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Reversible reactions and

equilibrium
Section 14.1

Completion reactions and reversible


reactions
Completion Reactions: a chemical
reaction in which all of the reactants
are changed into products.
Reversible Reactions: a chemical
reaction in which the products reform the original reactants.

Reversible Reaction
Example
CaCl2(aq) + Na2SO4(aq) CaSO4(s) +
2NaCl(s)
Because Cl- and Na+ are spectator ions, the net ionic
equation better describes what is happening

Ca2+(aq) + SO42-(aq) CaSO4(s)


At the same time, CaSO4 is breaking down to re-form ions

CaSO4(s) Ca2+(aq) + SO42-(aq)


These forward and reverse reactions take place at the
same time. When the forward and reverse reaction rates
are equal, we have chemical equilibrium

Ca2+(aq) + SO42-(aq)

CaSO4(s)

As HI is formed,
fewer collisions
occur between H2
and I2 molecules and
the rate of forward
reaction drops

When the forward


and reverse rate are
equal, the system is
at chemical
equilibrium

As HI molecules are
made, more
collisions occur and
the rate of reformation of H2 and
I2 increases.

Chemical Equilibria are Dynamic


Static equilibrium: a state in which
nothing changes
Dynamic equilibrium: two opposite
changes occur at the same time in
which there is no net change in the
system
https://www.youtube.com/watch?v=wlD_ImYQAgQ
https://www.youtube.com/watch?v=JsoawKguU6A

Chemical Equilibria are


Dynamic

Higher concentration of
products than reactants.
Products are favored.
Higher concentration of
reactants than products.
Reactants are favored.

Equilibria Involving Complex


Ions
Complex Ion: any metal or ion that
is bonded to more than one atom or
molecule a.k.a coordination
compound
Many complex ions consist of a metal
ion surrounded by a number of
ligands
Ligand: a molecule, such as NH3+ or
H2O, or anions such as cyanide, CH- that
readily bond to metal ions.

Equilibria Involving Complex


Ions
Complex ions form cations (+) or
anions (-)
The charge on a complex ion is the
sum of the charges on the species
from which the complex ion forms
[CoCl4]2Co2+ bonds with four Cl- ligands
Total charge = (+2) +4(-1) = -2

Complex ions often form in systems


that reach equilibrium
https://www.youtube.com/watch?v=cWr3UDo-WeU

The protein haemoglobin has an iron atom that is


co-ordinately bonded to four nitrogen atoms that are
part of larger molecules. Oxygen co-ordinates with

Chapter 14: Section 2

SYSTEMS AT EQUILIBRIUM

Objectives
1. Write Keq expressions for reactions in
equilibrium, and perform
calculations with them.
2. Write Keq expressions for the
solubility of slightly soluble slats,
and perform calculations with them.

The Equilibrium Constant, Keq


There is a mathematical relationship
between product and reactant
concentrations at equilibrium.
This relationship can be expressed
using Keq, Equilibrium Constant
The value of Keq is unitless
We do not include solids or liquids in
the expression

Equilibrium Constant
A general equation can be written for
a reversible reaction
aA + bB cC + dD
The ratio of products to reactants is
expressed as:

Ke
q

Equilibrium Constant
The value of Keq gives us an
indication of whether the reaction
favours the products or reactants
If K > 1 then equilibrium favours
products i.e. there will be more
products than reactants
If K < 1 then equilibrium favours the
reactants i.e. there will be more
reactants than products

Keq big:
numerator
(products) is
smaller than the
denominator
(reactants).
Concentrations of
reactants will be
greater than
those of

Keq small:
numerator
(products) is
larger than the
denominator
(reactants).
Concentrations of
products will be
greater than
those of
reactants. This is
a favorable
reaction.

Calculating Keq from Concentrations of


Reactants and Products
An aqueous solution of carbonic acid reacts to reach
equilibrium as described below:
H2CO3 + H2O HCO3- + H3O+
The solution contains the following solute
concentrations: carbonic acid 3.3 x 10-2 mol/L;
bicarbonate ion 1.19 x 10-4 mol/L; hydronium ion
1.19 x 10-4 mol/L. Determine the Keq.

Calculating Keq from Concentrations of


Reactants and Products
Keq for the equilibrium below is 1.8 x 10-5 at a
temperature of 25C. Calculate [NH4+] when [NH3] =
6.82 x 10-3
NH3 + H2O NH4+ + OH-

Point of Solubility
Solubility
Equilibrium is
dynamic as ions
crystallize at the
same rate as ions
re-enter solution in
a saturated
solution.

