Chapter 15

Lecture presentation

Chemical Kinetics

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Catching Lizards and Ectotherms

Lizards, and other cold-blooded creatures, are
ectotherms or animals whose body temperature matches
their environments temperature.
When a lizards body temperature drops, the chemical
reactions that occur in its body slow down as do all
chemical reactions when cooled.
This causes the lizard to become lethargic and to
slow down.

Chemical kinetics is the study of the factors that affect

the rates of chemical reactions, such as temperature.

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Chemical Kinetics
The speed of a chemical reaction is called its
reaction rate.
The rate of a reaction is a measure of how fast
the reaction makes products or uses reactants.
The ability to control the speed of a chemical
reaction is important.

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Factors Affecting Reaction Rate:

Reactant Concentration
Generally, the greater the concentration of reactant
molecules, the faster the reaction.
This increases the frequency of reactant molecule
contact.
Concentration of gases depends on the partial
pressure of the gas.
Higher pressure = higher concentration
Concentrations of solutions depend on the solute-tosolution ratio (molarity).

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Factors Affecting Reaction Rate:

Temperature
Increasing temperature increases the
reaction rate for most reactions.
In general, for every 10 C rise in
temperature, the speed of the reaction
doubles.
Svante Arrhenius discovered a mathematical
relationship between the absolute
temperature and the speed of a reaction.
This relationship will be examined later.
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Factors Affecting Reaction Rate: Nature of

the Reactants
Nature of the reactants refers to what kind of reactant molecules
there are and what physical condition they are in.
Small molecules tend to react faster than large molecules.
Gases tend to react faster than liquids, which react faster than
solids.
Powdered solids are more reactive than blocks.
More surface area for contact with other reactants
Certain types of chemicals are more reactive than others.
For example, potassium metal is more reactive than sodium.
Ions react faster than molecules.
No bonds need to be broken.

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Defining Rate

Rate is how much a

quantity changes in a
given period of time.

The speed at which you

drive your car is a rate:
The distance your car
travels (miles) in a
given period of time
(1 hour)
So, the rate at which
you drive your car
has units of mi/hr.
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Defining Reaction Rate

The rate of a chemical reaction is measured in terms of
how much the concentration of a reactant decreases (or the
product concentration increases) in a given period of time.
For reactants, a negative sign is placed in front of the
definition.

The rate of chemical reaction over two time periods can be

written as follows:

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Reactant and Product Concentrations as a Function of Time

As time goes on, the rate of a reaction generally slows down because the concentration of the
reactants decreases.

At some time the reaction stops, either because the reactants run out or because the system has
reached equilibrium.

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Average Rate
The average rate is the change in measured
concentrations in any particular time period.
Linear approximation of a curve
The larger the time interval, the more the average rate
deviates from the instantaneous rate.

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Instantaneous Rate
The instantaneous rate is the change in
concentration at any one particular time.
Slope at one point of a curve
The instantaneous rate is determined by taking
the slope of a line tangent to the curve at that
particular point.
In calculus: first derivative of the function

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Reaction Rate and Stoichiometry

In most reactions, the coefficients of the balanced equation are not
all the same.
H2(g) + I2(g) 2 HI(g)
For these reactions, the change in the number of molecules of one
substance is a multiple of the change in the number of molecules of
another.
For the above reaction, for every 1 mol of H2 used, 1 mol of I2 will
also be used and 2 mol of HI made.
Therefore, the rate of change will be different.
To be consistent, the change in the concentration of each
substance is multiplied by 1/coefficient.

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H2(g) + I2(g) 2 HI(g)

Using [H ], the instantaneous rate
2
at 50 s is as follows:

Using [HI], the instantaneous rate

at 50 s is as follows:

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Practice Problem: Reaction Rates

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Measuring Reaction Rate

To measure the reaction rate you need to be able to
measure the concentration of at least one component in
the mixture at many points in time.
There are two ways of approaching this problem:
For reactions that are complete in less than 1 hour, it is
best to use continuous monitoring of the concentration.
For reactions that happen over a very long time,
sampling of the mixture at various times can be used.
When sampling is used, often the reaction in the
sample is stopped by a quenching technique.

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Continuous Monitoring

Total pressurethe total pressure of a gas mixture is

stoichiometrically related to partial pressures of the gases in the
reaction.

Polarimetrythis measures the change in the degree of rotation of

plane-polarized light caused by one of the components over time.

Spectrophotometrythis measures the amount of light of a

particular wavelength absorbed by one component over time.
The component absorbs its complementary color.

