Equilibrium

Wednesday, 17 October 2018

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.

Reversible Reactions: Irreversible Reactions:

 Weak acids  Combustion
 Hydrated and anhydrous forms  Strong acids
 State changes  Photosynthesis
 Dissolution

Reversible reactions must take place in closed systems, otherwise matter will escape and
equilibrium cannot be reached. In a closed system, energy cannot escape. Equilibrium is
achieved when both directions of a reversible reaction are occurring at the same rate. This is
known as dynamic equilibrium. Dynamic equilibrium have ΔG = 0

Gibbs Free Energy

ΔG is the measure of whether a reaction is spontaneous or not. If ΔG is negative, the
reaction is spontaneous – if ΔG is positive, the reaction is non-spontaneous. If it is 0, the
reaction is at equilibrium.

The formula for finding Gibbs Free Energy is ΔG = ΔH – TΔS

ΔH ΔS ΔG Reaction
Negative (-) Positive (+) (-) Always spontaneous
Energy is released Energy is dispersed Negative

Positive (+) Positive (+) (+) or (–) Spontaneous if ΔS is large and T is high
Energy is Energy is dispersed Positive or
absorbed negative

Negative (-) Negative (-) (+) or (–) Spontaneous if T is low

Energy is released Energy is Positive or
concentrated negative

Positive (+) Negative (-) (+) Never spontaneous

Energy is Energy is Positive
absorbed concentrated

Alternately, if no 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. In this state, all reactants have been used. If
a system is not closed, it can reach a steady state, but not equilibrium.
A 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 two methods of graphing equilibrium are concentration/time graphs and rate-of-
reaction/time graphs.
Concentration is shown with [square brackets] around the chemical in question.

In a homogenous equilibrium all species (reactants and products) involved in the reaction
are in the same state (i.e. H2O + CO ⇌ H2 + CO2), while in a heterogeneous equilibrium the
species are in different states.
When observing an equilibrium system, it will be characterised by constant macroscopic
properties – i.e. physical properties. The concentrations of reactants/products, the colour,
pressure, pH and electrical conductivity will remain constant from our perspective.
On an atomic level, there is a continuous change taking place in both directions, leading to
no net change.

An equilibrium can be approached from either direction.

Le Chatelier's Principle: When a change (stress) is imposed on a system at equilibrium, the
position of the equilibrium shifts to reduce the effect of the change. Therefore, when a
reactant on one side of an equation increases, the products (on the other side) increase, and
the other reactants (same side) decrease.
The changes that can affect the equilibrium include concentration, temperature, and (for
gases) pressure.

A + B ⇌ C + D + heat
If you add more A, the concentration of B will decrease and the concentration of C + D will
increase.
If you add more heat, the concentration of C + D will decrease and the concentration of A +
B will increase.
If you increase the pressure by decreasing volume, the reaction will go to the side with the
least moles of gas.
If you increase the pressure by adding an inert or spectator gas, it has no effect!
Adding a catalyst also has no effect.

H2O + Cr2O72- ⇌ 2H+ + 2CrO42-

When hydrogen ions are neutralised, the mixture becomes bluer. When hydrogen ions are
added, the mixture becomes redder.
These changes in equilibrium position can be described in three ways:
 Shifts to the right/left
 Favours the forward/reverse
 Favours formation of products/reactants

In written responses, use all of these and also quote “The system in equilibrium will shift to
counteract the change” – Le Chatelier

Collision Theory
Reactions occur when particles collide with enough kinetic energy (the minimum being the
activation energy) and the correct orientation to break the bonds and form an activation
complex for new substances to be formed. If the activation energy is low enough in both
directions, the reaction can occur in equilibrium.
Using collision theory, the rate of reaction can be sped up by increasing the energy or
chance of collisions in the correct orientation. This is done by decreasing container volume,
increasing reactant concentration and temperature, or adding a catalyst.
However, these processes also affect equilibriums (except catalysts) due to Le Chatelier’s
Principle. As such, when performing equilibrium reactions a compromise must be made!

The Equilibrium Constant

Written as Keq or Kc, this is a quantitative ratio of the species in the equilibrium reaction. In
reaction aA + bB ⇌ cC + dD where 'a' is the balanced coefficient of chemical A, the
equilibrium constant is given by K = [C]c x [D]d
[A]a x [B]b

This is called the equilibrium expression.

