Chemical

Kinetics
Unit 15
Chemical Kinetics
Dr. Jorge L. Alonso
Miami-Dade College
Kendall Campus
Miami, FL
Textbook Reference:
Chapter # 16
Module # 4
CHM 1046: General Chemistry and
Qualitative Analysis
Chemical
Kinetics
Thermodynamics vs Kinetics
Rusting of Iron:

2Fe
(s)
+ O
2 (g)
+ 2H
2
O
(l)
2Fe(OH)
2 (s)

Fe
2
O
3
(s)
+ 2 Al
(s)

Al
2
O
3
(s)
+ 2 Fe
(l)

AH
o
rxn
= -847.6 kJ
Thermite Reaction:
(with limited O
2
, magnetite Fe
3
O
4
is formed: FeOFe
2
O
3
)
{Thermite.Rxn}
AH
o
rxn
= -884.6 kJ
Mg ignition
{Kinetics: paper, Fe, C}
{FSH2} {FSH1}
Chemical
Kinetics
Kinetics
Studies the rate (speed) at which a chemical
process occurs.
Kinetics also sheds light on the reaction
mechanism (exactly how the reaction occurs).
Factors That Affect Reaction Rates:
Physical State of the Reactants
Concentration of Reactants
Temperature
Presence of a Catalyst
Chemical
Kinetics
Factors That Affect
Reaction Rates
1. Physical State of the
Reactants (surface area)
In order to react, molecules must
come in contact with each other:





The more homogeneous the
mixture of reactants, the faster the
molecules can react.
Finely ground substances have
more surface areas and react faster
than chunk pieces.

Gases, liquids or solutions react
faster than solids. (Higher pressure
and concentration also affects rate.)

(1) Gases, Liquids,
Solutions (High P & Conc.)
(2) Solids

{RxRate.LicopodiumPowder}
Which will react faster?
Chemical
Kinetics
Factors That Affect Reaction Rates
2. Concentration of Reactants
As the concentration of
reactants increases, so does
the likelihood that reactant
molecules will collide.
{*RxRate&Conc.Mg+HCl}
{*Rxn.withConcOxy}
{RxRate&Conc.Mg+HClGraph}
0.3 M 6 M
Chemical
Kinetics
Reaction
Rates
determined by monitoring
the change in
concentration of either
reactants or products as
a function of time.
-A[A]
At

A[B]
At

Rate = =




[A]& [B]
[B] [A]
A B
Spectrometer
{RxRateIntro}
Chemical
Kinetics
C
4
H
9
Cl(aq) + H
2
O(l)

C
4
H
9
OH(aq) + HCl(aq)
Reaction Rates
butyl chloride
butanol
Rate = =
-A[A]
At

A[B]
At

-A[A]

-A[A]
At
At
Chemical
Kinetics
Reaction Rates
The average rate of the reaction over each interval
is the change in concentration divided by the
change in time:
Ave. rate =
A[C
4
H
9
Cl]
At
C
4
H
9
Cl(aq) + H
2
O(l)

C
4
H
9
OH(aq) + HCl(aq)
Note that the average
rate decreases as the
reaction proceeds.
This is because as the
reaction goes forward,
there are fewer collisions
between reactant
molecules.
Chemical
Kinetics
Reaction Rates
The slope of a line
tangent to the curve at
any point is the
instantaneous rate at
that time.
C
4
H
9
Cl(aq) + H
2
O(l)

C
4
H
9
OH(aq) + HCl(aq)
All reactions slow down
over time.
Therefore, the best
indicator of the rate of
a reaction is the
instantaneous rate
near the beginning.
Concentration vs. Time Graph
Chemical
Kinetics
Reaction Rates and Stoichiometry
In this reaction, the ratio of
C
4
H
9
Cl to C
4
H
9
OH is 1:1

Thus, the rate of
disappearance of C
4
H
9
Cl is
the same as the rate of
appearance of C
4
H
9
OH.
C
4
H
9
Cl(aq) + H
2
O(l)

