TRANSITION STATE THEORY
- Anushree
Chaturvedi
Transition State Theory
• Transition State Theory was developed by Henry Eyring, Polanyi and Evans
in 1935.
• It is very significant, as it determines the rates of chemical reaction taking
place in an elementary reaction.
• This theory functions on quasi-equilibrium, which is a chemical equilibrium
that is established between the reactants when the reaction started and the
complexes that had attained an activated transition state.
Transition State Theory
• Transition State Theory cannot determine the absolute reaction rate of a chemical
reaction (as that will require a precise value of potential energy surfaces).
• It can efficiently calculate the Gibbs free energy ΔG♯ , Entropy ΔS♯ and Enthalpy of
activation ΔH♯ of a reaction whose reaction rate constant is known.
• Thus, transition theory provides a clear understanding of the rate of the reaction and
qualitative occurrence of a chemical reaction by assuming equilibrium between the
reactants and the activated complex formed at the transition state.
Transition State
• A transition state of a chemical reaction is basically a configuration attained by
reactants during complex formation along with the reaction coordinates where
maximum potential energy is attained.
• Therefore, the meaning of transition state can be simply explained as when two
reactants with a defined molecular arrangement undergo a chemical reaction,
between the initial and final arrangements of the molecules or atoms an intermediate
state of reaction is attained where maximum potential energy is observed.
• This particular intermediate configuration of atoms or molecules with the maximum
value of potential energy is called activated complex and the state is defined as
transition state.
Transition State
• The diagram shows the transition state of a chemical
reaction taking place.
• It is a potential energy graph that shows the minimum
energy required to convert reactants into products.
• The activation energy is a hurdle that the reactants
need to overcome during the chemical reaction to get
converted into their corresponding products.
• Therefore, numerically activation energy is the
difference of the potential energy between the
intermediate configuration of reaction coordinate and
the initial reactants,
Activation Energy = P.E. of intermediate configuration
- P.E. of initial reactants
TST/ACT
According to TST, the bimolecular reaction between two molecules A2 and B2
will proceed through the formation of an Activated Complex, which then
decomposes to yield the product AB, as shown:
TST/ACT
• The activated complex should be treated as a chemical species in
equilibrium with the reactants which then decompose into products.
• It can be given all the thermodynamic treatments like any other molecule.
• The differentiating property though is : along the reaction coordinate, one
vibrational degree of freedom is converted to translational degree of
freedom.
• The reaction coordinate is a measure of progress of a reaction.
TST/ACT
Consider a simple bimolecular reaction:
Where (AB)# is the activated complex and K # is the equilibrium constant between the
activated complex and the reactants .
The reaction rate is given by ,
TST/ACT
The concentration of activated complex [(AB) #] can be calculated as;
K# = [(AB)#]/ [A][B]
where, [(AB)#] = K# [A][B]
Substituting in the rate equation,
K# [A][B]
Thus, the rate constant k 2 can be,
k2 = K#
TST/ACT
The equilibrium constant K# can be expressed in terms of other thermodynamic entities like,
This implies k2 can be written as ;
This is famously known as Eyring equation.
Transmission
• Coefficient
It is not necessary that every Activated Complex is converted into products.
• To allow for this, a Transmission coefficient κ is introduced in equation.
κ K# [A][B]
• For many reactions the value of κ is unity.
• It means that every activated complex becomes a product.
• However, the value of κ is less than unity in the following types of reactions:
1. Reactions in which there is change from one type of electronic state to another.
2. Bimolecular atom recombination in the gas phase.
3. The reverse decomposition of atomic molecules.
• In certain cases, value of κ is higher than unity due to quantum mechanical
tunneling.