Unit-5- chapters 6 &7

Energy In Reactions
Elementary Reactions
One last thing! What is an elementary reaction you may ask? An elementary reaction is a chemical reaction that
occurs in a single step and involves only a single molecule or a group of atoms. It is the most basic type of chemical
reaction and is the starting point for understanding more complex reactions.
As we've seen, elementary reactions can be either first-order or second-order, depending on whether the rate of the
reaction is dependent on the concentration of one species or two. Some specific examples of elementary reactions
include the reaction of hydrogen and oxygen to form water, the decomposition of ozone, and the ionization of a gas.
The key thing to remember is that elementary reactions involve the breaking of some bonds and the formation of
other bonds and these concepts tie directly into how much energy is associated with a chemical reaction.

Endothermic vs. Exothermic PE Graphs

As you have probably seen, potential energy in a reaction can be represented as a curve with a hump as the reaction
progresses, with energy changes being able to be seen regarding the reaction. This is called a reaction coordinate or
a potential energy diagram.
Typically, these are used to tell us if a reaction is endothermic or exothermic, that is to say, is the
system gaining energy or losing energy with respect to its initial and final energies? Here are what the differing
graphs look like:

You can ignore "activation energy" for now, we'll get into that in the next section. What's important for you to
understand is that in a reaction, energy is either released or absorbed and this will affect the energy involved in
getting the reaction started.
Here is what you should notice and recognize:
 In an endothermic reaction, the potential energy of the reactants is less than the potential energy of the products. This
means that there must be energy put into the reaction in order to raise the particles up to a higher energy level. In other
words, energy is put into the reaction or absorbed.

o You can think of an endothermic reaction as Reactants + Energy → Products

  In an exothermic reaction, the potential energy of the reactants is greater than the potential energy of the products. This
means that there has to be some sort of "loss" of energy throughout the reaction. In other words, some of the potential energy
of the reactants is released into the surroundings.

o Where does it go? Well, it typically is converted into kinetic energy, which is the heat released in exothermic
reactions.

o You can think of an exothermic reaction as Reactants → Products + Energy

So far, when you take a look at a potential energy diagram, you should be able to tell if it is showing the energy of
an endothermic reaction or an exothermic reaction.

The Progress of a Reaction

There are three main parts of a reaction that are shown in a reaction coordinate: the reactants, the activated complex,
and the products.
1. The reactants, as you know, are the chemicals that go into the reaction. It is always going to be at the very left of a PE graph,
as the x-axis represents the progress of the reaction.

2. The activated complex, also known as the transition state, is the highest point on the PE graph. Since it is the highest point,
this complex has the highest energy and is therefore the most unstable point of the reaction.

1. You can think of this as the middle point, where the reaction is transitioning from reactants to products. The bonds
are not yet completely broken or formed.

3. The products are what come out of the chemical reaction! They are always going to be the plateau at the very right of the PE
graph.
Activation Energy
What is Activation Energy?
Activation energy is actually quite simple—it is the energy required to break the bonds in a reaction to go from the
reactants to the activated complex to the products. It is defined formally as "the energy difference between the
reactants and the transition state" according to the College Board. On an energy diagram, this is shown by an arrow
from the reactants to the peak of the graph, as you can see in the prior images.
Conceptually, you can think of activation energy as the minimum amount of energy required to start a chemical
reaction. It is kind of like an energy barrier that must be overcome for the reactants to form the activated complex
and then proceed to the products.
The lower the activation energy, the more likely the reaction will occur, and the faster the reaction will proceed. On
the other hand, reactions with high activation energy are less likely to occur and proceed more slowly. Activation
energy is an important concept in understanding the kinetics of chemical reactions and can be used to predict the rate
of a reaction and the feasibility of a reaction.

The Arrhenius Equation

The Arrhenius equation is an empirical relationship that describes how the rate constant of a chemical reaction
changes with temperature. Remember how we kept emphasizing it? Well, Arrhenius' equation describes exactly how
much the rate constant of an elementary reaction changes with changes in temperature by relating it to the activation
energy needed to reach the transition state.

Note that for the AP exam, you will not have to use this equation to make calculations..

Chapter -7-

Mechanisms and Rate Laws

Something we haven't discussed yet is that each elementary step has its own rate constant and activation energy. What can this
tell us when looking at a reaction mechanism?

Rate-Determining Steps
Often when dealing with mechanisms, you will see one elementary step labeled "slow" and the others labeled "fast" since they
have their own respective rate constants. The slow step is also called the rate-determining step as it defines the rate law of the
overall reaction. This should make sense! A reaction can only proceed as fast as its slowest step.

Remember: The rate-determining step is the slowest step in a reaction mechanism and controls the overall rate of the reaction. The
overall rate of a reaction is equal to the rate of the rate-determining step.

For a conceptual understanding, in a multi-step reaction, the rate-determining step is typically the step that has the highest
activation energy. Since the rate of a reaction is directly proportional to the frequency of successful collisions between reactant
molecules with enough energy to overcome the activation energy barrier, a step with a higher activation energy will have a
lower rate constant and, therefore, will be slower than other steps. Thus, the rate-determining step sets the pace for the entire
reaction and all other steps must keep up with it.
Example of Rate-Determining Step
Let's go through this two-step reaction mechanism to better understand this concept and calculate the rate law of the overall
reaction.

The first step to calculating the rate law of the overall reaction is to actually figure out what the overall reaction is. If you add up
both elementary steps and then cancel out the intermediate (HI), you should get H₂ + 2ICl → I₂ + 2HCl.

The next step is to figure out which elementary step is the rate-determining step of the reaction. This is pretty easy; just find the
elementary step that is slow! In this mechanism, it is the first elementary step.

Now, it is time to calculate the rate law of the first elementary step since it is the rate-determining step. When dealing with
elementary steps (and only elementary steps), we can use the stoichiometric coefficients to tell us the order for each reactant.
Thus, looking at the slow reaction, we know that the rate law of the overall reaction is: R = k[H₂][ICl]

You can see why this concept can lead to lots of errors. If a student were to forget to use the rate law of the rate-determining
step, and rather calculated it by looking at the overall balanced equation, they would have had an exponent of two for ICl.

When the Slow Step Has Intermediates

An important thing to note is that sometimes the rate-determining step will have an intermediate in it. In this case, you will need
to use some math to make a substitution since you cannot have an intermediate in your rate law. This math involves a topic in
chemistry that you most likely learned called equilibrium. If you have, what you do is you essentially use the Keq of one of the
elementary steps (typically one will be in "fast equilibrium") and use some substitutions.

Example Mechanism
The following mechanism was actually part of the 2019 AP Chemistry examination. Let's try to find the rate law of the overall
reaction!

To find the rate law for this mechanism, we look to the slow, rate-limiting step. We find the rate-limiting step to be step one. By
using the stoichiometric coefficients (which again, we can ONLY do with elementary steps), we find the rate law to be R =
k[NO₂][NO₂], or once you simplify it, R = k[NO₂]².