C
4
H
9
OH(aq) + HCl(aq)
Rate =
-A[C
4
H
9
Cl]
At
=
A[C
4
H
9
OH]
At
Chemical
Kinetics
Reaction Rates and Stoichiometry
To generalize, then, for the reaction
a A + b B c C + d D
What if the ratio is not 1:1?
2 HI(g) H
2
(g) + I
2
(g)
Rate =
1
2
A[HI]
At
=
A[I
2
]
At
| | | | | | | |
t
D
d
1
t
C
c
1
t
B
b
1
t
A
a
1
Rate
A
A
=
A
A
=
A
A
=
A
A
=
Rate =
A[HI]
At
=
2 A[I
2
]
At
Rate
1
=

A[HI]
At
Rate
2
=
A[I
2
]
At
How do rates
compare?

Chemical
Kinetics
Practice
Problems
| |
5 2
10 x 8 . 1
t
O
s 100
0035 . 0
2
1
Rate

=
A
A
=
|
.
|

\
|
=
| | | |
t
O
b t
NO
a
Rate
A
A
+ =
A
A
=
2 2
1 1
| | | |
t
B
2
1
t
A
3
1
Rate
A
A
=
A
A
=
Chemical
Kinetics
051 . 0 ) 073 . 0 124 . 0 ( =
| |
sec / mol 10 x 2 . 2
10
022 . A
.
3 -
= =
A
A
=
s t
rate ave
Chemical
Kinetics
Data shows the relationship between the
reaction rate and the conc. of reactants.
How does Concentration affect Rate?
NH
4
+
(aq) + NO
2

(aq) N
2
(g) + 2 H
2
O(l)
The data demonstrates:
Rate [NH
4
+
]
Rate [NO
2

]
Rate [NH
4
+
] [NO
2

]

or
Rate = k [NH
4
+
] [NO
2

]


This equation is the rate law, and k is
the rate constant @ particular temp.

Chemical
Kinetics
Generalized Rate Laws
The exponents, x and y, express the order of reaction and bear no
necessary relationship to the coefficients of the balanced equation* they
must be determined experimentally!
This reaction is: x - order in [A] y - order in [B]
Overall rate = x + y
Rate = k [A]
x
[B]
y
a A + b B c C
* Only if reaction occurs in one step mechanism will x and y equal
coefficients of balanced equation.
| | | | | |
=
A
A
+ =
A
A
=
A
A

t c t b t a
C 1 B 1 A 1
The overall reaction order can be found by adding the exponents on the
reactants in the rate law.
The previous reaction is second-order overall.
Chemical
Kinetics
Rate = k [A]
2
[B]
0
=

k [A]
2



Experiment
Number

[A] (M)

[B] (M)
Initial Rate
(M/s)
1 0.100 0.100 4.0 x 10
-5
2 0.100 0.200 4.0 x 10
-5
3 0.200 0.100 16.0 x 10
-5
Determination of Rate Law from
Reaction Rate Data
If rate not affected by [A], then order with respect to [A] is x = 0
[2A] rate= k, [3A] rate= k etc. the same applies to [B]
Rate = k [A]
x
[B]
y
If the rate affected by [A] in linear fashion, then order [A] is x = 1,
[2A]
1
rate= 2x, [3A]
1
rate= 3x,etc. the same applies to [B]
If rate affected by [A] in exponential fashion, order [A] is x = 2,
[2A]
2
rate =4x, [3A]
2
rate =9x, etc. the same applies to [B]
*
What are the possible
values for x and y?
Possibilities for x and y:
Zero order = no effect
1
st
order = linear effect
2
nd
order = exponential
Chemical
Kinetics
Integrated Rate Laws
Rate = = k [A]
x
For reaction: a A Products
Reaction rate can be defined in two mathematical ways: (1) empirically, as
change in conc. over time, or (2) as a function of concentration (rate law).
-A[A]
At
[A]
t
= kt + [A]
0
ln [A]
t
= kt + ln [A]
0
For zero order rxn (x=0) For first order rxn (x=1) For second order rxn (x=2)
= k [A]
0
-A[A]
At
= k [A]
2
-A[A]
At
= k [A]
1
-A[A]
At
1
[A]
t