K demonstrates how far to the 'left' or 'right' the equilibrium is:
 If K is very large, that means there is more product than reactant and the equilibrium
is far to the 'right'.
 If K is very small, that means there is more reactant than product and the equilibrium
is far to the 'left'.

Each individual equilibrium reaction has its own value of K which remains the same
regardless of the concentration - as long as the reaction is maintaining equilibrium. If a
stress (e.g. change of one chemical's concentration) causes the equilibrium to shift, the
equilibrium expression temporarily DOES NOT equal K. However, due to Le Chatelier's
Principle it will always return to K as a new equilibrium is established. The exception to this
is temperature, which changes K!!

K for the reverse form of a reaction is the reciprocal (flip the fraction) of the forward
reaction.
It is used for gases and aqueous solutions, but not solids or pure liquids as it is impossible to
work out the concentration of these.
When calculating using K, it is best to use whole number coefficients to avoid square roots
and pain.
While we cannot compare one K value directly with another, the magnitude of the K value
for a given reaction tells us something about the equilibrium position for that reaction.

When K is large: (> 103)

The equilibrium lies well to the right, thus the concentration of products will be very high
compared to the concentration of the reactants.

e.g. Zn2+ + 4CN- ↔ Zn(CN)42- K = 1017 mol-4 L-4 (at 298K)

When K ≈ 1: (0.1 - 10)

The equilibrium lies in the middle, neither favouring reactants nor products, hence both will
be in similar concentrations.

e.g. N2O4(g) ↔ 2NO2(g) K = 0.48 mol L-1 (at 373K)

When K is small: (< 10-3)

The equilibrium position lies well to the left, thus the concentration of reactants will be very
high compared to the concentration of the products.

e.g. 2SO3(g) ↔ 2SO2(g) + O2(g) K = 10-12 mol L-1 (at 500 K)

ATAR Notes Key Point:

To answer Keq questions:

1. Write out a balanced chemical equation.

2. Write out the general expression for the Keq of the system.
3. Write out a table (remember ICE: Initial, Change, Equilibrium/Final)
4. Fill in the table, find all values and solve for the desired quantity.

A rise in temperature will increase the value of K for endothermic reactions and decrease it
for exothermic reactions (the reverse is also true).
Temperature is the only factor that changes the equilibrium constant for a given reaction.
Changing other factors may cause a shift in the equilibrium system, defined by the
reaction quotient Q (or position of the equilibrium if not defined in terms of K) but after
the system has responded, there will be no change the K value.

If we write the energy term as a part of the reaction equation; a product for exothermic
reactions and a reactant for endothermic reactions, it makes it easier to analyse these
systems.

e.g. Exothermic equation: 2SO2(g) + O2(g) ⇌ 2SO3(g) + heat

As the temperature increases, the equilibrium shifts to the left. This increases the
concentration of the reactants (denominator) and thus decreases the value of K.

This is an important reaction in the manufacture of sulphuric acid (from SO3). Highest
yields of SO3 occur at low temperatures, however very low temperatures reduce reaction
 rates and thus overall yields. Once again compromise temperatures (450oC) and catalysts are
used. Excess oxygen is also used to drive the equation towards the right.

e.g. Endothermic equation: N2O4(g) + heat ⇌ 2NO2(g)

As the temperature increases, the equilibrium shifts to the right. This increases the
concentration of the product (numerator) and thus increases the value of K.

ATAR Notes Key Points:

 Only changes in temperature will change the value of Keq.
 Increasing the temperature in an exothermic reaction will decrease Keq.
Increasing the temperature in an endothermic reaction will increase Keq.

When a salt is dissolved in water, the crystal is broken down as water molecules draw off
the ions (the ions are hydrated), forming ion-dipole bonds.

This continues to occur until the solution becomes saturated.

This now also represents an equilibrium as the rate of dissociation of solid from the crystal,
is balanced by the rate of association of the salt (as ions in solution combine to form the solid
crystal.)

e.g. NaCl(s) ⇌ Na+ + Cl- ΔH = +ve

In the next section we will analyse this special type of equilibrium constant called the
solubility product (Ksp).

Solubility
Tuesday, 13 November 2018

Technically, all substances are soluble – some are just more soluble than others.
Ionic compounds are usually soluble in water, as they dissociate/dissolve into their two
parts due to the dipole-dipole attraction to the polar water molecules.
Dissolution is endothermic – this is why hot water is better at dissolving!
A complex of water and an ion is called a ligand.

