LINDEMANN MECHANISM

In chemical kinetics, the Lindemann mechanism is a schematic reaction mechanism for

unimolecular reactions. Frederick Lindemann proposed the concept in 1922.[1][2]
1. HISTORY
At early 19th century, it was found that all unimolecluar reaction, such as gaseous
decomposition and isomerization, is of first-order. In 1919, Perrin proposed that, for
unimolecular reaction, the reactant molecule was activated by absorption of infrared radiation
from the container or other molecules – radiation activation theory.

A 
radiation
 A* 
k1
P
dP
 k1[A* ]
dt

Collision theory (1916-18) states that for a bimolecular reaction, before reaction takes place,
reactants must collide with each other to acquire enough activation energy. This may lead to a
conclusion that all gaseous reaction should be second-ordered.
As in unimolecular processes only one reactant molecule takes part in the reaction, it is
rather difficult to understand how do the molecule attain their activation energy to form
products. The unimolecular gas-phase reactions are of first order under certain conditions, but
they become of second order at low pressures. It is obvious that the collision theory does not
give satisfactory answer to this problem.
It was Lindemann (1922) who showed how a collision of these types can give rise to first-
order kinetics. [3]
2. What is Reaction Mechanism?
Most of the chemical reactions are complex in nature. These occur in a series of steps.
These steps are called elementary processes. The stepwise sequence of elementary reactions
that convert reactants into products is called the mechanism of the reaction. That is, the
detailed pathway consisting of a sequence of chemical changes on molecular level is called the
reaction mechanism. This means that mechanism of a reaction is theoretically proposed path
for it which is consistent with the known data for the reaction and is liable to be changed in the
light of new experimental and theoretical data. Therefore, one would be tempted to believe that
the proposed mechanism is correct ; we cannot assert this. All that we can say with certainty is
that it is a probable mechanism.
An experimental of determination of order of reaction and the changes produced in it, and
in the rate of reaction, by changes in the concentrations of involved substances and other
experimental conditions, help in suggestion (porposing) a mechanism of a reaction or reaction
mechanism. [4]

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 LINDEMANN MECHANISM

3. Lindemann Time-Lag Theory

It is necessary that collision between the molecules must occur so as to let the molecules
attain sufficient energy to react. For a collision to occur, at least two molecules are required to
collide ; this lead to the feeling that a unimolecular reaction will show a bimolecular (second
order) behaviour. Lindemann Time-Lag theory is now consider as most satisfactory in order to
explain this behaviour of unimolecular reactions.
(a) Postulates of Lindemann’s Time-Lag Theory :

1. The molecules acquire activation energy through collision with other molecules, as
a result some molecules are activated. Thus added energy increases the amplitude
of the vibration and thus leads to decomposition.
2. The activated molecules do not decompose into products immediately but remain
in activated form for finite period. That is, there is time-lag between the moment of
activation and moment of decomposition.
3. When this time-lag is relatively large, there is a every possibility for most of the
activated molecules being deactivated through subsequent collision with ordinary
or less energetic molecules.
4. As a result of this type of deactivation, the rate of decomposition of activation
molecules into product will not be directly proportional to all the activated
molecules but only to those activated molecules which remain survive during the
time-lag.
5. The activated molecules, therefore, disappear through two parallel processes,
namely, through deactivation and through decomposition.[5]
(b) Lindemann’s Collision Mechanism of Unimolecular Reaction :
On the basis of his postulates, Lindemann suggested the following mechanism for the
process of activation, deactivation and decomposition.
Step 1. Activation
By collision a fraction of molecules becomes energized and gain a critical energy
quantity E°. The rate depends on the number of bimolecular collisions and is calculated from
the simple collision theory (independent of energy content,):

𝑨+𝑨→𝑨+𝑨∗ (k1)
Where A = Normal (ordinary i.e., less energetic) molecule
A* = Activated molecules which possess sufficient energy to pass into products.
Rate of activation of [A*] = k1[A][A]
= k1[A]2
Step 2. Deactivation
Energized molecules are de-energized by collision, the rate is equated to the collision
number only (every collision leads to de-energization).

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 LINDEMANN MECHANISM
A* + A → A + A (k2)

Rate of deactivation of [A*] = k2[A*][A]

Step 3. Decomposition
Alternatively the excited molecule might shake itself apart and form the product P.
That is, it might undergo the unimolecular decay.

