Chemical Kinetics
Chemical Kinetics
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)
.40
.20
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
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
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
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
rate kH 2SeO3 H I
2 3
Sum: 1 + 2 + 3
= 6
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
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
reasonable reactions
appear in steps
used in subsequent
SLOWEST step
Bottleneck
Model for Kinetics
Collision Theory
rate determined by particle collisions
collision frequency and energy
rate Z f a p
Z: no. of bimolecular collisions per second
fa : fraction with Ea
P: fraction with correct orientation
k: rate constant
Ea: activation energy (minimum required)
T:absolute temperature
R: universal gas constant
A: orientation factor
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
Types
Homogeneous
Heterogeneous
Effective Effective
Number of collisions
with a given energy
Number of collisions
collisions collisions
Ea (catalyzed )
E a (uncatalyzed )
Energy Energy
(a) (b)
Adsorption, activation, reaction, desorption