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GENERAL CHEMISTRY

Principles and Modern Applications PETRUCCI HERRING MADURA


TENTH EDITION

BISSONNETTE

Chemical Kinetics
PHILIP DUTTON
UNIVERSITY OF WINDSOR DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

14

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General Chemistry: Chapter 14

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Chemical Kinetics

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General Chemistry: Chapter 14

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Chemical Kinetics

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General Chemistry: Chapter 14

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14-1 The Rate of a Chemical Reaction

Rate of change of concentration with time.


2 Fe3+(aq) + Sn2+ 2 Fe2+(aq) + Sn4+(aq) t = 38.5 s t = 38.5 s [Fe2+] = 0.0010 M [Fe2+] = (0.0010 0) M [Fe2+] t 0.0010 M 38.5 s

Rate of formation of Fe2+=

= 2.610-5 M s-1

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2 Fe3+(aq) + Sn2+ 2 Fe2+(aq) + Sn4+(aq)

1 [Fe3+] [Sn4+] 1 [Fe2+] = = t t 2 t 2

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General Rate of Reaction


aA+bBgG+hH Rate of reaction = negative of rate of disappearance of reactants 1 [B] 1 [A] ==b t a t = rate of appearance of products 1 [H] 1 [G] = = h t g t
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14-2 Measuring Reaction Rates

H2O2(aq) H2O(l) + O2(g)


Measure the rate by monitoring O2 volume or by chemical analysis of aliquots

2 MnO4-(aq) + 5 H2O2(aq) + 6 H+ 2 Mn2+ + 8 H2O(l) + 5 O2(g)

FIGURE 14-1 Experimental setup for determining the rate of decomposition of H2O2 Slide 7 of 56 General Chemistry: Chapter 14
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or by chemical analysis of aliquots

2 MnO4-(aq) + 5 H2O2(aq) + 6 H+ 2 Mn2+ + 8 H2O(l) + 5 O2(g)

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Initial Rate of Reaction


-(-2.32 M / 1360 s) = 1.71 10-3 M s-1

Rate =

-[H2O2] t

-(-1.7 M / 2800 s) =

Rate of Reaction at time t

6.1 10-4 M s-1

FIGURE 14-2 Graphical representation of kinetic data for the reaction H2O2(aq) H2O(l) + O2(g) Slide 9 of 56 General Chemistry: Chapter 14
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14-3 Effect of Concentration on Reaction Rates: The Rate Law

a A + b B . g G + h H . rate of reaction = k[A]m[B]n . Rate constant = k Overall order of reaction = m + n + .

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Method of Initial Rates


2 HgCl2(aq) + C2O42-(aq) 2 Cl-(aq) + 2 CO2(g) + Hg2Cl2(s)

rate of reaction = k[HgCl2]m[C2O42-]n

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General effect of doubling the initial concentration of a particular reactant (with other reactant concentrations held constant).
Zero order in the reactantthere is no effect on the initial rate of reaction. First order in the reactantthe initial rate of reaction doubles. Second order in the reactantthe initial rate of reaction quadruples. Third order in the reactantthe initial rate of reaction increases eightfold.

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General Chemistry: Chapter 14

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14-4 Zero-Order Reactions

A products Rrxn = k [A]0 Rrxn = k = (0 - [A]0) (tf 0) = [A]0 tf

[k] = mol L-1 s-1

FIGURE 14-3 A zero-order reaction: A Slide 13 of 56 products General Chemistry: Chapter 14


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Integrated Rate Law


-[A] t = k
Move to the infinitesimal

-d[A] dt

= k

And integrate from 0 to time t

- d[A]
[A]0

[A]t

= k dt
0

-[A]t + [A]0 = kt [A]t = - kt + [A]0


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14-5 First-Order Reactions


H2O2(aq) H2O(l) + O2(g) d[H2O2 ] = -k[H2O2] dt [k] = s-1

An Integrated rate Law for a First-Order Reaction


[A]t

[A]0

t d[H2O2 ] = - k dt [H2O2] 0

ln

[A]t [A]0

= -kt

ln[A]t = -kt + ln[A]0

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General Chemistry: Chapter 14

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FIGURE 14-4 Test for a first-order reaction: Decomposition of H2O2(aq) Slide 16 of 56 General Chemistry: Chapter 14
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Half-Life, t the time taken for one-half of a reactant to be consumed.


ln [A]t [A]0 = -kt

[A]0 ln = -kt [A]0 - ln 2 = -kt ln 2 0.693 t = = k k


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Reactions Involving Gases


ButOOBut(g) 2 CH3CO(g) + C2H4(g)

FIGURE 14-5 Decomposition of di-t-butyl peroxide (DTBP) at 147C Slide 18 of 56 General Chemistry: Chapter 14
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General Chemistry: Chapter 14

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14-6 Second-Order Reactions Rate law where sum of exponents m + n + = 2


