Lecture Presentation

An Introduction To

Chemical Kinetics

Dr BP Gumbi Chemical
Online Learning 2020 Kinetics

© 2015 Pearson Education, Inc.

 Chemical Kinetics: lecture 1
 Introduction
 Chemical kinetics examines how fast a chemical reaction occurs

 Factors That Affect Reaction Rates

 Described the relationship between reaction rates and the factors that
affect those rates: Concentration, physical states of reactants,
temperature, presence of catalyst, surface area and Orientation of
reacting species.

 Experimental Techniques
 Learn that rates of chemical techniques are measured by using
techniques that monitor the concentrations of species present in the
reaction mixture.
 Lecture 1 quiz
 Quiz is available on Moodle

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 Chemical Kinetics
• In chemical kinetics we study the rate (or
speed) at which a chemical process occurs.
• Besides information about the speed at
which reactions occur, kinetics also sheds
light on the reaction mechanism, a
molecular-level view of the path from
reactants to products.

Chemical
Kinetics

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 Factors that Affect
Reaction Rates
1) Physical state of the reactants
2) Reactant concentrations
3) Reaction temperature
4) Presence of a catalyst
5) Orientation of Reacting Species
6) Surface Area
Chemical
Kinetics

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 Physical State of the Reactants
• The more readily the reactants collide,
the more rapidly they react.
• Homogeneous reactions are often
faster.
• Heterogeneous reactions that involve
solids are faster if the surface area is
increased; i.e., a fine powder reacts
faster than a pellet or tablet. Chemical
Kinetics

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 Reactant Concentrations
• Increasing reactant
concentration generally
increases reaction rate.
• Since there are more
molecules, more
collisions occur.

Chemical
Kinetics

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 Temperature
• Reaction rate generally increases with
increased temperature.
• Kinetic energy of molecules is related to
temperature.
• At higher temperatures, molecules
move more quickly, increasing numbers
of collisions and the energy the
molecules possess during the collisions.
Chemical
Kinetics

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 Presence of a Catalyst
• Catalysts affect rate without being in the
overall balanced equation.
• Catalysts affect the kinds of collisions,
changing the mechanism (individual
reactions that are part of the pathway
from reactants to products).
• Catalysts are critical in many biological
reactions.
Chemical
Kinetics

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 Experimental Techniques

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• Experimental techniques have been developed to
monitor reactions over timescales varying from hours
or days all the way down to a few femtoseconds (1 fs
= 10-15 s). While it is relatively simple to monitor the
kinetics of a slow reaction (occurring over minutes to
hours or longer), highly specialised techniques are
required in order to study fast reactions, some of
which will be considered here.
• Most of the techniques are batch techniques, in which
reaction is initiated at a single chosen time and
concentrations are then followed as a function of time
after initiation.
Chemical
Kinetics
Techniques for mixing reactants and initiating
reaction

• Flow method

• Flash photolysis and laser pump probe technique

• Relaxation method

• Shock tubes
•
• Life-time methods
 Flow technique

 Flow techniques are typically used to study reactions occurring on timescales of

seconds to milliseconds.