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Sampling the Reaction Mixture at Specific Times

Aliquots (samples from the reaction mixture) are drawn off at specific
times during the reaction, and quantitative analysis is performed.
Titration for one of the components
Gravimetric analysis

Gas chromatography can measure the concentrations of various

components in a mixture.
For samples that have volatile components
Separates mixture by adherence to a surface

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Finding the Rate Law: The Initial Rate

Method
The rate law must be determined
experimentally.
The rate law shows how the rate of a reaction
depends on the concentration of the reactants.
Changing the initial concentration of a reactant
will therefore affect the initial rate of the reaction.

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The Rate Law: The Effect of Concentration

on Reaction Rate
The rate law of a reaction is the mathematical relationship
between the rate of the reaction and the concentrations of
the reactants and homogeneous catalysts as well.

Rate = k [A]n
The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power.
For the reaction aA + bB products, the rate law would
have the form given below.
n and m are called the orders for each reactant.
k is called the rate constant.
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Reaction Order
The exponent on each reactant in the rate law is called
the order with respect to that reactant.
The sum of the exponents on the reactants is called the
overall order of the reaction.
The rate law for the reaction 2 NO(g) + O2(g) 2 NO2(g)
is as follows:
Rate = k[NO]2[O2]
The reaction is
second order with respect to [NO];
first order with respect to [O2].
The reaction is third order overall.

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Zero Order: Rate = k[A]n

If a reaction is zero order, the rate of the reaction
does not change.
Doubling [A] will have no effect on the
reaction rate.
Rate law:
Rate = k[A]0 = k
Rate constant (k) units:
Rate = M/sec, k = M/sec (M sec1)

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First Order: Rate = k[A]n

If a reaction is first order, the rate is directly
proportional to the reactant concentration.
Doubling [A] will double the rate of the reaction.
Rate law:
Rate = k[A]1 = k[A]
Rate constant (k) units:
When Rate = M/sec, k = sec1

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Second Order: Rate = k[A]n

If a reaction is second order, the rate is directly
proportional to the square of the reactant
concentration.
Doubling [A] will quadruple the rate of the
reaction.
Rate law:
Rate = k[A]2
Rate constant (k):
When Rate = M/sec, k = M1 sec1
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Reactant Concentration versus Time:

A Products

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Determining the Rate Law When There Are

Multiple Reactants
Changing each reactant will affect the overall
rate of the reaction.
By changing the initial concentration of one
reactant at a time, the effect of each reactants
concentration on the rate can be determined.
In examining results, differences in reaction rate
are compared that differ only in the
concentration of one reactant.
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Practice Problem: Reaction Orders

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Practice Problem continued

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Integrated Rate Laws

For the reaction A products, the rate law
depends on the concentration of A.
Applying calculus to integrate the rate law gives
another equation showing the relationship
between the concentration of A and the time
of the reaction; this is called the integrated
rate law.

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First-Order Reactions
Rate law:
Rate = k[A]1 = k[A]
Integrated rate law:

ln[A] = kt + ln[A]initial
A graph of first order:
ln[A] versus time results in a straight line
where slope = k
y-intercept = ln[A]initial
Half-life:
t = 0.693/k
The half-life of a first order reaction is constant.
Rate constant: k = s1
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Practice Problem: Reaction Orders

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Practice Problem continued

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Practice Problem: First-Order Integrated

Rate Law and Graph

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Practice Problem: First-Order Integrated

Rate Law and Concentration Determination

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Second-Order Reactions
Rate law:
Rate = k[A]2
Integrated rate law:

1/[A] = kt + 1/[A]initial

A graph of second order:

1/[A] versus time results in a straight line
where slope = k
y-intercept = 1/[A]initial
Half-life:
t = 1/(k[A0]).
Rate constant: k = M1 s1
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Practice Problem: Second-Order

Integrated Rate Law and Graph

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Zero-Order Reactions
Rate law:
Rate = k[A]0 = k
Integrated rate law:

[A] = kt + [A]initial
A graph of zero order:
[A] versus time results in a straight line
where slope = k
y-intercept = [A]initial
Half-life:
t = [Ainitial]/2k
Rate constant: k = M s1
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Rate Law Summary Table

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Half-Life of First-Order Reaction

NOTE: The half-life, t, of any
reaction is the length of time it
takes for the concentration of
the reactant to fall to its
initial value.
The half-life of the reaction
depends on the order of the
reaction.
First-order half-life is
t = 0.693/k or ln(2)/k
The half-life of a first-order
reaction is constant.

