Unit 2: Equilibrium

Consider a Glass of Water

When is going up the down escalator like equilibrium?

When you’re walking up, the stairs are moving down, but your position in space remains constant.

Concept of Dynamic Equilibrium

What is equilibrium?
Some reactions are reversible.
A reversible reaction occurs when the reactants react to form products and then the products can react
together to re-form the original reactants.
For Example:
Forward Reaction:
N2(g) + 3H2(g)  2NH3(g)

Reverse Reaction:
2NH3(g)  N2(g) + 3H2(g)

Reversible Reactions are usually written as follows:

N2(g) + 3H2(g)  2NH3(g)

Definition:
A reversible reaction is said to be at EQULIBRIUM when the __________of the forward reaction _________
the __________ of the reverse reaction
Equilibrium ONLY exists if:
the reaction is done in a _______________; that is nothing is able to enter or leave the reaction vessel.
The __________________ of the system is constant
The _______________ of the system is constant

4 Main Points of Equilibrium

1. The _______ of the forward and reverse reactions are ________. This means the concentrations of the
reactants and products are _____________ (not changing)….BUT the concentrations are _______
(necessarily) ___________ to each other.

2. The Macroscopic Properties are ____________

Macroscopic properties like ____________________________________________________ do not change
This means, from the outside, nothing appears to be happening.
 BUT things are happening at the _________________ level because the forward and reverse reactions
are still going on, at the same rate
In fact, that’s why they call it ________________ Equilibrium

The reactions are still ________________ (microscopically).

_______________________________
3. Equilibrium can be reached from __________________
Can start from the _____________, or start from the _____________, either way eventually
equilibrium will be reached.
4. A system at equilibrium will stay that way ____________, without being disturbed by outside forces.
Systems not at equilibrium, will tend towards _________________

Characteristics of Dynamic Equilibrium

Examine this reversible Reaction:
REACTANTS  PRODUCTS
Let’s examine what happens to the rate of reaction (both forward and reverse) as the reaction progresses.
First we only have ______________.

REACTANTS
The Forward Reaction rate would be _________.
The Reactants start being ____________
_____________ would then start to form
With some products now.
REACTANTS products

The Reverse reaction starts up Some reactants are made. Forward reaction
continues

Eventually, the _________ become equal and equilibrium is reached

REACTANTS products
Note: the concentrations may not be equal,

but they are no longer changing at equilibrium

On a concentration vs time graph this would look like this:

The concentration of the reactants would decrease as they reacted to form

products.

The forward reaction would slow down over time. WHY?

As more products are formed, the reverse reaction rate increases. (Initially it was zero!)

At equilibrium the reverse rate equals the forward rate of reaction.

To summarize at Dynamic Equilibrium:

 Rate of consumption of reactants = Rate of production of reactants.
 [Reactants] ___________ from [Products], in general.
 [Reactants] is now constant in time and [Products] is constant in time.
 The forward and reverse rates __________________ as time passes. (The rates do change as they are
coming to equilibrium.)
 A system which is not at equilibrium will tend to move towards ________________
 The molecules continue to react at equilibrium, but there is no ________ formation of products or
reactants.
 Spontaneity of a Chemical Reaction
Predicting Whether a Chemical Reaction is Spontaneous or not
Spontaneous Rxn:
is a reaction which occurs __________, without outside help
Actually, the reaction may need a little assistance in starting, but once started it will continue on
without any other outside influence.
For example:
Use a match to ignite a piece of paper and the paper will continue to burn on its own.

In exothermic reactions, the enthalpy goes from ________________

This means enthalpy is _______________
Lower enthalpy is more ____________ than high enthalpy.
Reactions favor __________________

 So, in EXOTHERMIC reactions the _________________________ is favored because:

 The forward rxn Ea is lower
 The enthalpy is decreasing towards the products and this is more stable

This reaction will not continue on its own. This would be not be a spontaneous reaction. Chemists say
the reactants would be “favoured” in endothermic reactions.

