Chemical Kinetics Chapter 14.

1-2
Last semester we talked about chemical reactions such as
NO2(g) + CO(g)  NO(g) + CO2(g)

This semester we are going to talk about how fast these reactions occur, how
they occur and indeed whether they occur at all.
The study of how reactions occur is called chemical kinetics.
Chemical kinetics has two parts.
• The study of how individual molecules react is called chemical dynamics.
It provides answers to the question of if two molecules collide what is the
probability of a reaction taking place…(and what is the reaction…)..
• The study of the rate at which reactions occur and whether there is only a
single molecular reaction or a series of them is called (confusingly)
chemical kinetics
Chemical Kinetics
Dynamics by itself does not tell us all we need to know about a reaction.
After all except in the most detailed of experiments we have a bunch of
molecules in some sort of container doing their thing.
So what can we measure?
We can measure the amount of various reactants and products.
• As a function of time.
• As a function of temperature
• As functions of the concentration of reactants
Reaction Mechanisms
• A series of reactions is called a reaction mechanism and results in an
overall chemical reaction
• A single step is called an elementary reaction
Consider the following mechanism
Start by dissociating Cl2 into two Cl atoms by heating it or exposing the Cl2 to
light whose wavelength is shorter than 400 nm
Cl2  Cl + Cl (add heat) (1)
One of the chlorine atoms can react with chloroform CHCl3 abstracting the
hydrogen atom to form HCl and CCl3
Cl + CHCl3  HCl + CCl3 (2)
Another Cl atom reacts with the CCl3 to form carbon tetrachloride
Cl + CCl3  CCl4 (3)
The three elementary reaction can be added up to find the overall reaction
----------------------------------
Cl2 + CHCl3  HCl + CCl4 (4)
Elementary Reactions
Cl2  Cl + Cl (add heat) (1)
Cl + CHCl3  HCl + CCl3 (2)
Cl + CCl3  CCl4 (3)
----------------------------------
Cl2 + CHCl3  HCl + CCl4 (4)

We could either study the elementary reaction (1-3) or the overall reaction
(4). It is usually easier to study the overall reaction.

To study the overall reaction we could monitor the concentrations of the

reactants or the products as functions of time and initial concentrations.
Reactions
Here is a simple reaction A B. As the reaction proceeds the amount of A
decreases and the amount of B increases. The shapes of the curves, as we will see
in the next lecture, gives important information about how the reaction occurs
 Hydrolysis of Aspirin
Since how the concentration changes as a function of time tells us much about how
the reaction occurs, learning how to plot the change of concentration with time is vital

Time
[Aspirin] (M) [Salicylic Acid] (M)
(h)
0 5.55 × 10−3 0
2.0 5.51 × 10−3 0.040 × 10−3
5.0 5.45 × 10−3 0.10 × 10−3
10 5.35 × 10−3 0.20 × 10−3
20 5.15 × 10−3 0.40 × 10−3
30 4.96 × 10−3 0.59 × 10−3
40 4.78 × 10−3 0.77 × 10−3
50 4.61 × 10−3 0.94 × 10−3
100 3.83 × 10−3 1.72 × 10−3
200 2.64 × 10−3 2.91 × 10−3
300 1.82 × 10−3 3.73 × 10−3
Rates of Reaction
Following the decomposition of dinitrogen pentoxide is an example

2 N2O5(g)  4 NO2(g) + O2(g).

If we start with only N2O5(g). For every 2 moles of N2O5(g) that

decompose, we form 4 moles of NO2(g) and one mole of O2(g).
We can monitor the amount of oxygen that is formed as a function of
time using mol/L as the units of concentration
 Instantaneous Rates of Reaction
2 N2O5(g)  4 NO2(g) + O2(g).
0.008
t [𝑂2 ]
0 0
We can compute the
0.007 D[O2] =
0.00093 mol/L
rate of appearance of
300 0.00111
O2 between any two
0.006
Dt =1700s 1000 0.00315 times.
CONCENTRATION OF O2/ mol /L

0.005 Rate =
∆[𝑂2 ] 0.00093 𝑚𝑜𝑙/𝐿
∆𝑡
=
1700 𝑠
1500 0.00422 ∆[𝑂2 ]
2000 0.00506
0.004
∆𝑡
2500 0.00571

3200 0.00638
0.003
3500 0.00661
D[O2] = 0.00204 mol/L
0.002 4000 0.00692
∆[𝑂2 ] 0.00204 𝑚𝑜𝑙/𝐿 4900 0.00731
Rate = =
∆𝑡 700 𝑠
0.001

Dt =700s

0.000
0 2000 4000 6000
TIME/s
 Instantaneous Rates of Reaction
2 N2O5(g)  4 NO2(g) + O2(g).
0.008

In discussing chemical kinetics this is

0.007
often very inconvenient. It is better
to talk about the instantaneous
0.006
change of the concentration at any
CONCENTRATION OF O2/ mol /L

time.
0.005
This is the same as the slope of the
0.004 tangent to the curve

0.003

0.002

0.001

Dt =700s

0.000
0 2000 4000 6000
TIME/s
 Instantaneous Rates of Reaction
The slope of the tangent to the curve is the limit of

[O2](t+Dt)−[O2](t)
as Dt becomes vanishingly small.
Dt

𝑑[𝑂2](𝑡)
This is called the derivative and is written as .
𝑑𝑡

[O2](t+Dt)
[O2](t+Dt)-[O2](t)
[O2](t)
The derivative of a function
is just the slope of the
tangent to the function at
Dt any point and for kinetics,
the instantaneous rate of
t t+Dt change of concentrations
 Rate of Reaction
For a reaction

aA + bB  cC +dD
the reaction rate is the instantaneous rate of change of the concentration of each
reactant or product divided by its stoichiometric coefficient.

