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EQUILIBRIUM

What Is Equilibrium?
Consider

mixing the reactants nitrogen


gas (N2) and hydrogen gas (H2).

When

reactants are put together the


forward reaction starts.
Since there are no products there is no
reverse reaction.

What Is Equilibrium?
As

the forward reaction proceeds the


reactants are used up so the forward
reaction slows.
The products build up, and the reverse
reaction speeds up.

Equilibrium
Eventually

you reach a point where the


reverse reaction is going as fast as the
forward reaction.
This is dynamic equilibrium.

Equilibrium
The

double arrow implies the process is


dynamic.

N2O4(g)

2NO2(g)

Equilibrium
The

rate of the forward reaction is


equal to the rate of the reverse
reaction.
The concentration of products and
reactants stays the same, but the
reaction is still running.

Equilibrium
Catalysts

speed up both the forward


and reverse reactions.

Equilibrium

products
K
coefficients
reactants
coefficients

where K is the equilibrium constant

Equilibrium

Note that the equilibrium constant


expression has products over
reactants.
Coefficients become exponents.
Square brackets [ ] mean
concentration/molarity (moles/liter).

Equilibrium

Pure liquids and pure solids are omitted


from the equation!
Pure liquids and solids have a fixed
concentration which will always be
constant, so there is no need to include
that in the equilibrium constant
expressions.

Equilibrium
For

example

2C (aq) + D (aq) 3A (aq) + 2B (s)

the equilibrium constant expression is

A
K 2
C [ D ]
3

Writing Equilibrium Expressions


Write the equilibrium expression for the
following reaction.
a) 3H2(g) + N2(g)
2NH3(g)

K = [NH3]2
[H2]3
[N2]

Writing Equilibrium Expressions


Write the equilibrium expression for the
following reaction.
b) NiO (s) + CO (g) Ni (s) + CO 2 (g)

K =

[CO2]
[CO]

Writing Equilibrium Expressions


Write the equilibrium expression
for:
c) 2NO (g) N2 (g) + O2 (g)
[N2]
K = [O ]
2
2
[NO]

Writing Equilibrium Expressions


Write the equilibrium expression for:
d) 2O3 (g) 3O2 (g)

K =

[ O ]3
2

[ O3 ]
2

Writing Equilibrium Expressions


Write the equilibrium expression for:
e) NH3 (aq) + H2O (l)
NH4+ (aq) + OH- (aq)

[NH4+]
K = [OH-]
[NH3]

Writing Equilibrium Expressions


Write the equilibrium expression
for:
f) 2H2 (g) + O2 (g) 2H2O (l)
K =

1
[H2]2 [O2]

Le Chteliers Principle
Regaining Equilibrium

Le Chteliers Principle
If

something is changed in a system at


equilibrium, the system will respond to
relieve the stress until a new
equilibrium is established.
Three types of stress can be applied.

Changing Concentration
Adding

a reactant or product shifts the


equilibrium away from the increase.
Removing a reactant or product shifts
the equilibrium towards the decrease.

Changing Concentration
1) Consider the reaction
X + Y A + B
If the concentration of X is increased,
the reaction will shift to the _____.
right

Changing Concentration
2) Consider the reaction
X + Y A + B
If the concentration of Y is decreased,
the reaction will shift to the _____.
left

Changing Concentration
3) Consider the reaction
X + Y A + B
If the concentration of A is increased,
the reaction will shift to the _____.

left

Changing Concentration
4) Consider the reaction
X + Y A + B
If the concentration of B is decreased,
the reaction will shift to the _____.
right

Changing Temperature
Reactions

either require or release heat.


For an endothermic reaction, H > 0
and heat can be considered as a
reactant.
For an exothermic reaction, H < 0 and
heat can be considered as a product.

Changing Temperature
Adding

heat (i.e. increasing the


temperature) favors away from the
increase.
Removing heat (i.e. decreasing the
temperature) favors toward the increase.

Changing Temperature
5) Consider the reaction
2 SO2 + O2 2 SO3 + heat
If the temperature is decreased, the
reaction will shift to the _____.
right

Changing Temperature
6) Consider the reaction
N2 + O2 + heat 2 NO
If the temperature is decreased, the
reaction will shift to the _____.
left

Changing Temperature
7) Consider the reaction
2 SO2 + O2 2 SO3
H is negative
If the temperature is increased, the
reaction will shift to the _____.
left

Changing Temperature
8) Consider the reaction
N2 + O2 2 NO
H is positive
If the temperature is increased, the
reaction will shift to the _____.
right

Changes in Pressure
An

increase in pressure favors the


direction that has fewer moles of gas.
A decrease in pressure favors the
direction that has the greatest moles of
gas.
In a reaction with the same number of
product and reactant moles of gas,
pressure has no effect.

Changing Pressure
9) Consider the reaction

N2O4(g)

2NO2(g)

If

the pressure is increased, the reaction


will shift to the _____.
left

Changing Pressure
10) Consider the reaction
2H2(g) + O2(g) 2 H2O(g)
If

the pressure is decreased, the


reaction will shift to the _____.
left

Changing Pressure
11) Consider the reaction
CO2 (g) + H2 (g) + heat CO (g) + H2O (g)
If

the pressure is decreased, the reaction


will shift to the _____.
No shift

Adding a Catalyst
If

a catalyst is added, the reaction will


NOT shift.
Equilibrium will only be reached
sooner.

Altering the Yield


The

yield of a product will be


increased if the reaction shifts to the
product side (the forward reaction).

Altering the Yield


12)

N2 (g) + 3H2 (g) 2NH3 (g)

H = 92.4 kJ
How can the yield of NH3 be increased by
manipulating the following?
a) (add or remove) more N2
b) (increase or decrease) the pressure
c) (increase or decrease) the temperature

Calculating Equilibrium
If

K > 1, products are favored. In other


words, forward reaction is favored.
If K < 1, reactants are favored. The
reverse reaction is favored.

Calculating Equilibrium
K,

the equilibrium constant, it is only


affected by temperature.
K increases when a temperature
change favors the products (the
forward reaction).
K decreases when a temperature
change favors the reactants (the
reverse reaction).

Calculating Equilibrium
13) H2(g) + I2(g) 2HI (g) H = 10.4 kJ
If

temperature is increased, the reaction


will shift _____.
left

Shifting

this direction will cause the


value of K to ______.
decrease

Le Chatelier and Entropy


Entropy

(S) is a measure of the


disorder or randomness of the particles
that make up a system.
A transformation (shift) will not proceed
in any direction that reduces the amount
of total entropy.

Entropy
Entropy
of a
solid
A solid

Entropy
of a
liquid

Entropy
of a
gas

has an orderly arrangement.


A liquid has the molecules next to each
other.
A gas has molecules moving all over the
place.

Problem
14a) Which side of the reaction has
greater entropy?

(left)

Problem
b) Which side of the reaction has greater
entropy?

(right)

Problem
15a) Predict the change in entropy (increase
or decrease).

(increase)

Problem
15b) Predict the change in entropy (increase
or decrease).

N2 (g) + 3 H2 (g) 2NH3 (g)


(decrease)