Chapter 7 Kinetics Students

CHEMICAL KINETICS
CHM 3010-Chemical Kinetics 1

Chemical Kinetics
1. To show how the rate of a reaction can relate to
change in reactant or product concentration with
time.
2. To explain the various factors including
chemical nature and concentration of the
reactants, temperature, catalyst that affect
reaction rates.
3. To illustrate how rate laws give reaction rate as
1. Rates of reaction, rate l a function of reactant concentrations.
laws, order of reaction; 4. To define order of reaction with respect to
2. Mechanism of the reaction, coefficient of a rate law.
determination of order of 5. To demonstrate (i) how integrated rate laws give
reaction. concentration as a function of time for First Order
3. Molecular collisions theory. Reaction (ii) the reciprocal of the concentration is
4. Transition complexs theory. related linearly to time for Second Order Reaction
(ii) to understand what is Zero Order Reaction.
6. To explain what is half-life of a species in
accordance to First Order and Second Order
Reactions.
7. To describe the kinetics theories in terms of
molecular collisions that are based on rate of
effective collisions between reacting molecules,
molecular orientation and activation energy.

Kinetics is a branch of chemistry which studies:
i) How a reaction occurs. (the changes from reactants to
products
ii) How rapid/fast the reaction occurs.
iii) The factors affecting the reaction rate.

Reaction rate: the central focus of chemical kinetics

The Structural Change Of Molecules From Reactants To Products
Intermediate Complex
Energy Level
Products
Reacants
Reaction pathway

The chemical reactions have different rate. Some reactions
proceed very fast and the others very slowly.
Fe2O3
PbI2
The reaction between O2

The reaction between Pb(NO3)2
gas with Fe metal in the
solution with KI solution is very fast
atmosphere is very slow
Pb(NO3)2 + 2KI PbI2 + 2KNO3
2Fe + 3O2 2Fe2O3
Colourless soluion Yellow Precipitate
black

1. Rate of Reaction
2. Rate Law
3. Order of Reaction
4. Reaction Mechanism
5. Effective Collision
6. Catalyst

Kinetics is the study of rates of chemical
reactions and the mechanisms by which they
occur.
The reaction rate is the increase in
concentration of a product per unit time or
decrease in concentration of a reactant per unit
time.
A reaction mechanism is the series of
molecular steps by which a reaction occurs.

Brady 576
Rate of reaction describes how fast the reactants

are consumed and the products are formed.
It is usually expressed as a change of reactants or
products concentration in unit time.
For reaction: A + B === > C
The rate = -dA/dt = -dB/dt = dC/dt
Reactant concentration change Time change Product concentration change
(-) indicate that the concentration decreases

Graphically, the change of concentration against time, is shown below:
A == > B
Product (B)
Concentration (mol/dm3)
dB Rate of product formation = dB/dt
dt
Rate of reactant disappearance = - dA/dt

dA
dt Reactant (A)
Time (second/min/hour)

Example 16-1
Rate of Reaction:
At some time, we observe that the reaction:
2N2O5(g) 4NO2(g) + O2(g) is forming NO2 at
the rate of 0.0072 mol L-1 s-1.
[O 2 ]
(a) what is the rate of change of [O2],
t
-1 -1
in mol L s , at this time ?
(b) what is the rate of change of [N2O5], [ N 2O5 ]
-1 -1 t
in mol L s , at this time ?
What is the rate of reaction at this time ?

Solution:

The Rate of a Reaction
Thermodynamics determines if a reaction can occur.
Kinetics determines how quickly a reaction occurs.
Some reactions that are thermodynamically

feasible are kinetically so slow as to be
imperceptible.
Cdiamond O 2g CO 2g G o298 396 kJ

VERY SLOW
H +aq + OH-aq H 2 O l G o298 = -79 kJ
INSTANTANEOUS

Rate law for a reaction is an expression that relates the rate of
reaction to the concentration of the reactants:
Let us consider the following reaction:
A + B == > C
== > What do you think the rate law for this reaction is?
The rate law may be written as;
rate = k [A]x [B]y .
The rate law can only be determined by experimental method. It
cannot be determined by just looking at the stoichiometric
equation of a reaction.
Example: rate = k[B]o
B == > D, it may be written as rate = k[B]1
rate = k[B]2

The Rate of Reaction
Rate Law Expressions must be determined
experimentally.
The rate law cannot be determined from the
balanced chemical equation.
This is a trap for new students of kinetics.
The balanced reactions will not work because most
chemical reactions are not one-step reactions.
Other names for rate law expressions are:
1. rate laws
2. rate equations
3. rate expressions

The exponents in the rate law are generally unrelated
to the chemical equations coefficients
Never simply assume the exponents and coefficients are
the same
The exponents must be determined from the results of
experiments
The exponent in a rate law is called the order of
reaction with respect to the corresponding reactant

There is a rate law for:
i) Zero order reaction
ii) First order reaction
iii) Second order reaction
iv) . And so on
There are two forms of rate law:
i) Differential form
ii) Integrated form

