Introduction

the Arrhenius equation

To react, the potential energy of the reaction complex must be higher than
that of the barrier.
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 Summary

Microscopic pictures of the desorption of atoms and molecules via mobile and immobile transition states.
If the transition state resembles the ground state, we expect a prefactor of desorption on the order of
1013 s−1. If the adsorbates are mobile in the transition state, the prefactor increases by one or two orders
of magnitude. For desorbing molecules, free rotation in the transition state increases the prefactor even
further. The prefactors are roughly characteristic for atoms such as C, N, and O and molecules such as N2,
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 The Partition Function
Statistical mechanics

• In physics, a partition function describes the statistical properties of a

system in thermodynamic equilibrium.
• Partition functions are functions of the thermodynamic state variables, such as
the temperature and volume.
• Most of the aggregate thermodynamic variables of the system, such as the
total energy, free energy, entropy, and pressure, can be expressed in terms
of the partition function or its derivatives.
• The partition function is dimensionless, it is a pure number.
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 The Boltzmann Distribution and the Partition Function
The Boltzmann distribution:
The chance Pi (probability)
In statistical mechanics and mathematics, a Boltzmann distribution (also
called Gibbs distribution) is a probability distribution or probability
measure that gives the probability that a system will be in a certain state
as a function of that state's energy and the temperature of the system.

at a temperature T in a state with

energy εi
kB : Boltzmann constant

the entropy of a system with many members that is in equilibrium is at maximum.

Suppose we have a large ensemble of particles (electrons, atoms, molecules)

with energy levels εi, with i = 0, 1, 2,…, N, where N may also be infinitely large.

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 The Boltzmann Distribution and the Partition Function
a partition function

where gi is the degeneracy factor, which ensures that all states are taking
into account even if they have the same energy.

• The partition function is a thermodynamic function of state which, through

the sum over all the energy levels ε, contains all properties of the system.

• Important properties of a system, such as average energy, free energy

(chemical potential), and entropy follow straightforwardly from the partition
function.

The average energy of the molecules follows by logarithmic differentiation:

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Partition Functions of Atoms and Molecules
• Partition functions are very important in estimating equilibrium constants
and rate constants in elementary reaction steps.
• Motion, or translation, is the only degree of freedom that atoms have.
• Molecules also possess internal degrees of freedom, namely vibration and
rotation.

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Partition Functions of Atoms and Molecules
▪ We assume that the different degrees of freedom are independent and
that the total energy of the system can be written as the sum of the
energies of the individual members.
▪ Our system consists of N particles in total, distributed over Ni particles
with energy εi, all adding up to the total energy Etot.
▪ Again, N must be a very large number, a condition usually fulfilled in most
practical cases.
▪ The probability for finding particle i with the energy εi is Pi:

The total energy Etot is given by

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Partition Functions of Atoms and Molecules
Justification for Equating λ2 with 1/T
If we consider the system to be a monatomic gas in a one-dimensional box
(which can easily be generalized to three dimensions), the energy levels of the atom are
given by quantum mechanics as
where h is Planck’s constant, m is
the mass of the atom, and l is the
length of the box.

=> This result follows from the fact that the atom has to be described by a
simple wave function that equals zero at the walls of the box.

indicating that λ2 = 1∕T is simply the

reciprocal temperature

where q is the translational partition

function in one dimension:

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Partition Functions of Atoms and Molecules
Maxwell–Boltzmann Distribution of Velocities
Transform the Boltzmann distribution of energies into the Maxwell–Boltzmann
distribution of velocities, thereby changing the variable from energy to velocity or,
rather, momentum px

The Maxwell–Boltzmann distribution in one dimension:

three dimensions

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Partition Functions of Atoms and Molecules
Maxwell–Boltzmann Distribution of Velocities
in Cartesian coordinates

in spherical coordinates, with the magnitude of the velocity.

