Chemical Kinetics

Chapter 16
 Kinetics
Reaction Rates
Factors affecting rate
Quantitative rate expressions
Determination
Factors
Models for Rates
Reaction Mechanisms
Effects of catalysts
 Rates
Change in concentration of a reactant or product
per unit time

A B
Change in conc, A At - A0 A

Change in time, t tt - t0 t
12_292

1.00
Rate = 5.4 x 10-4 mol/L.s
.80
[N2O5] (mol/L)

Rate = 2.7 x 10-4 mol/L.s

.60

.40

.20

400 800 1200 1600 2000

Time (s)
 Factors affecting rates

Nature of the reactants

State of subdivision/surface area
Concentration
Temperature
Catalysts
 Reactants

Complexity
Bond strengths
Etc.
C2 H 4 O3 C2 H 4 O O 2
C2 H 4 O3 C2 H 4 O O 2
C2 H 4 O3 C2 H 4 O O 2
Concentrations as functions of time
2NO2 2NO O2
Time(s) [NO2] [NO] [O2 ]
0 0.0100 0.0000 0.0000
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035
 Graph: Concentration vs. time
NO2 NO2 400 - NO2 0 0.0031 - 0.0100
1.725 105 M
t t 400 - t 0 400 - 0

Concentration vs Time

0.012

0.01
[NO2] 2NO2 2NO O2
0.008
Conc.,mol/L

[NO]

0.006

0.004 [O2]

0.002

0
0 50 100 150 200 250 300 350 400 450

Time, sec
 Average Rate
Change of concentration in a time interval
-[NO2 ]/t time period(s)
4.20E-05 0 - 50
2.80E-05 50 - 100
2.00E-05 100 - 150
1.40E-05 150 - 200
1.00E-05 200 - 250
1.00E-05 250 - 300
8.00E-06 300 - 350
6.00E-06 350 - 400
1.75E-05 0 - 400
 Average Rate
Slope of line between two points on the graph
NO2 NO2 400 - NO2 0 0.0031 - 0.0100 5 M
Concentration vs Time 1.725 10
t t 400 - t 0 400 - 0 s
0.012

[NO2]
0.01

0.008
[NO]
Conc.,mol/L

0.006

[O2]
0.004

0.002

0
0 50 100 150 200 250 300 350 400 450
Time, sec
 Instantaneous rate
Slope of tangent line at a point on the graph
y
slope of tangent line
x
NO2
rate
t
NO2 0.009 M
rate @ 100 s
t 375 s
M
rate @ 100 s 2.4 10 -5
s
 Instantaneous Rate
Concentration vs Time

0.012

0.01
[NO2] 0.009 M
0.008
Conc.,mol/L

[NO]

0.006

0.004 [O2]

0.002

0
0 50 100 150 200 250 300 350 400 450

Time, sec
375 s
12_291
0.0100

NO2

0.0075
Concentrations (mol/L)

0.0026 [NO 2 ]
0.0006

t 70s
0.005
110 s

NO

0.0003
0.0025 70s

O2

50 100 150 200 250 300 350 400

Time (s)
 Initial Rate (t = 0)
Concentration vs Time

0.012

0.01
[NO2]

0.008 [NO]
Conc.,mol/L

0.006

0.004
[O2]

0.002

0
0 50 100 150 200 250 300 350 400 450

Time, sec
 Initial rate
Slope of tangent line at time 0 (y intercept)
y
slope of tangent line
x
NO2
rate
t
NO2 0.010 M
rate @ 0 s
t 225 s
M
rate @ 0 s 4.4 10 -5
s
 Rate Laws

rate kA B
m n

k = rate constant
m, n = order

2NO2 2NO O2

rate = k[NO2]n
 Introduction to Rate Laws
Reversible chemical reactions

Forward: 2NO2 2NO O2

Backward: 2NO O2 2NO2

Equilibrium: 2NO2 2NO O2

 Introduction
Dominant Reaction: 2NO2 2NO O2

NO2
Rate Law: rate - kNO2 n
t
O 2
rate k NO2 n
t
k, k: specific rate constant
n: order of reactant
can be zero, fractional, or negative
 Method of Initial Rates

rate kA B
m n

Unknown: k, m, n

Initial rate: instantaneous rate just after

reaction is initiated
 Initial Rates, NO2 decomposition

2NO2 2NO O2
NO2
rate - kNO2 n
t
Initial Conc. Rate [O2]
Experiment [NO2] Formation
-5
1 0.01 7.1 x 10
-4
2 0.02 2.8 x 10
 Order of Reaction
rate 2 - k 2 NO2
n
General:

rate 1 - k1 NO2 n

Substituting: 2.8 10 -4
- k 2 0.020
n

7.1 10 -5
- k1 0.010n

Solution:
4 (2) n
so n2
ln 4 n ln 2
 Rate constant
NO2
rate - kNO2 n
t
Rate 1
7.1 x 10-5 M s-1 = -k[0.01 M]2
k = 0.71 M-1 s-1
Rate 2
2.8 x 10-4 M s-1 = -k[0.02 M]2
k = 0.70 M-1 s-1
NO2
rate law 0.70NO2 2
t
 You try

H 2 I 2 2HI

Initial Conc. Initial Conc.