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Relationship between Order and HalfLife

For a zero order reaction, the lower the initial
concentration of the reactants, the shorter the half-life.
t1/2 = [A]init/2k
For a first order reaction, the half-life is independent of
the concentration.
t1/2 = ln(2)/k or 0.693/k
For a second order reaction, the half-life is inversely
proportional to the initial concentration. Increasing the
initial concentration shortens the half-life.
t1/2 = 1/(k[A]init)
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Practice Problem: Half-Life

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The Effect of Temperature on Rate

Changing the temperature changes the rate constant of the

rate law.
This relationship is given by
where
T is temperature in kelvins
R is the gas constant in energy units, 8.314 J/(K mol)
Ea is the activation energy, the extra energy needed to
start the molecules reacting
A is a constant referred to as the frequency factor
The rate the reactant energy approaches the
activation energy
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Activation Energy Barrier Illustration

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Activation Energy and the Activated

Complex
There is an energy barrier to almost all reactions.
The activation energy is the amount of energy needed to
convert reactants into the activated complex.
The activated complex is also know as transition state.
The activated complex is a chemical species with partially
broken and partially formed bonds.
Always very high in energy because of its partial bonds

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Energy Profile for the Isomerization of

Methyl Isonitrile

The activation energy is the

difference in energy between the

reactants and the activated
complex.

The frequency is the number of

molecules that begin to form the
activated complex in a given
period
of time.

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Energy Profile for the Isomerization of

Methyl Isonitrile

As the reaction begins, the C

N bond weakens enough for
the
C

N group to start to rotate.

The activated complex is a

chemical species with partial
bonds.

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The Arrhenius Equation:

The Exponential Factor
The exponential factor in the Arrhenius equation is a number
between 0 and 1.
It represents the fraction of reactant molecules with sufficient
energy so they can make it over the energy barrier.
The higher the energy barrier (larger activation energy), the fewer
molecules that have sufficient energy to overcome it.
That extra energy comes from converting the kinetic energy of motion
to potential energy in the molecule when the molecules collide.
Increasing the temperature increases the average kinetic energy
of the molecules.
Therefore, increasing the temperature will increase the
number of molecules with sufficient energy to overcome the
energy barrier;
reaction rate.
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Summarizing Temperature and Reaction Rate

The frequency factor is the number of times that the

reactants approach the activation barrier per unit time.

The exponential factor is the fraction of the approaches

that are successful in surmounting the activation barrier
and forming products.

The exponential factor increases with increasing

temperature but decreases with increasing activation
energy.

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Arrhenius Plots: Experimental Measurements

of Frequency Factor and Activation Energy
The Arrhenius equation can be algebraically solved to
give the following form:

This equation is in the form y = mx + b,

where y = ln(k) and x = (1/T).
A graph of ln(k) versus (1/T) is a straight line
[8.314 J/(mol K)](slope of the line) = Ea (in Joules)
y-intercept = A (unit is the same as k)

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Practice Problem: Arrhenius Plot to Determine

Kinetic Parameters

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Arrhenius Equation: Two-Point Form

If you have only two (T,k) data points, the following
forms of the Arrhenius equation can be used:

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Practice Problem: Two-Point Form of the

Arrhenius Equation

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Effective Collisions: Kinetic Energy Factor

For a collision to lead to overcoming

the energy barrier, the reacting
molecules must have sufficient kinetic
energy so that when they collide the
activated complex can form.

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Collision Frequency and Effective Collisions

The collision frequency is the number of collisions that happen per
second.
The more collisions there are per second, the more collisions can
be effective and lead to product formation.
The higher the frequency of effective collisions, the faster the
reaction rate.
Collisions in which these two conditions are met (and therefore
lead to reaction) are called effective collisions.
When two molecules have an effective collision, a temporary, highenergy (unstable) chemical species is formed: the activated
complex.
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Orientation Factor
The proper orientation results when the atoms are
aligned in such a way that the old bonds can break and
the new bonds can form.
The more complex the reactant molecules, the less
frequently they will collide with the proper orientation.
Reactions in which symmetry results in multiple
orientations leading to a reaction have p slightly less
than 1.
For most reactions, the orientation factor is less than 1.

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Effective Collisions: Orientation Effect

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An Example of a Reaction Mechanism

Overall reaction:
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)
Mechanism:

1. H2(g) + ICl(g) HCl(g) + HI(g)

2. HI(g) + ICl(g) HCl(g) + I2(g)
The reactions in this mechanism are elementary
steps, meaning that they cannot be broken down
into simpler steps and that the molecules actually
interact directly in this manner without any
other steps.
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Elements of Mechanism Intermediates

H (g) + 2 ICl(g) 2 HCl(g) + I (g)
2
2
1) H (g) + ICl(g) HCl(g) + HI(g)
2
2) HI(g) + ICl(g) HCl(g) + I (g)
2

Notice that the HI is a product in step 1, but it is a reactant

in step 2.
Because HI is made but then consumed, HI does not
show up in the overall reaction.
Materials that are products in an early mechanism step
but reactants in a later step are called intermediates.
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Molecularity: Characterization of a
Mechanisms Elementary Steps
The number of reactant particles in an elementary step is
called its molecularity.
A unimolecular step involves one particle.
A bimolecular step involves two particles.
However, they may be the same kind of particle.
A termolecular step involves three particles.
However, these are exceedingly rare in elementary steps.

