Chem27 Chap15 Lecture 2021

Chapter 15 Chemical Kinetics
2H2(g) + O2(g)  2H2O(l)

Chapter 15, J. Ren, 2021 1
Reaction Rate
Reaction Rate:
• Change in concentration of a reactant or product
per unit time.
• Rate of a reaction is not a constant.
For a general reaction: A B
[A] [A]t2 - [A]t1
Average Rate = =
t t2-t1
d[A]
Instantaneous Rate = The slope of the tangent line
dt
[A] = concentration of A, mol/L

Decomposition of NO2
2NO2(g)  2NO(g) + O2(g)
Quickly heat nitrogen

dioxide to 300°C • NO2 is consumed the same rate as
NO is formed
• O2 is produced half as fast as NO

2NO2(g)  2NO(g) + O2(g)

Average Rate
2NO2(g)  2NO(g) + O2(g)
Note: find average rate from 050 (s), and from 50100 (s)
5
Chapter 15, J. Ren, 2021
Average Rate
2NO2(g)  2NO(g) + O2(g)
Rate of a reaction is
not a constant.
6
Instantaneous Rate
2NO2(g)  2NO(g) + O2(g)
Instantaneous rate:
slope of the tangent line
Rate of NO2 at 100s
Rate of NO2 at 100s = 2.4 x 10-5 mol/L s
Rate of NO at 250s
Rate of NO at 250s = 8.6 x 10-6 mol/L s

Rate of O2 at 250s
Rate of O2 at 250s = 4.3 x 10-6 mol/L s
7
Decomposition of N2O5 as a Function of Time
Instantaneous Rates
2N2O5(soln)  4NO2(soln) + O2(g)
What is the instantaneous rate when [N2O5] is at 0.90 mol/L and 0.45 mol/L?
8
Decomposition of N2O5 as a Function of Time
Instantaneous Rates
2N2O5(soln)  4NO2(soln) + O2(g)
What is the instantaneous rate when [N2O5] is at 0.90 mol/L and 0.45 mol/L?
0.9
0.45
9
Introduction to Rate Law
Rate Law:
Experimentally determined equation that can be used to
predict the relationship between the rate of reaction and
the concentration of the reactants.
aA + bB dD + eE
Rate = k[A]n[B]m k: rate constant

m, n: order of the reaction
• The values of k, m, and n are determined experimentally

• n, m are not related to the reaction coefficient.
• The concentration of the products does not appear in the
rate law

Determining the Form of the Rate Law
Method of Initial Rates
Example-1
Determine the values of m, n, k, and the form of the Rate Law
NH4+(aq) + NO2−(aq)  N2(g) + 2H2O(l)
Ans: Rate = k[NH4+][NO2-]; k = 2.7 x 10-4 L/mol s

11
m+n = 2, overall second order reaction Chapter 15, J. Ren, 2021
Method of Initial Rates
NH4+(aq) + NO2−(aq)  N2(g) + 2H2O(l)
Question: Determine the values of m, n, k, and the form of the Rate Law
12
note
13
Example-2
Ans: Rate = k[BrO3¯][Br¯][H+]2
k = 8.00 L3mol-3 s-1
Overall order: m+n+p = 4
14
note
15
Two Forms of the Rate Law
Differential Rate Law (Rate Law):

Expresses how the rate depends on concentration.
Rate = k[A]n[B]m
Integrated Rate Law:

Expresses how the concentrations depend on time
first-order, second-order, zero-order

First-Order Rate Law
ln[A]t = -kt + ln[A]o [A]o: initial concentration

or [A]t: concentration at time t
[A]o Plot of ln[A]t vs. t gives a straight line
ln = kt
[A]t
17
Example: Decomposition of N2O5
2N2O5(g)  4NO2(g) + O2(g)
t, sec [N2O5], mol/L
0 0.1000
50 0.0707
100 0.0500
200 0.0250
300 0.0125
400 0.00625
a) Verify that the rate law is first order

b) Find the rate constant
c) Calculate the concentration of N2O5 at 150 second.
Ans:
a) plot of In[N2O5] versus time
b) k = 6.93 x 10-3 s-1
c) At 150 s, [N2O5] = 0.0353mol/L
18
Example: Decomposition of N2O5
2N2O5(g)  4NO2(g) + O2(g)
t, sec [N2O5], mol/L note
ln[N2O5]
0 0.1000 -2.303
50 0.0707 -2.649
100 0.0500 -2.996
200 0.0250 -3.689
300 0.0125 -4.382
400 0.00625 -5.075
1.386
200
19
Half-Life of a First-Order Reaction
The time required for a reactant to reach half of
its original concentration
Half-life is independent of concentration [A], but

depends on k.
Example: Half-Life of a First-Order Reaction
2N2O5(g)  4NO2(g) + O2(g)
21
Example: Half-Life
A first-order reaction has a half-life of 20.0 min
a) Calculate the rate constant for this reaction
b) How much time is required for this reaction to
be 75% complete?

