Equilibrium Notes

Reversible Reactions

We explain chemical reactions using collision theory. Reactant molecules collide with
each other, producing an activated complex. The activated complex may either revert
to reactants or convert to products.

But what is stopping product molecules from colliding with each other, forming the
activated complex and forming reactants? In most cases, nothing at all. In fact, many
reactions do this. We call such reactions reversible.

Consider a hypothetical, reversible reaction where A changes to B and B changes to A.

The forward reaction is AB. The reverse reaction is BA. We can combine these
two equations into: AB

Physical Model for Equilibrium

Consider a reversible reaction A B

We can simulate this with a physical model. In the model, we have two graduated
cylinders, A and B. A begins half-filled with water. We will transfer water from A to B
using a glass tube or straw. At the same time, we will transfer water from B to A using a
narrower glass tube or straw to simulate the reverse reaction.

What will eventually happen?

Hypotheses suggested:
1. A would have more water than B
2. An equilibrium will occur and the height of A and B will be the same
3. A and B will be at equilibrium

Adapted from W. B. Mahaffy Page 1 2017

 4. Eventually the water levels will become equal in both A and B
5. When the volume of A is much less than that of B the amounts being transferred
will become equal and an equilibrium will occur
6. All the water will be transferred from A to B eventually

Explanation:

We started off by transferring A into B. No B was transferred to A initially because there

was no B. But after the level of water in B increased, we began to convert B back into
A.

At first, we were transferring A to B much faster than B to A. That is because the height
of the water column in A was much greater than that of B. We are getting rid of A faster
than we are making it. Levels of A drop. The rate of A B slows down. Meanwhile,
the height in the B graduated cylinder is going up. That is because we are making B
faster than we are getting rid of it. Gradually, the rate of BA increases. The rate of
the forward reaction is gradually slowing down while the rate of the reverse reaction is
gradually increasing. Eventually, the rate of the forward reaction will become equal to
the rate of the reverse reaction. Then we have equilibrium. What does equilibrium
mean?

Note that the height in A is not equal to the height in B at equilibrium. The two tubes
making the transfers have different diameters. In order to have equilibrium, the rate of
transfers must be equal. The volume transferred from A to B and from B to A must be
the same. The narrower tube must contain a great height of water to contain the same
volume.

The same thing happens in chemical reactions. The forward reaction begins because
we begin with reactants. Initially, the reverse reaction does not happen at all. But the
reverse gradually goes faster. Meanwhile the forward reaction slows down.

Because the activation energy is different

for the reactants converting to products
than it is for products converting to
reactants, the equilibrium will be achieved
when the concentrations of products and
reactants are different.

Because the activation energy for the

reverse reaction is greater than for the
forward reaction, a smaller percentage of
the molecules, at any given time, will be
able to react. To make sure that the same
# of molecules are converting from products to reactants as there are reactant molecules
converting to products, we need a larger amount of product present than reactant.

Adapted from W. B. Mahaffy Page 2 2017

Equilibrium Constants

For the physical model, the ratio of height of B to height of A was 1.5:1 on average. The
ratio of B to A at equilibrium is a constant, dictated by the relative sizes of the glass
tubes used for the experiment. For a chemical reaction A B, there would also be a
ratio of products to reactants. For a simple reaction such as this one, we would find that,
[ B]
for a given set of conditions, that the ratio of is a constant. We call that constant
[ A]
the equilibrium constant or Keq. What purpose would this serve? It is a good indicator
of how much product we have compared to reactant at equilibrium. This has great
practical applications. If we are trying to prepare a compound for some industrial
process, it would be very helpful to be know how extensively the reactants convert to
products. If the ratio is a very large number, we will know that there is a great deal of
the product compared to reactant. Conversely, if the ratio is a small fraction, we will
know that there is very little product compared to the amount of reactant present at
equilibrium. If Keq is on the order of magnitude of 1, we know that we will have a great
deal of both product and reactant at equilibrium.

But what about reactions with more than one reactant or product? How do we obtain a
ratio of three or four materials? Consider

H2 + I2 2HI

A ratio of products to reactants would have to include two reactants. We could play
around with different rational expressions.

[ HI ] [ HI ]
are two possibilities. Does either one give a constant ratio?
[ H 2 ][ I 2 ] [H2 ] [I2 ]
No. But the first one will with a little adjustment. Consider the original reaction:

H2 + I2 2HI

What if we re-write it as: H2 + I2 HI + HI

Think of the two HIs as separate items. Does that suggest a solution?

