Dr.

Pedro Julio Villegas

[email protected]
 TEXTBOOK
 Hill, J. W.; Petrucci, R. H.; Mc Creary, T.
W.; Perry, S. S. “General Chemistry,
Chapter 13: Rates and Mechanisms of
Chemicals Reactions” Pearson
Education Ed. Fourth Edition, USA,
2010.
 INTRODUCTION (1)
 Chemical kinetics is the study of
the rates of chemical reactions, the
factors that affect these rates, and
the reaction mechanisms by which
reactions occur.
 Reaction rates vary greatly – some
are very fast (burning) and some
are very slow (disintegration of a
plastic bottle in sunlight).
 INTRODUCTION (2)
A reaction mechanism is the step by step
sequence of elementary reactions by
which overall chemical process occurs.
 A mechanism describes in detail exactly
what takes place at each stage of an
overall transformation. It also describes
each reactive intermediate, activated
complex, and transition state, and which
bonds are broken (and in what order),
and which bonds are formed (and in what
order).
 INTRODUCTION (3)
 A complete mechanism must also account for
all reactants used, the function of a catalyst,
stereochemistry, all products formed and the
amount of each. It must also describe the
relative rates of the reaction steps and the rate
equation for the overall reaction.
 Mechanisms describe in a stepwise manner the
exact collisions and events that are required
for the conversion of reactants into products.
 Mechanisms achieve that goal by breaking up
the overall balanced chemical equation into a
series of elementary steps
 OBJECTIVES (1)
1. Learn how to use a table of concentration versus time
data to calculate an average rate of reaction over a
period of time.
2. From the coefficients of a balanced reaction, know
how to express the rate of reaction in terms of the
change in concentration of a reactant or product with
time.
3. Understand how to determine instantaneous rates
from a graph of reactant or product concentration as a
function of time.
4. From initial rate data, learn how determine the order of
reaction with respect to each reactant, the overall
order of reaction, the rate law, the rate constant, the
units of the rate constant, and the initial rate for any
other set of initial concentrations.
 OBJECTIVES (2)
5. Know how to use integrated first and second order
rate laws to find the value of one variable, given
values of the other variables.
6. Learn how to explain the concept of reaction half-life
and describe the relationship between half-life and
rate constant for first-order and second-order
reactions.
7. Understand how to use the collision model of
chemical reactions to explain how reactions occur
at the molecular level.
8. Learn how to solve the Arrhenius Equation for any
variable given the others, and determine the
activation energy from the slope of the Arrhenius
plot (ln k versus 1/T).
 OBJECTIVES (3)
9. Know how to explain the concept of activation
energy and how it relates to the variation of
reaction rate with temperature.
10.Given a reaction mechanism, understand how to
identify the reaction intermediates and catalysts,
determine the overall reaction, and determine the
molecularity of each step.
11.Derive a rate law from a reaction mechanism or
choose a plausible mechanism given a rate law.
12.Learn how to describe the effect of a catalyst on
the energy requirements for a reaction and
explain the differences between homogeneous
and heterogeneous catalysts.
Factors that affect Reaction Rates
 Concentrations of reactants: Reaction rates
generally increase as the concentrations of
the reactants are increased.
 Temperature: Reaction rates generally
increase rapidly as the temperature is
increased.
 Surface area: For reactions that occur on a
surface rather than in solution, the rate
increases as the surface area is increased.
 Catalysts: Catalysts speed up reactions and
inhibitors slow them down.
The Meaning of the Reaction Rate
 The rate of a reaction is the change in
concentration of a product per unit of
time (rate of formation of product).
 Also viewed as the negative of the
change in concentration of a reactant per
unit of time (rate of disappearance of
reactant).
 The rate of reaction has the units of
moles per liter per (unit of) time. Usually,
this is expressed as mol L-1 s-1 or Ms-1.
 General Rate of Reaction
 The general rate of reaction is obtained by
dividing the rate of disappearance of a
reactant or the formation of a product by the
stoichiometric coefficient of that reactant or
product in the balanced chemical equation.
aA + bB  cC + dD
Average vs. Instantaneous Reaction Rate
 The rate of a chemical reaction tends to
slow down as time goes on in the
reaction. The average rate of the
reaction is the reaction rate divided by
the time interval of the reaction.
 At the beginning of the reaction, the rate
is faster than the average and near the
end of the reaction, the rate is slower
than the average.
 The rate of reaction at a particular
instant of time is called an
instantaneous rate of reaction.
 Example of Reaction Rates
Measuring: Decomposition of H2O2
Time Accumulated mass of O2 [H2O2]
0 0 0.882
60 2.960 0.697
120 5.056 0.566
180 6.784 0.458
240 8.160 0.372
300 9.344 0.298
360 10.336 0.236
420 11.104 0.188
480 11.680 0.152
540 12.192 0.120
600 12.608 0.094
Some Kinetic Data
Kinetic data for the reaction:
H2O2(aq)  H2O(l) + ½ O2(g)
Rates are obtained from the
slopes of the straight lines:
• An average rate from the
purple dotted line
• The instantaneous rate at
t = 300s from the red line
• The initial rate from blue line.
 Measuring Reaction Rates
 In general, the greater the concentration
of a reactant, the faster the reaction goes.
 The average rate of reaction during an
experiment is the negative of the slope of
the reaction rate.
 The instantaneous rate at a particular
time is the negative of the slope of the
tangent line at that time.
 The instantaneous rate at the beginning
of a reaction is called the initial rate of
reaction.
The Rate Law of a Chemical Reaction
The rate law for a chemical reaction
relates the rate of reaction to the
concentrations of reactants. For the
hypothetic reaction:
aA + bB…  cC + dD …