Order of Differential Integrated
Reaction
Zero order dc/dt = k[A]0 x = kt

First Order dc/dt = k[A]1 ln a/(a-x) = kt
Second order dc/dt = k[A]2 x /a(a-x) = kt
dc/dt = k[A][B]

Important terminology for kinetics.
The order of a reaction can be expressed in terms of
either:
1 each reactant in the reaction or
2 the overall reaction.
Order for the overall reaction is the sum of the orders for
each reactant in the reaction.
For example:
2 N 2 O 5g 4 NO 2g + O 2g
Rate = kN 2 O 5
This reaction is first order in N 2 O 5
and first order overall.
A second example is:
CH 3 3 CBraq OH-aq CH 3 3 COHaq Br-aq

Rate = k [ CH 3 3 CBr ]
This reaction is first order in CH 3 3 CBr,
zero order in OH- , and first order overall.

A final example of the order of a
reaction is:
2 NOg + O 2g 2 NO 2g
Rate = k NO O 2
2
This reaction is second order in NO,

first order in O 2 , and third order overall
REMEMBER, ALL RATE EXPRESSIONS ARE
DETERMINED EXPERIMENTALLY

Given the following one step reaction and its rate-
law expression.
Remember, the rate expression would have to be
experimentally determined.
2 A g B g C g
Rate = kA
2
Because it is a second order rate-law expression:

If the [A] is doubled the rate of the reaction
will increase by a factor of 4. 22 = 4
If the [A] is halved the rate of the reaction
will decrease by a factor of 4. (1/2)2 = 1/4

A reaction rate is generally not constant throughout
the reaction
Since most reactions depend on the concentration
of reactants, the rate changes as they are used up
The rate at any particular moment is called the
instantaneous rate
It can be calculated from a concentration versus
time plot

Brady 576
How can the rate of a reaction be

determined?
(Rates of reaction are measured by
monitoring change in concentration
over time)
1. By carrying out an experiment in the lab.
Reactants mixed
2. Reactant(s) are mixed together. together and the
3. The mixture is heated if necessary reaction allowed to
take place
4. The concentrations of the reactants or
products are measured and the changes
are followed against time.

5. The data is collected
example:
Con. [HI] (M) 0.1 0.0716 0.0558 0.0457 0.0387 0.0336 0.0296 0.0265
Time (sec) 0 50 100 150 200 250 300 350
6. A graph of concentration against time is plotted, (as shown in

the next slide)
7. Calculate the gradient at various points of the curve obtained
(as in the next slide).

The rate of the reaction
= gradient of the curve
example
HI (mol/dm3)
Time ( second )
To enable us to calculate the rate of a reaction, we have
to know the concentration of the reactants at various
time during the reaction.
How can it be done? .
What can you observe when a chemical reaction is
taking place?
i) change in colour All these changes
are related to the
ii) gas evolved concentrations of
iii) change in intensity of the colour the reactants or
products
iv) change in the conductivity . So on

Conductometer Manometer
Voltmeter
Stopwatch Radiation meter

Experimental Method
There are two methods which can be
used to determine the concentration of a
reactant at various time:
1. Continuous method
2. Sampling method
1. Continuous method
Zn + HCl
The reactant(s) are mixed in a reactor
and the change of concentration is
followed continuously to the end of the
reaction .

Experimental Method cont.
2. Sampling method
The reactant(s) are mixed in a reactor and the change
of concentration is followed by taking out a sample
of the mixture from time to time and analysed.

Concentrations of Reactants: The Rate-Law Expression
This is a simplified representation of the effect

of different numbers of molecules in the same
volume.
The increase in the molecule numbers is indicative
of an increase in concentration.
A(g) + B (g) Products
A B A B A B
B A B
A B A B A B
4 different possible A-B 6 different possible A- 9 different possible A-
collisions B collisions B collisions

Integrated rate laws and reaction order
[A]t = -kt + [A]0

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

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

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Table 16.4 An Overview of Zero-Order, First-Order, and

Simple Second-Order Reactions
Zero Order First Order Second Order
Rate law rate = k rate = k [A] rate = k [A]2
Units for k mol/L*s 1/s L/mol*s
Integrated rate law in [A]t = ln[A]t = 1/[A]t =

straight-line form k t + [A]0 -k t + ln[A]0 k t + 1/[A]0
Plot for straight line [A]t vs. t ln[A]t vs. t 1/[A]t = t
Slope, y-intercept k, [A]0 -k, ln[A]0 k, 1/[A]0
Half-life [A]0/2k ln 2/k 1/k [A]0

For zero order reaction, the rate of reaction does not depend on the
concentration of the reactant.
A product
The rate law is written as
Rate = dA/dt = k[A]o since [A]o = 1
rate = k
[product]
Time
rate
Time
Zero order always occur in heterogeneous reaction system, especially
involving the gas phase and solid phase reactants

Brady 587
Example: Plot [A] vs t
The decomposition reaction of

H2O2 occurs as follows:
[A]
2H2O2 (aq) H2O (l) + O2 (g)
(A) (B) (C)
Experimentally it was found that
the reaction was first order in
[H2O2]
the rate law for the reaction is:

