IB Chemistry Equilibrium

Dynamic Equilibrium
A reversible reaction is at equilibrium if the rates of the forward
and reverse reactions are equal.
The system will seem macroscopically static (constant properties),
but be active microscopically (dynamic).
A Chemical equilibrium must:
1. Be a closed system (for matter).
2. Have observable properties constant.
3. Have a reversible reaction with forward and reverse rates
equal.
Note: Systems are often kept at constant temperature (isothermal)
by adding or removing heat.
1. Closed system:
Products and reactants must be contained so forward and reverse
reactions can occur.
A gaseous reaction in a sealed container
A solid, liquid or aqueous reaction in a beaker
Phase equilibrium in a sealed container
2. Observable properties are constant (macroscopic properties)
An undisturbed system at equilibrium will look as if nothing is
occurring or changing.
How can you determine if a system is in dynamic equilibrium, or
not reacting at all?
3. Forward and reverse reaction rates are equal.
Must have a reversible reaction.
What does this mean about the Ea of a reaction?
What role can a catalyst play?
Forward and reverse rates must be equal. This is symbolized with

What if forward and reverse rates are not equal?

IB Chemistry Equilibrium
Consider the reversible reaction:
A(g) + B(g) C(g) + D(g)
What will happen if we put only some A and B in an empty sealed
container?
What will happen to:
Concentration of all species?
Forwards and reverse rates?
What will happen if we put only some C and D in a sealed
container?

Consider the reversible reaction that is already at an equilibrium

with some of A, B, C, and D in the container:
A(g) + B(g) C(g) + D(g)
What will you observe?
What will happen if some A is now added?
What will happen to the rates of the reaction immediately after the
following changes are made and how will the equilibrium adjust if:
Some A is added?

Some D is added?

Some B is removed?
Some C is removed?

Important Notes:
Equilibrium systems will adjust to get to equilibrium.
If stressed (changed so as to not be in equilibrium), the system will
also adjust to return to equilibrium

IB Chemistry Equilibrium
Phase Equilibrium is
an Equilibrium
between a liquid and
its vapour. The
position of this
equilibrium is
described by the term
vapour pressure.
This term describes
the pressure of the gas
above a liquid at
equilibrium.
The size and shape of
the container have no
effect on this
equilibrium pressure.
Which curve is water?
What are the boiling points of these liquids?
Why does vapour pressure increase with temperature?

Why does the shape of the container not matter?

This is a diagram of a liquid system reaching equilibrium. Explain

each step.

IB Chemistry Equilibrium
The rate of condensation varies with the concentration of the
vapour. The concentration will vary until the rate of condensation
equals the rate of vaporization.
p. 432 figure 12.6
For each substance shown on the graph, explain the following
processes:
a) Each liquid is placed in an evacuated container and reaches
equilibrium.
b) Each gas is placed in a container and allowed to reach
equilibrium.
c) Explain differences between the different substances at
equilibrium and intermolecular forces.
Follow Up Problems 16.4, 5
Problems 12.13, 14; 17.1, 3

Le Chteliers Principle
Le Chteliers Principle allows us to make a prediction about how
an Equilibrium system will react to a change.
Stress A factor that changes that disturbs an equilibrium system
Shift Reaction to a stress. Shift to right produces more
products. Shift to the left produces more reactants.
Le Chteliers Principle:
A system at equilibrium, subjected to stress, will shift to try and
minimize the change that caused the stress.
The shift is caused by the forward and reverse rates no longer
being equal.
Changes in Concentration
If a species concentration is lowered the equilibrium will shift
towards that species to increase its concentration. (Minimize the
decrease)
If a species concentration is raised the
equilibrium will shift away that
species to decrease its concentration.
(Minimize the increase)
H2(g) + I2(g) 2 HI(g) + 57 kJ
Some H2 is added to this equilibrium.
How will the equilibrium shift?

HI

[ ]

I2

H2

time
rate

4
time

IB Chemistry Equilibrium
H2(g) + I2(g) 2 HI(g) + 57 kJ
Some HI is removed from this equilibrium.
How will the equilibrium shift?
HI

[ ]

I2
rate

H2

time

time

Pressure changes for a gaseous system through a volume change

If the volume of the container is changed, the pressures of the
gasses are changed, and the equilibrium will adjust.
The shift will try to minimize the change in pressure.

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

This reaction at equilibrium has its volume increased:
Pressure change?
Shift?
Sketch the concentration and rate graphs
Repeat for a volume decrease.