 Water is a polar molecule that contains a slightly negative end (δ-) and two slightly positive ends (δ+)
 Due to the electrostatic attraction, the δ+ end (H) of the molecule is attracted to Cl- ions, while the δ-
end (O) is attracted to the Na+ ions.
 The electrostatic attraction that exists between these particles is stronger than the ionic bond that exists
between Na+ and Cl-, and as a result, the ions attach to, and are surrounded by, the water molecules and
are broken away from the structure.

We can refer to the Na+ and Cl- ions in the aqueous solution as ‘hydrated’ because they move
freely in the aqueous solution.
Not all ionic substances are soluble in water, because in these compounds, the electrostatic
attraction between the ions is stronger than the electrostatic attraction to water molecules

One example of this is acids and bases. Acids dissociate into Hydrogen ions (single protons)
and negative ions. The stronger the acid, the more that it dissociates and the more free
protons it produces per mole of acid. An example of a strong acid is HCl.
For acids, the strength of the acid is determined by how much they dissociate vs how many
intact molecules are left
Strength is different from concentration, as concentration is about how many moles of acid
there are per litre of water. Strong acids can be dilute or concentrate, as can weak acids
(e.g. HI).

A special form of the equilibrium constant (calculated the same way) is the acid ionisation
constant (Ka). If Ka is large, the acid is strong; if Ka is tiny, the acid is weak.
Another special form is the solubility constant (Ksp), also calculated the same way - however,
the equilibrium expression for this never has a denominator, as the reactant (chemical to be
dissolved) is a solid.
Ksp can be considered a mark of when a solution is saturated – if it is bigger than the Q value
from a non-equilibrium solution, the solution is not saturated, and if it is smaller the
solution is saturated.
If Ksp is large, the substance is very soluble; if it is very small, the solution is insoluble; and in
between, a solution is partially soluble.

A(s) + heat ⇌ C(aq) + D(aq)

At equilibrium, dissolution and precipitation occur at the same rate.
Most dissolution reactions are endothermic - the more heat you apply, the more
reactant/solid can dissolve, pushing equilibrium RIGHT.
Adding more of the solid will increase the concentration of ions in the solvent and push
equilibrium LEFT (more precipitation).
Adding any other solids with those ions will also increase the ion concentration/push
equilibrium. This is called the common ion effect.
Once the solution reaches saturation, adding more ion-containing solid will not affect the
equilibrium.
NAGSAG, LMS and CaStroBar
 Nitrates (NO3-) are always soluble
 Acetates C2H3O2-) are always soluble Solubility is how readily something will dissolve
Ksp is a measure of solubility/saturations
 Group I ions are always soluble Molar Solubility is how many moles will dissolve
 Sulfates (SO42-) are always* soluble
 Ammonium (NH4+) is always* soluble
 Group VII (7) ions are always* soluble
*Exceptions:
 LMS 7: Lead (Pb2+), Mercury (Hg2+), Silver (Ag+) – for Group 7
 CaStroBar: Calcium (Ca2+), Strontium (Sr2+), Barium (Ba2+)

Acids and Bases

Thursday, 6 December 2018
Need-to-Know Acids
Ethanoic/acetic acid (in vinegar): CH3COOH

Definitions
In ancient times, acids and bases were defined by their physical properties such as taste and
effects.
Scientists then began to investigate more closely. Lavoisier thought that all acids contained
oxygen (a substance he discovered and named after the Latin word for sour), but Davy
realised all acids actually contained hydrogen after he discovered HCl.
Arrhenius defined an acid as a substance which contained H and produced H +(aq) in solution,
and a base as a substance which contained OH and produced OH-(aq). This explained
neutralisation, as H+ + OH-  H2O.
However, this definition was slightly flawed. For example, ammonia (NH3) acts exactly like a
base (neutralises acids, shows up on indicators) but does not contain hydroxide (OH). On the
other hand, in solution with water, NH3 + H2O  NH4+ + OH-, still producing a hydroxide ion!
This led to Bronsted and Lowry coming up with the new definition: acids are substances
which donate protons, and bases are substances which accept protons. The stronger the
acid, the more that it dissociates and the more free protons (H+) it donates per mole of acid.
The stronger a base, the more it dissociates/ionises to produce OH- and thus the more
protons it can accept.
Generally, all acids except HCl, H2SO4, H3PO4, and HNO3 are considered weak - these acids
are so strong they have massive Ksp values.
With bases, Group 1 bases are strong and Group 2 bases are weak.

