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Chapter 13
Topics 6 and 16
1.
What do we mean by kinetics?
Kinetics refers to
the rate at which chemical
reactions occur.
The reaction mechanism or
pathway through which a reaction
proceeds.
2.
Topics for study in kinetics
Reaction Rates How we measure rates.
4.
Reaction Rates
[C4H9Cl]
Rate =
t
6.
Reaction Rates Calculation
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl (aq)
7.
Reaction Rate Determination
C4H9Cl(aq) + H2O(l) C4H9OH(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 the
reacting molecules.
8.
Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
A plot of concentration
vs. time for this reaction
yields a curve like this.
The slope of a line
tangent to the curve at
any point is the
instantaneous rate at
that time.
9.
Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
The reaction slows
down with time
because the
concentration of the
reactants decreases.
10.
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
-[C4H9Cl] [C4H9OH]
Rate = =
t t
11.
Reaction Rates & Stoichiometry
Suppose that the mole ratio is not 1:1?
Example
H2(g) + I2(g) 2 HI(g)
17.
The Rate Law
Exponents tell the order of the reaction
with respect to each reactant.
This reaction is
First-order in [NH4+]
First-order in [NO2−]
The overall reaction order can be found by
adding the exponents on the reactants in
the rate law.
This reaction is second-order overall.
19.
The First Order Rate Equation
Consider a simple 1st order reaction: A B
Rate = k[A]
How much reactant A is left after time t?
The rate equation as a function of time can
be written as
Where
CH3NC CH3CN
21.
First-Order Processes
CH3NC CH3CN
22.
First-Order Processes
24.
Half-Life of a First Order Reaction
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:
26.
First Order Rate Calculation
Example 1: The decomposition of compound A is first
order. If the initial [A]0 = 0.80 mol dm-3. and the rate
constant is 0.010 s-1, what is the concentration of [A]
after 90 seconds?
27.
First Order Rate Calculations
Example 2: A certain first order chemical reaction required
120 seconds for the concentration of the reactant to drop from
2.00 M to 1.00 M. Find the rate constant and the concentration
of reactant [A] after 80 seconds.
28.
First Order Rate Calculations
Example 2: A certain first order chemical reaction required
120 seconds for the concentration of the reactant to drop from
2.00 M to 1.00 M. Find the rate constant and the concentration
of reactant [A] after 80 seconds.
Solution
k =0.693/t1/2 =0.693/120s =0.005775 s-1
29.
First Order Rate Calculations
Example 3: Radioactive decay is also a first order process.
Strontium 90 is a radioactive isotope with a half-life of 28.8
years. If some strontium 90 were accidentally released, how
long would it take for its concentration to fall to 1% of its original
concentration?
30.
First Order Rate Calculations
Example 3: Radioactive decay is also a first order process.
Strontium 90 is a radioactive isotope with a half-life of 28.8
years. If some strontium 90 were accidentally released, how
long would it take for its concentration to fall to 1% of its original
concentration?
Solution
k =0.693/t1/2 =0.693/28.8 yr =0.02406 yr-1
32.
Second-Order Rate Equation
So if a process is second-order in A,
a graph of 1/[A] vs. t will yield a
straight line with a slope of k.
33.
Determining Reaction Order
Distinguishing Between 1st and 2nd Order
The decomposition of NO2 at 300°C is described by the
equation:
NO2 (g) NO (g) + 1/2 O2 (g)
A experiment with this reaction yields this data:
Time (s) [NO2], M
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
34.
Determining Reaction Order
Distinguishing Between 1st and 2nd Order
Graphing ln [NO2] vs. t yields:
• The graph is not a straight
line, so this process cannot
be first-order in [A].
37.
Sample Problem 1: Second Order
Acetaldehyde, CH3CHO, decomposes by second-order
kinetics with a rate constant of 0.334 mol-1dm3s-1 at 500oC.
Calculate the amount of time it would take for 80 % of the
acetaldehyde to decompose in a sample that has an initial
concentration of 0.00750 M.
38.
Sample Problem 2: Second Order
Acetaldehyde, CH3CHO, decomposes by second-order
kinetics with a rate constant of 0.334 mol-1dm3s-1 at 500oC. If
the initial concentration of acetaldehyde is 0.00200 M. Find
the concentration after 20 minutes (1200 seconds)
Solution
1 . = 0.334 mol-1dm3s-1 (1200s) + 1 .
[A]t 0.00200 mol dm-3
1 . = 0.334 mol-1dm3 s-1 (1200s) + 500 mol-1dm3
[A]t
= 900.8 mol-1dm3
[A]t = 1 _____. = 0.00111 mol dm-3
900.8 mol-1dm3
39.
Summary of Kinetics Equations
Integrat
ed Rate complicated
Laws
Half-
life
complicated
40.
Temperature and Rate
Generally speaking, the
reaction rate increases
as the temperature
increases.
