CHEMICAL KINETICS

Chapter 14
 Readings:

Be able to:

THE RATE OF A REACTION

Section 14.2
What are Chemical Kinetics?
• Chemical kinetics deals with the rate at which a
reaction occurs
• Reaction Rate - the change in the concentration
of a reactant or product with time (M/s)

• Slow Reactions Fast Reactions

Picture Sample
The progress of a reaction A  B at 10-sec
intervals over a period of 60 sec.
Gray molecules are A
Red molecules are B
Reactant and Product Concentrations as a
Function of Time
 Average Rate of Reaction Equation
It may be easier to express the change of A

Rate = conc. of A at time t2 – conc. Of A at time t1

t2-t1
OR Rate = Δ[A] / Δt
• Where A is the reactant or product being considered
• Square brackets ([ ]) indicate concentration in mol/L.
• The rates can come as positive(increase) or
negative(decrease), but we will always report these values as
positive.
 Average vs Instantaneous 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.

• 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.
• First derivative of the function (for all of you
calculus fans)
Sample Problem
• Consider the reaction
• A + B  2C
• Using the data in the table below, calculate the average
reaction rate over three different time intervals:

Experiment [A] (M) Time (s)

1 0.052 0.00
2 0.024 0.10
3 0.014 0.20
• After calculating the three values comment on the
differences among the three calculated values.
Rates based on time
• When looking at the rates of reactions we know that we
will be looking at concentration as a function of time
• Time is the independent variable
• What methods could we use to measure the conc. of:
• Solutions:
• Gases:
Think a little
• In aqueous solutions, molecular bromine reacts with
formic acid (HCOOH) as follows:
• Br2(aq) + HCOOH(aq)  2Br-(aq) + 2H+(aq) + CO2(g)
• Molecular bromine is reddish-brown in color
• What can you conclude from the pictures below:
Writing a reaction rate
• For the reaction
• 2A  B
• ____ moles of ____ for each ____ mole of ___ that forms.
• OR
• The rate at which ____ forms is ____ the rate at which
____ disappears
• These can be represented as follows:
• 1) Rate = -1/2 Δ[A] / Δt or 2) Rate = Δ[B]/Δt
Writing a Rate
• In general writing a reaction rate can be done in the
following general form
• aA + bB  cC + dD
• Rate = -1/a Δ[A] / Δt = -1/b Δ[B]/Δt = 1/c Δ[C]/Δt = 1/d
Δ[D]/Δt
Sample Problem
• Write the rate expressions for the following reaction:
• CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
 Readings:

Be able to:

THE RATE LAW: EFFECT OF

CONCENTRATION ON
REACTION RATE
Section 14.3
The Rate Law
• Rate Law - expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of the
reactants raised to some power
• aA + bB  cC + dD
• Rate = k[A]x[B]y

• Rate Constant (k) - A constant of proportionality between

the reaction rate and the concentration of reactant
• Where x and y are the order of the reaction (typically
whole numbers)
• k and x and y must be determined experimentally
 Orders of Reaction
• First Order Reactions - a reaction whose rate depends on
the reactant concentration raised to the first power
• Rate = k[A]

• Second Order Reactions – a reaction whose rate depends on

the concentration of one reactant raised to the second power
or on the concentrations of two different reactants, each raised
to the first power
• Rate = k[A]2 or Rate = k[A][B]

• Zero Order Reactions – a reaction whose rate is constant

(independent of the concentration of the reactant)
• Rate = k[A]0 = k
Reactant Concentration versus Time
A  Products
EASY MC QUESTIONS
• For the reaction • 1) What is the rate law
•A+B+CD for a 2nd order reaction?
• All of the following are
possible rate laws

• A) rate = k[A][B][C]
• B) rate = k[A][B][C]2 • 2) Which is the rate law
• C) rate = k[A][C] for a reaction that is 2nd
order with respect to B
• D) rate = k[A]3[B]2[C]
• E) rate = k[A][C]2
 SAMPLE PROBLEM
EXPERIMENT Initial Concentration of Reactants (M) Initial Rate of
Formation of D
(M/sec)
[A] [B] [C]
1 0.10 0.10 0.10 0.01
2 0.10 0.10 0.20 0.01
3 0.10 0.20 0.10 0.02
4 0.20 0.20 0.10 0.08

• We need to examine how changes in the

individual reactants affect the rate
• The easiest way to find the exponents is to see
what happens to the rate when the concentration
of an individual reactant is doubled.
CONTINUING THE SAMPLE PROBLEM
• Looking at [A], use • Looking at [B], use
EXP. 3 and 4 EXP 1 and 3

Looking at [C], use

EXP 1 and 2
Last Steps
• Once all exponents have been determined, any of the 4
experiments can be used to determine the rate constant
(k) for the reaction.

