Cl2]

Applying the steady-state approximation on the intermediate (N2O2), the concentration of the intermediate can be obtained in terms of reactants.

At steady state condition, the rate of formation of the intermediate is equal to the rate of destruction of the intermediate.

N2O2 is created in the forward reaction of step 1 and destroyed in the reverse reaction of step 1 and step 2.  Thus,

  Rateforwardreaction1=k1[NO2]2Ratereversereaction1=k1[N2O2]Ratereaction2=k2[N2O2][Cl2]

Now,

  Rateforwardreaction1=Ratereversereaction1+Ratereaction2k1[NO]2=k1[N2O2]+k2[N2O2][Cl2]

Because the rate of step 2 is presumed to be much smaller than the rate of step 1, the second term is presumed to be negligibly small compared to the first term.

  Rateforwardreaction1Ratereversereaction1k1[NO]2=k1[N2O2][N2O2]=k1k1[NO]2

Now, the rate law can be modified as given below.

  Rate=k2(k1k1[NO]2)[Cl2]Rate=k'[NO]2[Cl2][k'=k2k1k1]

Therefore, the rate law of the reaction is Rate=k'[NO]2[Cl2].

(c)

Interpretation Introduction

Interpretation:

Another mechanism that does not agree with the same rate law has to be suggested.

(c)

Expert Solution
Check Mark

Explanation of Solution

Another mechanism that does not agree with the same rate law is given below.

The imaginary mechanism:

  NO+Cl2k1k1NOCl+ClSlowNO+Clk2NOClFast

The rate determining step is the slowest step in the mechanism.  Thus, the rate of the reaction is given below.

  Rate=k2[NO][Cl2]

