Equilibrium

Rates of a chemical reaction

Rate of reaction: How fast a reaction occurs. A low reaction rate means that products are produced slowly.
Rate: Measure to how quickly one quantity changes in comparison to another quantity.

Observing rate of reaction (Changes in macroscopic properties)

• Observe changes in colour to indicate changes in the concentration of reactants or products , Observe
formation of products, Observe consumption of reactants
• In a typical reaction, the reaction occurs relatively quickly and then the rate decreases as the reaction
proceeds

Can be measured by: How quickly a reactant disappears or How quickly a product is formed

Formula Rate of reaction = amount of reactant used ÷ time or Reaction = amount of product formed ÷ time

Factors affecting the rate of a chemical reaction

1. Nature of the reactants: Reactions of ions in solution tend to be rapid in comparison with reactions in which
strong bonds must be broken. In general, the higher ae for a system, the slower the reaction rate

2. Concentration of reactants: Increasing the concentration of one or more of the reactant species can result
in an increase in reaction rate since the greater the number of particles present, the greater the chance of
successful collisions occurring. The most common ways to increase concentration is to increase in the
amount of a substance present, or for gaseous species, decrease the volume of the system.

3. State of subdivision of the reactants: In heterogeneous systems increasing the exposed surface area of a
reactant will increase the rate of reaction as more particles are exposed to collisions. Therefore, a powdered
reactant will react more quickly than the same amount of reactant present as a solid lump.

4. Temperature: Temperature is a measure of the average kinetic energy of the particles of a substance. The
higher the temperature, the more particles that are likely to have energy equal to or greater than the
activation energy and so the reaction rate will be faster.

5. Catalyst: Substance that increases the rate of a chemical reaction without being consumed in the reaction.
Act by forming a different activated complex which has lower energy than the reaction without a catalyst.
Provides an alternative reaction pathway with a lower activation energy and so reaction proceeds more
quickly than it would if the catalyst was not present. Equally effects both sides of reaction.

Collision theory
States for a reaction between two (or more) chemical species to occur, these must be satisfied
1. Reactant particles collide with each other
2. Collisions between reactant particles must have sufficient energy to break the bonds in the reactant particles
3. Collisions between reactant particles must have suitable orientation for bond breaking and new bond formation
to occur
When particles (moving particles have kinetic energy) collide with appropriate energy and orientation, some of this
kinetic energy is converted to potential energy as bonds begin to break and total potential energy of the system
increases (as new bonds begin to form as products, potential energy of the system decreases)

Chemical reactions
• Irreversible (once chemical reaction has taken place it cannot be undone) or reversible (some chemical
reactions and physical changes) e.g: evaporation and condensation of water in a sealed bottle, dissolving
and crystallisation taking place in a saturated solution, reaction between ethanoic acid and water in a sealed
bottle of vinegar
 • May not go to completion (often in a chemical reaction system a mixture of reactants and products remains
after a prolonged period of time, considered reversible if does not go to completion assuming that products
are able to collide to reform the reactant species)
• At constant temperature liquid water is said to be in equilibrium with the water vapour as the rate of
evaporation is equal to the rate of condensation (physical equilibrium)

Definitions
Transition state (activated complex): Highest potential energy state reached in the system. Formed during bond-
breaking, bond-formation process. Unstable, never present as product of reaction.
Activation energy: Difference in potential energy between reactant particles and transition state. Minimum energy
required to begin the react to break the initial reactant bonds. For reaction to occur, particles must collide with energy
equal to or greater than activation energy.
Heat of reaction (△H): Difference between energy of reactant particles and potential energy of the product particle.
Exothermic reaction: When total energy of the reactant(s) is more than the total energy of the products, energy is
released to the surroundings. Energy released is greater than energy put in e.g: combustion, dilute acids on active
metals, neutralisation.
Endothermic reaction: When total energy of the reactant(s) is less than the total energy of the products, energy is
absorbed from surroundings. Energy put in is greater than energy released e.g: photosynthesis, electrolysis.

Open system: Matter can be exchanged with the surroundings. e.g: a plant undergoes photosynthesis absorbing carbon
dioxide from and releases oxygen to atmosphere. Will not reach a state of equilibrium.

Closed system: No matter (only energy) is exchanged with surroundings. Closed chemical system said to have reached a
state of chemical equilibrium when the rate of the forward reaction is equal to the rate of the opposite reaction.