Cartesian coordinate system

A Cartesian coordinate system in a plane is a

coordinate system that specifies each point
uniquely by a pair of numerical coordinates,
which are the signed distances to the point from
two fixed perpendicular oriented lines, measured
in the same unit of length.

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Partition Functions of Atoms and Molecules
Total Partition Function of a System
• Consider a particle (a molecule or atom) of which the different degrees of
freedom are independent and the energy is simply the sum of the energies
contained in the different degrees of freedom.
• The partition function as the product of the partition functions for the various
degrees of freedom.
• For an atom, this is rather trivial:

where qtrans describes the partition function for the translational degrees of freedom,
while qelec and qnucl are the partition functions related to the electrons and the nuclei of
the atom.

For molecules, this is complicated due to the internal degrees of freedom

related to vibrations and rotations.

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Partition Functions of Atoms and Molecules
Translational Partition Function
• Starting with the partition function of translation, consider a particle of mass
m moving in one dimension x over a line of length l with velocity vx.
• Its momentum equals px = mvx and its kinetic energy εx = p2x ∕ 2m.
• The coordinates available for the particle x, px in phase space can be divided
into small cells each of size h which is Planck’s constant.
The partition function

For a particle moving over an area A on a for a particle free to move

surface, the partition function of translation is inside a volume V:

The average kinetic energy of a particle in space

which is the expected result. In a classical system, each dimension contributes

1 ∕ 2kBT to the kinetic energy.
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Partition Functions of Atoms and Molecules
Vibrational Partition Function
Molecules also possess internal degrees of freedom, namely vibration and rotation.

The total partition function of vibration then becomes the product of the
individual partition functions:

the average vibrational energy of a molecule with N vibrational modes:

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Partition Functions of Atoms and Molecules
Rotational (and Nuclear) Partition Function
j is the rotational quantum
number, and I the moment of
inertia,

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Partition Functions of Atoms and Molecules
Rotational (and Nuclear) Partition Function

The average energy of a rotating molecule follows immediately by logarithmic differentiation:

the general formula for a larger molecule with moments of inertia IA, IB, and
IC along the three principal axes:

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Partition Functions of Atoms and Molecules
Electronic and Nuclear Partition Functions
The electronic partition function

where ωei denotes the degeneracy of state εi, and i > 0 refers to excited electronic
states.

The ground state of a system, for example, consider a diatomic molecule is usually

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PTK-IU 18
 Molecules in Equilibrium
Chemical reaction:

The Gibbs free energy:

=> The chemical potential:

=> The equilibrium constant

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 Collision Theory
• ρA and ρB the number of molecules A and B per unit volume.
• The diameters of the effective spheres that represent A and B,
namely dA and dB.
• the rate of collisions between the spheres A and B is

Collisions between molecules A and B occur if

the center of molecule B lies within a cylinder
with radius d = (dA + dB)∕2 and length uΔt.

where πd2 is an effective cross section for collision, with d = (dA + dB)∕2 the average
between the two diameters, σAB is a symmetry factor to prevent double counting if A and B
are identical molecules (δAB = 1 if A = B, and 0 if A ≠ B) and u is the average relative velocity
between the colliding molecules. 20
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 Collision Theory
• The relative velocity between the molecules not only determines whether A
and B collide, but also if the kinetic energy involved in the collision is
sufficient to surmount the reaction barrier.
• Velocities in a mixture of particles in equilibrium are distributed according to
the Maxwell–Boltzmann distribution in spherical coordinates:

Replaces the mass with the reduced mass μ

=> The masses in molar weights, and the energy per mol:

=> the rate of collisions between A and B per unit volume:

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 Collision Theory
The Rate of Surface Collisions

All molecules with velocity vx perpendicular to the

surface in the box with volume vxΔt dA will hit the
surface within the area dA.