Second-Order Rate Law

1 1
Integrated Rate Law: = kt +
[A]t [A]o
Plot of 1/[A]t vs. t gives a straight line
Half-Life
Half-life depends on both k and [A]o 23

Example: Butadiene Dimerization
2C4H6(g)  C8H12(g)
a) Is the reaction first-order or second-order?
b) What is the rate constant?
c) What is the half-life?
t, sec [C4H6], mol/L
0 0.01000
1000 0.00625
1800 0.00476
2800 0.00370
3600 0.00313
4400 0.00270
24
2C4H6(g)  C8H12(g)
t, sec [C4H6], mol/L Solution 1
0 0.01000
1000 0.00625
1800 0.00476
2800 0.00370
3600 0.00313
4400 0.00270
1
ln[C4H6] [C4H6]
-4.605 100
-5.075 160
-5.348 210
-5.599 270
-5.767 319 25
-5.915 370 Chapter 15, J. Ren, 2021
Figure 15.5:
(a) A plot of ln[C4H6] versus t.
(b) A plot of 1/[C4H6] versus t.
26
2C4H6(g)  C8H12(g)
t, sec [C4H6], mol/L Solution 2
0 0.01000
1000 0.00625
1800 0.00476
2800 0.00370
3600 0.00313
4400 0.00270
1
ln[C4H6] [C4H6]
-4.605 100
-5.075 160
-5.348 210
-5.599 270
-5.767 319 27
-5.915 370 Chapter 15, J. Ren, 2021
Zero-Order Rate Law
Differential Rate Law (Rate Law): Rate = k

Rate is a constant
Integrated Rate Law: [A]t = -kt + [A]o

Plot of [A]t vs. t gives a straight line
[A]o
Half-Life t1 2 =
2k
Half-life depends on both k and [A]o
Example of a Zero Order Reaction
2N2O(g)  2N2(g) + O2(g)
Once the Pt surface is fully covered with N2O, [N2O] has no net
effect on the reaction. The reaction rate becomes a constant.
Figure 15.7: Decomposition reaction takes place on a platinum surface (pt
is a catalyst)
29
Summary of the Rate Law
30
In-Class Exercise: Integrated Rate Law
For the following three reaction with the type A  products,
a) Use the integrated rate law to determine the order of each reaction
(without making a plot).
b) Determine the rate constant, k, for each reaction. Give correct unit.
c) Calculate the half-life for each reaction
d) Make a suitable linear plot for each reaction to determine the rate
constant, and compare with the results obtained in a) and b)
Reaction A Reaction B Reaction C

t, min [A], mol/L t, sec [A], mol/L t, sec [A], mol/L
0 0.1000 0 0.715 0 0.600

30 0.0725 22 0.605 100 0.497
45 0.0640 74 0.345 200 0.413
60 0.0568 132 0.055 300 0.344
31
First-Order Rate Law for Reaction of Gases
Plot of lnPt vs. t gives a straight line

Reaction Mechanism
Reaction mechanism:
A step-by-step detailed description of a chemical
reaction.
Elementary step (elementary reaction):

A reaction whose rate law can be written from its
molecularity.
Molecularity:
The number of species that must collide to produce
the reaction indicated by that step.
Molecular representation of the elementary steps
in the reaction of NO2 and CO.
NO2(g) + CO(g) → NO(g) + CO2(g)
Rate = k[NO2]2 (expt)
Two elementary bimolecular steps
NO3 is an intermediate.
Intermediate: A species that is formed and then consumed as34

the reaction proceeds Chapter 15, J. Ren, 2021
Rate-Determining Step
Rate-determining step:
The elementary step is much slower than all
other steps.
The overall reaction CANNOT be faster than the
rate-determining step.
35
Requirements for Reaction Mechanism
Reaction mechanism is a series of elementary steps
that mush satisfy two requirements:
1. The sum of the elementary steps must give the

