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Chemical Kinetics
Thermodynamics: scientific study of heat and other energy sources Kinetics: how fast does a rxn proceed Reaction rate - the change in the conc of a reactant or a product with time (M/s). A B D[A] rate = Dt rate = D[B] Dt

Chemical Kinetics
Chapter 13

D[A] = change in concentration of A over time period Dt D[B] = change in concentration of B over time period Dt
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D[A] is negative because it decreases with time

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red-brown Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

time D[A] rate = Dt rate = D[B] Dt

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t1< t2 < t3

393 nm light

Detector

D[Br2] a D Absorption

Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of tangent

slope of tangent

slope of tangent

rate a [Br2] rate = k [Br2] rate = rate constant [Br2] = 3.50 x 10-3 s-1
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average rate = -

[Br2]final [Br2]initial D[Br2] =Dt tfinal - tinitial

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k=

instantaneous rate = rate for specific instance in time

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2H2O2 (aq)

2H2O (l) + O2 (g) PV = nRT

n P= RT = [O2]RT V 1 [O2] = P RT rate = D[O2] 1 DP = RT Dt Dt

measure DP over time

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The Rate Law

Rate law: expresses the relationship of the rate of a rxn to the rate constant & the conc of the reactants raised to some powers

F2 (g) + 2ClO2 (g)

2FClO2 (g)

rate = k [F2]x[ClO2]y aA + bB cC + dD

Rate = k [A]x[B]y Double [F2] with [ClO2] constant Reaction is xth order in A Reaction is yth order in B Reaction is (x +y)th order overall
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Rate doubles x=1 Quadruple [ClO2] with [F2] constant Rate quadruples y=1
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rate = k [F2][ClO2]

Rate Laws
Rate laws are always determined experimentally. Reaction order is always defined in terms of reactant (not product) concentrations. The order of a reactant is not related to the stoichiometric coefficient of the reactant in the balanced chemical equation. F2 (g) + 2ClO2 (g) 2FClO2 (g)
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Determine the rate law and calculate the rate constant for the following reaction from the following data: S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
Experiment

[S2O82-] 0.08 0.08 0.16

[I-] 0.034 0.017 0.017

Initial Rate (M/s) 2.2 x 10-4 1.1 x 10-4 2.2 x 10-4

1 2 3

rate = k [S2O82-]x[I-]y y=1 x=1 rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2) Double [S2O82-], rate doubles (experiment 2 & 3) k=
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rate = k [F2][ClO2]

2.2 x 10-4 M/s rate = = 0.08/Ms [S2O82-][I-] (0.08 M)(0.034 M)

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First-Order Reactions
A product rate = D[A] Dt rate = k [A] D[A] = k [A] Dt

Graphical Determination of k 2N2O5 4NO2 (g) + O2 (g)

k=

rate M/s = = 1/s or s-1 M [A]

[A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0

[A] = [A]0ekt

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

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The reaction 2A B is first order in A with a rate constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A to decrease from 0.88 M to 0.14 M ? ln[A] = ln[A]0 - kt kt = ln[A]0 ln[A] t= ln[A]0 ln[A] = k ln [A]0 = 0.88 M [A] = 0.14 M

First-Order Reactions
The half-life, t, is the time required for the concentration of a reactant to decrease to half of its initial concentration. t = t when [A] = [A]0/2 ln [A]0 [A]0/2 k = ln 2 0.693 = k k

[A]0 [A] k =

ln

0.88 M 0.14 M = 66 s

t =

2.8 x 10-2 s-1

What is the half-life of N2O5 if it decomposes with a rate constant of 5.7 x 10-4 s-1? 0.693 t = ln 2 = = 1200 s = 20 minutes k 5.7 x 10-4 s-1
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How do you know decomposition is first order? units of k (s-1)

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Second-Order Reactions
First-order reaction A product A product rate = D[A] Dt rate = k [A]2 D[A] = k [A]2 Dt

# of half-lives [A] = [A]0/n 1 2 2 3 4 4 8

k=

rate M/s = 2 = 1/Ms M [A]2

1 1 = + kt [A] [A]0

[A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0

t = t when [A] = [A]0/2 16 t = 1 k[A]0

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Zero-Order Reactions
A product rate = M/s [A]0 D[A] rate = Dt rate = k [A]0 = k D[A] =k Dt