Advantages and disadvantages of open and close systems

System Advantages Disadvantages
Open • Easy to observe • You lose some of the reagent
• Easy to add more reagent • Contamination
• Cheap • You can't control the conditions such as
• Can use processes to concentrate solutions temperature and pressure
Closed • There's no loss of reagent • Expensive
• Minimal contamination • Difficult to observe
• It's easy to control the conditions • Requires a cooling system to prevent over
• Can be monitored by gauges pressurisation
Closed system: pressurised autoclave

In a system at chemical equilibrium:

1. Amounts of the reactant and product species remain constant and hence observable macroscopic properties
(temperature, pressure, colour) of the system are also constant.
2. Reaction is continuing but there is no net reaction since the rate of the forward reaction is equal to the rate
of the reverse reaction.
• Static equilibrium when particles are static e.g: unsaturated solution as no change in microscopic particles
 • In a chemical reaction the forward and reverse reaction occurring at the same time when the rate of the forward
reaction is equal to the rate of the reverse reaction the reaction has reached equilibrium.
• For a system to be at equilibrium a low activation energy for the reverse and forward reaction is desirable;
• whichever side has the higher activation energy would be less favoured
• However the concentration of the reactant and product don't have to be the same but they are no longer
changing .
• Chemical equilibrium is a dynamic changing process. The forward and the reverse reaction can occur even after
equilibrium has been reached, however, because the reaction rates are the same there is no change in the
concentration of reactants or products or any other macroscopic properties unless something in the chemical
system is altered
• Pressure at dynamic equilibrium also becomes constant as the molecules colliding become concerned due to the
constant forward and reverse reaction
• The greater the vapour pressure the more equilibrium favours the vapour phase
o The tendency to stay in a vapour phase also depends on the nature of the reactants and temperature
(intermolecular forces

Requirements for a system to be at equilibrium

1. Constantly occurring in both directions
2. Rate is same for forward and reverse
3. The concentration of the reactant and product don't have to be the same but they are no longer changing
4. The system must be closed

Equilibrium constant
Equilibrium constant: Constant value of the relationship between equilibrium concentrations of the reactant(s) and
products at a particular temperature
If the forward is favoured it means there is a greater conc of products
If the reverse is favoured it means there is a greater conc of reactants
• Large Kc means products are favoured
• Small Kc means reactants are favoured
• Lc close to one means significant conc for both are present.

**** Only can add liquid and aqueous into the equation.
**** Must balance equation before writing
**** kC can also tell you about the dissociation of an acid. This can tell you
if the acid is weak or strong.

By knowing which side of the chemical reaction is favoured he can also determine whether something is a strong acid
due to the dissociation.

Writing equilibrium constant expressions

• Concentrations of products (forward reaction) are always written on top line of equation and the
concentrations of the reactants are written on the bottom line
• Substances that are solid or pure liquid are omitted from the expression (cannot talk about “concentration”
of a solid or pure liquid, thus assumed concentration is equal 1)
• Power to which a particular concentration is raised is equal to the coefficient for that species in the balanced
equation for the reaction
 1. Equilibrium constant is measured at a given temperature where the equilibrium constant for a particular
system will have different values at different temperatures
2. Value of equilibrium constant indicates the relative proportions of products and reactants (if value of K is
large, then there are only small amounts of reactant species present in system, if value of K is small, then
there are only small amounts of product species present in system)
3. Value of equilibrium constant has no relationship to reaction rate

Position of equilibrium (any equilibrium system) may be changed by:

Position of equilibrium: Relative amounts of reactants and products at equilibrium. Depends upon reaction conditions.
1. Adding or removing a reactant or product
2. Changing the pressure by changing the volume (for equilibria involving gases)
3. Diluting (for equilibria in solution)
4. Changing temperature

• Different reactions proceed to different extents (relative amounts of reactants and products at equilibrium
differ from one reaction to another)
• Careful control of reaction conditions allows chemists to maximise equilibrium yield of a desired
• product by moving the position of equilibrium to the right (increasing amount of products formed)

Le Chatelier’s Principle
Le Chatelier’s Principle: States that if a system at equilibrium is subjected to a change in conditions, the system will
adjust to re-establish equilibrium in such a way as to partially counteract the imposed change.

Change in temperature: If temperature is increased, net reaction will proceed

in direction that absorbs heat (endothermic direction). If temperature is
decreased, net reaction occurs in the direction that releases heat (exothermic).
• Collision theory explanation: Increasing temperature of a chemical
system results in particles gaining kinetic energy and an increase in
the number of particles having energy equal to or greater than the
activation energy for the reaction (∴ increase temperature results
in more successful collisions per unit time resulting in a faster
reaction rate)

Endothermic reactions are much more sensitive to temperature change than exothermic. This is due to the higher
activation energy than exothermic reactions. Raising the temperature of an equilibrium system increases the rate of the
endothermic reaction more than the exothermic.

Change in concentration (gaseous or aqueous, not solid or liquid): Net reaction will proceed in the direction that
consumes the species whose concentration has been increased. For gaseous or aqueous equilibria (not solid or liquid).
• Collision theory explanation: Increasing the concentration of a reactant will increase the total number of
collisions per unit time and therefore the number of successful collisions per unit time (more successful
collisions per unit time results in an increased rate of reaction)

Consider reversible reaction between hydrogen gas and nitrogen gas to from ammonia i.e: 3H₂(g) + N₂(g) ⇌ 2NH₃(g)
 • -If more nitrogen is added (at constant temperature) to an equilibrium mixture of the three gases, net
reaction will occur in the direction that uses up nitrogen (Le Chatelier’s Principle) therefore forward reaction
is favoured and more ammonia is formed
• -As the concentration of ammonia increases, rate of the
• reverse reaction increases and the rates of both reactions become equal again (new equilibrium is
established)
• -New equilibrium mixture will have more nitrogen, less
• hydrogen and more ammonia than the original equilibrium mixture, value of the equilibrium constant will
remain unchanged since the temperature of the system has not changed