 Continuous flow methods have the disadvantages that relatively large quantities of
reactants are needed, and very high flow velocities are required in order to study fast
reactions.
 Flash photolysis and laser pump probe technique
• In flash photolysis, reaction is initiated by a pulse of light (the ‘flash’) that
dissociates a suitable precursor molecule in the reaction mixture to
produce a reactive species, thereby initiating reaction.
• The shortest timescale over which reactions may be studied using this
technique is determined by the duration of the ‘flash’.
• In most modern experiments the flash is provided by a laser pulse, typically
with a duration of a few nanoseconds (1 ns = 10-9 s).
• Flash photolysis has the advantage that because reactants are produced
from well-mixed precursors, there is no mixing time to reduce the time
resolution of the technique.
• For very fast processes, the ‘pump-probe’ technique is often used, in which
pulsed lasers are employed both to initiate reaction (the ‘pump’) and to
detect the products via a pulsed spectroscopic technique (the ‘probe’).
Relaxation method
• The rate of relaxation to a new equilibrium position provides
information about the forward and reverse rate constants for the
reaction. Since a system at chemical equilibrium is already well
mixed, relaxation methods overcome the mixing problems associated
with many flow methods.
• A sudden increase in temperature on a system at equilibrium, an
experiment known as a ‘temperature jump’.
• This is often done by discharging a high voltage capacitor through the
solution (~10-7 s), or by employing a UV or IR laser pulse or
microwave discharge.
• After the temperature jump, the concentrations of A and B are
initially at the values [A]1 and [B]1, but the system is not at the
equilibrium composition for the higher temperature. The system
relaxes back to the new equilibrium concentrations [A]2 and [B]2 at a
rate determined by the new higher-temperature rate constants k2f
and k2r.
 Shock tubes

 The shock tube method provides a way of producing highly reactive

atomic or radical species through rapid dissociation of a molecular
precursor, without the use of a discharge or laser pulse.

 To initiate reaction, the diaphragm is punctured and a shock wave

propagates through the reaction mixture.

 The shock tube approach is often used to study combustion

reactions.

Dissociation using argon as the shock  The method does have some major drawbacks, not least of which is
gas include: the fact that the rapid heating is not selective for a particular
HCN → H + CH4 → CH3 + H molecules, and is likely to lead to at least partial dissociation of all
CN
of the species in the ‘reactants’ chamber.
SO2 → SO + O N2O → N2 + O
CH3 → CH2 + C2H2 → C2H _ H  This leads to a complicated mixture of reactive species and often a
H
large number of reactions occurring in addition to the reaction
H2S → HS + CF3Cl → CF3 + Cl
H under study.
NO → N + O C2H4 → C2H3 + H
NH3 → NH2 + C2H4 → C2H2 + H2
H
 Lifetime methods
• The Heisenberg uncertainty principle relates the uncertainty in position
and momentum, ΔxΔp ≥ h/4π. A similar uncertainty principle relates
energy and time.

 Lifetime techniques cover a broad range of timescales, from around 10-15s in photoelectron spectroscopy to
around 1 s in NMR.
Techniques for monitoring concentrations as a function of time
 For slow reactions, the composition of the reaction mixture may be analysed while the
reaction is in progress either by withdrawing a small sample or by monitoring the bulk.
 This is known as a real time analysis.
Another option is to use the quenching method, in which reaction is stopped a
certain time after initiation so that the composition may be analysed at leisure. For
example:
• sudden cooling
• adding a large amount of solvent
• rapid neutralisation of an acid reagent
• removal of a catalyst
• addition of a quencher
The key requirement is that the reaction must be slow enough (or the quenching
method fast enough) for little reaction to occur during the quenching process itself.
The real time and quenching techniques are combined by withdrawing and
quenching small samples of the reaction mixture at a series of times during the
reaction.
• For reactions in which at least one reactant or product is a gas, the reaction’s
progress may be followed by monitoring the pressure, or possibly the volume.
• For reactions involving ions, conductivity or pH measurements may often be
employed.
• If the reaction is slow enough, the reaction mixture may be titrated.
• If one of the components is coloured then colourimetry may be appropriate.
• Absorption or emission spectroscopy are common (more on these later)
• For reactions involving chiral compounds, polarimetry (measurement of optical
activity) may be useful.
• Other techniques include mass spectrometry, gas chromatography, NMR/ESR, and
many more.
• Fast reactions require a fast measurement technique, and as a
consequence are usually monitored spectroscopically. A few
commonly used techniques are outlined below.

 Absorption spectroscopy – Beer Lambert Law

 Resonance fluorescence - for detecting atomic species such as H, N,

O, Br, Cl or F.