A products d[A] dt = -k[A]2
[A]t

[k] = M-1 s-1 = L mol-1 s-1


t

[A]0

d[A] [A]2

= - k dt
0

1 1 = kt + [A]t [A]0
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FIGURE 14-6 A straight-line plot for the second order reaction A Slide 21 of 56 General Chemistry: Chapter 14

products
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Pseudo First-Order Reactions


Simplify the kinetics of complex reactions. Rate laws become easier to work with. CH3CO2C2H5 + H2O CH3CO2H + C2H5OH If the concentration of water does not change appreciably during the reaction. Rate law appears to be first order. Hold one or more reactants constant by using high concentrations use a low concentration of the reactant under study.
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14-7 Reaction Kinetics: A Summary


Calculate the rate of a reaction from a known rate law using: Rate of reaction = k [A]m[B]n .

Determine the instantaneous rate of the reaction by: Finding the slope of the tangent line of [A] vs t or, Evaluate [A]/t, with a short t interval.

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Determine the order of reaction by:


Using the method of initial rates. Find the graph that yields a straight line. Test for the half-life to find first order reactions. Substitute data into integrated rate laws to find the rate law that gives a consistent value of k.

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Find the rate constant k by: Determining the slope of a straight line graph. Evaluating k with the integrated rate law. Measuring the half life of first-order reactions. Find reactant concentrations or times for certain conditions using the integrated rate law after determining k.

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14-8 Theoretical Models for Chemical Kinetics Collision Theory


Kinetic-Molecular theory can be used to calculate the collision frequency. In gases 1030 collisions per second. If each collision produced a reaction, the rate would be about 106 M s-1. Actual rates are on the order of 104 M s-1. Still a very rapid rate. Only a fraction of collisions yield a reaction.
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FIGURE 14-8 Distribution of molecular kinetic energies Slide 27 of 56 General Chemistry: Chapter 14
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Collision Theory
If activation barrier is high, only a few molecules have sufficient kinetic energy and the reaction is slower. As temperature increases, reaction rate increases. Orientation of molecules may be important.

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General Chemistry: Chapter 14

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FIGURE 14-9 Molecular collisions and chemical reactions Slide 29 of 56 General Chemistry: Chapter 14
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For a reaction to occur there must be a redistribution of energy sufficient to break certain bonds in the reacting molecule(s). Activation Energy:
The minimum energy above the average kinetic energy that molecules must bring to their collisions for a chemical reaction to occur.

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FIGURE 14-11 An analogy for a reaction profile and activation energy Slide 31 of 56 General Chemistry: Chapter 14
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Transition State Theory

FIGURE 14-10 A reaction profile for the reaction N2O(g) + NO(g) Slide 32 of 56 General Chemistry: Chapter 14 N2(g) + NO2(g)
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14-9 Effect of Temperature on Reaction Rates Svante Arrhenius k = Ae-Ea/RT ln k = -Ea 1 + lnA R T

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k = Ae-Ea/RT

ln k =

-Ea 1 R T

+ ln A

ln k2 ln k1 =

-Ea 1 R

1 + ln A - -Ea - ln A T2 R T1

ln

k1 k2

-Ea 1 R T2

1 T1

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N2O5(CCl4) N2O4(CCl4) + O2(g)

-Ea R

= -1.2104 K

-Ea = 1.0102 kJ mol-1

FIGURE 14-12 Temperature dependence of the rate constant k for a reaction Slide 35 of 56 General Chemistry: Chapter 14
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14-10 Reaction Mechanisms

Step-by-step description of a reaction. Each step is called an elementary process.


Any molecular event that significantly alters a molecules energy of geometry or produces a new molecule.

Reaction mechanism must be consistent with:


Stoichiometry for the overall reaction. The experimentally determined rate law.
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Elementary Processes Unimolecular or bimolecular. Exponents for concentration terms are the same as the stoichiometric factors for the elementary process. Elementary processes are reversible. Intermediates are produced in one elementary process and consumed in another. One elementary step is usually slower than all the others and is known as the rate determining step.
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A mechanism with a Slow Step Followed by a Fast Step


H2(g) + 2 ICl(g) I2(g) + 2 HCl(g) Postulate a mechanism: H2(g) + ICl(g) HI(g) + ICl(g)
slow fast

d[P] dt

= k[H2][ICl]

HI(g) + HCl(g) I2(g) + HCl(g)

d[HI] dt d[I2] dt d[P] dt

= k[H2][ICl] = k[HI][ICl] = k[H2][ICl]

H2(g) + 2 ICl(g) I2(g) + 2 HCl(g)


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FIGURE 14-14 A reaction profile for a two-step mechanism Slide 39 of 56 General Chemistry: Chapter 14
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A Mechanism with a Fast Reversible First Step Followed by as Slow Step