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 Collision Theory
Reaction Probability

Molecules only react if they have sufficient energy to overcome the energy
barrier ΔE. The height of the barrier can be transformed into a minimum
velocity umin. In the above case, ΔE = 30 kJ∕mol and only for a gas at T = 1000
K or higher can a substantial number of molecules overcome the barrier.
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 Collision Theory
Reaction Probability
The fraction of collisions, P, for which the relative kinetic energy, 1∕2μu2, is
larger than ΔE. With umin corresponding to the velocity for which 1∕2μu2min =
ΔE, the fraction of reactive collisions becomes:

=> the rate of reaction per unit volume between two molecules, A and B, in the
collision theory:

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 Collision Theory
Fundamental Objection against Collision Theory
Consider the equilibrium

=> the equilibrium constant

Equilibrium thermodynamics

relation between K and the enthalpy of the reaction, instead of the free energy, and
the expression for the equilibrium is in conflict with equilibrium thermodynamics,
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 Activation of Reacting Molecules by Collisions:
The Lindemann Theory
• Use an asterisk to indicate a highly energetic or activated molecule, which has
sufficient energy to cross the barrier towards the product side, and
• M is a molecule from the surroundings; M may be from the same type as A:

intermediate A∗

the rate of reaction

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 Activation of Reacting Molecules by Collisions:
The Lindemann Theory
the rate of reaction

If A ≡ M

that is, second order in [A].

Hence, according to the Lindemann theory a truly unimolecular reaction does

not exist because collisions with surrounding molecules are needed to bring
the reacting molecule in a sufficiently energetic state that it becomes capable
of crossing the energy barrier.

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 Transition State Theory

the rate of the overall reaction

the transition state theory:

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 Transition State Theory
Thermodynamic Form of the Transition State Rate Expression

(kJ∕mol)

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 Transition State Theory of Surface Reactions
Adsorption of Atoms

• The direct adsorption process is one in which the particle collides with the
surface and stays at the point of impact as an adsorbed species.

• The indirect mode: the particle first adsorbs in a weakly bound precursor
state, in which it moves freely over the surface, until after some time it
forms a bond with an adsorption site.

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 Transition State Theory of Surface Reactions
Indirect Adsorption

The system we consider consists of a volume of gas containing Ng gas atoms

interacting with a surface containing M adsorption sites or N0 = M/A adsorption
sites per area. In terms of transition state theory, the rate of reaction is

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 Transition State Theory of Surface Reactions
Indirect Adsorption

where Ngas and N# are the numbers

of atoms in the two states

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 Transition State Theory of Surface Reactions
Direct Adsorption

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 Transition State Theory of Surface Reactions
Direct Adsorption

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 Transition State Theory of Surface Reactions
Adsorption Molecules
Precursor-Mediated or Indirect Adsorption

The sticking coefficient

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 Transition State Theory of Surface Reactions
Adsorption Molecules
Direct Adsorption

the rate of direct adsorption

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 Transition State Theory of Surface Reactions

CO adsorbed on a surface possesses five modes of vibration. Note that the surface
is not necessarily symmetric in x and y, and hence the vibrations in the x and y
direction do not have to be degenerate.

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 Transition State Theory of Surface Reactions
Reaction between Adsorbates

The equilibrium constant for this system

The rate of the surface reaction

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 Transition State Theory of Surface Reactions

Potential energy diagram for the

forward and reverse reaction

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 Transition State Theory of Surface Reactions
Reverse reaction

Transition state

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 Transition State Theory of Surface Reactions
Desorption of Molecules

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 Summary

Microscopic pictures of the desorption of atoms and molecules via mobile and immobile transition states.
If the transition state resembles the ground state, we expect a prefactor of desorption on the order of
1013 s−1. If the adsorbates are mobile in the transition state, the prefactor increases by one or two orders
of magnitude. For desorbing molecules, free rotation in the transition state increases the prefactor even
further. The prefactors are roughly characteristic for atoms such as C, N, and O and molecules such as N2,
PTK-IU CO, NO, and O2 42
 Summary

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 Summary

Equilibrium
If we assume equilibrium between
adsorption and desorption, we find
the Langmuir isotherm.

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