= k[H2O2]1 = k [A]1
t

Rearrange the above eqn and integrate them ([A] with respect to dt)
we will get:
Plot of ln [A] vs t should give a
differential
d [ A] straight line graph as shown below
Rate k[ A]
dt
[ A ]t t
d [ A]

[ A ]0
[ A]
kdt
0
m=-k
ln [A]
ln[ A] [ A ]t
[ A ]0 kt
[ A]t
ln kt
[ A]o
ln[ A]t kt ln[ A]0
t
ln[ A] ln[ A]0 kt
Integerated

Example of Analysis of First Order Reaction: N2O5 2NO2+ O2
[N2O5] M 0.10 0.079 0.062 0.049 0.039 0.03

t (s ) 0 400 800 1200 1600 2000
ln N2O5
N2O5
Time (s)
Plot of [N2O5] vs t Time (s) Plot of ln [N2O5] vs t
Sample Problem 16.4 Determining Reaction Concentration at a Given Time
PROBLEM: At 10000C, cyclobutane (C4H8) decomposes in a first-order

reaction, with the very high rate constant of 87s-1, to two
molecules of ethylene (C2H4).
(a) If the initial C4H8 concentration is 2.00 M, what is the
concentration after 0.010 s?
(b) What fraction of C4H8 has decomposed in this time?
PLAN: Find the [C4H8] at time, t, using the integrated rate law for a 1st order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
SOLUTION: [C4H8]0 2.00
ln = kt ; ln = (87s-1)(0.010s)
(a) [C4H8]t [C4H8]
[C4H8] = 0.83mol/L
(b) [C4H8]0 - [C4H8]t 2.00M - 0.87M

= = 0.58
[C4H8]0 2.00M
Silberberg

If the reaction involves gases the concentration of
the reactant(s) is (may be) replaced by the partial
pressure of the reactant(s).
A (g) + B (g) C (g)
( PA ) t
ln kt
( PA ) 0
PA = Partial pressure of reactant A

Half Life, t1/2 for First Order Reaction
Half-life ( t) is the time required for one-half of a
reactant to be consumed/reacted.
16 molecules
8 molecules
Concentration [A]o
reduced by
half from the
initial
[A]/2
t Time ( arbitrary Units )

Half-life

t for the first order reaction is constant or unchanged throughout the reaction.
[A]o
Concentration of A
[A]/2
[A]/4
[A]/8
(t)1 (t)2 (t)3 (t)4 Time

( arbitrary Units )

Half Life, t1/2 for First Order Reaction ...
Time required for one-half of a reactant to be
consumed/reacted.
t t1 when [ A]t 12 [ A]0

2
[ A]t 1
ln ln ln 2 kt1
[ A]0 2 2
ln 2 0.693
t1
2
k k
t1/2 for first order reaction is constant or unchanged

throughout the reaction.

Half Life, t1/2 for First Order Reaction
If we know the value of half-life of the reaction, it can be

used to determine the order of the reaction ( useful for
calculations regarding radioactivity)

Concentration vs. Time: The Integrated Rate Equation
Example 16-4: Cyclopropane, an anesthetic, decomposes to

propene according to the following equation.
CH2 CH
H2C CH2 H3C CH2
(g) (g)
The reaction is first order in cyclopropane with k = 9.2 s-1

at 10000C. Calculate the half life of cyclopropane at
10000C.
0.693 0.693
t1/2 -1
0.075 s
k 9.2 s
Brady 589
Case 1 Case 2
A product A+B product
Rate = k [A]2 Rate = k [A] [B]
1
[ A]
Rate k[ A]2 Slope = k
d [ A]
k[ A]2 1
dt [ A]0
[ A ]t t
d [ A]
2
kdt t
[ A ]0
[ A] 0
1 1 1 1
kt Half life 1 kt1
2 [ A]0 [ A]0
2
[ A]t [ A]0
1
t1
2
k[ A]0
The study of the decomposition of 2HI H2 + I2
gave the following data. Determine the order
and rate constant of the reaction.
Con. [HI] (M) 0.1 0.0716 0.0558 0.0457 0.0387 0.0336 0.0296 0.0265
Time (sec) 0 50 100 150 200 250 300 350
1/[HI] 10 13.96 17.92 21.88 25.84 29.76 33.78 37.74
1/[HI]
What do you have to do? ..

40
Solution 35
30
1.Complete the above table Gradient =k
25
2.Plot graph 1/[HI] vs t 20
3.Evaluate the gradient of the 15

graph 10
05
0 100 200 300 400
Time (s)
1/[HI] (mol/dm3)
Time (s)

Brady 581
Order of Reaction is the exponents of the concentration terms in the rate

law of a reaction
For Reaction: A+ B product
If the Rate = k [A]x [B]y
The order can be estimated with respect to a particular reactant
concentration. So the reaction order for [A]= x and for [B] = y
The overall reaction order is the total of the exponents= (x+y)
The value of x , y could be an integer (1,2,3) , fraction (0.5, 2/3) or
zero

Example:
For reaction:
NO2 (g) + CO (g) CO2 (g) + NO (g)
It was found from the experiment that the order for [NO2 ]
= 2 and for [CO] = 0
== > what is the overall order of the reaction ?
Can you write the expression for the rate law of the
reaction ? .