Change in volume/pressure of a gaseous system: Volume of gas is indirectly proportional to the pressure it exerts.
Increasing pressure means the system will move
to the side of the reaction with fewer moles
whereas decreasing pressure will move to the
side with more moles.
• Partial pressure: Pressure exerted by an
individual gas in a container.
Collision theory explanation: Pressure of a gas is
indirectly proportional to its volume at constant
temperature where if volume of a gas is
decreased, the pressure of the gas will increase
vice versa (decrease in volume increases
concentration, therefore an increased rate of
collisions with the walls of the container)
• Inert gas has no effect. Also vacuum takes out
gas meaning substance wont react with it,

Addition of a catalyst: Catalyst speeds up the rate of a chemical reaction by lowering the activation energy. Adding a
catalyst to a system that is already at chemical equilibrium speeds up the rate of the forward and reverse reaction
equally and therefore will have no effect of the system (no change in position of equilibrium or any of the observable
properties of the system).

Ocean equilibrium and atmospheric CO2

Human activities such as burning carbon based fuels is thought to be the main cause of the currently observed rising
atmospheric carbon dioxide concentration. This is a significant issue as carbon dioxide is greenhouse gas its presence in
the atmosphere contributes to the warmer temperatures by its ability to re absorb heat than would otherwise radiate
from the Earth's surface out into space. This helps prevent the surface temperature from plunging to below 0 however it
is understood that the rising or CO2 concentration is causing a steady rise in average global temperature.
Ocean temperature

Most marine organisms are ectothermic which means they are cold blooded as their internal body temperature is the
same as the surrounding environment. Temperatures outside of this range have significantly altered the rate at which
the metabolic processes have evolved to work efficiently.

• Coral and algae is an example

Ocean as a carbon sink

An important chemical equilibrium exists between the atmosphere gases like N2 O2 and CO2 present in seawater.This
equilibrium hopes to moderate any changes in the atmospheric concentration of these gases importantly the ocean
plays a major role in moderating the human induced anthropogenic rising atmospheric carbon dioxide concentration.

The ocean absorbs around 1/3 of humankind's annual emissions of CO2 in this way the ocean plays a vital role in
regulating the extent of CO2 induced climate change however this comes at cost as it is causing an effect known as a
ocean acidification. This decrease in the ocean pH can directly impact the health and populations of many calcifying
species like

• Oysters, clams, sea urchins, coral, calareo

Changing populations of these organisms will impact many aspects of the wider marine environment

Atmospheric CO2 and ocean equilibrium

The two major effects of ocean acidification are

• increase its hydrogen ion concentration

• decrease its carbonate ion concentration

The concentration of these two ions are connected to the presence of atmospheric carbon dioxide through several
chemical equilibrium

Firstly wind and wave action allow atmospheric carbon

dioxide to dissolve in seawater. The dissolved CO2 then
becomes further involved in a series of equilibrium
reactions where it initially forms carbonic acid. This
weak acid then undergoes partial ionisation to form
hydrogen ions , hydrogen carbonate ions and carbonate
ions

CO2 (gas) <-> CO2 (aqueous)

CO2 (aqueous) + H2O (liquid) <-> H2CO3 (aqueous)

H2CO3 (aqueous) <-> H+ (aqueous ) + HCO3- (aqueous)

H2CO3 (aqueous) <-> H+ (aqueous ) + CO3-2 (aqueous)

The presence of calcium carbonate in sea floor sediments and reef structures can potentially counteract the increased
hydrogen ion concentration by reacting with it to form free calcium ions and hydrogen carbonate ion. However ocean
depths and a slow rate of vertical ocean mixing mean this can be a slow and unresponsive equilibrium process.
CaCO3 (solid)+ H+ (aqueous) <-> Ca+2 (aqueous) + HCO3- ( aqueous)

As ocean acidification increases, available carbonate ions (CO32-) bond with excess hydrogen, resulting in fewer
carbonate ions available for calcifying organisms to build and maintain their shells, skeletons, and other calcium
carbonate structures. If the pH gets too low, shells and skeletons can even begin to dissolve.

Rising atmospheric carbon dioxide and ocean acidification

Ocean acidification is a term used to describe the lowering of the ocean pH due to increased atmospheric carbon
dioxide. Studies show that seawater has maintained a steady pH of 8.2 for many millions of years. However in the last
250 years since the industrial era the average ocean pH has fallen by 0.1. this means the 30% increase. Computer
modelling predicts a further 0.4 fall in pH could be expected by 2100

The process of ocean acidification can be understood using the principles of chemical equilibrium. This reveals how
rising atmospheric carbon dioxide concentration has led to falling pH. Initially an increasing atmospheric carbon
dioxide concentration causes an increase in the rate of CO2 dissolving. This shifts equilibrium above to the right and
increases the carbon dioxide concentration in the ocean. A higher carbon dioxide concentration in the ocean then
increases the rate of formation of carbonic acid in the 2nd reaction. This shifts equilibrium to the right increasing the
carbonic acid concentration. The raised carbonic acid concentration has a flow on effect causing equilibria shift to the
right thus raising the concentration of both hydrogen ion and hydrogen carbonate ion.