The General rate of reaction is:

The exponents in a rate law must be
determined experimentally. They are
not derived from the stoichiometric
coefficients in a chemical equation.
The values of exponents establish the
order of a reaction for each species
and overall order for the reaction.
The proportionality constant (k) is the
rate constant and its value depends on
the reaction, the temperature, and the
presence or absence of a catalyst.
Rate Law Expressions (1)
 For the hypothetic reaction:
aA + bB…  cC + dD …

The General rate of reaction is:

The Rate law is: Rate = k*[A]m*[B]n …

 In the rate law, [A], [B], … are the molarities of
the reactants at a particular time.
 The exponents m, n, … are generally small,
integers. They can be negative!
 The units of k depend on the values of m,n,…
Rate Law Expressions (2)
 Lets see an example decomposition of H2O2
into H2O and O2:
2 H2O2 (aq)  2 H2O (l)  O2 (g)
 The general expressions for the rate is:
 1   d[H2O2 ]   d[O2 ]   1   d[H2O] 
Rate     *      * 
2  dt   dt   2   dt 
 The experimentally determined form of the
rate law is:
Rate  k * [H2O2 ]
Rate Law Expressions (3)
 Let’s look at the reaction of nitrogen dioxide
with fluorine to produce nitryl-fluoride
2 NO2 (g) + F2 (g)  2 NO2F (g)
 The experimentally determined form of the
rate law is:
Rate  k * [NO2 ] * [F2 ]
 It can be conclude the following:
• The reaction is first order in NO2
• The reaction is First order in F2
• The overall reaction order is: 1+1 = 2
 Distinction between Rate
and Rate Constant
 The rate of a reaction (k) is the change in
concentration with time, whereas the rate
constant is the proportionality constant relating
reaction rate to the concentrations of reactants.
 The rate constant remains constant throughout a
reaction, regardless of the initial concentrations
of the reactants.
 The rate and the rate constant have the same
numerical values and units only in zero-order
reactions.
 For reaction orders other than zero, the rate and
rate constant are numerically equal only when
the concentrations of all reactants are 1 M. Even
then, their units are different.
 Method of Initial Rates
 The method of initial rates involves
a series of experiments in which
the initial concentrations of some
reactants are held constant and
others are varied in convenient
multiples in order to determine the
rate law for that reaction.
An Example of the Initial Rates Method

Initial Rates of the Re action 2NO (g)  Cl 2(g)  2NOCl (g)

Comparing:
Exp. 1 with Exp. 2: [NO] same [Cl2] doubles
Exp. 1 with Exp. 3: [NO] doubles [Cl2] same
Summary of the Initial Rates Method