Experiment [H2] [I2] Rate
1 0.0113 0.0011 1.9 x 10-23
2 0.0220 0.0033 1.1 x 10-22
3 0.0550 0.0011 9.3 x 10-23
4 0.0220 0.0056 1.9 x 10-22
O2 + 2 NO 2NO2
 Overall Order

rate kH 2SeO3 H I
2 3

Sum: 1 + 2 + 3
= 6

Overall order of reaction: 6

 Types
Differential:
Rate dependence on concentration
NO2
rate - kNO2 n
t
O 2

rate k NO2
n
t

Integrated:
Concentration dependence on time
 First Order Reactions
For aA products
A
Differential: rate - kA
t

Integrated: ln At - kt ln A0

ln
A 0
kt
A t
 Half-life, first order reactions

Integrated law:
ln
A 0
kt
A t
Half-life:
ln2
t1
Half of initial reacted 2 k
[A]t = [A]0 0.693
t1
2 k
Independent of [A]0
 Second Order Reactions
For aA products
A
Differential: rate - kA2
t

1 1
kt
Integrated:
At A0
1 1
kt
At A0
 Half-life, second order reactions

Integrated law: 1 1
kt
At A0
Half-life:
1
t1
kA 0
Half of initial reacted
2
[A]t = [A]0

Inversely proportional to [A]0

 Zero Order Reactions
For aA products

A
Differential: rate - kA k
0
t

At - kt A0
Integrated:
At A0 - kt
 Graphical Method

First order ln At - kt ln A0
1 1
Second order kt
At A0
Zero order At - kt A0

Straight line y mx b
 First order

ln[A]0
ln At - kt ln A0
slope = -k
y mx b
ln[A]

Plot:
ln[A] vs. time

time
 Second order

1 1
kt
At A0 slope = k

y mx b
1
[A]
Plot:
1
1 vs. time [A]o
[A]
time
 Zero order

At - kt A0
[A]0

slope = -k
y mx b
[A]

Plot:
[A] vs. time

time
 Summary
Conditions set so dominant forward reaction

Differential Rate Laws

rate as a function of concentration
method of initial rates

Integrated Rate Laws

concentration as a function of time
graphical method

Experimental data collection

Rate law types can be interconverted
 Reaction Mechanism
Chemical equation: Summary

Mechanism: Series of elementary steps

Elementary Steps: Reactions with rate laws

from molecularity

Molecularity: Number of species that must

collide to produce reaction
 Reaction Mechanism

Proposed elementary steps must satisfy conditions:

reasonable reactions

sum of steps = overall balanced reaction

mechanism rate law = experimental rate law

 Intermediates

appear in steps

produced in one step

used in subsequent

not in overall equation

 Rate-determining step
In a multi-step process:

SLOWEST step

Determines overall reaction rate

Bottleneck
 Model for Kinetics

Collision Theory
rate determined by particle collisions
collision frequency and energy

Transition State Theory

how reactants convert to products
 Collision Theory (Bimolecular Collsions)

rate Z f a p
Z: no. of bimolecular collisions per second
fa : fraction with Ea
P: fraction with correct orientation

Ea: activation energy

 Arrhenius Equation
Ea

k Ae RT

k: rate constant
Ea: activation energy (minimum required)
T:absolute temperature
R: universal gas constant
A: orientation factor

Energy & orientation requirements for reaction

Hydrolysis of an ester
 Transition State Theory
Ea and internal energy:
Bonds breaking and forming
Atoms rearranging

Transition State
Unstable intermediate
At point of highest energy
forward reaction reverse reaction
exothermic reaction
I- + CH3Cl Cl- + CH3I
 Catalysts
Speed reaction
Are not consumed

Alternative pathway for reaction with lower Ea

Types
Homogeneous
Heterogeneous

Enzymes are biological catalysts

 12_304

Effective Effective
Number of collisions
with a given energy

Number of collisions
collisions collisions

with a given energy

(uncatalyzed) (catalyzed)

Ea (catalyzed )
E a (uncatalyzed )
Energy Energy
(a) (b)
Adsorption, activation, reaction, desorption