IB Chemistry Equilibrium
H2(g) + I2(g) 2 HI(g) + 57 kJ
The volume of the container is decreased
HI
I2

[ ]

rate

H2

time

time

Change in temperature
A temperature change has a greater affect on the endothermic
reaction.
A temperature increase will cause a shift away from the energy
term to consume energy and lower the temperature.
A temperature decrease will cause a shift towards the energy term
to produce energy and increase the temperature.
H2(g) + I2(g) 2 HI(g) + 57 kJ
The temperature is decreased.
HI
I2

[ ]

rate

H2
time

time

H2(g) + I2(g) 2 HI(g) + 57 kJ

The temperature is increased.

HI

[ ]

I2
rate

H2
time

time

IB Chemistry Equilibrium
Adding a Catalyst
A catalyst speeds up both the forward and reverse reaction rates
equally.
The rates are both increased, but still equal: no shift.
Add an inert gas. This increases the pressure of the system, but not
the pressures or concentration of the reactant or products. NO
SHIFT.
Haber Process for making ammonia
N2(g)+3H2(g) 2 NH3(g)
H = -92 kJ
What conditions would favour the production of large amounts of
ammonia?
Why is this process run successfully at high pressures and
temperatures?
The contact process to make Sulphuric Acid has an equilibrium
step in it:
2 SO2(g) + O2(g) 2 SO3(g)

H < 0

What conditions should be used to maximize yield?

Why is this process done at 1 atm, and high temperature with a
catalyst (VO2)?
Handout: 17-23
Handout: 24-28 Indicate how the forward and reverse rates will be
affected for these questions.
Problem 17.99

IB Chemistry Equilibrium
Mathematical model for Equilibrium:
For: aA + bB cC + dD
The Equilibrium expression Keq is:
K eq =

[C]c [D]d
[A]a [B]b

If concentrations are used in this expression it is called Kc

Example 1:
Write the equilibrium expression for:
N2(g) + 3 H2(g) 2 NH3(g)

N2(g) + H2(g) + H2(g) + H2(g) " NH3(g) + NH3(g)

c) H2(g) + I2(g) 2 HI(g)

The equilibrium expression deals with concentrations that are

variable.
Solids and pure liquids have constant concentrations.
They are omitted from the equilibrium expression.
Example 2:
Write the Equilibrium expression for:
HF(aq) + H2O(l) H3O+(aq) + F(aq)

CaCO3(s) CaO(s) + CO2(g)

PbCl2(s) Pb2+(aq) + 2 Cl(aq)

IB Chemistry Equilibrium
Keq describes a relationship between product and reactants:

K eq =

[products]
[reactants]

The size of the numeric value of K will show if the equilibrium

favours reactants or products.
An equilibrium that favours products:

K eq =

[products] large
=
= large #
[reactants] small

An equilibrium that favours reactants:

K eq =

[products] small
=
= small #
[reactants] large

ONLY TEMPERATURE
CHANGES WILL AFFECT
THE VALUE OF K
Changes of pressure or concentration will shift the equilibrium, but
they will NOT change the value of K.
If the temperature changes, we can determine the change in the
value of Kc by using Le Chteliers principle.
A shift to the products side corresponds with an increase in Kc.
A shift to the reactants side corresponds with a decrease in Kc.
Example 3:
a) For A(g) B(g) + Energy.
What is the change in Kc if the temperature is decreased?

b) An equilibrium has its value of Kc decrease for a temperature

increase. Is the reaction endothermic or exothermic?

IB Chemistry Equilibrium
Given the concentrations of all species at equilibrium, the value of
Kc can be calculated.
Given the value of Kc and one unknown species concentration,
the unknown can be found.
Example 4:
For: N2(g) + 3 H2(g) 2 NH3(g)
At equilibrium there are 0.012 mole of ammonia, 1.35 moles of
hydrogen, and 1.85 moles of nitrogen in a 5.0 L container. What is
the value of the equilibrium constant at this temperature?

Example 5:
For H2(g) + I2(g) 2 HI(g)
Kc = 6.3x104
The [HI] = 2.45 M, and [I2] = 0.023M. What is the equilibrium
concentration of H2?

If we must calculate how much a reaction shifts to get to

equilibrium, we use an ICE Table.
I = initial concentration
C = change in concentration
E = equilibrium concentration.
Example 6:
For the reaction A(g) + B(g) 2 C(g)
Initially, 1.0 moles of each gas was placed in a 2.0 L container.
At equilibrium, [C] = 0.80 M. What is the value of Kc for this
equilibrium?

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IB Chemistry Equilibrium
Example 7:
For the reaction:
N2(g) + 3 H2(g) 2 NH3(g)
1.00M of ammonia was placed in a 1.00 L container. After some
time, [H2] = 1.35 M, and was not changing. What is the value of
Kc?