So, in EXOTHERMIC reactions the ___________________________ is favored because:

 The forward rxn Ea is lower
 The enthalpy is decreasing towards the products and this is more stable
  The side that has minimum energy (minimum enthapy) is said to be favoured.

Try:

BUT WAIT! Another factor that has to be looked at in determining spontaneity ______________
Entropy = the amount of randomness in a system

Entropy is disorder, chaos.

It requires less energy to be random than to be organized.
So reactions where entropy is _____________ are _____________

An Analogy:
A teen’s room is usually a mess. It is much easier (takes less energy) to be random (messy) that to be
neat and tidy (organized).

How do reactions increase entropy (chaos)?

 Overall randomness depends on state:

Gases >> Aqueous Solutions > liquids > solids

The most random state (maximum entropy) always favours the side with ____________ number of
molecules in the most random state.

 1st – Look at the state with most entropy

 2nd – Look for which side has most moles of that state

For example:
A(g) + B(l)  2 C(g) + D(g)
-Gas is most random state
-Products have more moles of gas
-Therefore maximum entropy will favor ______________

Try:

Conclusion:
 Highly RANDOM states are ______________ over highly ORDERED states.
 Entropy tends to a _____________ value (more disorganized state.)
 This means that there are two tendencies that drives all reactions.
1) ____________________ (minimum energy)
2) _____________________ (maximum randomness)
Let’s look at a few scenarios:
EX-1

This reaction is _______________ so enthalpy is ____________________.

So Enthalpy favors the ____________
The state with most entropy in this rxn is a ______
Gas is on the _____________ side
So entropy favors the ______________
Both Entropy and Enthalpy favor ____________ so this reaction will favor ____________ and the
____________reaction will be spontaneous.
When the forward reaction is favored, the reaction is said to ____________
EX-2

This reaction is ____________ so enthalpy is ____________

So Enthalpy favors the ____________
The state with most entropy in this rxn is a _______
More gas is on the ____________ side
So entropy favors the ____________
Both Entropy and Enthalpy favor ____________ so this reaction will favor ____________ and the
____________reaction will be spontaneous.
When the reverse reaction is favored, the reaction ____________
EX-3

This reaction is ____________ so enthalpy is ____________

So Enthalpy favors the ____________
The state with most entropy in this rxn is a ______
More gas is on the ____________ side
So entropy favors the____________
Enthalpy favors ____________, Entropy favors the ____________
So this reaction will favor ____________ and the ____________ reaction will be spontaneous.
So this reaction will ____________
So in Summary:
1. When the two tendencies ____________ (one favors reactants, the other favors products), the reaction will
____________

2. When _______the tendency toward minimum enthalpy and toward maximum entropy favor the products,
the rxn will ____________

3. When _____ the tendency toward minimum enthalpy and toward maximum entropy favor the
____________, will ____________

Try:
Le Chatelier’s Principle
Let’s examine a simple reaction:
N2O2(g)  2 NO2(g)

Over time more and more molecules of NO2 are formed from the N2O2
As more of the NO2 molecules are formed they bounce into each other and reformed some of the original
N2O2
Eventually equilibrium is established where the number of each type is kept constant.

What would happen if we ____________ the system by ________________ after equilibrium has been
established?

Since there are more N2O2 molecules they would bounce into each other and form ____________.This would
remove some of the ____________.

Note how the equilibrium seems to ________ some of the change made to the system. We added a stress of
____________N2O2, but the system counteracted the stress ____________N2O2 to make NO2!
Le Chatelier’s principle is all about ____________ what will happen to the concentrations of the reactants
and products as a result of a stress.