 Laser-induced fluorescence - In laser-induced fluorescence a laser is

used to excite a chosen species in a reaction mixture to an
electronically excited state.
Temperature control and measurement
• For any reaction with a non-zero activation energy, the rate constant is dependent
on temperature. The temperature dependence is often modelled by the Arrhenius
equation.

• This temperature dependence means that in order to measure an accurate value for
k, the temperature of the reaction mixture must be maintained at a constant, known
value.

• If activation energies are to be measured as part of the kinetic study, rate constants
must be measured at a series of temperatures.

• The temperature is most commonly monitored using a thermocouple, due to its

wide range of operation and potential for automation; however, standard
thermometers are also commonly used.
 Chemical Kinetics: lecture 2
 Reaction Rates
 Learn the difference between average and instantaneous reaction
rates, and use reaction stoichiometry to determine the relative the
relative rates of reactant disappearance and product appearance

 Lecture 2 quiz
 Quiz is available on Moodle

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 Reaction Rate
• Rate is a change in concentration over
a time period: Δ[ ]/Δt.
• Δ means “change in.”
• [ ] means molar concentration.
• t represents time.
• Types of rate measured:
average rate
instantaneous rate
initial rate Chemical
Kinetics

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 Following Reaction Rates

 Rate of a reaction
is measured using
the concentration
of a reactant or a
product over time.
 In this example,
[C4H9Cl] is
followed.
Chemical
Kinetics

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 Following Reaction Rates

 The average rate

is calculated by the
–(change in
[C4H9Cl]) ÷
(change in time).
 The table shows
the average rate
for a variety of time
intervals. Chemical
Kinetics

© 2015 Pearson Education, Inc.

 Plotting Rate Data
• A plot of the data gives more
information about rate.
• The slope of the curve at one
point in time gives the
instantaneous rate.
• The instantaneous rate at
time zero is called the initial
rate; this is often the rate of
interest to chemists.
• This figure shows Note: Reactions
instantaneous and initial rate typically slow down
Chemical
of the earlier example. over time! Kinetics

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 Relative Rates
• As was said, rates are followed using a reactant or
a product. Does this give the same rate for each
reactant and product?
• Rate is dependent on stoichiometry.
• If we followed use of C4H9Cl and compared it to
production of C4H9OH, the values would be the
same. Note that the change would have opposite
signs—one goes down in value, the other goes up.

Chemical
Kinetics

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Relative Rates and Stoichiometry
• What if the equation is not 1:1?
• What will the relative rates be for:
2 O3 (g) → 3 O2 (g)

Chemical
Kinetics

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 Determining Concentration
Effect on Rate
• How do we determine what effect the
concentration of each reactant has on
the rate of the reaction?
• We keep every concentration constant
except for one reactant and see what
happens to the rate. Then, we change a
different reactant. We do this until we
have seen how each reactant has
affected the rate. Chemical
Kinetics

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 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

 Rate of a Chemical Reaction
Exercise 1:
Consider the following hypothetical reaction:
A(aq)  B(aq). The initial concentration of A was
0.065 M. Given the following data, calculate the
average rate of disappearance of A for each 10
minute interval in units of mol dm-3 s-1.

Time (sec) 0 10 20 30 40
Molarity (M) 0.065 0.051 0.042 0.036 0.031
 Rate of a Chemical Reaction
Exercise 1 - Solution:
Calculate the change in concentration, and time for
each time period:
Time (sec) 0 10 20 30 40
Molarity (M) 0.065 0.051 0.042 0.036 0.031

Rxn Rate D[A] (0.051 – 0.065)

= = -1.4 x 10-3 M s-1
(0 – 10) = aDt (10 – 0)

Time 0  10 10  20 20  30 30  40
Rate - 1.4 x 10-3 - 0.9 x 10-3 - 0.6 x 10-3 - 0.5 x 10-3