Summary of the Kinetics of Zero-Order, First-Order and Second-Order Reactions

Concentration-Time Equation [A] = [A]0 - kt ln[A] = ln[A]0 - kt 1 1 = + kt [A] [A]0

k=

Order 0 1

Rate Law rate = k rate = k [A] rate = k [A]2

Half-Life t = [A]0 2k

[A] = [A]0 - kt

[A] is the concentration of A at any time t [A]0 is the concentration of A at time t = 0

t = t when [A] = [A]0/2 t = [A]0 2k

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t = ln 2 k 1 t = k[A]0

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A+ B Exothermic Reaction

AB +

C+D Endothermic Reaction

Temperature Dependence of the Rate Constant

k A e( Ea / RT )
(Arrhenius equation)
Ea is the activation energy (J/mol) R is the gas constant (8.314 J/Kmol) T is the absolute temperature A is the frequency factor

Alternate format: The activation energy (Ea ) is the minimum amount of energy required to initiate a chemical reaction.
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ln k = -

Ea 1 + lnA R T
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Importance of Molecular Orientation Alternate Form of the Arrhenius Equation

At two temperatures, T1 and T2

effective collision

or

ineffective collision
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Reaction Mechanisms
The overall progress of a chemical reaction can be represented at the molecular level by a series of simple elementary steps or elementary reactions. The sequence of elementary steps that leads to product formation is the reaction mechanism. 2NO (g) + O2 (g) 2NO2 (g)

2NO (g) + O2 (g)

Mechanism:

2NO2 (g)

N2O2 is detected during the reaction! Elementary step: + Elementary step: Overall reaction: NO + NO N 2 O2 + O 2 2NO + O2 N 2 O2 2NO2 2NO2
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Intermediates are species that appear in a reaction mechanism but not in the overall balanced equation. An intermediate is always formed in an early elementary step and consumed in a later elementary step. Elementary step: + Elementary step: Overall reaction: NO + NO N 2 O2 + O 2 2NO + O2 N 2 O2 2NO2 2NO2

Rate Laws and Elementary Steps

Unimolecular reaction Bimolecular reaction Bimolecular reaction A A+ B A+A products products products rate = k [A] rate = k [A][B] rate = k [A]2

Writing plausible reaction mechanisms: The sum of the elementary steps must give the overall balanced equation for the reaction. The rate-determining step should predict the same rate law that is determined experimentally.

The molecularity of a reaction is the number of molecules reacting in an elementary step. Unimolecular reaction elementary step with 1 molecule Bimolecular reaction elementary step with 2 molecules Termolecular reaction elementary step with 3 molecules
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The rate-determining step is the slowest step in the sequence of steps leading to product formation.
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Sequence of Steps in Studying a Reaction Mechanism

The experimental rate law for the reaction between NO 2 and CO to produce NO and CO2 is rate = k[NO2]2. The reaction is believed to occur via two steps: Step 1: Step 2: NO2 + NO2 NO3 + CO NO2+ CO What is the intermediate? NO3 What can you say about the relative rates of steps 1 and 2? rate = k[NO2]2 is the rate law for step 1 so step 1 must be slower than step 2 NO + NO3 NO2 + CO2 NO + CO2

What is the equation for the overall reaction?

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A catalyst is a substance that increases the rate of a chemical reaction without itself being consumed.

k A e( Ea / RT )
Uncatalyzed

Ea

k
Catalyzed

In heterogeneous catalysis, the reactants and the catalysts are in different phases. Haber synthesis of ammonia Ostwald process for the production of nitric acid Catalytic converters

In homogeneous catalysis, the reactants and the catalysts are dispersed in a single phase, usually liquid. ratecatalyzed > rateuncatalyzed Ea < Ea
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Acid catalysis Base catalysis

Haber Process

Ostwald Process
4NH3 (g) + 5O2 (g)
Pt catalyst

4NO (g) + 6H2O (g)

2NO (g) + O2 (g) 2NO2 (g) + H2O (l)

2NO2 (g) HNO2 (aq) + HNO3 (aq)

N2 (g) + 3H2 (g)

Fe/Al2O3/K2O catalyst

2NH3 (g)

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Pt-Rh catalysts used in Ostwald process

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Catalytic Converters

Enzyme Catalysis

CO + Unburned Hydrocarbons + O 2 2NO + 2NO2

catalytic converter catalytic converter

CO2 + H2O 2N2 + 3O2

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Enzyme Kinetics Binding of Glucose to Hexokinase

rate =

D[P] Dt

rate = k [ES]

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