Chemical Kinetics

The area of chemistry that concerns reaction rates.

Reaction Rate
Change in concentration (conc) of a reactant or product per unit time.

12_291

0.0100

NO2 0.0075

Concentrations (mol/L)

0.0026

[NO2 ]
0.0006

0.005

t 110 s
NO

70s

0.0003 0.0025 O2 70s

50

100

150

200

250

300

350

400

Time (s)

12_1575

Time

Time

(a)

(b)

(c)

Rate Laws
Rate = k[NO2]n k = rate constant n = rate order

Types of Rate Laws

Differential Rate Law: expresses how rate depends on concentration. Integrated Rate Law: expresses how concentration depends on time.

C4H9Cl + H2O C4H9OH + HCl

Method of Initial Rates

Initial Rate: the instantaneous rate just after the reaction begins. The initial rate is determined in several experiments using different initial concentrations.

NH4+(aq) + NO2-(aq) N2(g) 2H2O(l)

Overall Reaction Order

Sum of the order of each component in the rate law. rate = k[H2SeO3][H+]2[I]3 The overall reaction order is 1 + 2 + 3 = 6.

2ClO2 + 2OH- ClO3- + ClO2- + H2O

Experiment 1 2 3 [ClO2] M 0.060 0.020 0.020 [OH-] M 0.030 0.030 0.090 Rate, M s-1 0.0248 0.00276 0.00828

1. Determine the rate law for the reaction.

2. Calculate the rate constant.

3. What is the overall reaction order?

ICA

First-Order Rate Law

For aA Products in a 1st-order reaction,

Integrated first-order rate law is ln[A] = kt + ln[A]o

CH3NC CH3CN
Conversion of methyl isonitrile to acetonitrile

Half-Life of a First-Order Reaction

t1/2 = half-life of the reaction k = rate constant

For a first-order reaction, the half-life does not depend on concentration.

Half-Life of a First Order Rx

12_294

[N2O5]0

0.1000 0.0900 0.0800

[N2O5] (mol/L)

0.0700 0.0600

[N2O5]0
2

0.0500 0.0400 0.0300 0.0200 0.0100 50 t1/2 100 150 t1/2 Time (s) 200 250 t1/2 300 350 400

[N2O5]0
4

[N2O5]0
8

O (g) + NO2 (g) NO (g) + O2 (g)

Types of Radioactive Decay

alpha production (): helium nucleus4 He 2

beta production (): 0 e 1

Types of Radioactive Decay

gamma ray production ():

High energy photon

Decay Series
A radioactive nucleus reaches a stable state by a series of steps.

21_475

120

202 80

Hg (1.53:1 ratio)

100

Number of neutrons (AZ)

Unstable region (too many neutrons; spontaneous beta production)

St zo able ne n of ucli sta de bil s in ity th

80

1:

tro u ne

to n-

n to o pr

io at r

60

110 Cd 48

(1.29:1 ratio)

40

20
6 3 Li

Unstable region (too many protons; spontaneous positron production) (1:1 ratio) 100

20

40 60 80 Number of protons (Z)

21_476

238 236 234 232 230 228 Th Ra Th Pa

U U

Mass number (A)

226 224 222 220 218 216 214 212 210 208 206 204 0 Pb Pb Bi Po Pb Bi Po Po Rn

82 83 84 85 86 87 88 89 90 91 92 93 Atomic number (Z)

Rate of Decay
rate = kN
The rate of decay is proportional to the number of nuclides. This represents a firstorder process.

Decay of Strontium-90
21_477

10.0

8.0

(g)

90 38 Sr

6.0

1 halflife

Mass of

4.0

2 halflives 3 halflives 4 halflives 120

2.0

0 20 40 60 80 100 t 1/2 = 2 8.8 t1/2 = 2 8.8 t1/2 = 2 8.8 t 1/2 = 2 8.8

Time (yr)

Radioactive Decay

Second-Order Rate Law

For aA products in a second-order reaction,

Integrated rate law is

Half-Life of a Second-Order Reaction

t1/2 = half-life of the reaction k = rate constant Ao = initial concentration of A

The half-life is dependent upon the initial concentration.

Zero Order Rate Laws

Rate = k [A]0
Integrated Form [A] = -kt + [A]o

A Summary
1. Simplification: Conditions are set such that only forward reaction is important.
2. Two types: differential rate law integrated rate law 3. Which type? Depends on the type of data collected - differential and integrated forms can be interconverted.

A Summary
(continued)

4. Most common: method of initial rates.

5. Concentration v. time: used to determine integrated rate law, often graphically. 6. For several reactants: choose conditions under which only one reactant varies significantly (pseudo n-order conditions).

12_06T

Table 12.6 Summary of the Kinetics for Reactions of the Type aA Products That Are Zero, First, or Second Order in [A]
Order Zero Rate law Integrated rate law Plot needed to give a straight line Relationship of rate constant to the slope of straight line Half-life Rate = k [A] = -kt + [A]0 [A] versus t Slope = -k t1/2 = [A]0 2k First Rate = k[A] ln[A] = -kt + ln[A]0 ln[A] versus t Slope = -k t1/2 = 0.693 k Second Rate = k[A]2 1 1 = kt + [A] [A]0 1 versus t [A] Slope = k t1/2 = 1 k[A]0

Reaction Mechanism
- The series of steps by which a chemical reaction occurs.
- A chemical equation does not tell us how reactants become products - it is a summary of the overall process.

Reaction Mechanism
(continued)

The reaction

O3 + O 2O2
has several steps in the reaction mechanism.

Often Used Terms

Intermediate: formed in one step and used up in a subsequent step and so is never seen as a product. Molecularity: the number of species that must collide to produce the reaction indicated by that step. Elementary Step: A reaction whose rate law can be written from its molecularity. uni, bi and termolecular

Rate-Determining Step
In a multistep reaction, it is the slowest step. It therefore determines the rate of reaction.

Collision Model
Key Idea: Molecules must collide to react.
However, only a small fraction of collisions produces a reaction. Why? Arrhenius: An activation energy must be overcome.

Arrhenius Equation
Collisions must have enough energy to produce the reaction (must equal or exceed the activation energy). Orientation of reactants must allow formation of new bonds.

Temperature and Ea
12_300

T1 T2 > T1 T2

0 Energy

Ea

Arrhenius Equation
(continued)

k = rate constant A = frequency factor Ea = activation energy T = temperature R = gas constant

Catalysis
Catalyst: A substance that speeds up a reaction without being consumed Enzyme: A large molecule (usually a protein) that catalyzes biological reactions.

Homogeneous catalyst: Present in the same phase as the reacting molecules. Heterogeneous catalyst: Present in a different phase than the reacting molecules.

Lower Ea for Catalyzed Rx

12_303

Uncatalyzed pathway Catalyzed pathway Products E Reactants Reaction progress

Energy

Heterogeneous Catalysis
Steps: 1. Adsorption and activation of the reactants.

2. Migration of the adsorbed reactants on the surface.

3. Reaction of the adsorbed substances. 4. Escape, or desorption, of the products.

END