Note – rate decreases with time

 Concentration Affects Reaction Rate Constant
• Here’s another way of looking at reaction rates…
2N2O5(g)  4NO2(g) + O2(g)
• Notice that for every 1 mole of O2 that appears, 4 x as many
moles of NO2 will also appear. In the meantime, twice as many
moles of N2O5 will be disappearing as moles of O2 forming.
• Changes in concentrations of the reactants and/or products is
inversely proportional to their stoichiometric proportions.
• This means that the rate of the reaction could be written like
this…
Rate = −½ ∆ [N2O5]/∆t = ¼ ∆[NO2]/∆t = ∆[O2]/∆t

* (Notice the negative sign on the rate of [N2O5] reminds us that it is disappearing.)

•In general, for a reaction that looks like this… aA + bB cC +

Dan Reid
dD
Champaign CHS

Rate = −1 ∆[A] = −1 ∆[B] = 1 ∆[C] = 1 ∆[D]

a ∆t b ∆t c ∆t d ∆t
 Chemical Kinetics: lecture 3
 Concentration and Rate Laws
 Learn how to determine rate laws, expressions that quantitatively
express reaction rates in terms of reactant concentrations and
experimentally determined rate constants.

 Lecture 3 quiz
 Quiz is available on Moodle

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 An Example of How
Concentration Affects Rate
• Experiments 1–3 show how [NH4+] affects rate.
• Experiments 4–6 show how [NO2−] affects rate.
• Result: The rate law, which shows the
relationship between rate and concentration for all
reactants:
Rate = k [NH4+] [NO2−]

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 More about Rate Law
• The exponents tell the order of the reaction with
respect to each reactant.
• In our example from the last slide:
Rate = k [NH4+] [NO2−]
• The order with respect to each reactant is 1. (It is
first order in NH4+ and NO2−.)
• The reaction is second order (1 + 1 = 2; we just
add up all of the reactants’ orders to get the
reaction’s order).
• What is k? It is the rate constant. It is a
temperature-dependent quantity. Chemical
Kinetics

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 Rate Laws

• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1
 Rate Law
• In general, rates of reactions increase as concentrations increase
since there are more collisions occurring between reactants.
• The overall concentration dependence of reaction rate is given in a
rate law or rate expression.
• Here’s what a general rate law for a reaction will look like…
Rate = k [A]m [B]n
- [A] & [B] represent the reactants.
- The exponents m and n are called “reaction orders”.
- The proportionality constant k is called the rate constant.
- The overall reaction order is the sum of the reaction orders:
m+n
 The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD

Rate = k [A]m[B]n

reaction is mth order in A

reaction is nth order in B
reaction is (m+n)th order overall
 Rate Law Example
• Consider the following reaction:
NH4+(aq) + NO2-(aq)  N2(g) + 2H2O(l)
• Let’s say that the following observations from several
experiments were made…
– as [NH4+] doubles the rate doubles with [NO2-] constant.
– as [NO2-] doubles the rate doubles with [NH4+] constant.

• The rate of this reaction would be expressed as….

Rate = k[NH4+][NO2-]
• The reaction is said to be “first order” with respect to [NH4+] and
“first order” with respect to [NO2-].
• But the overall order of the reaction is said to be “second order.”
• Reaction rates come from experiment data, not stoichiometry!
 Order ≠ Stoichiometry

• The order of the reaction must be

determined experimentally. It is not
necessarily related to the balanced
equation!
 Determining the Rate Law
1. Method of Initial Rates
For the reaction:
A + B  Products
We have the following data:
Initial Conc (mol L-1) Initial Rate
Expt (mol L-1 s-1)
[A] [B]
1 0.10 0.10 0.20
2 0.20 0.10 0.40
3 0.30 0.10 0.60
4 0.30 0.20 2.40
5 0.30 0.30 5.40
 Determining the Rate Law
1. Method of Initial Rates
Runs 1 – 2:
[B] is constant at 0.10 M  the change in the rate
is due to the change in [A].

