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Eyring Equation

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12 views6 pages

Eyring Equation

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myself_ritesh
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Eyring Equation
Peter Keusch

German version

"If the Lord Almighty had consulted me before embarking upon the
Creation,
I should have recommended something simpler."
Alphonso X, the Wise of Spain (1223-1284)

"Everything should be made as simple as possible, but not simpler."


Albert Einstein

Both the Arrhenius and the Eyring equation describe the


temperature dependence of reaction rate. Strictly speaking,
the Arrhenius equation can be applied only to gas
reactions. The Eyring equation is used in the study of gas,
condensed and mixed phase reactions - all places where the
simple collision model is not very helpful. The Arrhenius
equation is founded on the empirical observation that
conducting a reaction at a higher temperature increases the
reaction rate. The Eyring equaion is a theoretical construct,
based on transition state model.
According to the 'transition state theory', the reactants are getting over into an unsteady
intermediate state on the reaction pathway.

As the two reactants A and B approach each other closely, an 'activated complex' or
'transition state' AB≠ is formed. The complex represents an unstable molecular
arrangement, in which bonds break and form to generate the products C or to degenerate
back to the reactants A and B.

The concentration change of the complex AB≠ can be described as follows:

Due to the equilibrium between the 'activated complex' AB≠ and the reactants A and B,
the components k1 · [A] · [B] and k-1 · [AB≠] cancel out. Thus the reaction rate is
proportional to the concentration of AB≠:

k2 is given by statistical mechanics:

kB = Boltzmann's constant [1.381·10-23 J · K-1]


h = Plank constant [6.626·10-34 J · s]

k2 is called 'universal constant for a transition state' (~ 6 · 10-12 sec-1 at room


temperature).

Additionally, [AB≠] can be derived from the quasi stationary equilibrium between AB≠
and A, B by applying the mass action law:

K≠ = thermodynamic equilibrium constant

Due to the equilibrium that will be reached rapidly, the reactants and the activated
complex decrease at the same rate. Therefore, considering both equation (4) and (5),
equation (3) becomes:

Hence the rate constant k of the overall reaction is

Additionally, thermodynamics gives a further description of the equilibrium constant:

Furthermore ∆G≠ is given by

∆G≠ = free activation enthalpy [kJ · mol-1]


∆S≠ = activation entropy [J · mol-1 · K-1]
∆H≠ = activation enthalpy [kJ · mol-1]

∆H≠ is the enthalpy difference between


the transition state of a reaction and the
ground state of the reactants. It is called
activation enthalpy (Fig. 1).
S is for the entropy, the extent of
randomness or disorder in a system. The
difference between the entropy of the
transition state and the sum of the
entropies of the reactants is called
activation entropy ∆S≠.
∆G≠ is the free activation enthalpy
(Gibb's free energy) . According to
equation (9) ∆ G≠ is equal to the
Figure 1: Energy profile change in enthalpy ∆H≠ minus the
E: Potential energy product of temperature T (which is in
Reaction coordinate: Bond length or bond angle
Transition state: Maximum of energy in the path kelvin) and the change in entropy ∆S≠
way, i.e. along the reaction coordinate of the system.
∆G≠ represents the determining driving
power for a reaction. The sign of ∆G≠
determines if a reaction is spontaneous
or not.

∆G≠< 0 ⇒ reaction is spontaneous


∆G≠ = 0 ⇒ system at equilibrium, no
net change occurs
≠
∆G > 0 ⇒ reaction is not
spontaneous
.

Combining Equation (8) and the expression (9) and solving for lnk yields:

The Eyring equation: is found by substituting equation (10) into equation (7):

A plot of ln(k/T) versus 1/T produces a


straight line with the familiar form y = -mx
+ b (Fig. 2), where

x = 1/T
y = ln(k/T)
m = - ∆H≠/ R
b = y (x = 0)

∆H≠ can be calculated from the slope m of


Figure 2: Determination of ∆H≠
this line: ∆H≠ = -m · R .

Using the y-intercept

∆S≠ can be determined and thus the calculation of ∆G≠ for the appropriate reaction
temperatures according to equation (9) is enabled.

A comparison between the Arrhenius equation

and the Eyring equation (12) shows, that Ea and ∆H≠ or lnA and ∆S≠ are analogous
quantities. The activation energy Ea is related to the activation enthalpy ∆H≠ as follows

• Small values of Ea and ∆H≠ ⇒ fast rate


• large values of Ea and ∆ H≠ ⇒ slow rate

Typical values for Ea and ∆H≠ run from 20 to 150 [kJ / mol].

• small values of lnA correspond to negative values of ∆S≠ ⇒ slow rate


• large values of lnA correspond to positive values of ∆S≠ ⇒ fast rate

The study of the temperature dependence supplies the above all mechanistically
important values lnA or ∆S≠, equivalent in their mechanistical significance. lnA- and
∆S≠-values are sensible sensors. They give informations about the level of order in a
system.

• lnA small, corresponding to large negative values for ∆S≠ (unfavorable)


The activated complex in the transition state has a more ordered or more rigid
structure than the reactants in the ground state. This is generally the case if on
going from the ground state to the transition state degrees of freedom of translation,
rotation or vibration are "frozen". The reaction is slower than normal.
• lnA large, corresponding to positive values for ∆S≠ (favorable)
A positive change in entropy of activation indicates that the system has become
more ordered. Degrees of freedom are liberated on going from the ground state to
the transition state. The reaction is fast.
Although the determination of the activation parameters must be performed
accurately, it should not pretend an excessive accuracy. The values of the activation
energy and activation enthalpy are rounded to one decimal place. The value of
activation entropy is basically written in whole numbers. Values of entropies ∆S≠ < ±
10 are written to one decimal place of accuracy. The value of lnA shall be expressed
with an accuracy of two decimal places.
An precise determination of the activation enthalpy (and the other acivation
parameters) requires at least three rate constants obtained at different reaction
temperatures. The temperature intervals should be at least 5°C. If the data points in
the plot of ln(k/T) versus 1/T (Fig. 2) do not lie exactly on a straight line, a linear
regression analysis providing the 'line of best fit' will not increase the accuracy. If
the plotted points deviate significantly from the straight line, the rate constant
should be determined at a further reaction temperature, since each of the three data
points can be "wrong". Basically, it recommends to increase the accuracy of the
measured values by improvement of the measuring method (accurate thermostating
of the reaction mixture).

Sometimes the data points are on a curve concave or convex toward the abscissa
axis.

A concave Arrhenius or Eyring plot can be attributed to several factors, although


the most common interpretation is that at least two different rate-limiting steps are
involved. Convex Arrhenius and Eyring plots are observed in experiments on
enzyme catalyzed reactions involving two competing enzymatic forms, each
dominating in a different temperature range.

References:
Chemical Kinetics
Kinetics: Characterization of Transition States
Temperature and the Rates of Reaction

>

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