This is because k is
temperature dependent.
As a rule of thumb a
reaction rate increases
about 10 fold for each
10oC rise in temperature
41.
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.
These collisions must occur with
sufficient energy and at the
appropriate orientation.
42.
The Collision Model
Furthermore, molecules must collide with
the correct orientation and with enough
energy to cause bonds to break and new
bonds to form
43.
Activation Energy
In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
Just as a ball cannot get over a hill if it does not roll
up the hill with enough energy, a reaction cannot
occur unless the molecules possess sufficient
energy to get over the activation energy barrier.
44.
Reaction Coordinate Diagrams
It is helpful to
visualize
energy changes
throughout a
process on a
reaction
coordinate
diagram like
this one for the
rearrangement
of methyl
isonitrile.
45.
Reaction Coordinate Diagrams
It shows the energy of
the reactants and
products (and,
therefore, E).
The high point on the
diagram is the
transition state.
Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.
As the temperature
increases, the
curve flattens and
broadens.
Thus at higher
temperatures, a
larger population of
molecules has
higher energy.
48.
Maxwell–Boltzmann Distributions
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.
49.
Maxwell–Boltzmann Distributions
This fraction of molecules can be found through the expression:
50.
Arrhenius Equation
Svante Arrhenius developed a mathematical relationship
between k and Ea:
51.
Arrhenius Equation
1
RT
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T.
52.
Arrhenius Equation for 2 Temperatures
When measurements are taken for two different
temperatures the Arrhenius equation can be
symplified as follows:
Write the above equation twice, once for each of the two
Temperatures and then subtract the lower temperature
conditions from the higher temperature. The equation then
becomes:
53.
Arrhenius Equation Sample Problem 1
The rate constant for the decomposition of
hydrogen iodide was determined at two different
temperatures
2HI H2 + I2.
At 650 K, k1 = 2.15 x 10-8 dm3 mol-1s-1
At 700 K, k2 = 2.39 x 10-7 dm3 mol-1s-1
Find the activation energy for this reaction.
2.39 x 10-7 Ea
Ln ---------------- = - ------------------------ x
2.15 x 10-8 (8.314 J mol-1 K-1) [ 1
700K 650K
1
------ -- ------
]
Ea = 180,000 J mol-1 = 180 kJ mol-1
54.
Overview of Kinetics Equations
First order Second order Second order
Rate
Laws
Integrated
Rate Laws complicated
Half-life complicated
Rate and
Temp (T)
55.
Reaction Mechanisms
56.
Reaction Mechanisms
Reactions may occur all at once or
through several discrete steps.
Each of these processes is known as
an elementary reaction or elementary
process.
57.
Reaction Mechanisms
58.
Multistep Mechanisms
In a multistep process, one of the steps will
be slower than all others.
The overall reaction cannot occur faster
than this slowest, rate-determining step.
59.
Slow Initial Step
NO2 (g) + CO (g) NO (g) + CO2 (g)
60.
Slow Initial Step
A proposed mechanism for this reaction is
Step 1: NO2 + NO2 NO3 + NO (slow)
Step 2: NO3 + CO NO2 + CO2 (fast)
The NO3 intermediate is consumed in the second step.
As CO is not involved in the slow, rate-determining step, it
does not appear in the rate law.
61.
Fast Initial Step
62.
Fast Initial Step
A proposed mechanism is
Step 1 is an equilibrium-
it includes the forward and reverse reactions.
63.
Fast Initial Step
64.
Fast Initial Step
65.
Fast Initial Step
66.
Fast Initial Step
67.
Catalysts
Catalysts increase the rate of a reaction by
decreasing the activation energy of the reaction.
Catalysts change the mechanism by which the
process occurs.
Some catalysts also make atoms line up in the
correct orientation so as to enhance the reaction
rate
68.
Catalysts
Catalysts may be
either homogeneous or
heterogeneous
A homogeneous
catalyst is in the same
phase as the
substances reacting.
A heterogeneous
catalyst is in a different
phase
69.
Catalysts
One way a
catalyst can
speed up a
reaction is by
holding the
reactants
together and
helping bonds
to break.
Heterogeneous
catalysts often
act in this way
70.
Catalysts
Some catalysts AlCl3 + Cl2 Cl+ + AlCl4-
help to lower
the energy for Cl+ + C6H6 C6H5Cl + H+
formation for
the activated H+ + AlCl4- HCl + AlCl3
complex or
provide a new Overall reaction
activated
complex with a C6H6 + Cl2 C6H5Cl + HCl
lower activation
energy
71.
Catalysts & Stratospheric Ozone
In the stratosphere, oxygen molecules absorb ultraviolet
light and break into individual oxygen atoms known as free
radicals
72.
Catalysts & Stratospheric Ozone
The presence of chlorofluorcarbons in the
stratosphere can catalyze the destruction of ozone.
UV light causes a Chlorine free radical to be released
74.
75.