rate = k [A]m[B]n
[A]2 0.20 nnnn Rate 2 0.40
= = 2.0 = = 2.0
[A]1 0.10 Rate 1 0.20

Note:
if [A] is doubled, the rate doubles,
if [A] is tripled, then the rate triples;
 m = 1.
 Determining the Rate Law
1. Method of Initial Rates
Runs 3 – 5:
[A] is constant at 0.30 M  the change in the rate
is due to the change in [B].
[B]5 0.30 nnn Rate 5 5.40
= = 3.0 = = 9 = 32
[B]3 0.10 Rate 3 0.60
Note:
if [B] is doubled, the rate increases fourfold, ie. 22;
if [B] is tripled, then the rate increases ninefold, ie. 32;
 n = 2.

Rate = k[A]1 [B]2 48

 Determining the Rate Law
1. Method of Initial Rates
For this reaction:

Rate = k[A]1 [B]2

The value of k can be calculated using any set of

experimental data:

Rate 2.40
k= 1 2
= = 200 L2 mol-1 s-1
[A] [B] (0.30)(0.20)2
 Example Reaction:
Concentration and Rate

Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
 Concentration and Rate

Likewise, compare Experiments 5 and 6:

when [NO2-] doubles, the initial rate doubles.
 Concentration and Rate

This equation is called the rate law,

and k is the rate constant.
 Rate Laws

• A rate law shows the relationship between the reaction

rate and the concentrations of reactants.
– For gas-phase reactants use PA instead of [A].

• The rate constant k is a constant that has a specific value

for each reaction.
• The value of k is determined experimentally. For example

“Constant” is relative here:

k is unique for each reaction
k changes with Temperature
 Rate Laws

• 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.
 Chemical Kinetics: lecture 4
 The Change of Concentration with Time
 Learn that rate equations can be written to express how concentrations
change with time and look at several classification of rate equations:
Zero-order, first-order, and second-order reactions.
 Zero-order
 First-order

 Lecture 4 quiz
 Quiz 4 is available on Moodle

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 Order of Reactions

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 Order of Reactions
• A reaction is zero order in a reactant if the change in
concentration of that reactant produces no effect.
• A reaction is 1st order if doubling the concentration causes the
rate to double.
• A reaction is 2nd order if doubling the concentration causes a
quadruple increase in rate.
-3rd order…doubling concentration leads to 23 (or 8 times) the rate.
• Note-- The rate constant, k, does not depend on concentration!
• Once we have determined the rate law and the rate constant, we can use
them to calculate initial reaction rates under any set of initial
concentrations. (See Practice Problems for examples.)

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 Zero-Order Reactions

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 Zero-Order Reactions

D[A]t
rate = - rate = k [A]0 = k
Dt
[A]t is the concentration of A at any time t
[A]t - [A]0 = kt [A]0 is the concentration of A at time t=0

Half life for zero order

t½ = t when [A]t = [A]0/2
[A]0
t½ =
2k

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 Change of Concentration with Time
For Zero order reactions:
Rate = k[A]0 = k
Rate does not change with concentration.
So… [A]t = -kt + [A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M/s
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of [A]t vs. t is a straight line with slope (-k) and intercept [A]0.

(slope= -k)
[A]t

Time (s)

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 First Order Reactions

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 First Order Reactions

• Some rates depend only on one

reactant to the first power.
• These are first order reactions.
• The rate law becomes:
Rate = k [A]

Chemical
Kinetics

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 Relating k to [A] in a
First Order Reaction
• rate = k [A]
• rate = −Δ [A] / Δt
• So: k [A] = −Δ [A] / Δt
• Rearrange to: Δ [A] / [A] = − k Δt
• Integrate: ln ([A] / [A]o) = − k t
• Rearrange: ln [A] = − k t + ln [A]o
• Note: this follows the equation of a line:
y = mx + b
Chemical
• So, a plot of ln [A] vs. t is linear. Kinetics