= kt +
1
[A]
0

Integrate Integrate Integrate
y = mx + b
y = mx + b y = mx + b
Using calculus we can integrate the rate law equation to gives us a
mathematical relationship that shows us how the concentration varies over a
period of time. Rate expressions are then rearranged into linear equations.
= k



Chemical
Kinetics
[A]
t
= kt + [A]
0
ln [A]
t
= kt + ln [A]
0
For zero order rxn (x=0) For first order rxn (x=1) For second order rxn (x=2)
= k [A]
0
-A[A]
At
= k [A]
2
-A[A]
At
= k [A]
1
-A[A]
At
1
[A]
t

= kt +
1
[A]
0

Integrate Integrate Integrate
Integrated Rate Laws
[A]
[A]
ln[A]
1
[A]
[A]
ln[A]
= k
y = mx + b
Chemical
Kinetics
How many moles of X were initially in the
flask?




How many molecules of Y were produced in
the first 20 minutes of the reaction?











What is the order of this reaction with respect
to X? Justify your answer.





Write the rate law for this reaction.

X
(g)
2 Y
(g)
+ Z
(g)
1
] X [
] X [
1

=
Chemical
Kinetics

Calculate the specific rate constant for this
reaction. Specify units.













Calculate the concentration of X in the flask
after a total of 150 minutes of
reaction.
X
(g)
2 Y
(g)
+ Z
(g)
ln [A]
t
= kt + ln [A]
0
Chemical
Kinetics
Practice Problems
0
] [
1
] [
1
A
kt
A
t
+ =
kt
A A
t
=
0
] [
1
] [
1
) 100 (
] 0100 . 0 [
1
] 0065 . 0 [
1
0
s k
t
=
k =

100
100 154
Chemical
Kinetics
Half-Life
t
1/2
=

0.693
k
1
k[A]
0

[A]
0

2k
t
1/2
=

t
1/2
=

For a zero-order
process,
For a first-order
process,
For a second-
order process,
{1stOrder&Life}
Half-life is defined as the time required for one-half of a reactant to react.


[A]
0







[A]

Because [A] at t
1/2
is one-half of the original [A],
[A]
t
= 0.5 [A]
0
.
*



Chemical
Kinetics
Half-Life
For a first-order process,
0.5 [A]
0

[A]
0

ln = kt
1/2

ln 0.5 = kt
1/2
0.693 = kt
1/2
= t
1/2

0.693
k
NOTE: For a first-order
process, the half-life does not
depend on [A]
0
.
For a second-order process,
1
0.5 [A]
0

= kt
1/2
+
1
[A]
0

2
[A]
0

= kt
1/2
+
1
[A]
0

2
[A]
0

= kt
1/2

1
[A]
0

-
= t
1/2

1
k[A]
0

1
[A]
t

= kt +
1
[A]
0

ln [A]
t
= kt + ln [A]
0
ln 0.5[A]
0
= kt
1/2
+ ln [A]
0
Chemical
Kinetics
Practice
Problems
1
1

= = s
s
k
= k [A]
0
-A[A]
At
= k [A]
2
-A[A]
At
= k [A]
1
-A[A]
At
For each of the following rate expression, determine the units of the rate constant, k.
= k [M]
0
-A[M]
At
= k [M]
1
-A[M]
At
= k [M]
2
-A[M]
At
= t
1/2

