The Arrhenius Equation (College Board AP Chemistry)

• The effect of temperature on reaction rate can be explained in terms of kinetic theory
  • Increasing temperature greatly increases the fraction of molecules with very high velocity and high kinetic energies
  • These molecules are more likely to react on collision and produce enough energy equal to or greater than the activation energy
  • Hence, the higher the temperature, the larger the fraction of molecules that can provide the activation energy required for reaction
• Based on the collision model, the rate constant for an elementary reaction was given as

k = p × Z  ×  f            (equation 1)

• Where:
  • Z, the collision frequency
  • f, the fraction of collisions p, the steric factor
• The steric factor, p, is presumably temperature-independent
• The collision frequency, Z, is relatively insensitive to temperature
  • For example, when the temperature increases from 500 to 600 K, Z increases by less than 10%
• On the other hand, the relationship between the fraction of collisions with energy greater than the activation energy and temperature has been shown as:

f = e^-Ea/RT                   (equation 2)

• Where:
  • e is a mathematical constant (can be found on your calculator - it has the approximate value of 2.718
  • E_a is activation energy measured in J/mol
  • R is the gas constant (8.314 Jmol^-1K^-1)
  • T is the absolute temperature in K

• A combination of equations 1 and 2 gives the Arrhenius equation, which shows how the rate constant is dependent on temperature

k = Ae^-Ea/RT

• Where A is a constant and called the frequency factor
• This factor is related to the frequency of collisions, Z and the steric factor, p
• In general, as the value of E_a increases, k decreases
  • This is because the fraction of molecules that possess the required energy is smaller
• On taking the natural log of both sides of the Arrhenius equation, the equation becomes:

ln k = ln A - E_a/RT

• A plot of ln k against 1/T gives a straight line with a negative slope:

Arrhenius’s Plot

            Graph showing the relationship between absolute temperature and the rate constant of a reaction