Chemistry Notes: Term 1 Year 12

Some chemical reactions can occur in only

one direction as the reactants can convert to
the products, but the products cannot
Irreversible reactions convert back to the reactants. The reaction
proceeds in only one direction. E.g.
combustion, because the products are stable
and won’t react with one another.
A reversible reaction is a reaction in which
the conversion of reactants to products and
the conversion of products to reactants
Reversible reactions occur simultaneously. In a reversible
reaction the reactants and products are never
fully consumed. The reaction can proceed
in both directions.
Equilibrium Reversible reactions lead to equilibrium,
Static equilibrium occurs when there is no
exchange between reactants and products.
E.g. example of static equilibrium is
diamond turning into graphite. If no
Static equilibrium reaction is occurring in either direction it is
static equilibrium. A static equilibrium
occurs at the completion of an irreversible
reaction, where all particles are at rest and
the chemical reaction cannot continue.
Chemical equilibrium is a state in which the
rate of the forward reaction equals the rate
of the backward reaction. In other words,
there is no net change in concentrations of
Dynamic equilibrium
reactants and products. No macroscopic
change should be noticeable but
microscopic changes should be happening
constantly.
An isolated system cannot transfer energy
Isolated system
or matter with its surroundings.
A closed system can transfer energy with its
Closed system
surroundings but not matter.
An open system is where energy and matter
Open system
can be exchanged with its surroundings.
Module 5

Features of a equilibrium system

• The reaction must be reversible, both forward and reverse happen simultaneously
under the same conditions.
• The reactants and products are confined within a closed system.
• Neither the forward or reverse can run to completion.
• The chemical equilibrium is dynamic in nature.
Theoretically, all reactions can happen in both directions and are reversible (⇌). However, in
reality some reactions can only proceed in one direction as the other direction requires so
much energy as to be impractical. Thus, these are referred to as irreversible reactions.
*All equilibrium reactions are reversible however not all reversible reaction reach an
equilibrium.
Irreversible Reactions Reversible reactions
• Weak acids
• Combustion
• Hydrated and anhydrous forms
• Strong acids
• State changes
• Photosynthesis
• Dissolution and precipitation
• Reversible reactions must take place in closed systems, otherwise matter will escape,
and equilibrium cannot be reached (reactions happening in aqueous solution are
considered closed systems). Equilibrium is achieved when both directions of a
reversible reaction are occurring at the same rate. This is known as dynamic
equilibrium. Dynamic equilibrium happens when ΔG = 0.

Dissolution and Precipitation as Reversible Reactions

Solubility of a substance: the concentration of a particular solvent in its saturated solution at a
specific temperature.
Saturated solution: is a solution where no more solute can be added (maximum
concentration). It is in a state of dynamic equilibrium, as the solute is both dissolving and
crystallising at the same rate.
The concentration of a particular solvent in
Solubility of a substance its saturated solution at a specific
temperature.
It is when no more solute can be added
(dissolved) to a solution (maximum
Saturated solution concentration). It is in a state of dynamic
equilibrium, as the solute is both dissolving
and crystallising at the same rate.
In dissolution, the solute particles separate
Dissolution from each other and are surrounded by
solvent molecules.
Precipitation is the process of a compound
coming out (precipitation out) of solution.
Precipitation
In precipitation, the solute particles find
each other and form a solid together.

• Precipitation occurs if the concentration of relevant ions is greatly above what they
should be in a saturated solution, precipitation continues until the concentration of
ions fall back to the saturated solution levels at this point dynamic equilibrium is
reached as an equal number of ion pairs are breaking away from the solid to go back
into solution.
 • Dissolution of a solid and precipitation of a solid from solution are basically the same
reaction just going in opposite directions.
Enthalpy and entropy
∆H: refers to the enthalpy change of the reaction. Enthalpy is a measure of heat in the system.
Enthalpy change in a reaction, ΔH describes the difference in stored chemical potential
energy, or the overall input/output in the reaction.
- ∆H reaction is exothermic, as system is
+ q as surroundings are gaining heat energy
releasing/losing heat energy
+ ∆H reaction is endothermic, as system is - q as surrounding are losing heat energy
absorbing/gaining heat energy
*system refers to the reactants, surroundings refer to the area around the system
Is a reaction that occurs naturally under
Spontaneous
certain conditions, exothermic reactions.
Is a reaction that will not take place unless it
is “driven” by the continual input of energy
Non-spontaneous
from an external source, endothermic
reactions.
Refers to the distribution of available
energy among the particles. The more ways
Entropy (S) the energy can be distributed the higher the
entropy. It describes the degree of disorder
or randomness of a system.
increases as the temperature of a substance
is raised, which corresponds to the greater
Entropy (ΔS) spread of kinetic energies. When a
substance melts or vaporizes, it experiences
a significant increase in entropy.
Entropy change formula ΔSo = ΣSo products – ΣSo reactants
It is the total stored internal chemical
energy of a system under constant pressure,
Enthalpy (H)
in a spontaneous chemical reaction, it tends
to decrease naturally (ΔH<0)
ΔHoreaction=∑ΔHfo(products) −