• Although the extra carbonic acid produces the same molar amount of hydrogen ions and hydrogen
carbonate ions the actual factor increase in the hydrogen ions concentration is much greater than
hydrogen carbonate ions.

This happens as the hydrogen ions concentration is initially extremely low much lower than the hydrogen carbonate
ions concentration. The net effect of this is to cause the equilibrium reaction to shift to the left. The reverse reaction
speeds up more because the concentration of hydrogen ions has increased by a greater factor than the hydrogen
carbonate ions this change partially negates the increased hydrogen ion concentration while also reducing the normal
carbonate concentration. The overall effect of ocean acidification is to slightly increase the concentration of both
hydrogen carbonate ions and hydrogen ions while reducing the concentration of carbonate ions. Both the increase in
hydrogen ion concentration and the reduced carbonate ion concentration are very significant issues for calcifying
species.

Impact of ocean acidification

Ocean acidification will directly affect the health of classifying species like oysters clams sea urchins and coral and
calcareous plankton. These rely on constant pH and carbonate ion concentration to maintain the integrity of their shells
and skeleton. They absorb calcium ions and carbonate ions from seawater to produce the calcium carbonate based
exoskeleton. However, as Ocean acidification reduces the carbonate ion concentration, these organisms become
stressed. They must expend more energy to absorb the necessary carbonate needed to grow their shells and skeletons.
This impacts their survival and population. Furthermore, the elevated hydrogen ion concentration has the potential to
dissolve calcium carbonate already present in the shells and exoskeletons of these organisms.

Plankton species that have calcium carbonate based shells could be affected by more acidic environments as with the
populations or many marine organisms that rely on them from food source. we go on an existing call with fail to protect
coastlines from harsh ocean waves. always also provide habitat for many fish species so without the reef system there
would be a loss of marine life.

Future of our oceans

When pH changes in the ocean have occurred over a very long period of time the ocean has been able to compensate.
This happens because large collections of sediment at the bottom of the ocean contain large amount of calcium
carbonate mostly from the shells of deceased marine creatures. Over long time periods these sediments dissolved to
decrease the hydrogen ion concentration and replenish the carbonate ion lost to the reaction with excess hydrogen
ions. However the changes we are seeing today in the oceans pH levels have happened rapidly in terms of the geological
timescale. Because the acidification is occurring over a short period of time and in water close to the surface, the
sediment reserve on the ocean floor has not had the chance to dissolve and counteract the effects of added acidity.

Research on the impact of ocean acidification on marine animals and ecosystems is still in its infancy. Efforts to monitor
ocean acidification worldwide are just beginning so it is difficult to predict exactly how the impacts will cascade
throughout the marine food chain and affect the overall structure of marine ecosystems. It appears the most effective
way of preventing ocean acidification and rising ocean temperatures is to stabilise and reduce the level of greenhouse
gases in the atmosphere.

How to write equations

Every chemical reaction is made up of substances that combine, called reactants, to produce new
substances called products. The reactants involved could be one of the following:

1. A metal: a substance only made up of metal atoms (e.g. magnesium).

2. An ionic compound: a substance made of metal atoms and non-metal atoms in the form of ions
(e.g. sodium chloride).
3. A covalent molecular compound: a substance only made up of non-metallic atoms to a fixed size
(e.g. ammonia or water).
4. A covalent network compound: a substance made up of non-metallic atoms of a variable size (e.g.
graphite). These substances are normally inert and are infrequently involved in chemical reactions.

General rules:

· If a chemical reaction involves a metal as a reactant, it can only be involved in forming an ionic
compound. There are substances called organometallic compounds but these are uncommon.

hydrochloric acid + magnesium metal >magnesium chloride + hydrogen gas

HCl(aq) + Mg(s) > MgCl2(aq) + H2(g)

In this chemical reaction, the magnesium metal has formed magnesium chloride, an ionic compound. So,
if you see a metal involved, then one of the products should be an ionic compound.

· If a chemical reaction has a reactant that is an ionic compound, then it will be involved in producing
either a metal (uncommon), a covalent molecular compound (also uncommon) or, more commonly,
another ionic compound.
sodium chloride > sodium metal + chlorine gas

NaCl(aq) à Na(l) + Cl2(g)

silver nitrate + sodium chloride > silver chloride + sodium nitrate

AgNO3(aq) + NaCl(aq) > AgCl(s) + NaNO3(aq)

In a majority of chemical reactions where an ionic compound is a reactant, it will result in its ions forming
different ionic compounds. If a covalent molecular compound is formed, it will be a small molecule, such
as chlorine gas, water, carbon dioxide or ammonia.