overall balanced equation.
2. The mechanism must agree with the
experimentally determined rate law.
The rate for the overall reaction is determined by the
rate-determining step
Comment: We cannot proof if a mechanism is absolutely
correct. We can only say that a mechanism satisfy the two
requirements and is possibly correct.
Femtosecond Spectroscopy
Formation of cyclobutane from 2 ethylene
Two possible mechanisms, one without
involving an intermediate, and one involves
an intermediate
Femtosecond spectroscopy shows that the
Intermediate was in fact formed and had
Ahmed Zewail lifetime of 700 fs.
(1946-2016)
Nobel Prize in
Chemistry, 1999
“For his studies of

the transition states
of chemical
reactions using
femtosecond
spectroscopy” Chapter 15, J. Ren, 2021 37
Reaction Mechanism, Example 1
Decomposition of Ozone
2O3 (g) → 3O2 (g)
[O 3 ]2
Experimental rate law: Rate = k (Rate = k[O3]2[O2]-1)
[O 2 ]
Proposed mechanism
Step 1: fast, equilibrium
k
O3 (g) 1 O2 (g) + O (g)
Step 2: slow, RDS K-1
k2
O3 (g) + O (g) → 2 O2 (g)
Very the mechanism and give the expression of the rate law (in
particular the rate constant)
Ans: Rate = k[O3]2/[O2], (k = k2k1/k-1) 38
Reaction Mechanism, Example 2
The gas-phase reaction of chlorine with chloroform is described by the following
equation. The rate law determined from experiment has a noninteger order.
A proposed mechanism for this reaction follows:
Is this an acceptable mechanism for the reaction?
Give the expression of the rate law including rate constant

Ans: Rate = k[Cl2]1/2[CHCl3], k = k2(k1/k-1)1/2
The Steady-State Approximation
Used in cases where a specific rate-determining
step cannot be chosen.
The steady-state approximation:

The concentration of any intermediate remains
constant as the reaction proceeds.
Rate of formation of the intermediate =

Rate of consumption of the intermediate

Example: The Steady-State Approximation
The reaction between nitric oxide and hydrogen, may proceed via the
following mechanism.
In this mechanism the intermediate is N2O2. To apply the steady-state

approximation to this mechanism, we assume the concentration of N2O2
remains constant.
Rate of production of N2O2 = rate of consumption of N2O2
1) Use the steady-state approximation to determine the form the rate law
2) Assume step 2 is the rate determining step, determine the form of the
rate law
3) Under what condition, both methods give the same form of the rate law?
41
Exercise: Reaction Mechanism
Given the reaction with the proposed mechanism, answer the following two
questions:
a) Assume the second elementary step is the rate-determining step, derive
the rate law for the overall reaction.
b) Use the steady-state approximation to derive the rate law for the overall
reaction.
c) Under what condition, will the rate law derived using the steady-state
approximation to have the same form as the one derive in question a)?
2NO(g) + O2 2NO2(g)
k1
step 1 2NO(g) N2O2(g)
k2
step 2 k3
N2O2(g) + O2(g) 2NO2(g)

A Model for Chemical Kinetics
Collision theory (collision model):

Molecules must collide to react
Transition state theory:

An activated complex (a hypothetical species)
exist in a transitory state (transition state) that lies
between the reactants and the products.

The change in potential energy as a function of
reaction progress for the reaction
2BrNO(g)  2NO(g) + Br2(g) exothermic
Ea: Activation Energy

(influence reaction rate)
ΔE: Energy change

of the reaction
(has no influence on
reaction rate).
45
Collision Model
Reaction rate depends on:
1) Collision frequency:
Must have sufficient collision frequency
2) Collision energy:
The collision must involve enough energy (equal or
greater than Ea).
3) Collision orientation:
The orientation of the reactants must allow the
formation of new bonds.
Effective collisions (items 2 and 3)
Rate constant: k = zpe-Ea/RT
z: collision frequency; p: effective orientation
e-Ea/RT: fraction of collision with sufficient energy 46

Orientation of the Collisions
2BrNO(g)  2NO(g) + Br2(g)
Several possible orientations for a collision
between two BrNO molecules.
Reaction
Reaction
No Reaction

The Effect of Temperature on Reaction Rates
A plot showing the exponential dependence of the rate
constant on the absolute temperature
A + B  Products
Rule of thumb:
An increase of 10 K in
temperature doubles the
reaction rate (rate constant).

