Increasing the temperature a reaction takes place at increases the rate of reaction.

At higher
temperatures, particles can collide more often and with more energy, which makes the reaction take
place more quickly. ... Both reactions release a gas and both finish at the same volume .

In chemistry and physics, activation energy is the minimum amount of energy that must be provided to
compounds to result in a chemical reaction. The activation energy (Ea) of a reaction is measured in
joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol).

Activation Energy Problem

A second-order reaction was observed. The reaction rate constant at three degrees Celsius was found to
be 8.9 x 10-3 L/mol and 7.1 x 10-2 L/mol at 35 degrees Celsius. What is the activation energy of this
reaction?

Solution

The activation energy can be determined using the equation:

ln(k2/k1) = Ea/R x (1/T1 - 1/T2)

where

Ea = the activation energy of the reaction in J/mol

R = the ideal gas constant = 8.3145 J/K·mol

T1 and T2 = absolute temperatures (in Kelvin)

k1 and k2 = the reaction rate constants at T1 and T2

Step 1: Convert temperatures from degrees Celsius to Kelvin

T = degrees Celsius + 273.15

T1 = 3 + 273.15

T1 = 276.15 K

T2 = 35 + 273.15

T2 = 308.15 Kelvin

Step 2 - Find Ea
ln(k2/k1) = Ea/R x (1/T1 - 1/T2)

ln(7.1 x 10-2/8.9 x 10-3) = Ea/8.3145 J/K·mol x (1/276.15 K - 1/308.15 K)

ln(7.98) = Ea/8.3145 J/K·mol x 3.76 x 10-4 K-1

2.077 = Ea(4.52 x 10-5 mol/J)

Ea = 4.59 x 104 J/mol

or in kJ/mol, (divide by 1000)

Ea = 45.9 kJ/mol

Answer: The activation energy for this reaction is 4.59 x 104 J/mol or 45.9 kJ/mol.

How to Use a Graph to Find Activation Energy

Another way to calculate the activation energy of a reaction is to graph ln k (the rate constant) versus
1/T (the inverse of the temperature in Kelvin). The plot will form a straight line expressed by the
equation:

m = - E a/R

where m is the slope of the line, Ea is the activation energy, and R is the ideal gas constant of 8.314
J/mol-K. If you took temperature measurements in Celsius or Fahrenheit, remember to convert them to
Kelvin before calculating 1/T and plotting the graph.

If you were to make a plot of the energy of the reaction versus the reaction coordinate, the difference
between the energy of the reactants and the products would be ΔH, while the excess energy (the part of
the curve above that of the products) would be the activation energy.

Keep in mind, while most reaction rates increase with temperature, there are some cases where the
rate of reaction decreases with temperature. These reactions have negative activation energy. So, while
you should expect activation energy to be a positive number, be aware that it's possible for it to be
negative as well.

In some cases, rates of reaction decrease with increasing temperature. ... Elementary reactions
exhibiting these negative activation energies are typically barrierless reactions, in which the reaction
proceeding relies on the capture of the molecules in a potential well.
Activation Energy

Before going on to the Activation Energy, let's look some more at Integrated Rate Laws. Specifically, the
use of first order reactions to calculate Half Lives.

Let's review before going on...

Integrated forms of rate laws:

In order to understand how the concentrations of the species in a chemical reaction change with time it
is necessary to integrate the rate law (which is given as the time-derivative of one of the concentrations)
to find out how the concentrations change over time.

1. First Order Reactions

Suppose we have a first order reaction of the form, B + . . . . → products. We can write the rate
expression as rate = -d[B]/dt and the rate law as rate = k[B]b . Set the two equal to each other and
integrate it as follows:

The first order rate law is a very important rate law, radioactive decay and many chemical reactions
follow this rate law and some of the language of kinetics comes from this law. The final Equation in the
series above iis called an "exponential decay." This form appears in many places in nature. One of its
consequences is that it gives rise to a concept called "half-life."

Half-life

The half-life, usually symbolized by t1/2, is the time required for [B] to drop from its initial value [B]0 to
[B]0/2. For Example, if the initial concentration of a reactant A is 0.100 mole L-1, the half-life is the time
at which [A] = 0.0500 mole L-1. In general, using the integrated form of the first order rate law we find
that:

Taking the logarithm of both sides gives:

The half-life of a reaction depends on the reaction order.

First order reaction: For a first order reaction the half-life depends only on the rate constant:

Thus, the half-life of a first order reaction remains constant throughout the reaction, even though the
concentration of the reactant is decreasing.

Second order reaction: For a second order reaction (of the form: rate=k[A]2) the half-life depends on the
inverse of the initial concentration of reactant A:

Since the concentration of A is decreasing throughout the reaction, the half-life increases as the reaction
progresses. That is, it takes less time for the concentration to drop from 1M to 0.5M than it does for the
drop from 0.5 M to 0.25 M.

Here is a graph of the two versions of the half life that shows how they differ (from
http://www.brynmawr.edu/Acads/Chem/Chem104lc/halflife.html)
Let's try a simple problem: A first order reaction has a rate constant of 1.00 s-1. What is the half life of
the reaction?

Since the reaction is first order we need to use the equation: t1/2 = ln2/k

t1/2 = ln2/(1.00 s-1) = 0.6931 s

Now let's try a harder problem:

The half-life of N2O5 in the first-order decomposition @ 25°C is 4.03×104s. What is the rate constant?
What percentage of N2O5 will remain after one day?

There are 24 hours * 60 min/hr * 60 sec/min = 8.64×104 s in a day

So 22.6 % remains after the end of a day.

NOW, Activation Energy:

The Activation Energy (Ea) - is the energy level that the reactant molecules must overcome before a
reaction can occur.

You probably remember from CHM1045 endothermic and exothermic reactions:

In order to calculate the activation energy we need an equation that relates the rate constant of a
reaction with the temperature (energy) of the system. This equation is called the Arrhenius Equation:

Where Z (or A in modern times) is a constant related to the geometry needed, k is the rate constant, R is
the gas constant (8.314 J/mol-K), T is the temperature in Kelvin. If we rearrange and take the natural log
of this equation, we can then put it into a "straight-line" format:

So now we can use it to calculate the Activation Energy by graphing lnk versus 1/T.

When the lnk (rate constant) is plotted versus the inverse of the temperature (kelvin), the slope is a
straight line. The value of the slope (m) is equal to -Ea/R where R is a constant equal to 8.314 J/mol-K.

 
"Two-Point Form" of the Arrhenius Equation

The activation energy can also be found algebraically by substituting two rate constants (