The effects of doubling one initial

concentration:
 For zero order reactions, no effect on rate.
 For first order reactions, the rate doubles.
 For second order reactions, the rate
quadruples.
 For third order reactions, the rate
increases eightfold.
The value of k for the reaction can be
calculated.
 First Order Reactions
 A first order reaction can be represented as:
A  Products
 The rate law is: Rate = k*[A]1 = k*[A] (rate vs
conc.)
 The integrated rate law is an equation that
describes the concentration of a reactant as a
function of time. (conc. vs. time)
 A o 
ln   lnA t  lnA o  kt
 A t 
lnA t  kt  lnA o  y  mx  b
Plotting ln[A]t vs t we get an straight line.
First Order Reaction Example:
Decomposition of H2O2

The slope of in the plot of

ln[H2O2] vs time is: –k
 An Example Problem:
Decomposition of N2O5
 The decomposition of N2O5 is first order
reaction:
2 N2O5 (g)  4 NO2 (g) + O2 (g)
The kinetic constant of this reaction at 45 0C is
4.80*10-4 s-1.
a)If the initial concentration of N2O5 is 1.65*10–2
M, what is the concentration of N2O5 after
825s?
b)How long would it take for the concentration of
N2O5 to decrease to 1.00*10–2 M from its initial
value?
An Example Problem: Decomposition of N2O5
 The decomposition of N2O5 is first order reaction:
2 N2O5 (g)  4 NO2 (g) + O2 (g)
The kinetic constant of this reaction at 45 0C is
4.8*10-4 s-1.
a) If the initial concentration of N2O5 is 1.65*10–2 M,
what is the concentration of N2O5 after 825s?
lnN2O5 825 s  kt  lnN2O5 o
  –2
ln N2O5 825 s  4.8 * 10 s * 825s  ln(1.65 * 10 )
- 4 -1

lnN2O5 825 s  0.396  4.104  4.5

N2O5   1.11* 10–2 M
An Example Problem: Decomposition of N2O5
 The decomposition of N2O5 is first order reaction:
2 N2O5 (g)  4 NO2 (g) + O2 (g)
The kinetic constant of this reaction at 45 0C is
4.80*10-4 s-1.
b) How long would it take for the concentration of N2O5
to decrease to 1.00*10–2 M from its initial value?
 lnN2O5 t  lnN2O5 o 
t    
 k 
  
