10/5/2012

Intro to Equilibrium

You can start with a reactant and make a product, or take the
Unit 2a – Equilibrium Theory product and turn it back into the original reactant using the
same reaction.

This means that some reactions can go backwards and
Chemistry 12
forwards, therefore, reversible reactions should exist.

There are separate activation energies for the forward and
reverse reactions (remember kinetics?).

As the forward reaction proceeds, the reactants are used up and the
forward reaction rate decreases.
If a reaction forms products in an open

As the reverse reaction proceeds, the products are used up and the system, and the products are able to escape
reverse reaction rate decreases. from the reaction vessel (gases), then the
products will not be available for the reverse

Equilibrium:
reaction.

A state of a closed system in which all measurable properties are
constant.
In order for an equilibrium to occur, the

No observable (macroscopic) changes are taking place. reaction must take place in a closed system.

Observable properties like colour and pressure become constant.
Closed System:

A reversible reaction is at equilibrium when the rate of the forward
A system where nothing can get in or out.
reaction is equal to the rate of the reverse reaction.

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When dealing with an equilibrium system, we need to also

consider changes that occur that we cannot see. Characteristics of Equilibrium

Dynamic Equilibrium:

At equilibrium:

An equilibrium situation in which microscopic changes occur, but

forward rate = reverse rate
macroscopic changes do not.

Occurs in a closed system.

The reactants are changing into products and the products are

[REACTANTS] and [PRODUCTS] are constant in time.
changing into reactants but there is no net change because the
rates of the forward and reverse reactions are equal.
The forward and reverse reaction rates do not change as time
passes.
At equilibrium all the observable properties
A system that is not at equilibrium will tend to move toward
are constant, but at the molecular level there
is a constant back and forth reaction between a position at equilibrium
reactants and products which is in perfect
balance.

Concentration vs. Time for an Equilibrium System Rate vs. Time for an Equilibrium System
A point is ultimately
reached where the rates
FORWARD
of the forward and
reverse reactions are
the same.
Concentrations
remain constant
in a state of At this point,
equilibrium. equilibrium is
REVERSE achieved.

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Homework: Predicting Whether or Not a Reaction is

Spontaneous

Read:

Pages 43 - 49
Spontaneous Change:

Do:
a change which occurs by itself, without outside assistance.

#1 - 13

There are two factors to consider when deciding whether a
reaction will be spontaneous or not:
1. Enthalpy (energy)
2. Entropy (randomness)

Endothermic reactions require the input of energy and

Tendency to Minimum Enthalpy hence we would not expect such reactions to occur
spontaneously.

When the energy barrier is low enough, a reaction is

For Example:
expected to move spontaneously to the side of the reaction

A ball does not roll uphill on its own.
having the minimum energy (exothermic direction).

The tendency to go to minimum enthalpy is the tendency to

For Example: go to and stay on the “downhill” side in a reaction.

Burning paper, explosions,
The side of the reaction having minimum energy (minimum
sodium reacting in water. enthalpy) is "favoured" because molecules will tend to go to
or remain at minimum energy, so…
Enthalpy favours a
minimum side.

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Consider the following potential energy diagram:

In exothermic
reactions, the
product side is
favoured.

In endothermic
reactions, the
The above diagram represents an endothermic reaction.
reactant side is
One would assume that the reaction is non-spontaneous, but
favoured. we see from the demo that it is not.

This brings us to the the second tendency to consider…

Tendency to Maximum Entropy
Naturally there are more random states possible than ordered
ones.

Entropy:

The probability of having a disorganized state of matter is far

The amount of randomness in a system.
greater than an organized one.

Nature favours CHAOS!!!

We get that…

For example:
the greater the difference in the
amount of randomness of
products versus reactants, the
greater the "entropy drive" of the
system.