This method requires the determination of half-life (t) of the
reaction at various initial concentration of reactant (Co).
The relationship between half-life (t ) and initial concentration
(Co) is given as:
t = 2(n-1) -1
(n-1) [Co]n-1 k
or log t = log 2n-1 -1 - (n-1) log [Co]
(n-1) k
y = c mx
Where n = reaction order, k = rate constant
Co = initial concentration of reactant

A plot of log t versus log Co should give a straight
line graph, as shown below:
log t
Gradient = (n-1)
log Co
Therefore n (order of reaction) can be determined

Example
The following data was recorded for the decay of ClO-
radicals. Determine the order of the reaction.
[ClO-]ox10-3 8.7 8.44 7.48 7.39 7.13
t (ms) 4.79 4.90 5.45 5.50 5.65
log [ClO-]
log t log t
What are you going to do about it?
0.75
1. Find the log [ClO]o and log t Gradient = n-1
0.73
2. Plot graph of log [ClO]o and log t
0.71
3. Calculate the gradient of the graph
0.69
4. Gradient = (n-1) == > Calculate n
0.85 0.87 0.89 0.91 0.93 0.95
log [ClO]o

1. This method involves the determination of the
concentration (Ct or at or (a-x)) of the reactant at various
time (t)
2. Substitute the data obtained in the rate law expression
3. If the calculation gives the constant value of (k) (rate
constant), then the order of the reaction is equivalent to
the rate law employed.
4. We can also plot the graph. == > It should give a
straight line.

Brady 584
The decomposition of SO2Cl2 == > SO2+ Cl2 at

certain T gave the following data. What is the
order of the reaction?
[SO2Cl2]o M 0.100 0.200 0.300 0.400
ro (M/s) 2.2x10-6 4.4x10-6 6.6x10-6 8.8x10-6
log[SO2Cl2]o
log ro
log ro
How do you solve the
problem?
Solution
1.Complete the above table,

2.Plot graph log ro vs log log[SO2Cl2]o
3.Evaluate the gradient of the graph
log[SO2Cl2]o

For reaction A == > G, it is found that the rate increases by a factor
of 2.25 when the concentration of A is increased by a factor of 1.5.
What is the order with respect to A for this reaction ?
Solution
rate = k [A]x
1.0 = k[1.0]x eqn (1) 2.25 = k [1.5]x eqn (2)
Eqn (2)/(1) == > 2.25 = k [1.5]x / 1.0 = k[1.0]x
2.25 = [1.5]x == > log 2.25 = x log [1.5]
== > 0.3522 = x (0.1761)
== > x = 0.3522/0.1761 = 2

Enrichment - Rate Equations to
Determine Reaction Order
Example 16-10: Concentration-versus-time data for the
decomposition of nitrogen dioxide are given in the
table below. Use the graphs to determine the rate of
the reaction and the value of the rate constant

2 NO2 g
2 NOg O2g at 500K
59
Time
(min) 0 1 2 3 4 5
[NO2] 1.0 0.53 0.36 0.27 0.22 0.18
ln [NO2] 0.0 -0.63 -1.0 -1.3 -1.5 -1.7
1/[NO2] 1.0 1.9 2.8 3.7 4.6 5.5
60
Once again, we will make three different graphs of
the data.
1. Plot [NO2] (y-axis) vs. time (x-axis).
If the plot is linear then the reaction is zero order with
respect to NO2.
2. Plot ln [NO2] (y-axis) vs. time (x-axis).
If the plot is linear then the reaction is first order with
respect to NO2.
3. Plot 1/ [NO2] (y-axis) vs. time (x-axis).
If the plot is linear then the reaction is second order with
respect to NO2.
61
to Determine Reaction
Order
Plot of [NO2] versus time.
Is it linear or not?
[NO2] vs. time
1.2
1
0.8
[NO2]
0.6
0.4
0.2
0
0 1 2 3 4 5
Time (min)
62
Order
Plot of ln [NO2] versus time.
ln [NO2] vs. time
0
0 1 2 3 4 5
-0.5
ln [NO2]
-1
-1.5
-2
Time (min)
63
Order
Plot of 1/[NO2] versus time.
1/[NO2] vs.time
6
5
4
1/[NO2]
3
2
1
0
0 1 2 3 4 5
Time (min)
64
Note that the only graph which is linear is the plot of
1/[NO2] vs. time.
Thus this is a second order reaction with respect to
[NO2].
Next, we will determine the value of the rate constant
from the slope of the line on the graph of 1/[NO2] vs.
time.
65
Order
y 2 - y1 5.50 (1.90) 1 M
slope
x 2 - x1 5 1 min
3.60 1 M
slope 0.90 1 M min
4 min
From the equation for a first order reaction we know
that the slope = a k
In this reaction a = 2.
slope 0.90 2 k
1
Thus the rate constant k 0.45 M min -1
66
Integrated rate laws and reaction order
ln[A]t = -kt + ln[A]0