• Does the final solution makes sense with the data given
and the balanced equation?
 Readings:

Be able to:

THE DEPENDENCE OF
CONCENTRATION ON TIME
Section 14.4
Intro
• So far we have seen the relationship between rate of
reaction and the concentration of reactants

• Often times we will want to look at relationship between

concentration of a reactant and time (duration of experiment)

• Another way to think about it, how long will it take a reactant
to be gone from a system (toxic compounds in air or water
for example)

• By integrating the already established rate laws, we are able

to show this relationship
 First-Order Reactions
• Rate law: rate = k[A]1 = k[A]
• Integrated rate law:
• ln[A] = −kt + ln[A]initial
• Graph ln[A] versus time—
straight line with slope = −k
and y-intercept = ln[A]initial
• Used to determine the rate
constant
• When rate = M/sec, k = s–1
 Second-Order Reactions
• Rate = k[A]2
• 1/[A] = kt + 1/[A]initial
• Graph 1/[A] versus time—straight
line with
slope = k and
• y-intercept = 1/[A]initial
• Used to determine the rate
constant
• t½ = 1/(k[A0])
• When Rate = M/sec, k = M−1 · s−1
Zero-Order Reactions
• Rate = k[A]0 = k
• Constant rate reactions
• [A] = −kt + [A]initial
• Graph of [A] versus time—straight line with
slope = −k and y-intercept = [A]initial
• t ½ = [Ainitial]/2k
• When Rate = M/sec, k = M/sec
Sample Problem
• The reaction 2A  B is first order in A with a rate constant
of 2.8 X 10-2 s-1 at 80°C. How long in seconds will it take
for A to decrease from 0.88M to 0.14M?
Half-Life
• The half-life, t1/2, of a
reaction is the time required
for the concentration of the
reactant to fall to half its initial
value.

• The time it takes for 1.0 M to

reduce to .5M and the time it
takes for .1M to reduce
to .05M are equal.

• The half-life of the reaction

depends on the order of the
reaction.
Sample Half-Life Problem
• Calculate the half-life of the decomposition of N2O5 from
the following data:
t (sec) [N2O5] (M) ln [N2O5]
0 0.91 -0.094
300 0.75 -0.29
600 0.64 -0.45
1200 0.44 -0.82
3000 0.16 -1.83
 SAMPLE PROBLEM
• Butadiene reacts to A)Is the reaction first order or
second order?
form its dimer B) What is the value of the rate
according to the constant for the reaction?
equation C) What is the half-life for the
reaction under the conditions of
4 6 • 2C4H6 
[C H ] (mol/L) C(s)
Time
8H12 this experiment?
0.010000 0
0.00625 1000
0.00476 1800
0.00370 2800
0.00313 3600
0.00270 4400
0.00241 5200
0.00208 6200
 Sample Problem
• The reaction A  B + C is known to be zero order in A with a
rate constant of 5.0 X10-2 mol/L·s at 25°C. An experiment was
run at 25°C where [A]0 = 1.0 X 10-3M.
• The integrated rate law is
• A) [A] = kt
• B) [A] – [A]0
• C) [A] / [A]0 = kt
• D) ln [A] / [A]0 = kt
• E) [A]0 – [A] = kt

• What is the concentration of B after 5 X 10-3 seconds has

passed?
SAMPLE PROBLEM
• A first order reaction is
38.5% complete in 480s.
• A. Calculate the rate
constant
• B. What is the value of
the half-life?
• C. How long will it take
for the reaction to go to
25%, 75% and 95%
completion?
 Readings:

Be able to:

ACTIVATION ENERGY AND

TEMPERATURE DEPENDENCE
OF RATE CONSTANTS
Section 14.5
 The Effect of Temperature on Rate
• The rate constant of the rate law, k, is temperature
dependent.
• The Arrhenius equation shows the relationship:

where T is the temperature in kelvin.

R is the gas constant in energy units, 8.314 J/(mol · K).

A is called the frequency factor, the rate the reactant energy approaches the activation energy.

E is the activation energy, the minimum energy needed to start the reaction.
a
 Activation Energy
• The energy that must be over
come to produce a chemical
reaction is known as the
activation energy (Ea).
• When molecules collide they
form a species known as an
activated complex (aka
transition state) – a temporary
species formed by the reactant
molecules as a result of the
collision before they form the
product
• A + B  AB♮  C + D
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.
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.

The Frequency Factor

The frequency factor represents the

number of approaches to the activation

barrier per unit time.