Temperature Effect:
Explanation Based on Collision Model
Plot showing the number of collisions with a particular energy
Shaded area:
Number of collisions
Fraction of effective collision
• The fraction of effective

collision at T2 is greater
than that at T1.
• The rate at T2 is faster
than that at T1.
Effective collision:
The fraction of the collisions that possess enough energy to
overcome Ea Chapter 15, J. Ren, 2021
49
The Arrhenius Equation
-E a / RT
k  Ae
or
Ea 1
ln k = - ( )( ) + ln A
R T
A: Pre-exponential factor (Frequency factor)
Ea: Activation energy
R: Gas constant, 8.314 J/mol K
Plot of lnk vs. 1/T gives a straight line, slope = -(Ea/R)
Useful work equation at two temperatures:
50
The Arrhenius Equation
Derive the work equation at two temperatures:
Note: When temperature changes, the rate constant is changed, but

the activation energy remains the same.
51
Example: The Arrhenius Equation
2N2O5(g)  4NO2 + O2(g)
For the reaction, the experimental rate constant
measured at several temperatures are given.
1) Determine Ea in kJ/mol
2) Determine the k value at 25 oC
(Intercept = 30.69)
Ans 1): 1.0 x 102 kJ/mol

Ans 2): 6.9 x 10-5 s-1
Example: The Arrhenius Equation
A  Product
For the given reaction, Ea = 1.01 x 105 J/mol. At 25 oC the rate
constant is 3.71 x 10-5 s-1. At what temperature, the k value is
9.63 x 10-5 s-1? Ans: 306 K

Relationship between Reaction Mechanism and Energy Profile
H2(g) + 2ICl(g)  I2 + HCl(g); ΔHrxn = -218 kJ/mol
Step1: H2 + ICl  HI + HCl
Step2: HI + ICl  I2 + HCl
1) How many intermediate?

2) How many transition states?
3) Which one is the faster step? 54
4) Is each step endothermic or exothermic? Chapter 15, J. Ren, 2021
Catalysis
Catalyst:
A substance that speed up a reaction without
being consumed itself.
How does a catalyst work?
A catalyst changes the reaction pathway to the
one with a lower activation energy
(note: catalyst does not change the overall reaction enthalpy)
Homogeneous catalyst:
Is one that is present in the same phase (physical state)
as the reacting molecules.
Heterogeneous catalyst:
Exists in a different phase, usually as a solid.
55
Energy plots for catalyzed and uncatalyzed pathways
for a given reaction
A catalyst lowers the activation

energy, and therefor enhances
number of effective collision energies.
56
Heterogeneous catalysis of the
hydrogenation of ethylene.
H H H H
Ni (catalyst)
C C + H2 H C C H
H H H H
Ethylene Ethane
1. Adsorption and activation of the reactants

2. Migration of the adsorbed reactants on the surface
3. Reaction among the adsorbed substances
4. Escape, or desorption, of the products
57
An example of homogeneous catalysis
The activation energy is lowered in the presence of

H+, a catalyst for the decomposition of HCOOH
O
+
H H
H O C O + H 2O
solution

Homogeneous Catalysis
NO catalyzes the formation of ozone at lower atmosphere
NO catalyzes the decomposition of ozone at upper atmosphere
Internal combustion
engines of automobiles
N2 + O 2 2NO
lower atmosphere
Upper atmosphere
NO + 1/2O2 NO2
NO + O3 NO2 + O2
light
NO2 NO + O
O + NO2 NO + O2
O2 + O O3
59
Heterogeneous Catalyst
In auto exhaust systems — Pt, NiO, Rh
deposited on ceramic honeycomb
2CO + O2 → 2CO2
2NO → N2 + O2
60
Enzyme Catalysis
Lock-and-key model of enzyme action
k1
E+S ES
k-1
k2
ES E+P
61
End of Chapter 15

1. For the following reaction, calculate:
a) Average rates at 0-200 sec and 400-600 sec.
b) Assume that the rate is a constant value in the period of 0-200 sec, calculate
[H2O2] at 100 sec.
H2O2(aq) H2O(l) + 1/2O2(g)
t, sec 0 200 400 600

[A], mol/L 2.32 2.01 1.72 1.49

2. Given three reaction with the type A  products, answer the following three
questions:
a) Use the integrated rate law to determine the order of each reaction (without
making a plot).
a) Determine the rate constant, k, for each reaction. Give correct unit.
c) Make a suitable linear plot for each reaction to determine the rate constant,
and compare with the results obtained in a) and b)
Reaction A
t, min 0 30 45 60
[A], mol/L 0.10 0.0752 0.0640 0.0568
Reaction B
t, sec 0 22 74 132
[A], mol/L 0.715 0.605 0.345 0.055
Reaction C
t, sec 0 100 200 300
[A], mol/L 0.600 0.479 0.413 0.344

