CHEMICAL REACTION

KINETICS
Effect of temperature on the rate constant-Arrhenius equation
Effect of temperature on the rate constant-Arrhenius equation
• Rate of a chemical reaction increases with increase in temperature. But this
increase of reaction rate is not uniform with every same change of
temperature. This fold change of reaction rate is known as temperature
coefficient.

• where kt and kt+10 is the rate constant of a chemical reaction at t0C and (t +
10)0C respectively.
• Arrhenius proposed an empirical formula that correlates rate constant of a
chemical reaction (k) with temperature at kelvin (T) also known as
Temperature dependent rate equation.

k A (T )  Ae  Ea / RT (1)
• where, kA is the rate constant of a reaction at T kelvin; A is a constant called
pre-exponential factor or sometime called frequency factor; E in J/mol is
activation energy and R is universal gas constant.
• The activation energy, E, is determined experimentally by carrying out the
reaction at several different temperatures.
• By taking natural logarithm of equation 1, it can be written as:
Ea  1 
In k A  In A    (2)
R T 
• If at T1 and T2 temperature, the rate constant of a chemical reaction is k1
and k2, then according to Arrhenius equation, we can write

• By taking natural logarithm, the above reactions can be written as:

• The integrated form of the Arrhenius equation is also useful (Equation
below). This variation of the Arrhenius equation involves the use of two
Arrhenius plots constructed on the same graph to determine the activation
energy. The above equation, shows temperature's effect on multiple rate
constants. This allows easy inference of the rate constants' sensitivity to
activation energy and temperature changes.

• From this equation the value of activation energy (Ea) can be determined.
 Arrhenius plot
• The Arrhenius equation can be rearranged to deal with specific situations.
For example, taking the logarithm of both side of equation 1 in the form
y=-mx+b yields equation 2
• Then a plot of Ink vs 1/T and all the variables can be found
• This form of the Arrhenius equation makes it easy to determine the
slope and y-intercept from an Arrhenius plot. It is also convenient to
note that the above equation shows the connection between temperature
and rate constant. As the temperature increases, the rate constant
decreases according to the plot.
 Activation energy: implications
• The smaller the activation energy of a reaction, the lower is the sensitivity
of the reaction to temperature change
• The higher the activation energy of a reaction, the greater is the sensitivity
of the reaction to temperature change
• The higher the Ea , the slower the rate will be.
• Endothermic reactions have higher Ea and hence are slower than
exothermic ones
• The effect of a rise in temperature is more on the rate of an endothermic
reaction than on an exothermic one because of the value of the Ea