If a closed system at equilibrium is subjected to a stress, processes will occur that tend to ________________
“What ever we do (...to a system) natures tries to undo”

There are 4 stresses you can do to system (reaction) at equilibrium or steady state:

1. ________________
2. ________________
3. ________________
4. ________________
Let’s examine each one in turn
1. The effects of Concentration Changes
2 NO(g) + Cl2(g)  2 NOCl(g) + 76 kJ
What would happen if we _____________the concentration of Cl2?
The Stress = ___________
__________________= by ____________the extra Cl2 by shifting the reaction to the ________
This produces _______ products and reduces the concentration of the reactants
Explanation:
Adding more Cl2 to the reactants would cause more collisions between the Cl2 and the NO and hence
increase the forward rate.
This would result in more products being formed increasing the reverse reaction rate. When the two
reaction rates are equal again, a ____________will be re-established and no further shift will occur.

2. The Effect of Temperature Changes

2 NO(g) + Cl2  2 NOCl(g) + 76 kJ
What would happen if we decrease the temperature?
Stress = ____________ in temperature ____________
Counteract the stress = by ____________. This is done by shifting the reaction towards the heat term, to
the _________.
This will cause the reactants to ____________, and products to ____________.

That was for an exothermic reaction. What about for endothermic reactions?
N2O4(g) + heat  2 NO2(g)
What would happen if we ____________ the temperature?

Stress = ____________ in temperature ____________

Counteract the stress = by ____________. This is done by shifting the reaction towards the heat
term, to the _______.
This will cause the reactants to ____________, and products to ____________.
https://www.youtube.com/watch?v=tlGrBcgANSY

3. The effects of Pressure Changes

N2O4(g) + heat  2 NO2(g)
What would happen if we____________the pressure?
Increasing the pressure, decreases the volume and vice versa

Let's say we had 2 molecules of NO2 only in a certain volume:

 The NO2 molecules bump against the container creating pressure on the walls of the container

Now, suppose we were to completely convert those two molecules of NO2 into N2O :

Now there are _______ molecules bumping into the walls of the container.
What will happen to the pressure in the container?
It will be much ______
So, more moles of gas = _______ pressure and vice versa

What would happen if we increase the pressure?

Stress = ____________ in pressure
Counteract the stress = ____________the pressure.
This is done by shifting to the side with _______ moles of gas (to the ________)
This will cause the reactants to _________, and products to ____________

Let’s look at the reaction:

2 NO(g) + 1 Cl2(g)  2 NOCl(g) + 76 kJ
What would happen if we ____________ the pressure?
Note that there are 3 gas molecules on the reactant side and only 2 gas molecules on the product side.

Stress = ____________ in pressure

Counteract the stress = by ____________ the pressure.
This is done by shifting to the side with _______ moles of gas (to the ______)
This will cause the reactants to ____________, and products to ____________

SUMMARY:
If the pressure is increased, then the reaction will always shift towards the side that has the _________
number of moles of gas.
If the pressure is decrease, then the reaction will always shift towards the side that has the
____________number of moles of gas.

4. The effects of Adding a Catalyst.

Using a catalyst will decrease the activation energy for the __________ reaction and for the ____________
reaction by the same amount.
 This means the forward reaction will speed up, but so will the ____________

This means that a catalyst will _______ cause a shift to either side.
It just reaches equilibrium ____________

Try:

Le Chatelier’s Graphs
Let’s say Cl2 was added to the system. How would this look on a graph?
2 NO(g) + Cl2(g)  2 NOCl(g) + 76 kJ
Temperature changes
2 NO(g) + Cl2(g)  2 NOCl(g) + 76 kJ

Increase in Pressure: 2 NO(g) + Cl2(g)  2 NOCl(g) + 76 kJ

Summarizing Graphs:
 Changing the ____________ of a single reactant or product causes the reaction to shift away from
that species side and has a ____________on the graph.
 Changing the temperature of a reaction will ____________ shift towards or away from the heat
energy side. There will be ____________on the graph.
 Changing the pressure changes the concentration of all species initially either by ____________
____________and then ____________ change to adjust to equilibrium.