· If a chemical reaction has a reactant that is a covalent molecular compound, the substance will be
involved in forming either another covalent molecular compound or an ionic compound. An acid is
termed a covalent molecular compound.

methane + oxygen gas > carbon dioxide + water

CH4(g) + O2(g) > CO2(g) + H2O(l)

ammonia + chlorine gas > ammonium chloride

NH3(g) + Cl2(g) > NH4Cl(s)

hydrochloric acid + magnesium metal > magnesium chloride + hydrogen gas

HCl(aq) + Mg(s)> MgCl2(aq) + H2(g)

So, to recap:

Reactant: Most common product involving atoms of this reactant: Less common:

When looking at chemical reactions, always look at the types of atoms you have available and use them
to predict products.

For the acid base equations: Solution or substance in water. If the Hydrogen is infront of another molecule,
in water it will usually create H3O+ which is the conjugate acid
Acid and bases

Acid-Base properties:
Arrhenius Theory: an acid is a substance that ionises in solution to produce H+ ions, a base is a substance that ionises in
solution to release OH- ions.
HNO3 -> H+ + NO3-
NaOH -> Na+ + OH-
According to arhenius, a stong ascid is more fully ionised in aqueous solutions than a weak acid. A singl =e arrow
indicates full ionisation whereas reversible reactions ssho partial. This means that reversible reactions have weak acoids
as they only partially ionise..
Limitations with Arrhenius’ theory
1. Some substances that behave as bases (produce OH-) in solution do not contain OH in the formula e.g: NH3,
CO₃²⁻.
2. Only applies to solutions of acids and bases in water (eg aqueous solutions) and not to solutions in other
solvents e.g: acetic acid, liquid ammonia.
3. Reactions e.g: HCl(g) and NH3(g) to form NH4Cl(s) cannot be explained.
4. Not all salts (ionic compounds produced when an acid reacts with a base) are neutral. Many salts behave as
acids or bases.
5. Hydrogen ion cannot exist for very long in water (reacts with water to form hydronium ions).
 Bronsted-Lowry Theory: an acid is a substance that donates protons, a base is a substance that accepts protons. All of
his equations represent reversible equations
HCl + H2O -> H3O+ + Cl-
• HCl acts as acid, H2O acts as base
NH3 + H2O -> OH- + NH4+

• NH3 acts as base, H2O acts as acid

· Monoprotic acids are acids that only contain one proton. Example: hydrochloric acid (HCl).
· Polyprotic acids are acids that contain more than one proton. Example: sulfuric acid (H2SO4).
Conjugate acid base pairs:
HF + H2O ⇌ H3O+ + F-
Acid Base Conjugate acid Conjugate base
NH3 + H2O ⇌ OH- + NH4+
Base Acid Conjugate base Conjugate acid

Acid donates protons and base accepts protons

Acid Strength and the Properties of Salts:
When an acid reacts with water, the equilibrium constant is known as Ka, or the acidity constant.
HA (aq) + H2O (l) -> H3O+ (aq) + A- (aq)
Ka = ([H3O+][A-] / [HA]
The size of Ka shows the tendency of an acid to ionise in solution (for proton transfer to go to completion).
• A large Ka represents a larger concentration of products relative to reactants and suggests that the acid prefers
to dissociate into ions.
• A small Ka represents a larger concentration of reactants relative to products and suggests that the acid prefers
to remain in its covalent form.
An acid that prefers to remain in its covalent molecular form is known as a weak acid. An acid that prefers to remain in
its dissociated form is a strong acid. The strength of an acid refers to the extent that proton transfer occurs in a chemical
reaction.
HALOGENS: HF is weaker than HCl is weaker than HBr is weaker than HI. This is due to the difference in electronegativity
of the halogens. Because fluorine is so electronegative, it prefers to bond to a hydrogen atom and it is difficult to break
that bond. Halogens that are less electronegative than fluorine have less of a tighter hold onto hydrogen atoms.
Note: All organic acids are weak acids.