[ HI ][ HI ] [ HI ]2
or
[ H 2 ][ I 2 ] [ H 2 ][ I 2 ]

In general, for a chemical reaction: xA + yB + zC + wD +

we will use a rational expression:

[C ] z [ D ]w ...
Keq =
[ A] x [ B ] y ...

Adapted from W. B. Mahaffy Page 3 2017

Dealing with Pure Liquids and Pure Solids

Consider the reaction:

HF(aq) + H2O(l) F-(aq) + H3O+(aq)

We would ordinarily write its Keq expression as:

[ F ][ H 3O ]
Keq =
[ HF ][ H 2O]

But the concentration of any pure solid or pure liquid is a constant. Why not collect the
constants, Keq and [H2O] together?

[ F ][ H 3O ]
Keq[H2O] =
[ HF ]

For simplicitys sake, we will re-define Keq to include all of the constant concentrations
within its value.

[ F ][ H 3O ]
In other words, Keq =
[ HF ]

In general, then, equilibrium constant expressions will not include the concentrations of
pure solids and pure liquids because they are constant.

The concentrations of gaseous and aqueous solutions will be included in equilibrium

constant expressions.

Overall, if the

[Products] = [reactants] Keq = 1

[Products] > [reactants] Keq > 1 and thus the products are favoured

[Products] < [reactants] Keq < 1 and thus the reactants are favoured

For a reaction that reaches a chemical equilibrium, the concentrations of the substances
in the reaction can be used to calculate the Keq value for that specific chemical reaction.

Adapted from W. B. Mahaffy Page 4 2017

Le Chateliers Principle

Consider the second part of the physical model of equilibrium lab.

In the second part of the lab, after reaching equilibrium, we added more water to the A
cylinder. In a chemical reaction, this would be the same as increasing the concentration
of reactant A.

What effect did this have on the rate of transfer from A to B?

It increased the rate of transfer from A to B. A was transferred to B faster than B was
transferred to A.

Was the system still at equilibrium?

The system was not at equilibrium. The forward rate became faster than the reverse
rate (Rf>Rr). A was being used up faster than it was being made. B was being created
faster than it was used up. So the height of A decreased and the height of B increased.
As the height of A decreased, the forward reaction slowed down. As the height of B
increased, the reverse reaction sped up. Eventually, the forward rate became equal to
the reverse rate as a new equilibrium was reached.

Similarly, if you had a hypothetical reaction A B , increasing the [A] increases the
rate of the forward reaction. A will be used up faster than it is made. [B] will gradually
increase, meaning that forward rate gradually increases. A new equilibrium will be
achieved. In order to reach the new equilibrium, some of the added A is used up.

When a change is imposed upon an equilibrium system, the system will attempt
to counteract the change to return to equilibrium. This is known as Le Chateliers
Principle.

Three types of stresses easily applied to chemical systems

1. Changes in concentration

With changes in concentration the system changes to minimize the original change.

CO2 g H 2Ol H 2CO3 aq

99% 1%

An increase in the concentration of reactants causes the formation of more products

(right shift).
A decrease in the concentration of reactants causes a pull in the direction of reactants or
a left shift.
An increase in the concentration of products will cause a left shift and likewise a
decrease in the concentration of product will cause a right shift.

Adapted from W. B. Mahaffy Page 5 2017

2. Changes in temperature

An increase in temperature will cause the reaction to shift in the direction that absorbs
the heat.
2SO2 g O2 g 2SO3 g heat
For this exothermic reaction, an increase in temperature causes a left shift. A decrease
in temperature for this exothermic reaction would result in a right shift.

The reverse would be true for an endothermic reaction.

3. Changes in pressure

Changes in pressure only affect an equilibrium with unequal number of moles of

gaseous reactants and products.
N 2 g 3H 2 g 2 NH 3 g
In the above example, an increase in pressure would cause a right shift because there
are fewer gaseous molecules on the right side. Similarly, a decrease in pressure would
cause a left shift because there are more molecules.

Remember that pressure and volume are inversely related to one another so if the
pressure of a gaseous system increases the volume of that system decreases (and vice
versa).

Another example:
C s H 2O g heat CO g H 2 g
a) decrease the temperature: left shift
b) increase the pressure: left shift
c) decrease [H2]: right shift

Haber-Bosch Process

At the turn of 20th century, there was more and more demand placed on farmlands.
This resulted in an increased demand for fertilizer. Haber (1868-1934) developed a
laboratory procedure for making ammonia from its elements.
N 2 g 3H 2 g 2 NH 3 g H = -92 kJ/mol

This procedure, along with Boschs contributions, allowed for this efficient production of
large quantities of ammonia for fertilizers and many other substances.

Adapted from W. B. Mahaffy Page 6 2017