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Chapter 11 Solutions

Chemistry: The Molecular Science

Ch. 11.3 - Prob. 11.6PSPCh. 11.3 - Prob. 11.7PSPCh. 11.4 - Prob. 11.6ECh. 11.4 - Prob. 11.7CECh. 11.4 - Prob. 11.8PSPCh. 11.4 - Prob. 11.8CECh. 11.5 - Prob. 11.9PSPCh. 11.5 - The frequency factor A is 6.31 108 L mol1 s1 and...Ch. 11.6 - Prob. 11.10CECh. 11.7 - Prob. 11.11ECh. 11.7 - The Raschig reaction produces the industrially...Ch. 11.7 - Prob. 11.12ECh. 11.8 - The oxidation of thallium(I) ion by cerium(IV) ion...Ch. 11.9 - Prob. 11.11PSPCh. 11.9 - Prob. 11.14CECh. 11 - An excellent way to make highly pure nickel metal...Ch. 11 - Prob. 1QRTCh. 11 - Prob. 2QRTCh. 11 - Prob. 3QRTCh. 11 - Prob. 4QRTCh. 11 - Prob. 5QRTCh. 11 - Prob. 6QRTCh. 11 - Prob. 7QRTCh. 11 - Prob. 8QRTCh. 11 - Prob. 9QRTCh. 11 - Prob. 10QRTCh. 11 - Prob. 11QRTCh. 11 - Cyclobutane can decompose to form ethylene: The...Ch. 11 - Prob. 13QRTCh. 11 - Prob. 14QRTCh. 11 - For the reaction 2NO2(g)2NO(g)+O2(g) make...Ch. 11 - Prob. 16QRTCh. 11 - Prob. 17QRTCh. 11 - Ammonia is produced by the reaction between...Ch. 11 - Prob. 19QRTCh. 11 - Prob. 20QRTCh. 11 - The reaction of CO(g) + NO2(g) is second-order in...Ch. 11 - Nitrosyl bromide, NOBr, is formed from NO and Br2....Ch. 11 - Prob. 23QRTCh. 11 - Prob. 24QRTCh. 11 - Prob. 25QRTCh. 11 - For the reaction these data were obtained at 1100...Ch. 11 - Prob. 27QRTCh. 11 - Prob. 28QRTCh. 11 - Prob. 29QRTCh. 11 - Prob. 30QRTCh. 11 - Prob. 31QRTCh. 11 - Prob. 32QRTCh. 11 - For the reaction of phenyl acetate with water the...Ch. 11 - When phenacyl bromide and pyridine are both...Ch. 11 - The compound p-methoxybenzonitrile N-oxide, which...Ch. 11 - Prob. 36QRTCh. 11 - Radioactive gold-198 is used in the diagnosis of...Ch. 11 - Prob. 38QRTCh. 11 - Prob. 39QRTCh. 11 - Prob. 40QRTCh. 11 - Prob. 41QRTCh. 11 - Prob. 42QRTCh. 11 - Prob. 43QRTCh. 11 - Prob. 44QRTCh. 11 - Prob. 45QRTCh. 11 - Prob. 46QRTCh. 11 - Prob. 47QRTCh. 11 - Prob. 48QRTCh. 11 - Prob. 49QRTCh. 11 - Prob. 50QRTCh. 11 - Prob. 51QRTCh. 11 - Prob. 52QRTCh. 11 - For the reaction of iodine atoms with hydrogen...Ch. 11 - Prob. 54QRTCh. 11 - The activation energy Ea is 139.7 kJ mol1 for the...Ch. 11 - Prob. 56QRTCh. 11 - Prob. 57QRTCh. 11 - Prob. 58QRTCh. 11 - Prob. 59QRTCh. 11 - Prob. 60QRTCh. 11 - Prob. 61QRTCh. 11 - Prob. 62QRTCh. 11 - Prob. 63QRTCh. 11 - Which of the reactions in Question 62 would (a)...Ch. 11 - Prob. 65QRTCh. 11 - Prob. 66QRTCh. 11 - Prob. 67QRTCh. 11 - Prob. 68QRTCh. 11 - Prob. 69QRTCh. 11 - Prob. 70QRTCh. 11 - Prob. 71QRTCh. 11 - For the reaction the rate law is Rate=k[(CH3)3CBr]...Ch. 11 - Prob. 73QRTCh. 11 - Prob. 74QRTCh. 11 - Prob. 75QRTCh. 11 - For this reaction mechanism, write the chemical...Ch. 11 - Prob. 77QRTCh. 11 - Prob. 78QRTCh. 11 - Prob. 79QRTCh. 11 - When enzymes are present at very low...Ch. 11 - Prob. 81QRTCh. 11 - The reaction is catalyzed by the enzyme succinate...Ch. 11 - Prob. 83QRTCh. 11 - Many biochemical reactions are catalyzed by acids....Ch. 11 - Prob. 85QRTCh. 11 - Prob. 86QRTCh. 11 - Prob. 87QRTCh. 11 - Prob. 88QRTCh. 11 - Prob. 89QRTCh. 11 - Prob. 90QRTCh. 11 - Prob. 91QRTCh. 11 - Prob. 92QRTCh. 11 - Prob. 93QRTCh. 11 - Prob. 94QRTCh. 11 - Nitryl fluoride is an explosive compound that can...Ch. 11 - Prob. 96QRTCh. 11 - Prob. 97QRTCh. 11 - For a reaction involving the decomposition of a...Ch. 11 - Prob. 99QRTCh. 11 - Prob. 100QRTCh. 11 - Prob. 101QRTCh. 11 - This graph shows the change in concentration as a...Ch. 11 - Prob. 103QRTCh. 11 - Prob. 104QRTCh. 11 - Prob. 105QRTCh. 11 - Prob. 106QRTCh. 11 - Prob. 107QRTCh. 11 - Prob. 108QRTCh. 11 - Prob. 109QRTCh. 11 - Prob. 110QRTCh. 11 - Prob. 111QRTCh. 11 - Prob. 112QRTCh. 11 - Prob. 113QRTCh. 11 - Prob. 114QRTCh. 11 - Prob. 115QRTCh. 11 - Prob. 116QRTCh. 11 - Prob. 118QRTCh. 11 - Prob. 119QRTCh. 11 - In a time-resolved picosecond spectroscopy...Ch. 11 - If you know some calculus, derive the integrated...Ch. 11 - If you know some calculus, derive the integrated...Ch. 11 - (Section 11-5) A rule of thumb is that for a...Ch. 11 - Prob. 11.BCPCh. 11 - Prob. 11.CCPCh. 11 - Prob. 11.DCP
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