When an acid reacts with a base, a salt and water are always produced. The salt produced is not always neutral:
· If one ion involved in a salt reacts with water and donates a proton to it, the resulting solution will be acidic:
NH4+ (aq) + H2O (l) -> H3O + (aq) + NH3(aq)
· If one ion involved in a salt reacts with water and accepts a proton from it, the resulting solution will be basic:
HCO3- (aq) + H2O (l) -> OH- (aq) + H2CO3(aq)
Another way to look at it is more simplistic:
• A strong acid and a strong base will produce a neutral salt.
• A weak acid and a weak base will produce a neutral salt.
• A strong acid and a weak base will produce an acidic salt.
• A weak acid and a strong base will produce a basic salt.
•
• Strong: Fully ionise (covalent-molecular)/dissociate (ionic).
• Weak: Partially ionise/dissociate. Take part in reversible reactions.
• Concentrated: Refers to the large amount of solute relative to solvent.
• Dilute: Refers to the small amount of solute relative to solvent.
• Conjugate acid-base pairs: Two species that differ by a proton. There
are two conjugate acid-base pairs in an acid-base reaction. The stronger a base, the weaker its
conjugate acid and vice versa (relative strength).
• Amphiprotic substances: Substance that can donate or accept protons
depending on what they are reacting with (behave as acid or base) e.g: HCl + H₂O ⇌ Cl⁻ + H₃O⁺
(water is base) and NH₃ + H₂O ⇌ NH₄⁺ + OH⁻ (water is acid). If solute is a stronger acid than water,
water will react as a base and vice versa. Monoprotic: Acid that donates one proton per molecule.
• Polyprotic: Acid that can donate more than one proton per molecule e.g: diprotic, triprotic.
• Le Chatelier’s Principle: States if an equilibrium system is subjected to a change, the system will
adjust itself to partially oppose the effect of the change.
• Electrolyte: Substance that conducts electricity (contains freely moving ions) when molten or when
dissolved in water. A weak electrolyte is a substance that partially ionises in aqueous
solution e.g: water whereby a strong electrolyte is a substance that fully dissociates (ionic)/ionises
(covalent molecular substances) in aqueous solution.
• Hydrolysis: Reaction of substances with water (how they interact with water). Partial ionisation into
H⁺ and OH⁻.

Conjugate acid and base pairs

Acidity Constant
The equilibrium constant for acid base proton transfer reactions is known as the acidity constant. The city constant is a
numerical measure of the extent to which the proton transfer reaction goes to completion hence it's an indicator of acid
strength.
• HA is the generic formula for a monoprotic acid
• The proton transfer equation is for the transfer of a single proton from the acid HA to a water molecule
• Water has a fixed concentration of 55.5 moles per litre and so it's not included in the city constant expression.

Strength vs concentration:
• STRENGTH refers to an acid or bases ability to ionise in solution.
• CONCENTRATION refers to the amount of acid or base per litre of solution.

Polyprotic acid

Acid like HCl and HNO3 are said to be monoprotic. These acids can only donate one proton per acid molecule. polyprotic
acids are able to donate more than one proton per molecule of acid. These include diprotic and triprotic. The conjugate
base of a Polyprotic acid is usually but not always acidic in relation to water. However its acid strength is always less than
the original acid. This Can be seen in the example below:

Acid base properties of salt

When an acid reacts with a base a salt and water are always produced. this is called a neutralisation reaction however
the salt formed in this reaction is not always neutral. Often may either be acidic or basic.

• This can be understood using the bronsted Lowry theory.

• If one of the islands present in assault reacts with water acting as a proton donor acid then its solution would be
acidic
• Ammonium chloride solution for example is acidic. Its acidity is due to the ammonium ion which acts as a weak
acid in water. The chloride ion is neutral

If a salt contains an iron that hydrolyzes by acting as a proton acceptor (base) then its solution will be basic.

• This is shown in the image below

Ionisation of water:
Water can dissociate into hydrogen ions and hydroxide ions. these are produced in an equal number called the
ionisation or simply self ionisation of water
Water has a covalent molecular structure but to a very small extent, dissociates into hydronium (H3O+) and hydroxide
(OH-) ions.
H2O(l) ⇌ H+(aq) + OH-(aq)
2H2O(l) ⇌ H3O+(aq) + OH-(aq)

The equilibrium strongly favours the formation of molecular water. In pure water [H+] = 1.0 x 10-7 molL-1 and [OH-] = 1.0 x
10-7 molL-1 .
The equilibrium constant expression for the reaction is:
Kw = [H+] [OH-] = 1.0 x 10-14

In water or any other solution in which hydrogen ions and hydroxide ions have the same concentration the solution is
said to be neutral meaning its properties are not basic or acidic. If an extra source of hydrogen ions or hydroxide ions
added then as with any equilibrium process the system will re establish a new equilibrium. this means adding acid to
water not only raises the hydrogen ion concentration but it also lowers the hydroxide ion concentration and vice versa.

Note: At higher temperatures, the reaction will favour the forward, endothermic process, so higher Kw and more
ionisation occurring.
Kw can be used to calculate the concentration of hydrogen ions or hydroxide ions in solution, which will eventually lead
to pH measurements.
As the concentration of hydrogen ions increase, the concentration of hydroxide ions decrease, and vice versa.

It also shows us the ionisation of water extremely small value showing its tendency to remain UNionised.

At a given temperature the constant value of KW means it can be used to find the hydrogen ion or hydroxide ion
concentration for any solution where either hydrogen or hydroxide concentration is known

The pH scale:
The pH scale is used to measure the acidity or basicity of a substance. If a substance has a pH lower than 7, it is said to
be acidic. If it has a pH greater than 7, it is said to be basic. If it has a pH equal to 7, it is said to be neutral. pH is based on
hydrogen (or hydronium) ion concentration and is calculated by using the formula:
pH = log10[H+]
Methods for testing pH of solutions:
• pH indicator strips
• pH meters
• volumetric analysis
• pH indicator solutions

Laboratories test for pH for a number of reasons. In the environmental analysis sector, pH and conductivity tests are
commonly used to identify contaminated water sources. In industrial mining, pH analysis is used to validate the
processes mines use to break down ores and liberate metal ions.
Example of pH calculations:
• What is the pH of a 0.5 molL-1 solution of hydrochloric acid?
• [H+] = [HCl] x 1 = 0.5 molL-1
• pH = log10[H+] = -log10(0.5) = 0.3

• B) What the pH of a 0.067 molL-1 solution of aluminium hydroxide?