Equation
First law of thermodynamics
Second law of thermodynamics
Third law of thermodynamics
∑ΔHfo(reactants)
The sum of the standard enthalpies of
formation of the products minus the sum of
the standard enthalpies of formation of the
reactants.
The first law of thermodynamics says that
energy cannot be created or destroyed in an
isolated system.
The second law of thermodynamics says
that chemical reactions that result in an
overall increase in the entropy of the
universe are spontaneous.
The third law of thermodynamics says that
the entropy of a perfect crystal at absolute
zero is exactly equal to zero. (The standard
molar entropy is the entropy content of one
mole of substance under a standard state. It
has a unit of J/mol/K).
 isolated system.
The second law of thermodynamics says
that chemical reactions that result in an
Second law of thermodynamics
overall increase in the entropy of the
universe are spontaneous.
The third law of thermodynamics says that
the entropy of a perfect crystal at absolute
zero is exactly equal to zero. (The standard
Third law of thermodynamics
molar entropy is the entropy content of one
mole of substance under a standard state. It
has a unit of J/mol/K).
ΔSuniv > 0 Spontaneous
ΔSuniv < 0 Non-spontaneous (spontaneous in the
opposite direction)
ΔSuniv = 0 Reversible (system is a equilibrium)

• Exothermic reactions are more likely to be spontaneous, as this leads to a reduction in

enthalpy and greater stability of the reaction products.
• An increase in entropy makes reactions more likely to be spontaneous, as greater
disorder leads to more uniform distribution of energy within the system.

• Exothermic reactions that involve increasing disorder will always be spontaneous,

with
ΔG < 0
• Similarly, endothermic reactions of increasing order will always be nonspontaneous,
with
ΔG > 0.
• The spontaneity of other reactions depends on the temperature of the system.

Collision theory, rate of reaction and chemical equilibrium

Temperature
• Temperature represents the average KE of reactant particles.
• An increase in temperature increases:
• the rate of collisions
• the strength of collisions
• the portion of reactant particles with KE > Ea

Concentration of reactants
• An increase in the concentration of a reactant means there will be more of the
chemical present.
• More reactant particles moving together allow for more collisions to happen and so
the reaction rate is increased.
Surface area
• Increasing the surface area of a reactant exposes more of its particles to the other
reactants.
• Because the contact area is larger the concentration increases, and the rate of reaction
is faster.
Pressure
• For gases increasing the pressure e.g. by making the volume smaller increases the rate
of reaction as the reactant particles are closer together causing more collisions.
Concentration and reaction rate are related
• The relationship between the two can be determined experimentally by first keeping
the concentration of other reactants and the temperature constant.
2H2(g) + 2NO(g) N2(g) + 2H2O(g)
• Four moles or reactant gas produce three moles of product gas; thus, the pressure of
the system diminishes as the reaction rate proceeds. The rate of reaction can therefore
be determined by measuring the change of pressure in the vessel with time.
Rate Law
• R = k[A]n[B]m
• A and B represent the molar concentrations of reactants, reaction rate is R, k is the
specific rate constant, n and m are the respective powers to which concentrations are
raised. The rate law is applicable for a specific reaction at a given set of conditions
and must be determined by experimental data.
• Rf = kf[reactants] and Rr = kr[products] where kf and kr are constants determined by

system temperature.
Spontaneous
Non-spontaneous
Gibbs free energy
Formula
Calculating ∆G and ΔGo
Reaching Equilibrium
ΔS > 0 (increase in entropy)
ΔS < 0 (decrease in entropy)
Is a reaction that occurs naturally under
certain conditions, exothermic reactions.
Is a reaction that will not take place unless it
is “driven” by the continual input of energy
from an external source, endothermic
reactions.
The combination of enthalpy, entropy, and
temperature of system. The Gibbs free
energy provides an effective way of
focusing on a reaction system at constant
temperature and pressure to determine its
spontaneity. For a reaction to be
spontaneous the Gibbs free energy must
have a negative value (ΔG < 0).
• ∆G = ∆H - T∆S
• ΔGor = ΣΔGof (products) – ΣΔGof
(reactants)
ΔH > 0 (endothermic) ΔH < 0 (exothermic)
ΔG < 0 at high temperature ΔG < 0 at any temperature
ΔG > 0 at low temperature Process is spontaneous at
Process is spontaneous at any temperature
high temperature (not spontaneously
(spontaneously reversible) reversible)
ΔG > 0 at any temperature ΔG < 0 at low temperature
Process is non-spontaneous ΔG > 0 at high temperature
at any temperature Process is spontaneous at
(not spontaneously low temperature
reversible) (spontaneously reversible)