2NO(g) + O2(g) 2 NO2(g) Postulate a mechanism:
fast
k1 k-1

d[P] dt

= -kobs[NO]2[O2] k1 k-1

2NO(g) K= k1 k-1

N2O2(g) [N2O2] [NO]


k2

[N2O2] =

[NO]2 = K[NO]2

slow

N2O2(g) + O2(g)

2NO2(g)

d[NO2] dt

= k2[N2O2][O2]

2NO(g) + O2(g) 2 NO2(g)


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d[NO2] k = k2 1 [NO]2[O2] dt k-1


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General Chemistry: Chapter 14

The Steady State Approximation


2NO(g) 2NO(g) k1 k-1 N2O2(g) N2O2(g) k3 2NO2(g) 2NO(g) N2O2(g) k1 k-1 N2O2(g) 2NO(g) k3 2NO2(g)

N2O2(g) + O2(g)

N2O2(g) + O2(g)

d[NO2] dt d[N2O2] dt

= k3[N2O2][O2]

= k1[NO]2 k-1[N2O2] k3[N2O2][O2] = 0

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The Steady State Approximation


d[N2O2] dt = k1[NO]2 k-1[N2O2] k2[N2O2][O2] = 0 k1[NO]2 = [N2O2](k-1 + k2[O2]) [N2O2] = d[NO2] dt
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k1[NO]2 (k-1 + k2[O2]) k1k2[NO]2[O2] (k-1 + k2[O2])


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= k2[N2O2][O2] =

General Chemistry: Chapter 14

Kinetic Consequences of Assumptions


2NO(g) k1 k-1 N2O2(g) 2NO(g) k3 2NO2(g)

d[NO2] dt

k1k2[NO]2[O2] (k-1 + k2[O2]) d[NO2] dt d[NO2] dt

N2O2(g)

N2O2(g) + O2(g)

Let k-1 << k2 Or Let k-1 >> k2

k1k2[NO]2[O2] ( k2[O2]) k1k2[NO]2[O2] ( k-1)

= k1[NO]2 k1k2 k-1

[NO]2[O2]

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Smog-An Environmental Problem with its Roots in Chemical Kinetics .

FIGURE 14-16 Smog component profile Slide 44 of 56 General Chemistry: Chapter 14


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Smog
N2 + O2 NO2 + h O2 + O O3 2 NO NO + O

Where does the NO2 come from? slow 2 NO + O2 2 NO2 NO + O3 fast NO2 + O2

But this would not account for the buildup of ozone in the smog. There must be another way to make NO2.
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Smog Unburned hydrocarbons provide a pathway to NO2.


RH + O RH + OH R + O2 RO2 + NO O CH3C-O-O + NO2
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R R RO2

+ OH + H2O

RO + NO2 O CH3C-O-O-NO2 PAN


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General Chemistry: Chapter 14

Catalytic Converters Dual catalyst system for oxidation of CO and reduction of NO.
cat CO + NO CO2 + N2

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14-5 Catalysis Alternative reaction pathway of lower energy. Homogeneous catalysis. All species in the reaction are in solution. Heterogeneous catalysis. The catalyst is in the solid state. Reactants from gas or solution phase are adsorbed. Active sites on the catalytic surface are important.

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14-5 Catalysis

FIGURE 14-17 An example of homogeneous catalysis Slide 49 of 56 General Chemistry: Chapter 14


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Catalysis on a Surface

Figure 14-18 Heterogeneous catalysis in the reaction 2 CO + 2 NO 2 CO2 + N2 Slide 50 of 56

Figure 14-19 Reaction profile for a surface-catalyzed reaction


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General Chemistry: Chapter 14

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General Chemistry: Chapter 14

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Enzymes as Catalysts

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General Chemistry: Chapter 14

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E+S

k1 k-1

ES

ES E + P

k2

FIGURE 14-20 Lock-and-key model of enzyme action Slide 53 of 56 General Chemistry: Chapter 14
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E+S

k1 k-1

ES E + P
d[P] dt

k2

d[P] dt

= k2[ES]

= k1[E][S] k-1[ES] k2[ES]= 0 k1[E][S] = (k-1+ k2 )[ES] [E] = [E]0 [ES]

k1[S]([E]0 [ES]) = (k-1+ k2 )[ES] [ES] = k1[E]0 [S] (k-1+ k2 ) + k1[S]

FIGURE 14-21 Effect of substrate concentration on the rate of an enzyme reaction. Slide 54 of 56 General Chemistry: Chapter 14
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E+S

k1 k-1

ES E + P
d[P] dt d[P] dt d[P] dt = k1k2[E]0 [S] (k-1+ k2 ) + k1[S] k2[E]0 [S] (k-1+ k2 ) + [S] k1

k2

= k2[E]0

d[P] dt

k2

KM

[E]0 [S]

d[P] dt

k2[E]0 [S] KM + [S]

FIGURE 14-21 Effect of substrate concentration on the rate of an enzyme reaction. Slide 55 of 56 General Chemistry: Chapter 14
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