• [OH-] = [Al(OH)3] x 3 = 0.067 x 3 = 0.201 molL-1
• Kw = [H+][OH-]
• [H+] = Kw / [OH-] = 1x10-14 / 0.201 = 4.97x10-14 molL-1
• pH = log10[H+] = -log10(4.97x10-14) = 13.3

• C) pH of 0.004 solution of Na2Co3

• Na2CO3 + H2O >< 2Na+ + HCO3- + OH-
• Na2CO3 + H2O >< HCO3- + OH-
• Na2CO3 = 0.004
• C032-= 1X(Na2CO3) = 0.004
• H+= 1.0 X10-14 / 0.004= 2.5 x 10-12
• pH= -LOG(2.5X10-12)= 11.6

pH indicators:
A pH indicator is a normal dye that changes colour at specific pH levels. They have the ability to release H+ ions, with one
form containing the H+ ion and having one colour and the other without the H+ ion and having a different colour.
HIn(aq) + H2O(l) ⇌ H3O+(aq) + In-(aq)
 acid colour base colour
When seeing this structural formula, focus on the hydrogen ions as it is a trick

Applications of Le Chatelier's Principle:

Adding acid to an indicator: this increases the [H3O+] which in turn pushes the
reverse reaction, increasing the yield of HIn and the acid colour.
Adding base to an indicator: hydroxide ions react with hydronium ions, lowering
their concentration. This in turn favours the forward reaction, increasing the
yield of In- and the base colour.
Indicator pH ranges:
• Phenolphthalein: pH 0-8 is colourless, pH 8-14 is pink
• Methyl orange: pH 0-4.5 is red/orange, pH 4.5-14 is yellow
• Bromophenol blue: pH 0-4.5 is yellow, pH 4.5-14 is blue
• Bromothymol blue: pH 0-6 is yellow, pH 6-14 is blue
• Methyl red: pH 0-6 is red, pH 6-14 is yellow
• Phenol red: pH 0-8 is yellow, pH 8-14 is red/pink
• Bromocresol green: pH 0-3.8 is yellow, onwards is blue

Buffer solutions:
A buffer is a solution that resists small changes in pH. It can contain:
• a weak acid and the salt of a weak acid (its conjugate base)
• a weak base and the salt of a weak base (its conjugate acid)
The concentration of the weak acid and conjugate base or weak base and conjugate acid must be concentrated enough
so they're not depleted. The concentrations of both species must also be similar.
Example: acetic acid and sodium acetate
CH3COOH(aq) + H2O(l) ⇌ CH3COO-(aq) + H3O+(aq)
· Adding base: adding hydroxide ions to this situation neutralises and removes some of the hydronium ions to form
water, which in turn pushes the forward reaction to produce hydronium ions, reducing and balancing the pH.
· Adding acid: adding hydronium ions to this situation increases their concentration, which in turn pushes the reverse
reaction, increasing and balancing the pH.

Equilibrium constant expression:

Kc = [CH3COO-][H3O+] / [CH3COOH]
Buffer capacity: a measure of the amount of acid or base the buffer can neutralise until the pH drastically changes.

Consists of a weak conjugate acid-base pair meaning a buffer could be made of a weak acid and its conjugate base or a
weak base and its conjugate acid. Important for processes that require stable and narrow pH ranges.

- e.g: If HCl added to buffer soln of CH3COOH/CH3COO−, extra H3O+ ions disturb the existing equilibrium of
the buffer solution (Le Chatelier’s principle predicts the system will respond to oppose the change to restore
equilibrium) where the addition H3O+ reacts with the CH3COO− ions thus producing more CH3COOH and
decreasing the concentration of H3O+ in soln
 - e.g: If strong base added to CH3COOH/CH3COO− buffer, OH− ions from base react with CH3COOH molecules
generating more CH3COO− ions and consumes most of the extra OH−

Buffer capacity: Measure of effectiveness of buffer soln at resisting a change in pH when a strong acid or a strong base is
added. Greatest when there is a high concentration of the weak acid and its conjugate base and when the
concentrations of the acid and its conjugate base are equal.

- Determines how much acid or base can be neutralised before the pH changes and by how much the pH will
change e.g: if HCl is added past the point the capacity is effective, there will be a sharp decrease in pH as
more is added
- For a buffer soln to be effective at maintaining pH, the ratio of the concentrations of the weak acid and its
conjugate base should be within the range of 10:1 and 1:10

Blood as a buffering system: Buffering in blood is crucial to our survival. The pH of blood must be kept constant for
normal body functions to work. If blood becomes too acidic, or too basic, then enzymes and proteins are unable to
function.

o CO2 (g) ⇌ CO2 (aq, in blood)

o CO2 (aq, in blood) + H20 (l) ⇌ H2CO3 (aq, in blood)

o H2CO3 (aq, in blood) + H2O (l) ⇌ H3O+ (aq) + HCO3-2 (aq)

The carbon dioxide we breathe in and the exhale can dissolve in our blood and this carbon dioxide can react with water
to form carbonic acid. Carbonic and and hydrogen carbonate is the buffer system.