The Solubility Product


Constant, Ksp
Solubility Product Constant, Ksp: the
equilibrium constant for a solid that is in
equilibrium with the solids dissolved ions
The dissolution of slightly soluble salts
are given a special name/symbol - K sp
CaF2(s) Ca2+(aq) + 2F-(aq)
Ksp = [Ca2+][F-]2 = 1.6 x 10-10
The reverse is also true when the solid
precipitates back out of solution.

Calculating Ksp from Solubility


Most parts of the oceans are nearly saturated with
CaF2. The mineral fluorite may precipitate when
ocean water evaporates. A saturated solution of
CaF2 at 25C has a solubility of 3.4 x 10-4 M.
Calculate the solubility product constant for CaF2.
CaF2(s) Ca2+(aq) + F-(aq)

Calculating Ionic Concentrations Using Ksp


Copper (I) chloride has a solubility product constant
of 1.2 x 10-6 and dissolves according to the equation
below. Calculate the solubility of this salt in ocean
water in which the [Cl-] = 0.55
CuCl(s) Cu+(aq) + Cl-(aq)

Using Ksp for Hydroxides


We use the concept of Ksp to extract
metals as hydroxides are slightly
soluble.
Mg(OH)2(s) Mg2+(aq) + 2OH-(aq)
[Mg2+][OH-]2 = Ksp = 1.8 x 10-11
Because the Ksp is below 1, the
reactants are favored.

Chapter 14: Section 3

EQUILIBRIUM SYSTEMS
AND STRESS

Objectives
1. State Le Chteliers principle
2. Apply Le Chteliers principle to determine
whether the forward or reverse reaction is
favored when stresses are applied to the system
Temperature
Concentration
Pressure

3. Discuss the common-ion effect in the context of


Le Chteliers principle
4. Discuss the practical uses of Le Chteliers
principle

Le Chteliers principle
The principle that states that a system in
equilibrium will oppose a change in a way that
helps eliminate the change
if a chemical system is at equilibrium and we
add a substance (either a reactant or a
product), the reaction will shift so as to
reestablish equilibrium by consuming part of
the added substance.
Conversely, removal of a substance will result
in the reaction moving in the direction that
forms more of the substance.

Change in Concentration
Add product = increases the
concentration of product
The system responds by decreasing
this new concentration and creating
more reactant.
An increase in the reverse reaction
occurs the equilibrium shifts left
Add reactant = the exact reverse
occurs

Change in Temperature
Recall: exothermic reactions release energy
& endothermic reactions absorb energy

Increase in Temperature: The reaction will


always shift in the direction that will absorb
heat.
Decrease in Temperature: The reaction will
always shift in the direction that will release
heat.

Forward
reaction
absorbs
heat

Heat added

Heat
removed

Moves to side to
consume added
heat

Moves to
side to add
heat
removed

Change in Pressure
In an equilibrium, a pressure increase
favors the reaction that produces fewer gas
molecules.
A pressure decrease favors the reaction
the produces more gas molecules.
Changes in pressure only affect gases in
equilibrium
If there are equal gas molecules on both
sides of the equation, pressure changes will
not affect equilibrium

2NO2(g) N2O4(g)

N2 + 3H2 2NH3

Effect on
Equilibrium
Shift to right
(produce more
products)
Shift to left
(produce more
reactants)

Change

What Occurs

Addition of
Reactant

Added reactant
consumed

Addition of
Product

Added product
consumed

Increase in
Pressure

Pressure
decreased

Shift to fewer gas


molecules

Decrease in
Pressure

Pressure
increased

Shift to more gas


molecules

Increase Temp.

Heat is
consumed

Shift in endo.
direction

Decrease Temp.

Heat is
produces

Shift in exo.
direction

The Common-Ion Effect


The phenomenon in which the addition of an ion
common to two solutes brings about
precipitation or reduces ionization
The reduction of the solubility of salt due to the
addition of a common ion.
If a common ion is added to a saturated solution
of a salt, then the salt will be precipitated.
The equilibrium will shift to consume excess ion
and as a result produce more reactant
(typically, an insoluble salt)

The Common-Ion Effect


CuCl(s) Cu+(aq) + Cl-(aq)
[Cu+][Cl-] = Ksp = 1.2 x 10-6
The addition of sea water, which is rich in Cl-, will
result in an increase of [Cl-].
The equilibrium will shift left to consume this
excess and produce a precipitate of CuCl(s).
The ion Cl- is the common-ion in this case as the
Cl- comes from two sources

The Common-Ion Effect


BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp < 1
Na2SO4(s) 2Na+(aq) + SO42-(aq) .
BaSO4 is not very soluble but there is still
some Ba2+ produced.
This is poisonous to the human body so
Na2SO4 is added so that [Ba2+] is
decreased to a safe level.

Practical Uses of Le Chateliers


Principle
https://www.youtube.com/watch?v=
NWhZ77Qm5y4