[A]t = -kt + [A]0
1/[A]t = kt + 1/[A]0

Factors Affecting Reaction Rates
Nature of Reactants
Concentration of the reactants
Temperature
The presence of a catalyst

Chemical nature of the reactants
Bonds break and form during reactions
The most fundamental difference in reaction rates lie in
the reactants themselves
Some reactions are fast by nature and others slow
Ability of the reactants to meet
Most reactions require that particles (atoms,
molecules, or ions) collide before the reaction can
occur
This depends on the phase of the reactants

In a homogeneous reaction the reactants are in the
same phase
For example both reactants in the gas (vapor) phase
In a heterogeneous reaction the reactants are in
different phases
For example one reactant in the liquid and the second in
the solid phase
In heterogeneous reactions the reactants meet only
at the intersection between the phases
Thus the area of contact between the phases
determines the rate of the reaction

Effect of crushing a solid.
When a single solid is
subdivided into much smaller
pieces, the total surface area
on all of the pieces becomes
very large.

Concentration of the reactants
Both homogeneous and heterogeneous reaction
rates are affected by reactant concentration
For example, red hot steel wool bursts into flames in the
presence of pure oxygen
Temperature of the system
The rates for almost all chemical reactions increase
as the temperature is increased
Cold-blooded creatures, such as insects and reptiles,
become sluggish at lower temperatures as their
metabolism slows down

Presence of a catalyst
A catalysts is a substance that increases the rate of a
chemical reaction without being consumed
Enzymes are biological catalysts that direct our body
chemistry

Collision Theory

One of the simplest models to explain reactions
rates is collision theory
According to collision theory, the rate of
reaction is proportional to the effective
number of collisions per second among the
reacting molecules
An effective collision is one that actually gives
product molecules
The number of all types of collisions increase
with concentration, including effective
collisions

Not all collisions which occur among of the reactant molecules will
proceed to reaction.
Why?
example:
2HI(g) H2(g) + I2(g)
at concentration of 0.0001 M and at the temperature of 500oC in 1
second, there are 3.5 x1028 collisions of molecules/dm3 = 5.8x104
mol collisions per dm3
So expected rate of the reaction = 5.8 x 104 mol dm-3s-1
But the rate of the reaction was found to be

=1.2 x 10-8 mol dm-3 s-1 which is very much slower than expected.
What does it mean?

This means that not all of the collisions which occur
between the HI molecules are able to form H2 & I2.
Only a small portion of the collisions are effective
collisions to produce H2&I2.
What happen to most of the collisions ? They are not
effective collisions.
If z = number of collisions
f = ratio of effective collision
The Rate of Reactions is given as:
Rate f z

Collision Theory of Reaction Rates
Three basic events must occur for a reaction to

occur. The atoms, molecules or ions must:
1. Collide.
2. Collide with enough energy to break and form bonds.
3. Collide with the proper orientation for a reaction to
occur.

There are a number of reasons why only a small
fraction of all the collisions leads to the formation
of product:
Only a small fraction of the collisions are energetic
enough to lead to products
Molecular orientation is important because a
collision on the wrong side of a reacting species
cannot produce any product
This becomes more important as the complexity of the
reactants increases

p = measure of priority in orientation
rate pfz
And z the concentration reactant molecule
so z = zo[A]n[B]m
where zo= collision frequency at unit concentration
Therefore
rate = pfzo[A]n[B]m
= k[A]n[B]m where k = pfzo
(rate law from collision theory)
However one need to know the rate determining step.

One method to increase the number of collisions and
the energy necessary to break and reform bonds is to
heat the molecules.
As an example, look at the reaction of methane and
oxygen:
CH 4(g) O2 (g) CO2 (g) H 2O(g) 891 kJ
We must start the reaction with a match.

This provides the initial energy necessary to break the
first few bonds.
Afterwards the reaction is self-sustaining.

Illustrate the proper orientation of molecules that is
necessary for this reaction.
X2(g) + Y2(g) 2 XY(g)
Some possible ineffective collisions are :
X Y
Y Y X X X X Y Y
X Y

An example of an effective collision is:
X Y X Y X Y
+
X Y X Y X Y

This picture illustrates effective and ineffective
molecular collisions.

The key step in the decomposition of NO2Cl to NO2 and Cl2 is
the collision of a Cl atom with a NO2Cl molecules. (a) A poorly
orientated collision. (b) An effectively orientated collision.

An unsuccessful (a) and a successful (b) collision
for an exothermic reaction.

Transition State Theory
Transition state theory postulates that reactants

form a high energy intermediate, the transition
state, which then falls apart into the products.
For a reaction to occur, the reactants must
acquire sufficient energy to form the transition
state.
This energy is called the activation energy or Ea.
Look at a mechanical analog for activation
energy

The brief moment during a successful collision that
the reactant bonds are partially broken and the
product bonds are partially formed is called the
transition state
The potential energy of the transition state is a
maximum of the potential-energy diagram
The unstable chemical species that exists
momentarily is called the activated complex

Formation of the activated complex in the reaction between
NO2Cl and Cl.
NO2Cl+ClNO2+Cl2

Reactions generally have different activation energies
in the forward and reverse direction
Activation energy barrier for the forward and reverse reactions.