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Rate Laws for Elementary Steps

Each step in the mechanism is like its own little reaction
with its own activation energy and own rate law.
The rate law for an overall reaction must be determined
experimentally.
But the rate law of an elementary step can be
deduced from the equation of the step.

H (g) + 2 ICl(g) 2 HCl(g) + I (g)

2
2
1) H (g) + ICl(g) HCl(g) + HI(g)
2
2) HI(g) + ICl(g) HCl(g) + I (g)
2

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Rate = k [H ][ICl]
1 2
Rate = k [HI][ICl]
2

Rate Laws of Elementary Steps

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Another Reaction Mechanism to Investigate

NO (g) + CO(g) NO(g) + CO (g)
2
2

Rate

= k[NO ]2
obs
2

Proposed Mechanism
1.

NO (g) + NO (g) NO (g) + NO(g)

2
2
3
NO (g) + CO(g) NO (g) + CO (g)
3
2
2

2.

Rate = k [NO ]2
Slow
1
2
Rate = k [NO ][CO] Fast
2
3

The first step is slower than the second step because its
activation energy is larger.

The first step in this mechanism is the rate-determining

step: It is the slowest step.

The rate law of the first step is the same as the rate law of
the overall reaction.

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Validating a Mechanism: Criteria

To validate (not prove) a mechanism, two
conditions must be met:
1. The elementary steps must sum to the overall
balanced chemical reaction.
2. The rate law predicted by the rate-determining
step of the mechanism must be consistent with
the experimentally observed rate law.

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An Example of Mechanism with a Fast First Step

1. 2 NO(g)

N O (g)
2 2

Fast

2. H2(g) + N2O2(g) H2O(g) + N2O(g)

3. H2(g) + N2O(g) H2O(g) + N2(g)

Slow Rate = k [H ][N O ]

2 2 2 2
Fast

2 H (g) + 2 NO(g) 2 H O(g) + N (g) Rate

= k [H ][NO]2
2
2
2
obs
2

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Practice Problem: Reaction Mechanism

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Practice Problem continued

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Catalysts
Catalysts are substances
that affect the rate of a
reaction without being
consumed.
Catalysts work by
providing an alternative
mechanism for the
reaction with a lower
activation energy.
Catalysts are consumed
in an early mechanism
step and then made in a
later step.

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Mechanism without catalyst:

O (g) + O(g) 2 O (g) V. Slow
3
2

Mechanism with catalyst:

Cl(g) + O (g)
3

O (g) + ClO(g) Fast

2

ClO(g) + O(g) O (g) + Cl(g) Slow

2

Factors Affecting Reaction Rate: Catalysts

Catalysts are substances that affect

the speed of a reaction without
being consumed.

Most catalysts are used to speed up

a reaction; these are called positive
catalysts.
Catalysts used to slow a reaction
are called negative catalysts.

Homogeneous catalysts: all species

present in same phase

Heterogeneous catalysts: species

present in different phase

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Catalyst Types

Homogeneous catalysts are in the same phase as the

reactant particles.
Cl(g) in the destruction of O3(g)

Heterogeneous catalysts are in a different phase than

the reactant particles.
Solid catalytic converter in a cars exhaust system

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Illustration of the Catalyst Types

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Catalytic Hydrogenation Reaction:

H2CCH2 + H2 CH3CH3

1.
2.
3.
4.

Adsorption: The reactants are adsorbed onto metal surfaces.

Diffusion: The reactants diffuse on the surface until they approach each other.
Reaction: The reactants react to form the products.
Desorption: The products desorb from the surface into the gas phase.

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Enzymes: Biological Catalysts

Because many of the molecules are large and complex,
most biological reactions require a catalyst to proceed at a
reasonable rate.
Protein molecules that catalyze biological reactions are
called enzymes.
Enzymes work by adsorbing the substrate reactant onto an
active site that orients the substrate for reaction.

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1)

Enzyme + Substrate

EnzymeSubstrate

2)

EnzymeSubstrate Enzyme + Product Slow

Fast

EnzymeSubstrate Binding:
The Lock and Key Mechanism

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Enzymatic Hydrolysis of Sucrose

E+S

ES

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ES

E+P

fast

slow (rate determining step