 ln 1.00 * 10 2 t  ln 1.65 * 10-2
t  

o


4 
 4 . 8 * 10 
  4.605  4.104 
t   4   1044s
 4.8 * 10 
 Half-life of a Reaction
 Thehalf-life (t½) of a reaction is the time in
which one-half of the reactant originally
present is consumed.
ln[A]t – ln[A]0 = ln½[A]0 – ln[A]0 = -k t½
ln(½) = -k t½
t½ = - ln(½)/k = -(-0.693)/k = 0.693/k
 For a first-order reaction, the half-life is a
constant. It depends only on the rate
constant (k) and not on the concentration of
reactant.
 If k is known, t½ can be calculated and if t½ is
known, k can be calculated.
 Illustration of
half-live for a
first order
reaction:
Decomposition of
N2O5 at 67oC
 An Example Problem:
Isomerization of Cyclo-propane (1)
 The isomerization of Cyclo-propane
(C3H6) to propylene (CH2=CHCH3) is first
order in Cyclo-propane and first order
overall, the kinetic constant k is 9.2 s-1
at 1000°C.
a)Determine the half-life of the reaction.
b)How long would it take for the
concentration of Cyclo-propane to
decrease to 50% of its initial value? To
25% of its initial value?
 An Example Problem:
Isomerization of Cyclo-propane (2)
 The isomerization of Cyclo-propane
(C3H6) to propylene (CH2=CHCH3) is
first order in Cyclo-propane and first
order overall, the kinetic constant k is
9.2 s-1 at 1000°C.
a)Determine the half-life of the
reaction.
𝟎. 𝟔𝟗𝟑 𝟎. 𝟔𝟗𝟑
𝒕½ = = = 𝟎. 𝟎𝟕𝟓𝒔
𝒌 𝟗. 𝟐
 An Example Problem:
Isomerization of Cyclo-propane (3)
 The isomerization of Cyclo-propane (C3H6)
to propylene (CH2=CHCH3) is first order in
Cyclo-propane and first order overall, the
kinetic constant k is 9.2 s-1 at 1000°C.
b) How long would it take for the
concentration of Cyclo-propane to
decrease to 50% of its initial value? To
25% of its initial value?
𝟎. 𝟎𝟕𝟓
𝒕½ = 𝟎. 𝟎𝟕𝟓𝒔  𝒕¼ = = 𝟎. 𝟎𝟑𝟕𝟓𝒔
𝟐
 Collision Theory
 Before atoms, molecules, or ions can
react, they must first come together, or
collide.
 An effective collision between two
molecules puts enough energy into key
bonds to break them.
 The Activation Energy (Ea) is the minimum
energy that must be supplied by collisions
for a reaction to occur.
 The spatial orientations of the colliding
species also affect the reaction rate.
 A Reaction Profile:
CO(g) + NO2(g)  CO2(g) + NO(g)
 Effect of Temperature on
the Rates of Reactions
 The Arrhenius equation expresses the dependence of the
rate constant on absolute temperature and activation
energy: Ea RT
k  A*e
where: Ea is the activation energy; R is the ideal gas
constant (R=8.3145 J/mol*K; T is the absolute temperature
and A the frequency factor.
 The Arrhenius Equation used to be transformed into its
logarithmic form:
lnk  - Ea RT  ln A
 Plotting lnk vs 1/T we get a straight line where lnA is the
intercept and –Ea/R the slope.
 For two rate constants at two temperatures it is obtained:
 k2  Ea  1 1 
ln   -   
 k1  R  T2 T1 
 Reaction Mechanisms
 A reaction mechanism is a series of
simple steps that ultimately lead from
the initial reactants to the final
products of a reaction.
 The mechanism must account for the
experimentally determined rate law.
 The mechanism must be consistent
with the stoichiometry of the overall or
net reaction.
 Elementary Reactions
 An elementary reaction represents, at the
molecular level, a single stage in the progress
of the overall reaction.
 The molecularity of an elementary reaction
refers to the number of free atoms, ions, or
molecules that enter into the reaction.
• Uni-molecular reaction: It is an elementary
reaction that involves one reactant molecule;
• Bi-molecular reaction: It is an elementary
reaction that involves two reactant molecules;
• Ter-molecular reaction: It is an elementary
reaction that involves three reactant
molecules.
Rate Laws for Elementary Reactions
 For an elementary reaction, the rate is
proportional to the product of the
concentration of each reactant molecules
see below:
 For uni-molecular reactions: A  B + C
Rate = k*[A]
 For bi-molecular reactions: A + B  C + D
Rate = k*[A]*[B]
 For ter-molecular reactions: A+B+C D+E
Rate = k*[A]*[B]*[C]
 Reaction Mechanisms
 The rate determining step is the
crucial step in establishing the rate
of the overall reaction.
 Some two-step mechanisms have
a slow first step followed by a fast
second step, while others have a
fast reversible first step followed
by a slow second step.
A Mechanism with a Slow Step
followed by a Fast Step
 See an example of the I- catalyzed
decomposition of H2O2 into H2O and O2.
I-
2H2O2(aq) 
 2H2O(l)  O2(g)
 Some facts:
a) The rate of decomposition of H2O2 is a
first order in both H2O2 and I-, or second
order overall.
b) The reactant I- is unchanged in the
reaction and hence does not appear in
the equation for the net reaction.
 A Mechanism with a Slow Step
Followed by a Fast Step: a Plausible
Mechanism for H2O2 Decomposition
H2O2 + I-  H2O + OI- (slow step)
H2O2 + OI-  H2O + O2 + I- (fast step)
____________________________________________________

2 H2O2  2 H2O + O2 (Net equation)

 Here (I-) is the catalyst and (OI-) the
intermediate
 The slow step is the rate-determining step.
 Rate = rate of slow step = k*[H2O2]*[I-]
A Mechanism with a Fast Reversible
Step Followed by a Slow Step