Transition State Theory
The relationship between the activation
energy for forward and reverse reactions
is
Forward reaction = Ea
Reverse reaction = Ea + E
difference = E

The minimum energy kinetic energy the
colliding particles must have is called the
activation energy, Ea
In a successful collision, the activation
energy changes to potential energy as the
bonds rearrange to for products
Activation energies can be large, so only a
small fraction of the well-orientated,
colliding molecules have it.

Transition state theory explains what happens
when reactant particles come together
Potential-energy diagrams are used to help
visualize the relationship between the activation
energy and the development of total potential
energy
The potential energy is plotted against reaction
coordinate or reaction progress

Activation energies and heats of reactions can be
determined from potential-energy diagrams
Potential-energy diagram for an endothermic reaction.

The heat of reaction and activation energy are labeled.

The potential-energy diagram for an exothermic reaction.
The extent of reaction is represented as the reaction
coordinate.

Reaction Mechanisms and the Rate-Law
Expression
Use the experimental rate-law to postulate a

mechanism.
The slowest step in a reaction mechanism is the
rate determining step.
Consider the iodide ion catalyzed decomposition
of hydrogen peroxide to water and oxygen.
2 H 2 O 2 2 H 2 O + O 2g
I-

Expression
This reaction is known to be first order in H2O2 ,

first order in I- , and second order overall.
The mechanism for this reaction is thought to be:
Slow step H 2 O 2 + I - IO- + H 2 O

Fast step IO- + H 2 O 2 H 2O + O 2 + I -
Overall reaction 2 H 2O 2 2 H 2O + O 2
Experiment al rate law
R = k H 2O 2 I -

Expression
Important notes about this reaction:

1. One hydrogen peroxide molecule and one
iodide ion are involved in the rate determining
step.
2. The iodide ion catalyst is consumed in step 1
and produced in step 2 in equal amounts.
3. Hypoiodite ion (IO-) has been detected in the
reaction mixture as a short-lived reaction
intermediate.

Expression
Ozone, O3, reacts very rapidly with nitrogen

oxide, NO, in a reaction that is first order in
each reactant and second order overall.
O3g + NOg NO2g + O 2g

Experiment al rate - law is Rate = k O3 NO

Reaction Mechanisms and the Rate-
Law Expression
One possible mechanism is:
Slow step O3 + NO NO3 + O

Fast step O + NO3 NO 2 + O 2
Overall reaction O3 + NO NO 2 + O 2

Reaction Mechanisms and the Rate-Law Expression
A mechanism that is inconsistent with

the rate-law expression is:
Slow step O3 O 2 + O
Fast step O + NO NO 2
Overall reaction O3 + NO NO 2 O 2
The rate - law from this mechanism is Rate = kO3
which proves this mechanism cannot be correct.

Expression
Experimentally determined reaction orders indicate

the number of molecules involved in:
1. the slow step only or
2. the slow step and the equilibrium steps preceding
the slow step.

The overall rate law determined for the mechanism
must agree with the observed rate law
The exponents in the rate law for an elementary
process are equal to the coefficients of the reactants
in chemical equation
Elementary process :
2NO2 NO3 NO
rate k[NO2 ]2

Multistep reactions are common
The sum of the element processes must give the
overall reaction
The slow set in a multistep reaction limits how fast
the final products can form and is called the rate-
determining or rate-limiting step
Simultaneous collisions between three or more
particles is extremely rare

2A + B C + D
from experiment it was found that:
rate = k[A]2[B]
One suggestion is
2A + BC + D
Collision of 3 bodies simultaneously. Termolecule collision
A C
B
D
A
But this is not easy to occur (very rare). Another suggestion would be through a
series of processes involving two molecules.

A reaction that depends on a three-body collision
would be extremely slow
Thus, reaction mechanism seldom include
elementary process that involve more than two-
body or bimolecular collisions
Consider the reaction
2NO 2H 2 N 2 2H 2 O
rate k[NO]2 [H 2 ] (experimen tal)
The mechanism is thought to be

2NO N 2O 2 (fast)
N 2O 2 H 2 N 2 O H 2O (slow)
N 2O H 2 N 2 H 2O (fast)
The second step is the rate-limiting step, which
gives
rate k[ N 2O2 ][H2 ]
N2O2 is a reactive intermediate, and can be
eliminated from the expression

The first step is a fast equilibrium
At equilibrium, the rate of the forward and reverse
reaction are equal
rate(forward) k f [ NO]2
rate(reverse) k r [ N 2 O 2 ] thus
k f [ NO]2 k r [ N 2 O 2 ] or
kf
[ N 2O 2 ] [ NO] 2
kr

