CHEMICAL

EQUILIBRIUM

EQUILIBRIUM
A chemical reaction has reached equilibrium when the forward and
reverse reactions occur at equal rates (i.e. the concentration of each
product and reactant remains constant.
The rate of the forward reaction decreases as the reactants are used
up, and the rate of the product increases until the rates become
equal and equilibrium is formed.

EQUILIBRIUM
SYSTEMS AND STRESS
Le Chteliers principle tells how a system at equilibrium
reacts to an applied stress. Stress is defined as a change in
temperature, pressure, or concentration.

CONCENTRATION
When the concentration of a product or reactant is increased the
system compensates for this addition by favoring the other reaction.
Ex. Hydrogen gas is added to the equilibrium system described by
the reaction below. Which reaction is favored? Forward (Right)
H2(g) + I2(g) 2HI(g)
Ex. How does the system at equilibrium described above shift if the
concentration of iodine is decreased. Reverse (Left)

PRESSURE
An increase in pressure, caused by a decrease in volume, favors the
reaction with less moles of gas. Oppositely, a decrease in pressure
causes the system to maximize moles of gas present.
Ex. How should the pressure of the system described in the reaction
shown below be manipulated to increase the concentration of
dinitrogen tetroxide. Increase (minimize moles of gas)
2NO2(g) N2O4(g)

TEMPERATURE
A system at equilibrium responds to temperature based on its
thermodynamics, whether the forward reaction is exothermic or
endothermic
Ex. How would the concentration of the chloride ion in the
endothermic reaction below change if the temperature is increased.
Endothermic = heat reactant
Heat + Co(H2O)62+(aq) + 4Cl-(aq) CoCl42-(aq) + 6H2O(l)
When the heat is increased it favors the forward (left), decreasing [Cl-]

When a system is at equilibrium the mathematical product of the

concentration of the products, raised to an appropriate power, divided
by the mathematical product of the concentrations of the reactants,
raised to an appropriate power, is a constant, the equilibrium constant.
As temperature increases, Keq increases for endothermic reactions and
decreases for exothermic reactions.
Ex. Write the Keq expression for the reactions below
2NO2(g) N2O4(g)
[N2O4] = Keq
[NO2]2
.
Co(H2O)62+(aq) + 4Cl-(aq) CoCl42-(aq) + 6H2O(l)
[CoCl42-]
[Co(H2O)62+][Cl-]4
** Remember that solids and liquids are not included in the equilibrium
expression because their concentrations do not change

THE EQUILIBRIUM
CONSTANT, KEQ
For the following reaction, equilibrium is established at a
certain temperature when the following concentrations are
present: [CO2] = 0.012 M, [H2] = 0.014 M, [CO] = 0.019 M, and
[H2O] = 0.019 M. Calculate the Keq for this reaction.
CO2(g) + H2(g) CO(g) + H2O(g)
[CO][H2O] = Keq
[CO2][H2]
.
(0.019)2/[(0.012)(0.014)] = 2.15

THE EQUILIBRIUM
CONSTANT, KEQ
In the presence of a catalyst, methanol, CH3OH, can be prepared by the
reaction of hydrogen gas and carbon monoxide at high temperatures
according to the following equation:
CO(g) + 2H2(g) CH3OH(g)
What is the concentration of methanol if [H2] = 0.080 M, [CO] = 0.025 M,
and the equilibrium constant for this reaction is 209 at 700 K.
[CH3OH] = Keq
.
[CO][H2]2
[CH3OH] = 209
.
(0.025)(0.080)2

[CH3OH] = 0.418M

THE EQUILIBRIUM
CONSTANT, KEQ
If Keq is approximately equal to 1, there are roughly equal
concentrations of reactants and products at equilibrium.

If Keq is much larger than 1, the concentration at equilibrium of

products will be greater than the concentration of reactants.

If Keq is much smaller than 1, the concentration at equilibrium of

reactants will be greater than the concentration of products.

SOLUBILITY PRODUCT, KSP

In the last chapter we briefly discussed insoluble ionic compounds.
Well I lied a bit they are actually very slightly soluble. We can use
equilibrium constants to describe this solubility. We call this the
solubility product constant, Ksp.
Ex. Write the Ksp expression for the following dissociation reaction:
BaSO4(s) Ba2+(aq) + SO42-(aq)
Ksp = [Ba2+][SO42-]
Now do you see why it is named solubility product constant?

SOLUBILITY PRODUCT, KSP

Ex. Consider the dissociation of fluorite, CaF2, in water.
CaF2(s) Ca2+(aq) + 2F-(aq)
Most parts of the ocean are nearly saturated with fluorite. In a
region where evaporation raises the concentration of
dissolved materials, the fluorite may precipitate. A saturated
solution of fluorite has a concentration of 3.4x10-4 M.
Calculate the Ksp for CaF2.
Ksp = [Ca2+][F-]2
[CaF2] = 3.4x10-4 M [Ca2+] = 3.4x10-4 M & [F-] = 6.8x10-4 M
(3.4x10-4)(6.8x10-4)2= 1.57x10-10

SOLUBILITY PRODUCT, KSP

Ex. What is the concentration of Cu+ ions in a saturated solution

of copper (I) chloride, given that the Ksp of CuCl is 1.72x10-7 at
25C?
Ksp = [Cu+][Cl-]
[Cu+] = [Cl-]
1.72x10-7 = (x M)(x M)
[Cu+] = 4.15x10-4 M
IF the question dealing with copper (II) chloride (CuCl2)
Ksp = [Cu+2][Cl-]2
[CuCl2] = [Cu+2] = [Cl-]
Therefore if [Cu2+] is x then [Cl-] is 2x
1.72x10-7 = (x M)(2x M)2
1.72x10-7 = 4x3
[Cu+2] = 3.50x10-3 M