Follow Up Problems 17.3, 8, 9(b)

Problems 17.38, 41, 43, 49, 51, 53, 55

Equilibrium Calculations
To determine if a system is at equilibrium, we calculate a Ktrial or a
Q value and compare it to a known K value.
If Ktrial = Keq then the system is at equilibrium.
If Ktrial < Keq then the system will shift right.
If Ktrial > Keq then the system will shift left.
Example 1:
H2(g) + I2(g) 2HI(g)
4.00 Moles of HI, 2.00 Moles of H2, and 1.75 Moles of I2 are
placed in a 2.0 L reaction flask. Keq = 56.0
Is the reaction at equilibrium? If not, which way will it have to
shift to each equilibrium?

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IB Chemistry Equilibrium
Example 2:
For the reaction: Keq = 1.2 x 10-5
CO(g) + H2O(g) CO2(g) + H2(g)
A reaction mixture is found to contain: 3.5 M CO, 5.0 M H2O,
0.050 M CO2, and 0.0040 M H2.
How will the equilibrium shift to reach equilibrium?

Some ICE calculations require the use of an unknown in the

table.
If we are not given specific information about initial or equilibrium
concentrations, we often must use a value x, and solve for that
value.
Example 3:
A(g) B(g)

K = 15

0.50 moles of A are placed in a 1.0 L container and allowed to

reach equilibrium. What are the concentrations of A and B at
equilibrium?

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IB Chemistry Equilibrium
Example 4:
For H2(g) + I2(g) 2 HI(g)
K = 6.3 x 104
Initially, [H2] = [I2] = 0.75 M. The system is allowed to reach
equilibrium. What are the concentrations of all species?

Example 5:
CO(g) + H2O(g) CO2(g) + H2(g)
This reaction is at equilibrium with 2.00 moles of CO, 2.00 moles
of H2O, 1.00 moles of CO2, and 3.00 moles of H2 in a 1.00 L
container.
1.00 moles of H2 is added to the container. What are the new
equilibrium concentrations?

Problems
17.33, 113

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IB Chemistry Equilibrium

Entropy and Enthalpy

Every reaction has two factors that will determine if it does not
react, if it react completely, or if it ends in an equilibrium.
Enthalpy (energy) A system will tend to minimum potential
energy.
Entropy (randomness) a system will tend to maximum entropy.
Equilibrium Entropy and Enthalpy
From potential energy diagrams we can see the side favoured by
minimum potential energy (Enthalpy H)

Reaction coordinate

Reaction Coordinate

Entropy (S) will favour the side with the most randomness
the most particles in the most random phase.
Greater randomness is favoured because there are more ways to
arrange the particles randomly than orderly.
Gasses >> solutions > liquids >> solids
Entropy can be calculated from standard entropy values.
S = S(products) - S(reactants)
The values of the standard entropies can be found in the appendix
and in your IB Data booklet for some organic compounds.
Example 1:
Estimate and calculate the S for the following:
a) N2(g) + 3 H2(g) 2 NH3(g)
b) CaCO3(s) CaO(s)+ CO2(g)
c) NaCl(s) Na+(aq) + Cl(aq)

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IB Chemistry Equilibrium
A system will tend to minimum enthalpy and maximum entropy.
Both factors favour reactants practically no reaction.
Both factors favour products practically reacts to completion.
One factor favour reactants and the other products observable
equilibrium.
The tendency for a reaction to proceed can be calculated with a
function called Gibbs free (G) :
G = H - TS
If H, S, and the temperature are known, then G can be
calculated.
If G < 0 then the reaction is spontaneous.
If G > 0 then the reaction is not spontaneous.
If G = 0 the reaction is at equilibrium.
If the reaction is at standard state (298K, 25C) then Gibbs free
energy can be calculated with:
G = Gproducts - Greactants
Example 2:
Qualitatively, will the following reactions will the reaction not
proceed, be in equilibrium, or go to completion? Estimate the sign
of G.
a) Na2CO3(s )+ 2 HCl(aq) 2 NaCl(aq) + CO2(g) + H2O(l)
H = -27.7 kJ

b) 3 C(s) + 3 H2(g) C3H6(g)

H = 20.4 kJ

c) H2O(l) + energy H2O(g)

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IB Chemistry Equilibrium
Example 3:
For this process:
indicate what happens to spontaneity at high temperatures and low
temperatures.
At what temperature will the process be at equilibrium (G = 0)
H2O(l) + energy H2O(g)

Follow Up Problems 20.2, 4, 5, 6

Problems 20.5, 10, 12, 16, 18, 33, 35, 48, 50, 52, 54, 83

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