Substituting, the rate law becomes
rate k[ N 2 O 2 ][H 2 ]
kf
rate k [ NO] [H 2 ] or
2
kr
rate k '[ NO] [H 2 ]
2
Which is consistent with the experimental rate law

Effect of Temperature
Temperature increases the average kinetic
energy of the reacting particles

Temperature:
The Arrhenius Equation
Svante Arrhenius developed the relationship among (1)

the temperature (T), (2) the activation energy (Ea), and
(3) the specific rate constant (k).
Ea
- RT
k = Ae
or
Ea
ln k = ln A -
RT

The activation energy is related to the rate constant
by the Arrhenius equation
Ea / RT
k Ae
k = rate constant
Ea = activation energy
e = base of the natural logarithm
R = gas constant = 8.314 J mol-1 K-1
T = Kelvin temperature
A = frequency factor or pre-exponential factor

The Arrhenius equation can be put in
standard slope-intercept form by
taking the natural logarithm
ln k ln A Ea / RT or
ln k ln A ( Ea / R) (1 / T )

y c m x
A plot of ln k versus (1/T) gives a

straight line with slope = -Ea/R

Figure 16.11 Graphical determination of the activation energy

ln k = -Ea/R (1/T) + ln A

Kinetic energy distribution for a reaction at two different
temperatures. At the higher temperature, a larger fraction of the
collisions have sufficient energy for reaction to occur. The shaded
area under the curves represent the reacting fraction of the
collisions.

Effect of Temperature
The distribution of molecules possessing different
energies at a given temperature is represented in
this figure.

Table 16.5 The Effect of Ea and T on the Fraction (f) of Collisions

with Sufficient Energy to Allow Reaction
Ea (kJ/mol) f (at T = 298 K)
50 1.70x10-9
75 7.03x10-14
100 2.90x10-18
T f (at Ea = 50 kJ/mol)
250C(298K) 1.70x10-9
350C(308K) 3.29x10-9
450C(318K) 6.12x10-9

Figure 16.14
The effect of temperature on the distribution of collision energies

The activation energy can be related to the rate
constant at two temperatures
k 2 Ea 1 1
ln
k1 R T2 T1
The reactions mechanism is the series of simple
reactions called elementary processes
The rate law of an elementary process can be
written from its chemical equation

or
k 2 Ea 1 1
ln
k1 R T1 T2
or
k 2 E a T2 - T1
ln
k1 R T2T1

Temperature:
The Arrhenius Equation
Consider the rate of a reaction for which Ea=50

kJ/mol, at 20oC (293 K) and at 30oC (303 K).
How much do the two rates differ?
k 2 E a T2 - T1
ln
k1 R T2 T1
k 2 50,000 J mol 303 293
ln K
k1 8.314 K mol 303 293
J
k2
ln 0.677
k1
k2
e0.677 1.97 2
k1
Sample Problem 16.6 Determining the Energy of Activation
PROBLEM: The decomposition of hydrogen iodide,
2HI(g) H2(g) + I2(g)
has rate constants of 9.51x10-9L/mol*s at 500. K and 1.10x10-5

L/mol*s at 600. K. Find Ea.
PLAN: Use the modification of the Arrhenius equation to find Ea.
SOLUTION: -1
k2 Ea 1 1 k2 1 1
ln = - - Ea = - R ln -
k1 R T2 T1 k1 T2 T1
1.10x10-5L/mol*s 1 1
Ea = - (8.314J/mol*K) ln -
9.51x10-9L/mol*s 600K 500K
Ea = 1.76x105J/mol = 176kJ/mol

Figure 16.10 Dependence of the rate constant on temperature

Effect of Catalyst

A catalyst is a substance that changes the rate of a
chemical reaction without itself being used up
Positive catalysts speed up reactions
Negative catalysts or inhibitors slow reactions
(Positive) catalysts speed reactions by allowing the rate-
limiting step to proceed with a lower activation energy
Thus a larger fraction of the collisions are effective

Catalysts
Catalysts change reaction rates by providing an

alternative reaction pathway with a different
activation energy.

Reaction energy diagram of a catalyzed and an uncatalyzed
process

Catalysts can be divided into two groups
Homogeneous catalysts exist in the same phase as the
reactants
Heterogeneous catalysts exist in a separate phase
NO2 is a homogeneous catalyst for the production of
sulfuric acid in the lead chamber process
The mechanism is:

S O 2 SO 2
SO 2 O 2 SO 3
1
2
SO 3 H 2 O H 2SO 4
The second step is slow, but is catalyzed by NO2:
NO 2 SO 2 NO SO 3
NO O2 NO2 1
2

Heterogeneous catalysts are typically solids
Consider the synthesis of ammonia from hydrogen
and nitrogen by the Haber process
3H 2 N 2 2NH3
The reaction takes place on the surface of an iron
catalyst that contains traces of aluminum and
potassium oxides
The hydrogen and nitrogen binds to the catalyst
lowering the activation energy

The Haber process. Catalytic formation of ammonia molecules
from hydrogen and nitrogen on the surface of a catalyst.