A* → 𝑷 (k3)
Where P = Product formed
Rate of formation of product = k3[A*]
4. Mathematical Formulation of Lindemann’s Theory :
The activated molecules (A*) are short-lived and have small concentration at any time
during the process. It can therefore be assumed that the concentration does not change with
time. It means that steady-state approximation can be applied to A*. Mathematically,[6]

d [A* ]
0
dt ...(1)
Now the net rate of formation of [A*] is given by

d[A*] / dt = k1[A]2 – k2[A*][A] – k3[A*] …(2)

combining equation (1) ad (2),
k1[A]2 – k2[A][A*] –k3[A*] = 0
or
𝑘1[𝐴]2
[A ∗] =
𝑘2 [𝐴] + 𝑘3
…(3)

Now,
Rate of reaction = Rate with which the activated molecules decompose into products

i.e., rate of reaction = k3 [A*] …(4)

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 LINDEMANN MECHANISM

Combining equations (3) nd (4)

𝑘1𝑘3 [𝐴][𝐴]
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑘2 [𝐴] + 𝑘3
…(5)

5. Conditions of pressure and rate of reaction:

There are two situations under which such reactions can be studied.
(1) At High Pressure:
When the pressure of this reaction is higher, then the molecules of gaseous substance ‘A’
come very close to each other. The possibility for the collisions increase. In other words, the
comparison of deactivation and decomposition, shows that

k2 >> k3
k2[A*][A] >>> k3[A*]
k2[A] >>> k3

So, we neglect k3 in the denominator of equation (5)

𝑘1. 𝑘3 [𝐴][𝐴]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑘2. [𝐴]

𝑘1. 𝑘3[𝐴]
=
𝑘2
Rate of reaction = constant [A]1 …(6)

Which is the expression for first-order. This happens when time-lag is relatively large.
That is, this corresponds to a situation in which [A] is high enough to produce appreciable
deactivation of A* by collision with A so that the rate of deactivation is appreciably large in
comparision to rate of decomposition.
The equation (6) explains how, a first order kinetics could be obtain with preserving a
bimolecular collision mechanism for activation.

(2) At Low Pressure :

When the pressure of gaseous substance ‘A’ is low, then the molecules of type ‘A’ get
sufficient time to be deactivated. Step ‘3’ is more prominent than Step ‘2’. Hence.

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 LINDEMANN MECHANISM

k3>>>k2[A]

and k2[A] is neglected in the denominator

𝑘1𝑘2[𝐴][𝐴]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑘3

Rate of reaction = k1[A]2 ….(7)

At low pressure, reaction is second order. The change of first order to second order
reaction at low pressure has been observed with unimolecular reaction. This means that at
low concentration of A the process would follow a second order kinetics. [7]
6. Explanation for gaseous reactions
In gaseous reaction, as the pressure of the system is decreased, the number of collisions
decreases and hence rate of deactivation (k2[A][A*]) decreases. At low pressure, therefore,
the condition for first order kinetics fails and k2[A] is no longer greater than k3. Thus, the first
order kinetics changes into second order kinetics. It, therefore, explains why the first order
gaseous reactions behave as bimolecular (second order ) at low pressures.
As the pressure increases, the number of collisions increases and therefore, the rate of
deactivation increases i.e., k2[A] is large enough and therefore conditions for first order
kinetics prevail.
7. Conclusion
According to Lindemann’s time-lag theory, there is a change from first-order kinetics to
second-order as the pressure is lowered. This very fact has also been experimentally verified
in many unimolecular gaseous reactions as discussed below.
8. Evidence in favour of Collision-Mechanism of Lindemann
The collision-mechanism of unimolecular reactions as proposed by Lindemann predicts
that as the pressure is lowered the first-order behaviour change into second-order. This has
been observed experimentally in a number of first-order reactions, e.g., decomposition of
1 dP
azomethane, etc. When initial pressure (Pi) of azomethane, is plotted against - 𝑃𝑖 𝑑𝑡 , the graph
as shown in figure is obtained.
The graph shows that at high value of Pi, the curve is horizontal with pressure-axis (x-axis),
and at low pressure it increase proportionally with Pi. The unimoelcular reactions are thus
explained by collision-mechanism on the basis of Lindemann,s hypothesis.[8]

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 LINDEMANN MECHANISM

DECOMPOSITION OF AZOMETHANE
1/PI . DP/DT

INITIAL PRESSURE (PI )

9. Criticism of Lindemann’s Time-lag Theory

Although this theory gives a satisfactory qualitative interpretation reactions, yet
quantitatively it is not completely satisfactory and, therefore, requires certain
modifications. However, there are two difficulties met with simple Lindemann’s theory.
These are discussed below :
1. According to this theory , the rate of reaction of reaction of unimolecular reaction is
given by equation (5)

−𝑑[𝐴] 𝑘1𝑘3[𝐴][𝐴]
=
𝑑𝑡 𝑘2[𝐴] + 𝑘3
𝑘1𝑘3[𝐴]
=
𝑘3
𝑘2[𝐴]{1 + }
𝑘2[𝐴]

𝑘1𝑘3
{ } + [𝐴]
= 𝑘2
𝑘3
1+
𝑘2[𝐴]

….(8)

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 LINDEMANN MECHANISM
Suppose the first order rate constant, k is defined by
Rate of reaction = k [A] …(9)
Then, from equations (8) and (9)