For this reaction, the frequency factor

represents the rate at which the NC

part of the molecule wags (vibrates

side to side).
Arrhenius Equation: The Exponential Factor
• The exponential factor in the Arrhenius equation,
e – Ea/RT, is a number between 0 and 1.
• It represents the fraction of reactant molecules with
sufficient energy that 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.
• Increasing temperature will increase the number of
molecules with sufficient energy to overcome the energy
barrier.
• Increasing the temperature will increase the
reaction rate.
Summary
• 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
 Arrhenius plot
•Rate constants, activation energy and temperature can all be
related to each other via an arrhenius plot (taking the natural log
of both sides of the arrhenius equation)
• ln k = ln A – Ea / RT
• ln k = (-Ea/R)(1/T) + ln A
• y = mx + b
• This can then be seen as a
linear equation:
• ln k = y
• -Ea / R = m (slope)
•1/T=x
• ln A = b (intercept)
 Practice Problem
• The second-order rate constant for the decomposition of
nitrous oxide (N2O) into nitrogen molecule and oxygen atom
has been measured at different temperatures
K (1/M  sec) T(°C)
1.87 X 10-3 600
0.0113 650
0.0569 700
0.244 750

• Determine the activation energy graphically

Collision Theory
• Consider the reaction of A and B molecules
• The product is created from the direct combination of one
A with one B
• What would happen if we doubled the initial concentration
of A? WHY?
• What would happen if we doubled the initial concentration
of A and B? WHY?
More questions
• Do ALL collisions lead to reaction?
• WHY or WHY NOT?
 Readings:

Be able to:

REACTION MECHANISMS
Section 14.6
 What is a reaction mechanism
• Most chemical reactions take place in multiple different
steps.
• The equation below is thought to have the following steps:
• NO2 + CO2  NO + CO2

• Step 1: NO2 + NO2  NO3 + NO

k1

• Step 2: NO3 + CO  NO2 + CO2

k2

• Steps 1 and 2 are known as elementary steps (cannot be

simplified
• The k1 and k2 values are the rate constants for each
individual step.
Question
• In the previous slide what do you notice about the original
equation and the elementary steps??

• CO appears in the reaction mechanism but not in the

overall reaction equation
• This is known as a reaction intermediate – a substance
that is formed in one elementary step and consumed in
another.
 Types of Molecularity
• We characterize elementary steps by their
molecularity – the number of reactant particles
that are involved in the step

EXAMPLES OF ELEMENTARY STEPS

Elementary Steps Molecularity Rate Law
A  products Unimolecular Rate = k[A]
A + A  products Bimolecular Rate = k[A]2
A + B  products Bimolecular Rate = k[A][B]
A + A + B  products Termolecular Rate = k[A]2[B]
A + B + C  products Termolecular Rate = [A][B][C]
Rules to writing Mechanisms
• When writing mechanisms of reaction two rules must be
followed:
• 1. The sum of the elementary steps must give the overall
balanced equation for the reaction.

• 2. The mechanism must agree with the experimentally

determined rate law.
• Dependent on the rate determining step – the step that happens
the slowest. The rate at which the reaction happens cannot be any
faster than the slowest step.
EXAMPLE
• NO2 + CO2  NO + CO2
• Step 1: NO2 + NO2  NO3 + NO
k1

• Step 2: NO3 + CO  NO2 + CO2

k2

• If we assume that the reaction in step 1 is the rate

determining step then we can produce the rate law based
on the previous table
• Rate of formation of NO3 = k1[NO2]2 = overall rate
 2A2 + B2 2C
Step 1: A2 + B2  R + C (very slow)
Step 2: A2 + R  C (slow)

• What is the moleculartiy • What should the overall

of step 2? rate law be for this
reaction?

• Which step is the rate

determining step?
 Readings:

Be able to:

CATALYSIS
Section 14.7
 What is a catalyst?
• A catalyst is a substance that
speeds up a reaction without
being consumed itself.

• A catalyst works by lowering the

activation energy of the reaction
and therefore speeding up the
reaction.

• Almost all industrial processes

involve the use of a catalyst.
• A catalyst is also cheaper to use
than raising the temperature
and most likely safer.
 Two types of catalysis
Homogeneous catalyst Heterogeneous Catalyst

• A substance that is • A substance that exists in

present in the same a different phase (usually
phase as the reacting a solid).
molecules.
Heterogeneous Catalysis
• Most often observed when gaseous reactants are being
adsorbed on the surface of a solid catalyst.
• Adsorption is the collection of one substance on the
surface of another.
• Absorption is the process of one substance penetrating
another.
• Read pages 603-605 for more details on the process of
how a heterogeneous catalyst works
Homogeneous Catalysis
• Process by which the catalysis and the reactants are in
the same phase.
• Examples include the production of O-zone (O3)
• Read Page 654-656 for a description of this process.
• Read pages 656-658 for biological catalysts
 SAMPLE PROBLEM
• The reaction 2H2O2  2H2O + O2 has the following
mechanism.
• Step 1: H2O2 + I-  H2O + IO-
• Step 2: H2O + IO-  H2O + O2 + I-
• The catalyst in the reaction is:
• A) H2O
• B) I-
• C) H2O2
• D) IO-
• E) H2