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An Example: Conversion of Methyl
Isonitrile to Acetonitrile
• The equation for the reaction:
CH3NC → CH3CN
• It is first order.
Rate = k [CH3NC]

Chemical
Kinetics

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 Finding the Rate Constant, k

• Besides using the rate law, we can find

the rate constant from the plot of ln [A]
vs. t.
• Remember the integrated rate law:
ln [A] = − k t + ln [A]o
• The plot will give a line. Its slope will
equal −k.
Chemical
Kinetics

© 2015 Pearson Education, Inc.

 Half-life
• Definition: The amount of time
it takes for one-half of a
reactant to be used up in a
chemical reaction.
• First Order Reaction:
 ln [A] = − k t + ln [A]o
 ln ([A]o/2) = − k t½ + ln [A]o
 − ln ([A]o/2) + ln [A]o = k t½
 ln ([A]o / [A]o/2) = k t½
 ln 2 = k t½ or t½ = 0.693/k Chemical
Kinetics

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 Chemical Kinetics: lecture 5
 Continuation of lecture 4
 Second-order

 Lecture 5 quiz
 Quiz 5 is available on Moodle

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 Second Order
Reactions

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 Second-Order Reactions

• Some rates depend only on a reactant to

the second power.
• These are second-order reactions.
• The rate law becomes:
Rate = k [A]2

Chemical
Kinetics

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 Second Order
Reaction for A → Products
• rate = k [A]2
• rate = − Δ [A] / Δ t
• So, k [A]2 = − Δ [A]o / Δ t
• Rearranging: Δ [A]o / [A]2 = − k Δ t
• Using calculus: 1/[A]t = 1/[A]o + k t
• Note: The linear relationships for first
order and second order reactions differ!
 Example of a Second Order
Reaction:
Decomposition of NO2
A plot following NO2
decomposition shows
that it must be second
order because it is
linear for 1/[NO2], not
linear for ln [NO2].
Equation:
NO2 → NO + ½
O2
 Second Order Reactions

-d [A]
Rate = = k[A]2
ad t

1 1
– = kt

1/[A]t
[A]t [A]0
Slope = +k
Units of k = dm3 mol-1 s-1
Time/s
72
 Reaction Kinetics: A Summary

Order 0 1 2

Rate Law Rate = k Rate = k[A]1 Rate = k[A]2

Integrated
[A]t = –kt + [A]0 ln[A]t = –kt + ln[A]0 1/[A]t = kt + 1/[A]0
Rate Eqn

Straight line [A] vs time ln [A] vs time 1/[A] vs time

k – slope – slope + slope

Units mol L-1 s-1 s-1 L mol-1 s-1

[A]0 t½ = 0.693/k t½ = 1 / (k [A]o)
T1/2 t½ =
2k 73
 Half-Life and Second-Order Reactions

• Using the integrated rate law, we can see

how half-life is derived:
– 1/[A] = 1/[A]o + k t
– 1/([A]o/2) = 1/[A]o + k t½
– 2/[A]o −1/[A]o = k t½
– t½ = 1 / (k [A]o)
• So, half-life is a concentration dependent
quantity for second-order reactions!

Chemical
Kinetics

© 2018 Pearson Education, Inc.