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Several things must be considered before deciding whether 2. What if more than one phase is present in the reaction
products or reactants are favoured: equation?
1. What is the most random phase present?
The side with the most random phase has “greatest

Solids are very orderly, crystals have zero randomness. randomness”. Tendancy to max entropy

Pure liquids are much more random than solids.
For example: favours productsMost
Random

Solutions are more random than pure liquids because a
CaC2(s) + 2 H2O(l) ↔ C2H2(g) + CaOH2(aq)
mixture is much more scrambled than a liquid containing only
one type of molecule.
If both sides contain equally random phases, the side with the

Gasses are the most random of all. greatest number of particles in the most random phase will have

To summarize: the “maximum randomness”. Tendancy to max entropy
Most

For example: favours reactants.
Random
Solids Liquids Solutions Gases
2 A(g) + B(s) ↔ C(g) + D(s)
LEAST MOST

Once you identify the most random phase, there is no need

Try some: EQUILIBRIUM

to look at any other phase. C2H2(g) + 2 Cl2(g) → C2H2Cl4(l) + 386 kJ

Max. Entropy Min. Enthalpy

After examining the two tendencies, we can figure out
whether the system will: SPONT.
1. Go to completion (spontaneous) CH4(g) + O2(g) → CO2(g) + 2 H2O(g) + 394 kJ
2. Not react (non-spontaneous) Max. Entropy Min. Enthalpy
3. Reach equilibrium
NON-SPONT.
4 Au(s) + 3 O2(g) + 162 kJ → 2 Au2O3(s)
Max. Entropy Min. Enthalpy

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Homework: Le Chatelier’s Principle

Read:

Pages 50 - 56 If a closed system at
equilibrium is subjected

Do: to a change, processes

#14 - 16 will counteract that
change to return to
equilibrium.

What does this mean?

Factors Affecting Equilibrium

Le Chatelier proposed:
Consider the following equilibrium:

If an equilibrium system were subjected to a stress, the system 2 NO(g) +Cl2(g) ↔ 2 NOCl(g) + 76 kJ
would shift to relieve the stress and reestablish a new equilibrium.

Temperature:

Examples include heating, changing the pressure (and volume),

If we decrease the amount of heat energy (lower the
and addition or removal of one of the participants in the
temperature), the reaction shifts to produce more heat.
reaction.

The equilibrium will shift to the side of the equation which
contains the heat value (to attempt to replace what we
removed).

The reaction will shift to the right.

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The reaction shifts more to the product side due to a
We also need to understand what is going on in terms of
temperature decrease as follows: rates:

Forward Rate
RATE
Reverse Rate

TIME

Concentration:

If we increase the [Cl2], the reaction shifts to decrease the
amount of added Cl2:
If we just cooled the reaction 2 NO(g) + Cl2(g) 2 NOCl(g) + 76 kJ
↔
mixture for a short time, the
The Cl2 is on the reactant side. The reaction will shift to the
product side to use up the added Cl2.
reaction would be unchanged

If we add Cl2 to the reaction, the equilibrium will shift to the
once it came back to the original side which does not have Cl2.
temperature.

Note: solids have a constant concentration, so adding or
removing amounts of solid will not shift an equilibrium

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The reaction shifts more to the product side due to an Again with the rates
increase in [Cl2] as follows:

Forward Rate
RATE
Reverse Rate

TIME

Pressure:

A decrease in volume will increase the pressure and

Use the following method to predict the correct shift:
simultaneously increase the concentration of all gaseous species
Count up the number of gaseous molecules on both sides of the
present. reaction equation.
2 NO(g) + Cl2(g) ↔ 2 NOCl(g) + 76 kJ
Label the side of the reaction having the most gas molecules as

The reaction will shift in response to our change. "high” and label the other side as "low".

Since the pressure was increased, the equilibrium will respond
by shifting to the low pressure side, so draw an arrow from the
How do we "high" side to the "low" side to show the shift direction.
predict the
shift?

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Back to the example:

One last time
2 NO(g) + Cl2(g) ↔ 2 NOCl(g) + 76 kJ
HIGH LOW

The reaction shifts more to the product side due to an
increase in overall pressure as follows:
Forward Rate
RATE
Reverse Rate

TIME

Catalyst:

If the overall pressure is increased by adding
A catalyst accelerates the reaction rate and helps a system achieve
a non-reactive gas such as helium, the equilibrium more quickly.
concentration of the reacting gases is
The final position of the equilibrium (relative amounts of reactants
unaffected and there is no change in the and products) will remain unchanged.
equilibrium.
If a reaction is already at equilibrium, the forward and reverse

The volume is not changed and there are still reaction rates must be equal.
the same numbers of moles of reacting gases
Adding a catalyst speeds up the forward and reverse rates by an
in the same volume (same concentration). equal amount, so that the reaction remains at equilibrium.

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Homework:

Do:

#17 – 30

Study for quiz!

Assignment due next class.

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