Water
All acids are solutions in water - if hydrogen chloride gas (HCl) is cooled to become a liquid,
this liquid is neutral. It is NOT hydrochloric acid! Only when it is dissolved in water can it
dissociate and produce free protons - the cause of acidity.
Many bases are also solutions - these are called alkaline bases.
When hydrochloric acid dissolves in water, it gives a proton and water accepts it, forming a
hydronium ion (H3O+). The free protons bond to the water molecules through co-ordinate
covalent bonds (where one particle has no electrons to share like the hanger-on in a group
project). In this case, water is acting as a base. However, when ammonia dissolves in water,
it accepts a proton that water gives, forming ammonium (NH4+). In this case, water is acting
as an acid!
This is similar to the way transition metals act in redox reactions, where they are both
oxidants and reductants (can either gain or lose electrons) in different situations.

Conjugates
When an acid-water reaction occurs, the acid gives up its proton and the water accepts it.
This turns the acid into a negative (proton-needing) ion, and turns the water into (proton-
donating) hydronium. This means that the acid is now a (conjugate) base and the base/
water is now a (conjugate) acid!
When a water-base reaction occurs, the same process occurs in reverse, also creating a
conjugate acid/water and a conjugate base.
In order to figure out conjugate acids, remove a hydrogen from the chemical formula and
minus one from the charge.
Nomenclatures
Hydrohalic acids: 1 hydrogen ion + 1 Group 7 halogen ion (these are called halides) --> prefix
'hydro-' and suffix '-ic'
Oxyacids: hydrogen ion(s) +1 oxygen-containing polyatomic ion  suffix '-ate' becomes ‘-ic’/
suffix '-ite' becomes '-ous'
Bases: cation(s) + hydroxide

pH
Indicators are substances that change colour when pH changes. It is a weak organic acid in
equilibrium  shift the equilibrium towards acid, it changes to the acid colour etc.
Common indicators include methyl orange, bromothymol blue, and phenolphthalein.
Universal indicator is just lots of types of indicator mixed together!

pH is a logarithmic expression of the hydrogen ion concentration present in solution. This

means that [H+] = 10-pH
To find the pH of an acid, find the concentration of H+ (in molL-1) and use -log[H+].
To find the pH of a base, use the concentration of OH- (in molL-1) and use -log[OH-]. Then use
pH = 14 - pOH.

Acidity of Substances
Salts are ionic compounds composed of cations and anions. In order to figure out whether
the salt will be basic, neutral, or acidic when dissolved in water, look at what acid contains
the cation and what base contains the anion. If both are weak/both are strong, it will be
neutral. If only the acid is strong, it is an acidic salt; if only the base is strong, it is a basic salt!
The periodic table can be used to find acidic/basic oxides – metals form basic oxides, non-
metals form acidic oxides, and semi-metals are amphiprotic (except it's called amphiterric as
there are no protons).

Acids ionise in water releasing H+ ions (usually in the form of H3O+) and an appropriate
anion. The most common types of strong acids are:

HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq)

HNO3(aq) + H2O(l) → H3O+(aq) + NO3-(aq)

H2SO4(aq) + 2H2O(l) → 2H3O+(aq) + SO42-(aq)

The equilibria for the above ionisations lies well to the right, to the extent that we can
consider these acids to be completely ionised. Hence the single arrow is used. All of these
are strong acids. However not all acids are strong.

CH3COOH(aq) + H2O(l) ⇌ H3O+(aq) + CH3COO-(aq)

H2CO3(aq) + 2H2O(l) ⇌ 2H3O+(aq) + CO32-(aq)

The two acids above are weak acids. They only partially ionise in water and hence an
equilibrium is established. The acids are weak because of the low [H+] in the solutions. As
for any other equilibrium we can calculate the equilibrium constant, however in this case it
is given the special symbol Ka and is referred to as the acid ionisation constant.

The expression for Ka for the ionisation below:

HA ⇌ H+ + A-

is: Ka = [H+] [A-]

[HA]

Since [H2O] is redundant, it is not used in the calculation of Ka.

The smaller the Ka value, the lower the [H+] in the solution, the weaker the acid.