3. Given the reaction with the proposed mechanism, answer the following
two questions:
a)Assume the second elementary step is the rate-determining step, derive
b)Use the steady-state approximation to derive the rate law for the overall
reaction. Under what condition, will the rate law derived using the steady-
state approximation to have the same form as the one derive in question
a)?
2NO(g) + O2 2NO2(g)
step 1 k1
2NO(g) N2O2(g)
k2
step 2 k3
N2O2(g) + O2(g) 2NO2(g)

2. Given the reaction with the proposed mechanism, answer the following
two questions:
a)Assume the second elementary step is the rate-determining step, derive
b)Use the steady-state approximation to derive the rate law for the overall
reaction. Under what condition, will the rate law derived using the steady-
state approximation to have the same form as the one derive in question a)?
2NO(g) + O2 2NO2(g)
k1
step 1 2NO(g) N2O2(g)
k2
step 2 k3
N2O2(g) + O2(g) 2NO2(g)

Example: Half-Life
A first-order reaction has a half-life of 20.0 min
a) Calculate the rate constant for this reaction
b) How much time is required for this reaction to
be 75% complete?

The decay of a sample of strontium-90 over time.
10g
5g
2.5g
1.25g
0.625g

Starting with pure
nitrogen dioxide at
300°C
2NO2(g)  2NO(g) + O2(g)
71
Figure 15.9
The STM images of the reaction of CO and O2. (a) An O2
molecule (oval) and a CO molecule (circle) on a surface.
As the two molecules approach each other, a reaction
occurs (b) to form an O—CO—O complex (c). After an
electron pulse is applied to the complex, a newly formed
CO2 molecule exits the surface, leaving behind a single
O atom (d).

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Chapter 15 Chemical Kinetics

2H2(g) + O2(g)  2H2O(l)

[A] = concentration of A, mol/L

Quickly heat nitrogen

Chapter 15, J. Ren, 2021 3

Chapter 15, J. Ren, 2021 4

Rate of NO at 250s = 8.6 x 10-6 mol/L s

Rate of O2 at 250s = 4.3 x 10-6 mol/L s

Rate = k[A]n[B]m k: rate constant

• The values of k, m, and n are determined experimentally

Chapter 15, J. Ren, 2021 10

Ans: Rate = k[NH4+][NO2-]; k = 2.7 x 10-4 L/mol s

Differential Rate Law (Rate Law):

Integrated Rate Law:

Chapter 15, J. Ren, 2021 16

Differential Rate Law (Rate Law):

Integrated Rate Law:

ln[A]t = -kt + ln[A]o [A]o: initial concentration

a) Verify that the rate law is first order

Half-life is independent of concentration [A], but

Chapter 15, J. Ren, 2021 22

Differential Rate Law (Rate Law):

Half-life depends on both k and [A]o 23

Differential Rate Law (Rate Law): Rate = k

Integrated Rate Law: [A]t = -kt + [A]o

Reaction A Reaction B Reaction C

0 0.1000 0 0.715 0 0.600

Integrated Rate Law:

Plot of lnPt vs. t gives a straight line

Chapter 15, J. Ren, 2021 32

Elementary step (elementary reaction):

Intermediate: A species that is formed and then consumed as34

1. The sum of the elementary steps must give the

“For his studies of

A proposed mechanism for this reaction follows:

Is this an acceptable mechanism for the reaction?

Give the expression of the rate law including rate constant

The steady-state approximation:

Rate of formation of the intermediate =

Chapter 15, J. Ren, 2021 40

In this mechanism the intermediate is N2O2. To apply the steady-state

Rate of production of N2O2 = rate of consumption of N2O2

Chapter 15, J. Ren, 2021 42

Collision theory (collision model):

Transition state theory:

Chapter 15, J. Ren, 2021 44

Ea: Activation Energy

ΔE: Energy change

Chapter 15, J. Ren, 2021

Chapter 15, J. Ren, 2021 47

Chapter 15, J. Ren, 2021 48

• The fraction of effective

Plot of lnk vs. 1/T gives a straight line, slope = -(Ea/R)

Useful work equation at two temperatures:

Note: When temperature changes, the rate constant is changed, but

Ans 1): 1.0 x 102 kJ/mol

Chapter 15, J. Ren, 2021 53

1) How many intermediate?

A catalyst lowers the activation

1. Adsorption and activation of the reactants

The activation energy is lowered in the presence of

Chapter 15, J. Ren, 2021 58

Chapter 15, J. Ren, 2021 62

H2O2(aq) H2O(l) + 1/2O2(g)