Tema 3 – Cinética molecular

Molecular kinetics: The

effect of temperature.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Most reactions speed up as temperature increases.

f : some function
k = f (T )

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Arrhenius equation: Many chemical reactions have a linear or near linear behavior
when plotting lnk versus T-1.
A : Arrhenius factor
− Ea RT
k = Ae Ea : activation energy

• Take natural logarithms:

Ea 1
ln k = ln A −
R T

d ln k 2 d ln k
Ea = − R = RT
d (1 T ) dT

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

− Ea RT
k = Ae
 The Arrhenius parameters are characteristic to each reaction.
 The activation energy corresponds to the energy necessary for the chemical reaction
to occur.
 Reaction rate increases with temperature when Ea is positive. The larger the
activation energy the greater is the sensitivity of the reaction to changes in
temperature.
 A reaction with a negative activation energy usually indicates that the observed rate
constant is a composite of rate constants of elementary reactions contributing to a
complex mechanism.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Collision theory: Reaction occurs when two molecules collide with one another in a
bimolecular reaction.
 As in the kinetic theoy of gases (KMT), collision theory makes the assumption that
molecules are hard, structureless spheres which do not interact with each other until
they come into direct contact.
 A further assumption is that reaction only occurs
when molecules collide with a kinetic energy
greater than some threshold value.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

• Reaction coordinate is the collection of movements,

such as changes in the inter-atomic distances and in the
link angles that directly participate in the formation of
products from the reactants.

• Activated complex is the group of atoms that

corresponds to the region near the maximum potential
energy .

• Transition state is the configuration acquired by the

group of atoms such that any other small distortion
inevitably produces products.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

− Ea RT
k = Ae
 The activation energy corresponds to the energy necessary for the chemical reaction
to occur. Molecules must posses a minimum energy to react.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Consider the chemical reaction:

N2O (g) + O2 (g) → N2 (g) + NO2 (g)

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Arrhenius equation: The pre-exponential factor is a measure of the speed at which

collisions occur regardless of their energy.
 Only the fraction of collisions with a kinetic energy in excess of the energy Ea can
lead to the reaction, a fraction given by the Boltzmann distribution.
• Recall for KMT that the temperature for a system of
particles is described by a distribution.

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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Orientation factors: The orientation of a molecule during collision can have a

profound effect on whether or not a reaction occurs.
 Some collisions do not lead to reaction even if there is sufficient energy.

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 Tema 3 – Cinética molecular

The Arrhenius equation

 Arrhenius discovered that most reaction-rate data obeyed an equation based on three
factors:
(1) The number of collisions per unit time.
(2) The fraction of collisions that occur with the correct orientation.
(3) The fraction of colliding molecules that have an energy greater than or equal to Ea.

− Ea RT
k = Ae

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 Tema 3 – Cinética molecular

Determining the activation energy

Ea 1
ln k = ln A −
R T

• One can determine the activation energy of a reaction by

measuring the rate constant at two temperatures:

Ea 1
ln k 1 = ln A −
R T1
 k2  Ea  1 1 
ln  =  − 
Ea 1  k1  R  T1 T 2 
ln k 2 = ln A −
R T2
d ln k 2 d ln k
Ea = − R = RT
d (1 T ) dT
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 Tema 3 – Cinética molecular

Influence of temperature on reaction rates

 Not all chemical reactions show the behavior of Arrhenius. The most modern kinetic
theories predict that the velocity constant will exhibit a behavior of the type:

k = aT m e − E ' RT

where a and E’ are quantities that are independent of temperature, and m can adopt
values such as 1, ½ and - ½ depending on the details of the theory used to predict
the rate constant.

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 Tema 3 – Cinética molecular

Rate determining step

 Once the initial barrier that corresponds to a first step with the highest activation
energy has been overcome, the intermediates become products in cascade.

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