0.693
k
1
s M
s
M

= = k
1 1
s M
Ms
1
k

= =
ln 0.5[A]
0
= kt

+ ln [A]
0
ln [A]
t
= kt + ln [A]
0
0385 . 0 = k
075 . 0
2
0.150
150 . 0
2
300 . 0
300 . 0
2
600 . 0
= = =
min 18
3
min 54
=
Chemical
Kinetics
Kinetics
Factors That Affect Reaction Rates:
1. Physical State of the Reactants
2. Concentration of Reactants
3. Temperature
Activation Energy (Transition State Theory)
Reaction Mechanisms
4. Presence of a Catalyst
Rate = = k [A]
x
-A[A]
At
Rate
(s) (l ) (g)
Chemical
Kinetics
Factors That Affect Reaction Rates
3. Temperature
At higher temperatures,
reactant molecules have more
kinetic energy, move faster,
and collide more often and
with greater energy.
{RxRate&Temp}
Generally, as temperature
increases, so does the reaction
rate.
This is because k is temperature
dependent.
k is also dependent on activation
energy.
ln [A]
t
= kt + ln [A]
0
Chemical
Kinetics
Activation Energy:
The Collision Model
In a chemical reaction, bonds are broken and new bonds are formed.
Molecules can only react if they collide with each other with sufficient
(activation) energy (E
a
).
Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bond breakage and formation.
O
3
+ NO O
2
+ NO
2
{Ea.CollisionEnergy}
{Ea.Orientation}
{Ea.Ener+Orient}
( )
Activated Complex
+
Reactants
+
Products
Chemical
Kinetics
Transition State Theory
Potential
Energy
Reaction Coordinate
Reactants
Products

AH

Transition state
(Energy Level))
Energy Reaction Coordinate Diagrams:
Ea = Activation Energy
{Ea&TransS tate}
X
3
-YZ Activated Complex (the molecule)
*
( )
Activated Complex
+
Reactants
+
Products

AH

Chemical
Kinetics
MaxwellBoltzmann Distributions
Temperature is defined as a measure of the average kinetic energy of the
molecules in a sample.
At any temperature there is a
wide distribution of kinetic
energies.
As the temperature
increases, the curve flattens
and broadens.
Thus at higher
temperatures, a larger
population of molecules has
higher energy.
If the dotted line represents the activation energy, as the temperature
increases, so does the fraction of molecules that can overcome the
activation energy barrier.
As a result, the reaction rate increases.
Chemical
Kinetics
MaxwellBoltzmann Distributions
This fraction of molecules can be found through the
expression
where R is the gas constant and T is the Kelvin temperature.
f = e
E
a
/RT

Chemical
Kinetics
Arrhenius Equation
Svante Arrhenius developed a
mathematical relationship between
the rate constant k , the
temperature (T) at which the
reaction occurs and the activation
energy E
a
:
k = A e
E
a
/RT
where A is the frequency factor, a
number that represents the likelihood
that collisions would occur with the
proper orientation for reaction.
|
|
.
|

\
|
=
2 1
T
1
T
1
R
Ea
1
2
k
k
ln
Chemical
Kinetics
Arrhenius Equation
|
.
|

\
|
=
R
E
slope
a
R slope E
a
x =
Therefore, if k is determined
experimentally at several temperatures, E
a

can be calculated from the slope of a plot
of ln k vs. 1/T.
ln k =
-E
a ( ) + ln A

1
T
y = m x + b
Problem: Calculate the activation energy (in J/mol) for the reaction in plot above.
R= 8.31 J/molK
R
) K mol / J 31 . 8 (
00195 . 0 00215 . 0
) 7 . 6 ( ) 4 . 10 (
E
a

|
.
|

\
|

= x
mol / J 10 x 8 . 1 ) K mol / J 31 . 8 (
K 0002 . 0
7 . 3
E
4
1
a
x

=
|
.
|

\
|

=

k = A e
E
a
/RT
Taking the natural logarithm of both sides, the equation becomes


Chemical
Kinetics
Reaction Mechanisms
The detailed sequence of events that describes the actual
pathway by which reactants become products.
OH
-
(aq) + CH
3
Cl (g) CH
3
OH (aq) + Cl
-
(aq)
{RxMecha.Bimolecular.Intro}