They are all equal.

1 d [ A] 1 d [ B] 1 d [C ] 1 d [ D]
Rate  -  -  
a dt b dt c dt d dt
We are using the dread derivative notation, but remember, [A] is the concentration of
A, dt is a very small change in the time, and d[A]/dt is the ratio of the change in the
concentration of A with respect to a change in time. It is very simple
The negative sign for the reactants means that as the reaction proceeds, the reactants
are consumed. The positive sign for products means that as the reaction proceeds, the
products appear. By dividing each of the derivatives, (oops, changes in concentration
per unit time) by the stoichiometric coefficients we get a reaction rate independent of
the particular reactant or product that we are following.
Rate of Reaction
For the reaction
2 N2O5(g) 4 NO2(g) + O2(g)

the rate of change of oxygen concentration is opposite to the rate of

change of the concentration of N2O5(g). Also, since for every mole of O2
that forms two moles of N2O5(g) are consumed,

𝑑[𝑂2](𝑡) 1 𝑑[𝑁2𝑂5](𝑡)
Rate = =-
𝑑𝑡 2 𝑑𝑡

Note the minus sign. For ever mole of O2 formed four moles of NO2 are
formed so
𝑑[𝑂2](𝑡) 1 𝑑[𝑁𝑂2](𝑡)
Rate = =+
𝑑𝑡 4 𝑑𝑡
Measuring Reaction Rates
In order to measure the rate of a reaction we need to measure
concentrations of reactants or products as a function of time.

This leads us to the question of how you start a reaction because you have
to start measuring concentrations from some point in time in order to
measure the change of concentration over time.

What is the simplest, most brutal thing you can do?

You can mix chemicals together….pour them together in a beaker and

observe changes, for example, changes of color, or an increase in pressure.
 Slow Reactions
Many biological reactions are very slow and can be monitored by traditional
methods, by dipping into the reaction mixture and analyzing the samples or
by monitoring absorption. Such reactions can occur on time scales of
minutes to hours.
Measuring Reaction Rates
But reactions we want to study can often occur very rapidly and essentially
be over by the time the chemicals mix together. Many of the most
important reactions occur on time scales ranging from microseconds to
milliseconds.

You need fast ways of starting reactions. New ways of doing this were
discovered in the time span between 1945 and 1965.
The first was flash photolysis, discovered by Richard Norrish and George
Porter http://nobelprize.org/chemistry/laureates/1967/norrish-lecture.pdf
http://nobelprize.org/chemistry/laureates/1967/porter-lecture.pdf
Flash Photolysis

From LibreTexts Core

There are two flashlamps. The larger one above the reaction tube
photodissociated a molecule to produce a reactant, the concentration of
which could be followed by looking at the absorption from light produced
by the second flashlamp on the left. By varying the delay between the first
(initiation) and second (analysis) flashlamps, one can follow the course of a
reaction over periods as short as 10 ms. Today we replace the flashlamps
with lasers, but the principle remains the same.
Flash Photolysis
The first reaction Norrish and Porter studied (you should be able to
understand much of their Nobel prize speeches which discuss this reaction
and others) was the reaction of chlorine with oxygen, which they were
able to show had the following reaction mechanism
Cl2 + hn  Cl + Cl (set off by the big photolysis flashlamp)
Cl + O2  ClOO
ClOO + Cl  ClO + ClO
ClO + ClO  Cl2 + O2

Norrish and Porter were able to follow the change of concentrations of Cl2
and ClO with time.

It turns out that the third and fourth of these are important reaction for
destruction of stratospheric ozone by CFCs which provide sources of Cl
atoms in the stratosphere.
 Stop Flow
Another method that was introduced is called stop-flow, the method uses
two syringes which are pressed simultaneously to mix reactants together.
The progress of the reaction is monitored by looking at the absorption
spectrum of one of the reactants or products.

From LibreText Core

 Lasers
In 2000, with collaborators from Sandia National Laboratory in California, and
American University, we used laser flash photolysis to study the reaction of
vinyl radicals (C2H3) with nitric oxide. We used an excimer laser at 248 nm to
cleave vinyl iodide, creating the vinyl radicals and iodine molecules and then
measured the absorption of the vinyl radical as a function of time
C2H3I + hn248  C2H3 + I
C2H3 + NO  products
The data is shown on the right, a sketch of the apparatus on the left.
Rate Law
when is the relationship between the rate of reaction and the
concentrations of the reactants. There is such a relationship and it is called
a rate law.

1 d [ A]
rate    k[ A]m [ B]n
a dt

where k is the rate constant. In principal the exponents m and n can have
any value for a complex reaction, ie a reaction which is the sum of several
other elementary reactions given by a reaction mechanism.
Rate Constant
In the rate law
1 d [ A]
rate    k[ A]m [ B]n
a dt
all of the chemical dynamics are in the constant k, which, among
other things is a function of the temperature. The temperature is an
issue because it determines the average energy of a collision and the
number of collisions per second

For a complex mechanism, k includes the relative importance of each

of the steps and their rates.

In a simple example, if all of the rate constants in a mechanism are

fast except one, that is the rate limiting step, the bottleneck and it
determines the overall rate constant for the mechanism.
How to Determine the Exponents
In the rate law
1 d [ A]
rate    k[ A]m [ B]n
a dt
For an elementary reaction, the exponents of the REACTANTS
are simply the stoichiometric coefficients.

Cl + O2  ClOO rate = k1[Cl][O2]

ClOO + Cl  ClO + ClO rate = k1[ClOO][Cl]

ClO + ClO  Cl2 + O2 rate = k1[ClO][ClO] = k1[ClO]2

For a reaction that is not elementary m and n can be anything, even
fractions. They must be determined experimentally.