Catalysts
Examples of commercial catalyst systems include:
C8 H18g + 25 O 2g NiO
16CO 2g 18 H 2 O g
and Pt
2 CO g + O 2g NiO
2 CO 2g
and Pt
2 NOg NiO
N 2g O 2g
and Pt
Automobile catalytic converter system

Catalysts
Look at the catalytic oxidation of CO to CO2

Overall reaction
2 CO(g)+ O2(g) 2CO2(g)
Adsorption
CO(g) CO(surface) + O2(g)
O2(g) O2(surface)
Activation
O2(surface) O(surface)
Reaction
CO(surface) +O(surface) CO2(surface)
Desorption
CO2(surface) CO2(g)

Adsorption

Information sequence to determine the kinetic parameters of a reaction
Series of plots
of concentra-
tion vs. time Initial
rates Reaction Rate constant
Determine slope orders (k) and actual
of tangent at t0 for Compare initial rate law
each plot rates when [A] Substitute initial rates,
changes and [B] is orders, and concentrations Find k at
held constant and into general rate law: varied T
vice versa m
rate = k [A] [B] n
Activation
Rate constant energy, Ea
Integrated
Plots of rate law and reaction Find k at
concentration (half-life, order varied T
vs. time t1/2) Rearrange to
Use direct, ln or linear form and
inverse plot to graph
find order
Table 16.6 Rate Laws for General Elementary Steps
Elementary Step Molecularity Rate Law
A product Unimolecular Rate = k [A]
2A product Bimolecular Rate = k [A]2
A+B product Bimolecular Rate = k [A][B]
2A + B product Termolecular Rate = k [A]2[B]

Calculation
Plot Graph [A]/t , Slope
Unit =[A ]/time
Determination
c/dt k
Experimental
Unit order
Rate
Determination
Rate constant R = k[A]x[B]y
Order Kinetics
Exponent to [A] Reaction Rate Expression
Activation Energy
Mechanism Factors affect rate Temperature

Effective Collision T R
Serries of Elementary reaction Catalyst

k = A -Ea/RT
Concentration
Rate Determinating step Lower Ea
Slowest Elementary Step Change Mechanism

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CHEMICAL KINETICS

CHM 3010-Chemical Kinetics 1

CHM 3010-Chemical Kinetics 2

CHM 3010-Chemical Kinetics 3

CHM 3010-Chemical Kinetics 4

CHM 3010-Chemical Kinetics 5

The reaction between O2

CHM 3010-Chemical Kinetics 6

CHM 3010-Chemical Kinetics 7

CHM 3010-Chemical Kinetics 8

Rate of reaction describes how fast the reactants

(-) indicate that the concentration decreases

CHM 3010-Chemical Kinetics 9

dB Rate of product formation = dB/dt

Rate of reactant disappearance = - dA/dt

CHM 3010-Chemical Kinetics 10

CHM 3010-Chemical Kinetics 11

CHM 3010-Chemical Kinetics 12

Some reactions that are thermodynamically

Cdiamond O 2g CO 2g G o298 396 kJ

CHM 3010-Chemical Kinetics 13

CHM 3010-Chemical Kinetics 14

CHM 3010-Chemical Kinetics 15

CHM 3010-Chemical Kinetics 16

CHM 3010-Chemical Kinetics 17

Zero order dc/dt = k[A]0 x = kt

CHM 3010-Chemical Kinetics 18

A second example is:

CH 3 3 CBraq OH-aq CH 3 3 COHaq Br-aq

CHM 3010-Chemical Kinetics 20

This reaction is second order in NO,

CHM 3010-Chemical Kinetics 21

Because it is a second order rate-law expression:

CHM 3010-Chemical Kinetics 22

CHM 3010-Chemical Kinetics 23

How can the rate of a reaction be

CHM 3010-Chemical Kinetics 24

Time (sec) 0 50 100 150 200 250 300 350

6. A graph of concentration against time is plotted, (as shown in

CHM 3010-Chemical Kinetics 25

CHM 3010-Chemical Kinetics 27

Stopwatch Radiation meter

CHM 3010-Chemical Kinetics 28

CHM 3010-Chemical Kinetics 29

CHM 3010-Chemical Kinetics 30

This is a simplified representation of the effect

CHM 3010-Chemical Kinetics 31

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

CHM 3010-Chemical Kinetics 32

CHM 3010-Chemical Kinetics 33

CHM 3010-Chemical Kinetics 34

Table 16.4 An Overview of Zero-Order, First-Order, and

Zero Order First Order Second Order

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

Units for k mol/L*s 1/s L/mol*s

Integrated rate law in [A]t = ln[A]t = 1/[A]t =

Plot for straight line [A]t vs. t ln[A]t vs. t 1/[A]t = t

Slope, y-intercept k, [A]0 -k, ln[A]0 k, 1/[A]0

Half-life [A]0/2k ln 2/k 1/k [A]0

CHM 3010-Chemical Kinetics 35

CHM 3010-Chemical Kinetics 36

Example: Plot [A] vs t

The decomposition reaction of

Units for k mol/Ls 1/s L/mols