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CHM 305 note

The document discusses unimolecular reactions and the Lindemann theory, which explains first-order kinetics through the activation of reactant molecules by collision. It outlines the principles of the Lindemann mechanism, including the time delay between activation and reaction, and presents equations for determining reaction rates under different pressure conditions. The theory's limitations are also highlighted, noting its failure to account for energy dependence and specific molecular motions in unimolecular reactions.

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10 views

CHM 305 note

The document discusses unimolecular reactions and the Lindemann theory, which explains first-order kinetics through the activation of reactant molecules by collision. It outlines the principles of the Lindemann mechanism, including the time delay between activation and reaction, and presents equations for determining reaction rates under different pressure conditions. The theory's limitations are also highlighted, noting its failure to account for energy dependence and specific molecular motions in unimolecular reactions.

Uploaded by

Sann
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CHM 305

Chemical Kinetics

Department of Chemistry
Obafemi Awolowo University, Ile-Ife, Nigeria
THEORIES OF REACTION RATES

Theories of Unimolecular Reactions


Definition: UNIMOLECULAR REACTIONS
• A unimolecular reaction is one in which the activated complex is formed from a single reactant molecule.

• A single reactant isomerises or decomposes to give a product or products.

• At high pressures, some reactions such as the decomposition of azomethane:

𝐶𝐻3 𝑁2 𝐶𝐻2 → 𝐶2 𝐻6 + 𝑁2 show first order kinetics i.e

𝑑
𝐶𝐻3 𝑁2 𝐶𝐻3 = −𝑘1 𝐶𝐻3 𝑁2 𝐶𝐻3
𝑑𝑡

Other similar reactions are:

→ CH3CH= CH2

𝑅𝑋 → 𝑂𝑙𝑒𝑓𝑖𝑛𝑒 + 𝐻𝑋

𝐶6 𝐻5 𝐶𝐻2 𝐶𝐻3 → 𝐶6 𝐻5 𝐶𝐻2. + .𝐶𝐻3


Lindemann Theory
Lindemann (1922) showed that it is possible for activation by collision to give rise to first-order kinetics
under certain conditions.
The idea:
• Reactant molecules are supposed to be activated by collision with one another and at any given time, a
small fraction of the molecules should have sufficient energy to form products without having to receive
additional energy.
• The reactant molecules are activated by binary collision but there is a time lag between the collisional
activation and decomposition into product.
• It is assumed that as the molecules are activated, 𝐴∗ does not just go into another substance. A stationary
state is arrived at between the time lag and the formation of product.
The rate of reaction, being proportional to the concentration of activated molecules, will then be
proportional to the concentration of reacting molecules i.e the reaction will be first-order. The rate of
appearance of product will depend on the rate of disappearance of 𝐴∗
Principles of the Lindemann Mechanism
The mechanism is summarized as following these 3 Principles

1. Energy is transferred by collision (forward reaction of Equation 1)

2. There is a time delay Δt between collision and reaction (Equation 2)

3. Molecules may be de-activated by another collision during Δt (reverse

reaction of Equation 1)
Lindemann Theory –General Mechanism
Step 1: Bimolecular Activation of A
𝐴 + 𝐴 kk 𝐴∗ + 𝐴 −−− −(1)
1

1

Step 2 : Unimolecular reaction of A*


𝑘
∗ 2
𝐴 → product -------------- (2)

Hence,
𝑑 𝐴∗ 2
Overall rate = 𝑘1 𝐴 − 𝑘−1 [𝐴∗ ] 𝐴 + 𝑘2 [𝐴∗ ]
𝑑𝑡

𝑑 𝐴∗
∴ = 𝑘1 𝐴 2 − 𝑘−1 [𝐴∗ ] 𝐴 − 𝑘2 [𝐴∗ ] −−−− − (3)
𝑑𝑡
Overall rate = formation of A* – removal of A*
Lindemann Theory – General Equation
𝑑 𝐴∗
Applying the Steady State Approximation (SSA), i.e − =0
𝑑𝑡
We have 𝑘1 𝐴 2 − 𝑘−1 [𝐴∗ ] 𝐴 − 𝑘2 [𝐴∗ ] = 0
𝑘1 𝐴 2
:- 𝐴∗ = ------- (4)
𝑘2 +𝑘−1 [𝐴]

• The rate of formation of products is therefore


Rate = 𝑘2 𝐴∗
𝑘1 𝑘2 𝐴 2
Rate, v =
𝑘2 +𝑘−1 [𝐴]
𝒌𝟏 𝒌𝟐 𝑨 𝟐
v= ----- (5)
𝒌𝟐 +𝒌−𝟏 [𝑨]
Lindemann Theory – First-Order Condition
(1) At sufficiently high pressure, 𝑘−1 [𝐴] ≫ 𝑘2.

𝑘2 can therefore be neglected since 𝑘−1 [𝐴] ≫ 𝑘2.

• Equation 5 becomes

𝑘1 𝑘2 𝐴 2
𝑣= = 𝑘∞ 𝐴 −− −(6) → Reaction is first order
𝑘−1 [𝐴]

𝑘1 𝑘2
where 𝑘∞ =
𝑘−1
Lindemann Theory – Second-Order Condition

(2) At low pressures, 𝑘−1 𝐴 ≪ 𝑘2

Equation (5) becomes

𝑘1 𝑘2 𝐴 2 2
𝑣= = 𝑘1 𝐴 ---- (7) Hence, reaction is 2nd order
𝑘2

• This theory gives a satisfactory qualitative interpretation of


unimolecular reactions but not completely satisfactory quantitatively
Lindemann Theory – Determination of k’
Suppose that a first-order rate coefficient k’ is calculated from the data,
such a rate coefficient is given by the equation.
𝑣 = 𝑘 ′ 𝐴 −−−− − (8)
Equations 5 and 8 above give
𝑘1 𝑘2 [𝐴] 𝑘∞
𝑘′ = = 𝑘 -------------(9)
𝑘−1 𝐴 +𝑘2 1+𝑘 2 𝐴
−1
(i.e dividing through by 𝑘−1 𝐴 and relating it to eqn 6)
• Thus 𝑘 ′ is the constant in the higher pressure range but falls to zero
at lower pressures (Fig. 1).
Lindemann Theory – Determination of k’

Fig. 1: Plot of the first-order rate coefficient (k’) against the


concentration for a first order reaction.
Comparison of Experimental and Calculated Values of [A]

When compared with experimental results, Lindermann

theory breaks down for two main reasons.

Fig. 2: Comparison of Experimental and


Calculated Values of [A]
Failures of Lindemann Theory:
When compared with experimental results, Lindemann theory breaks down for
two main reasons.
1. The bimolecular steps taken no account of the energy dependence of
activation; the internal degrees of freedom of the molecule are completely
neglected, and the theory consequently underestimates the rate of activation
(𝑘1 values are larger than 𝑍𝑒 −𝐸𝑎 /𝑅𝑇 ).

2. The unimolecular step fails to take into account that a unimolecular reaction
specifically involves one particular form of molecular motion (e.g rotation
around a double bond for cis-trans isomerization).

Subsequent theories of unimolecular reaction have attempted to address


these problems. Hinshelwood theory offers a solution to problem (1).

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