ΔS > 0 (increase in entropy)
ΔS < 0 (decrease in entropy)
ΔG < 0 at high temperature
ΔG > 0 at low temperature
Process is spontaneous at
high temperature
(spontaneously reversible)
ΔG > 0 at any temperature
Process is non-spontaneous
at any temperature
(not spontaneously
reversible)
ΔG < 0 at any temperature
Process is spontaneous at
any temperature
(not spontaneously
reversible)
ΔG < 0 at low temperature
ΔG > 0 at high temperature
Process is spontaneous at
low temperature
(spontaneously reversible)

• When ΔG (ΔG < 0) is negative reaction is spontaneous.

• When ΔG = 0 the reaction is at equilibrium.
• When ΔS and ΔH have same signs the reaction is spontaneously reversible.
• When ΔS and ΔH have opposite signs the reaction is not spontaneously reversible.
• A system can only reach equilibrium if both the forward and reverse reactions occur
simultaneously under the same conditions.
Photosynthesis as a non-equilibrium reaction (6CO2(g) + 6H2O(l) C6H12O6(aq) + 6O2(g))
• ΔH > 0, solar energy is needed for the forward reaction to proceed (endothermic).
• ΔS < 0 (ΔS decreases) as 6 liquid H2O moles change into 1 glucose mole.
• When minimum enthalpy and maximum entropy both favour the products ΔG < 0.

Le Chatelier’s principle
• The position of equilibrium refers to the relative amounts of products and reactants
present at equilibrium. If a system at equilibrium is subject to change, the position of
equilibrium will shift in order to minimise the effect of the change.
Position of equilibrium shifts in the
Heating reaction
endothermic direction.
Position of equilibrium shifts in the
Cooling reaction
exothermic direction.
Position of equilibrium will shift in the
Increase in pressure for reactions with gas
direction that gives a decrease in the
moles
number of gas moles.
Position of equilibrium will shift in the
Decrease in pressure for reactions with gas
direction that gives an increase in the
moles
number of gas moles.
Position of equilibrium will shift to the
Concentration of one of the species is
opposite side of to the increase to reduce
increased
concentration of this species.
Position of equilibrium will shift to the
Concentration of one of the species is
same side of the decrease to reduce
decreased
concentration of the other species.

Equilibrium position: Activation energy & enthalpy change

• A reaction with high Ea has a low reaction rate, particularly when temperature is low.
Adding a catalyst increases the rate of reaction for both forward and reverse reactions
at the same degree when a system has reached its equilibrium: therefore, it has no
effect on the system’s equilibrium position. Since at the start of a reaction, there are
more reactants then products, adding a catalyst has more effect on the forward
reaction than reverse reaction. This will reduce the overall time for the system to
 reach equilibrium.
Effect on position of Effect on value of Keq
Condition
equilibrium
If a reaction involves a
change in the number of gas
molecules, an increase in
pressure results in the
Pressure No change
position of equilibrium
shifting in the direction that
gives a decrease in the
number of gas molecules.
The position of equilibrium
will shift to use up any
substance that has been
Concentration No change
added of replace any
substance that has been
removed.
No effect because both
Catalyst No effect forward and reverse reaction
rates increase equally.
If the temperature increases, For an endothermic reaction
the position of equilibrium the Keq increases as the
shifts in the endothermic
temperature increases. For
Temperature direction. If the temperature
an exothermic reaction the
is decreased the position of
Keq decreases as the
equilibrium shifts in the
exothermic direction. temperature decreases.
* Keq is determined by experiment and is only dependent on temperature.
• If Keq = Q the system has reached equilibrium.
• If Keq > Q the system moves to the right.
• If Keq < Q the system moves to the left.
Summary
• Some chemical reactions are reversible and therefore come to completion.
• If a dynamic equilibrium is set up, the forward rate equals the reverse reaction. No
macroscopic changes can be observed, however on a microscopic scale there is
continuous movement.
• Provided we start with appropriate amounts of materials, the final equilibrium state or
position is the same.
• Le Chatelier’s principle summarises the way in which an equilibrium adjusts when
experimental conditions are changed e.g. pressure, temperature, concentration.
• Reversible reactions can be driven to virtual completion using this principle.
• When a catalyst is added to a reversible system it lowers the activation energy for
both the forward and reverse reactions. The rates of both the forward and reverse
reactions are increased equally, so the catalyst doesn’t affect the relative proportions
of reactants and products or its equilibrium position. However, a catalyst reduces the
time for a system to reach equilibrium.
 Evaluating the equilibrium constant
• Write out a balanced chemical equation.
• Write out the general expression for the Keq of the system.
• Write out a table (remember RICE[E]: Reaction, Initial, Change, Equilibrium, Final
concentration).
• Fill in the table, find all values and solve for the desired quantity.
• Put into formular if necessary.
Formular: Keq = [products] / [reactants]
e.g. N2(g) +O2(g) ⇌ 2NO(g)
2
keq = [NO] / [N2][O2] (concentration of NO/concentration of N×O)
• Water is omitted from equilibrium expressions only if it is a solvent in that reaction
because it is a pure liquid i.e. not actively taking part in the reaction. We can't increase
the concentration of a pure liquid or pure solid and hence they are omitted from
the expression.