𝑘1𝑘3
{ 𝑘2 } [𝐴]
𝑘[𝐴] =
k3
1+
k2[A]

In which
𝑘1𝑘3
𝑘2
𝑘=
𝑘3
1+
𝑘2[𝐴]

….(10)
𝑘∞
𝑘=
𝑘3
1+
𝑘2[𝐴]

Where
The concentration [A]1/2 at which k should become equal to k∞/2 has been defined
by the equation
k1[A]1/2 = k∞
So

𝑘∞
[𝐴]1/2 =
𝑘1
Now, k∞ can be obtained from experiment and k1 can be obtained from
K1 = Z. e-E*/RT
Where E* = energy of activation

And therefore [A]1/2 is calculated. However, this procedure gave rise the result that first
order rate constant should fall at higher pressure than was actually observed. Since there can
be no doubt about determination of k∞, the error must be in the determination of k1 . It becomes,
therefore, necessary for the collision theory to be modified in such a manner as to give larger
values for k1. This difficulty was solved by Hinshelwood.

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 LINDEMANN MECHANISM

2. The second difficult with Lindemann theory becomes apparent when the
experimenatal results are plotted.
Writing equation (10) again

𝑘1𝑘3
𝑘=
𝑘3
𝑘2{1 + }
𝑘2[𝐴]

Therefore ,

𝑘3
1 𝑘2{1 + 𝑘2[𝐴]}
=
𝑘 𝑘1𝑘3

1 𝑘2 1
= +
𝑘 𝑘1𝑘3 𝑘1[𝐴]

i.e., a plot of 1/k against 1/[A] should give a straight line. However, the deviations from straight
line behaviour have been found experimentally and are shown in the figure on the next page.
These deviations have been explained by the theories of Kassel, Rice and Ramsperger, and
Stater.[9]

k r  k [A]

[A]
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 LINDEMANN MECHANISM
10. Decomposition of Nitrogen Pentaoxide
The decomposition of dinitrogen pentoxide to nitrogen dioxide and nitrogen trioxide
N2O5 → NO5 +NO3
is postulated to take place via two elementary steps, which are similar in form to the
schematic example given above:
1. N2O5 + N2O5 ⇌ N2O5* + N2O5
2. N2O5 → NO5 +NO3
Using the quasi steady-state approximation solution, the rate equation will be:

𝑘1𝑘3[𝑁2𝑂5][𝑁2𝑂5]
𝑅𝑎𝑡𝑒 = 𝑘3[𝑁2𝑂5] =
𝑘2[𝑁2𝑂5] + 𝑘3

Experiment has shown that the rate is observed as first-order in the original concentration
of N2O5 sometimes, and second order at other times.
 If k3>>k2 then the rate equation may be simplified by assuming that k2≈0. Then the
rate equation is[10]
Rate=k1 [N2O5]2
which is second order.
 If k3<<k2 , then the rate equation may be simplified by assuming k3≈0. Then the rate
equation is
𝑘1𝑘3[𝑁2𝑂5]
𝑅𝑎𝑡𝑒 =
𝑘2
= Kobs [N2O5]

which is first order with

𝑘1𝑘3
𝐾(𝑜𝑏𝑠) =
𝑘2

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 LINDEMANN MECHANISM

11. References

1. ^ Di Giacomo, F. (2015). "A Short Account of RRKM Theory of Unimolecular

Reactions and of Marcus Theory of Electron Transfer in a Historical Perspective".
Journal of Chemical Education. 92 (3): 476.

2. ^[Link] 15:53, 23 June 2018 Carlos

BCN (talk | contribs)
3. ^ Lindemann’s Mechanism, Dr Ghulam Nabi, Dr.B.A Khokhar and [Link]
Nasim Akhtar, Chemical kinetics. Physical Chemistry, Ilmi kitab khana (2016) p.434-
435
4. ^Reaction Mechanism, Ch. Sana Ullah , Chemical Kinetics, Physical Chemistry
Ilmi kitab khana (2016) 7.11.0 p.368
5. ^Lindemann’s Time-Lag theory, [Link], Chemical Kinetics, Advanced
Physical Chemistry S. Chand Higher Academy (2008) p.467
6. ^Atkins P. and de Paula J., Physical Chemistry (8th ed., W.H. Freeman 2006)
p.820-1
7. ^IRA. N. LEVINE ., Physical Chemistry (McGraw Hill Education 6th ed.,)
8. ^ Lindemann’s Time-Lag theory, [Link], Chemical Kinetics, Advanced
Physical Chemistry S. Chand Higher Academy (2008) p.467-8
9. [Link]
%20unimolecular%20reactions
10. [Link]
xtbook_Maps/Map%3A_Physical_Chemistry_(McQuarrie_and_Simon)/29%3A_
Chemical_Kinetics_II%3A_Reaction_Mechanisms/29.6%3A_The_Lindemann_M
echanism

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