 Exercise
The decomposition of N2O5 to NO2 and O2 is first order,
with a rate constant of 4.80 x 10-4 s-1 at
45 °C.
(a) If the initial concentration is 1.65 x 10-2 mol
dm-3, what is the concentration after 825 s?
ln [A]t = -kt + ln [A]O

ln[A]t = [-4.5 mol dm-3]

[A]t = 1.11 x 10-2 mol dm-3

(b) How long would it take for the [N2O5] to decrease to
1.00 x 10-2 mol dm-3 from its initial value, given in
(a)?
[ t = 8.562 s]
 Exercise
The gas phase decomposition of NOBr is second order with
respect to [NOBr], with k = 1.620 M-1 s-1 at 10 C. If we start with
4.00 x 10-3 M NOBr in a flask at 10 C, how long (in seconds) will it
take to use up 1.50 x 10-3 M of this NOBr?
2 NOBr(g)  2 NO(g) + Br2(g)

1/[A]t - 1/[A]o = kt

t = 257.2 s
 Example

The data given below were obtained for the

decomposition reaction, A → products.
(a) Establish the order of the reaction.
(b) What is the rate constant, k?
Solution
 Chemical Kinetics: lecture 6
 Temperature
Explore the effect of temperature on rate. In order to occur, most reactions
require a minimum input of energy called the activation energy. Also,
understand Arrhenius equation and it’s application in determination of
activation energy.

 Lecture 6 quiz
 Quiz 6 is available on Moodle

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Energy Needed for a Reaction to
Take Place (Activation Energy)
• The minimum energy needed for a reaction to take
place is called activation energy.
• An energy barrier must be overcome for a reaction
to take place, much like the ball must be hit to
overcome the barrier in the figure below.

Chemical
Kinetics

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 Kinetic Energy
When molecules collide with the correct orientation,
they must have a minimum amount of kinetic
energy in order to break the bonds between the
atoms.
- Activation Energy, Ea
- Maxwell-Boltzman distribution
N
= e -Ea/RT
NTotal

- If
 Temp   KE   Rate
81
 Energy and
Temperature
As temperature
increases the
probability of
finding molecules
of higher energy
increases.

• If the molecules require a certain kinetic energy to react

then the fraction with that energy is indicated by the
shaded portions in the above diagram.
• For this fraction of molecules the collisions will be
reactive.
• Notice how this fraction increases with temperature.

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 Arrhenius Equation

Svante Arrhenius developed a

mathematical relationship
between k and Ea:

•
•
where A is the frequency factor, a
John D. Bookstaver
St. Charles Community College

number that represents the

likelihood that collisions would
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 Arrhenius Equation
• This is how the rate constant of a
chemical reaction varies with
respect to temperature and other
variables.

where... k= rate constant

Ea = Activation Energy (in kJ/mole)
Dan Reid
R = Gas Constant
Champaign CHS
T = Kelvin temperature
A = “Frequency Factor”-- a constant indicating
how many collisions have
the correct
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orientation to lead
 Arrhenius Equation

Taking the natural

logarithm of both
sides, the equation
becomes
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.
• John D. Bookstaver
• St. Charles Community College

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 Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

-E 1
Ln k = - a + lnA
R T

Chung (Peter) Chieh

University of Waterloo

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 Arrhenius Equation

Taking the natural

logarithm of both
sides, the equation
becomes
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.
• John D. Bookstaver
• St. Charles Community College

© 2015 Pearson Education, Inc.

 1/T

Dan Reid
Champaign CHS

© 2015 Pearson Education, Inc.

 Example
The rate constant for the formation of
hydrogen iodide from the elements
H2(g) + I2(g) → 2HI(g)
is 2.7 x 10-4 dm3 mol-1 s-1 at 600 K and 3.5 x
10-3 dm3 mol-1 s-1 at 650 K.
(a) Find the activation energy.
(b) Calculate the rate constant at 700 K.

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 Example
• 7. The following values were obtained for the velocity
constant in the decomposition of N2O5:
•
• T/oC 0 25 45
65
• k/min-1 4.7x10-5 2.0x10-3 3.0x10-2
0.30
• Estimate the values of energy of activation and the pre-
exponential factor (Arrhenius constant) using the above
data.
•

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 Solution
• ln k = ln A - (Ea/RT)
• A plot of ln k versus 1/T gives a straight
line
• with gradient = -Ea/R

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