 See an example of the nitrogen

monoxide oxidation:
2 NO(g) + O2(g)  2 NO2(g)
 The rate of a reaction
experimentally found is:
Rate = k*[NO]2*[O2]
 A Mechanism with a Fast Reversible
Step Followed by a Slow Step: a
Plausible Mechanism for NO oxidation

k1
2 NO k-1
N2O2 (Fast step)

N2O2 + O2  2 NO2 (Slow step)

_______________________________________________

2 NO + O2  2 NO2 (Net equation)

 Catalysis
 Catalyst is a substance that
increases the reaction rate without
itself being changed by the
reaction.
 A catalyst works by changing the
mechanism of a chemical reaction.
Effect of Catalyst on Activation Energy
Catalyst lowers the activation energy needed by allowing
the reaction to occur through an alternative mechanism.
 Homogeneous Catalysis
 Homogeneous catalysis is a catalysis in a
solution by a soluble catalyst. Strictly speaking,
homogeneous catalysis are catalytic reactions
where the catalyst is in the same phase as the
reactants, so homogeneous catalysis applies to
reactions in the gas phase and even in a solid.
 The term is used almost exclusively to describe
solutions and it is often implies catalysis by
organometallic compounds. The area is one of
intense research and many practical
apprehended applications, e.g., the production
of acetic acid. Enzymes are examples of
homogeneous catalysts.
Homogeneous Catalysis illustration:
Decomposition of ozone.
Heterogeneous Catalysis
 Heterogeneous catalysis is a process that
usually involves two phases, typically gas-
solid. Many reactions are catalyzed by the
surfaces of appropriate solids.
 Four steps are can describe this kind of
catalysis:
 Reactant molecules are adsorbed;
 Reactant molecules diffuse along the
surface;
 Reactant molecules react to form product
molecules;
 Product molecules are desorbed (released
from the surface).
Heterogeneous Catalysis illustration
A Surface Catalyzed Reaction (1)
 Catalyzed reactions often occurs on the surface
of the catalyst. In terms of surface reactions
there are three theoretical mechanisms:
1. Langmuir-Hinshelwood Mechanism: The two
molecules A and B both adsorb to the surface.
While adsorbed to the surface, the A and B
"meet”, bond, and then the new molecule A-B
desorbs.
2. Rideal-Eley Mechanism: One of the two
molecules (A) adsorbs on the surface. The
second one (B) meets A on the surface, having
never adsorbed to the surface, and they react
and bind. Then the newly formed A-B desorbs.
A Surface Catalyzed Reaction (2)
 Catalyzed reactions often occurs on the
surface of the catalyst. In terms of
surface reactions there are three
theoretical mechanisms:
3. Precursor mechanism: One of the two
molecules (A) is adsorbed on the
surface. The second molecule (B)
collides with the surface, forming a
mobile precursor state. The molecule
B then collides with A on the surface,
they react, bind and the new molecule
A Surface Catalyzed Reaction (3)
 Any surface reaction can be described as
following one of these mechanisms, or some
combination of these mechanisms. In addition,
all of these above mechanisms can occur in
reverse (See next Figure).
 In general, the pathway for a reaction on a
surface is as follows. First the reactants adsorb
onto the surface. Through a series of bonds
being formed and being broken, adsorbed
intermediates are produced and destroyed.
 Then the final product(s) is produced and it
desorbs from the solid. Most metal surface
reaction occur by chain propagation.
A Surface Catalyzed Reaction (4)
 CONCLUSIONS (1)
 Rates of reactions are based on the
rate of disappearance of a reactant or
formation of a product.
 The rate law relates rate and
concentrations of reactants. It must
be determined experimentally.
 An integrated rate law relates
concentration and time.
 The half-life of a reaction is the time in
which one-half of the reactant initially
present is consumed.
 CONCLUSIONS (2)
 Chemical reactions occur when
sufficiently energetic molecules
collide in the proper orientation.
 Reactions generally go faster at
higher temperatures or in the
presence of a catalyst.
 Reaction mechanisms provide a
plausible explanation of how a
reaction proceeds.