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Advanced Chemical Kinetics IX

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18 views9 pages

Advanced Chemical Kinetics IX

Uploaded by

zsho.com8081
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Course Code: CH-484

Course Title: Advanced Chemical Kinetics


BS-Chemistry
Semester-VII

Dr. Khadija Munawar


Assistant Professor
Department of Chemistry, School of Natural Sciences,
National University of Sciences and Technology(NUST), Islamabad
Advanced Chemical Kinetics
Lecture # 10
21st October 2024
Collision theory: (Harpoon Mechanism)
Collision theory: (Harpoon Mechanism)
A harpoon reaction is a type of chemical reaction, first proposed by
Michael Polanyi in 1920, whose mechanism (also called the
harpooning mechanism) involves two neutral reactants undergoing
an electron transfer over a relatively long distance to form ions that
then attract each other closer together.For example, a metal atom
and a halogen might react to form a cation and anion, respectively,
leading to a combined metal halide.
Their main feature of these redox reactions is that, unlike most
reactions, they have steric factors greater than unity; that is, they take
place faster than predicted by collision theory. This is explained by
the fact that the colliding particles have greater cross sections than
the pure geometrical ones calculated from their radii, because when
the particles are close enough, an electron "jumps" (therefore the
name) from one of the particles to the other one, forming an anion
and a cation which subsequently attract each other. Harpoon
reactions usually take place in the gas phase, but they are also
possible in condensed media.
Collision theory: (Harpoon Mechanism)
Collision theory: The RRK Model
The steric factor P can also be estimated for unimolecular gas-phase
reactions, by a calculation based on the Rice–Ramsperger–Kassel
model (RRK model), which was proposed in 1926 by O.K. Rice and H.C.
Ramsperger and almost simultaneously by L.S. Kassel. The model has
been elaborated, largely by R.A. Marcus, into the ‘RRKM model’.
The essential feature of the model is that although a molecule might
have enough energy to react, that energy is distributed over all the
modes of motion of the molecule, and reaction will occur only when
enough of that energy has migrated into a particular location (such as a
particular bond) in the molecule. This distribution effect leads to a P
factor of the form

where s is the number of modes of motion over which the energy E may
be dissipated and E* is the energy required for the bond of interest to
break.
Collision theory: The RRK Model

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