Effects of a disturbance to a system’s Q and Keq

• If the equilibrium shifts towards the product side (right) Q < Keq
• If the equilibrium shifts towards the reactant side (left) Q > Keq
e.g. an exothermic reaction at low temperature will shift the equilibrium right causing an
increase in products and favouring the forwards reaction.
e.g. an endothermic reaction at low temperature will shift the equilibrium left causing an
increase in reactants and favouring the reverse reaction.

The ionisation constant is a measure of acid and base strength in solution

• The lower the concentration of hydronium (H₃O⁺) the higher the pH and the weaker
the acid.
• The higher the concentration of hydronium the lower the pH and the stronger the acid.
• Ka is the acid ionisation constant, like Keq it changed depending on temperature.
• Ka = products/reactants (concentration)
The equilibrium product constant Ksp describes how soluble a substance is
• A saturated solution contains the maximum amount of solute possible at any given
temperature with an undissolved excess of the substance.
• A saturated solution is not necessarily a concentrated solution. The concentration can
still be low if the solubility of the solute is low.
• A precipitate forms when at least one of the products or reactants is insoluble.
• Precipitation occurs to bring the Q value back to the Keq value.
• Ksp is the molar concentration of ions in solution (cannot be used when all
compounds are soluble).
2+ -
e.g. CaF2(s) ⇌ Ca (aq) + 2F (aq)

Ksp = [Ca2+][ F-]2

• If the ion product of [Ca2+][ F-]2 is less than the value of K sp at a particular
temperature the solution is unsaturated.
 2+ - 2
• If the ion product of [Ca ][ F ] is greater than the value of Ksp at a particular
temperature the solution is saturated and CaF2 precipitates.

• [Ca2+][ F-]2 < Ksp no ppt

• [Ca2+][ F-]2 > Ksp ppt

• The precipitate reduces the concentration of Ca2+ and F- ions until equilibrium is
reached.
3+ - -33
e.g. Al(OH)3(s) ⇌ Al (aq) + 3OH (Ksp = 1.9 × 10 )
3+ -3 -33
Ksp = [Al ][ OH ] = 1.9 × 10
-33 3
1.9 × 10 = (x)(3x)
x = ∜1.9 × 10-33/27
(Useful formular C1V1=C2V2)
Common ion effect
• By adding a common ion from a soluble salt, we can cause partially soluble salts in
solution to precipitate.
2+ -
e.g. CaF2(s) ⇌ Ca (aq) + 2F (aq) if we add soluble NaF to the solution, increasing the
-
concentration of F (aq) in the solution, the ion product can exceed Ksp causing CaF2 to
precipitate.

Solubility Laws (NAG SAG)

Always soluble Exceptions
-
Nitrates (NO3 )
• PMS
Acetates (C2H3O2-)
2+
• P Pb (lead)
Group 1 (Li+, Na+, etc)
• M Mercury (Hg2+)
+
2- • S Silver (Ag )
Sulfates (SO4 )
• Castro Bear
Ammonium (NH4+) •
+ 2+
Ca , Sr , Ba
2+
- - -
Group 17 (F , Cl , Br )
*green means both exceptions are insoluble in sulfates

Tests for anions