Activated Complex Products Reactants
Transition State
Methyl chloride
Methyl alcohol
Chemical
Kinetics
Reaction Mechanisms
Consider the following reaction:
A proposed mechanism for this reaction is
Step 1: NO
2
+ NO
2
NO
3
* + NO (slow)
Step 2: NO
3
* + CO NO
2
+ CO
2
(fast)
NO
2
(g) + CO (g) NO (g) + CO
2
(g)
{Movie1}
{RxMechanism.NO
2
+CO.Prop1}
{Movie 2}
Experimental Evidence: reaction rate is second order in [NO
2
] & does not
depend on [CO] at all, even though CO is required for reaction to occur.
Rate = k [NO
2
]
2
NO
3
* = intermediate reactant
*
Bimolecular mechanism: conc.
of both reactants affects rate.
The overall reaction cannot occur faster than this
slowest, rate-determining step.
Chemical
Kinetics
Determining Rx Mechanisms
Using radioactive isotope labeling can help us to
experimentally determine the reaction mechanism.
Better proposed mechanism is:
Step 1: NO
2
+ NO
2
NO
3
+ NO (slow)
Step 2: NO
3
+ CO NO
2
+ CO
2
(fast)
NO
2
(g) + CO (g) NO (g) + CO
2
(g)
{DeterRxMechanismIsotopLabel1.NO
2
+CO}
{DeterRxMechanismIsotopLabel2.NO
2
+CO}
The simplest proposed mechanism is
labeled
Chemical
Kinetics
Factors That Affect Reaction Rates
4. Presence of a Catalyst
Catalysts speed up reactions.
Catalysts are not consumed during
the course of the reaction.
{Catalyst of
SO
2
+ H
2
S}
{*Catalysis of H
2
O
2
by MnO
2
}
2 H
2
O
2 (l)
2 H
2
O
(l)
+ O
2 (g)
MnO
2
H
2
O
SO
2
+ 2 H
2
S 2 H
2
O
(l)
+ 3 S
(aq)
Chemical
Kinetics
Catalysts
Increase the reaction rate by changing the
mechanism, thus also changing (decreasing) the
activation energy by which the process occurs..
Add catalyst:
Ea
Ea
Chemical
Kinetics
NO
NO
N
2
O
2
Some Reactions an in Internal Combustion Engine:
2 C
8
H
18 (l)
+ 25 O
2 (g)
16 CO
2 (g)
+ 18 H
2
O
(g)
(+heat)
N
2 (g)
+ O
2 (g)
2 NO
(g)
(causes acid rain & ozone depletion))

{Pt Catalytic Converter: 2 NO
(g)
O
2(g)
+ N
2(g)
}
Surface Catalysis
Pt
Pt Surface
Pt
Reactant molecules attach to
Catalytic Surface
Bonds of attached
molecules are Broken

Atoms recombine to form
product, which are then
released from surface


Chemical
Kinetics
The catalyst (in the form of platinum and palladium) is
coated onto a ceramic honeycomb or ceramic beads that
are housed in a muffler-like package attached to the
exhaust pipe.
Catalytic
Converters
The catalyst helps to convert carbon monoxide into
carbon dioxide. It converts the hydrocarbons into carbon
dioxide and water. It also converts the nitrogen oxides
back into nitrogen and oxygen.
Chemical
Kinetics
Catalysis
One way a catalyst can speed up a reaction is by holding the
reactants together and helping bonds to break.
H
2
+ H
2
C=CH
2
H
3
C-CH
3
Ethylene Ethane
Ni
{Surface.Catalysis.
Hydrogenation}
Chemical
Kinetics
Enzymes: biological catalysts
Lock and Key Theory: the substrate (reactant) fits into
the active site of the enzyme much like a key fits into a
lock.
substrate
enzyme
Chemical
Kinetics
Chemical
Kinetics
Chemical
Kinetics
Additional
Practice
Problems
Where are the
answers?
Chemical
Kinetics

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Kinetics
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Kinetics
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Kinetics
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)
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2004
A
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B
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2005
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2006 (A)
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2007 (A)
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