Blood can become to acidic due to exercise. As you exercise sugars in your blood react with oxygen to produce carbon
dioxide and water. The second equation above shows that CO2 will react with water to produce carbonic acid. So due to
exercise, the blood will contain more CO2 and consequently make H2CO3. This will then push the forward reaction of
the last reaction listed above.

Increases in blood pH indicate alkalemia. Increases can be a result of a respiratory (or metabolic) disturbance.
Respiratory alkalosis is the result of alveolar hyperventilation. Hyperventilation causes removal of CO2 decreases
production of H3O, which lowers pH.

Hyperventilation eliminates CO2 faster than it is being produced and, as a result, pH increases; hypoventilation
eliminates CO2 more slowly than it is being produced and, as a result, pH decreases.
Haber process
Ammonia is one of the most important chemical materials. It produces fertalisers, polymers , explosives and cleaning
products. Ammonia is manufactured by the haber process which uses the equilibrium process,

The hydrogen from natural gas is methane reacted with with steam

Moderate temp (400-450) is optimal.

• High temperature can maxamise the reaction rate

• Low temperature favours the yield

High preassure is optimal. It Is also cheaper to do.

• High preassure favours the rate of reaction

• High preassure favours the yield.

Catalyst makes the reaction rate faster. Such as MgO, Al2O3, SiO2.

• Nothing to do with yield, just faster

The contact process
The contact process uses raw materials such as sulfur, water and oxygen in a reaction sequence to produce
sulfur dioxide which is used in phosphate fertalisers, explosives, detergents, in medicine, as a electrolyte and
catalyst, the list goes on. First sulfur dioxide is produced, then sulfur trioxide and finally, sulfur trioxide.
Stages to produce sulfuric acid
1. Molten sulfur is burnt in dry ait at around 1000 degrees. At this stage, only SO2 is produced even
though oxygen is in excess
.
This highly exothermic reaction goes to completion. The energy is used o generate steam for onsite
powerstation.
2. Sulfur dioxide is converted to sulfur trioxide according the the following equation

A high yield of sulfur trioxide is favoured by low temperature and high preassure as it is an reversible
reaction: this is expensive so catalyst is used.

3. The conversion of sulfur trioxide and water to produce sulfiric acid is achieved indrirectly by absorbing
sulfur trioxide into sulphric acid to produce an oily compound called oleum. Then adding water to the
oleum will produce 98% (18molL) sulfiric acid.

Conditions:
Mod temp of 400-450 degrees Celsius. V2O5 catalyst. 2 atm pressure.
Stoicheometry
A mole refers to 6.02 x 1023 particles of any substance.

The formula used to calculate the number of moles from the number of particles of a substance is:
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆𝒔
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 (𝒏) =
𝟔. 𝟎𝟐 × 𝟏𝟎𝟐𝟑

The formula used to calculate the number of moles of a substance from the mass is:
𝒎𝒂𝒔𝒔(𝒊𝒏 𝒈𝒓𝒂𝒎𝒔)
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔(𝒏) =
𝑴𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 (𝒊𝒏 𝒈𝒓𝒂𝒎𝒔 𝒑𝒆𝒓 𝒎𝒐𝒍𝒆)

The molarity of a solution is calculated using the following formula:

𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 (𝒏)
𝒎𝒐𝒍𝒂𝒓𝒊𝒕𝒚(𝒄) =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 (𝒊𝒏 𝒍𝒊𝒕𝒓𝒆𝒔)(𝑽)

To perform a reaction stoichiometry calculation, a strict process should be followed to limit the difficulty of the problem.
The steps of this process are:

• STEP 1: Identify the chemical reaction involved and balance it.

• STEP 2: Extract all information from the question.
• STEP 3: Use the information you have to calculate the number of moles.
• STEP 4: Use molar ratios to determine the number of moles of the relevant product.
• STEP 5: Use the number of moles of product to calculate the answer.

Concentration

Concentrations can be expressed in percentage units. There are three different types of percentage concentrations
commonly used:

Mass Percent: The mass percent is used to express the concentration of a solution when the mass of a solute and the
mass of a solution is given:
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑎𝑠𝑠 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 (%𝑤/𝑤) = × 100
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Volume Percent: The volume percent is used to express the concentration of a solution when the volume of a solute and
the volume of a solution is given:
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑉𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 (%𝑣/𝑣) = × 100
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Mass/Volume Percent: Another version of a percentage concentration is mass/volume percent, which measures the
mass or weight of solute in grams (e.g., in grams) vs. the volume of solution (e.g., in mL).
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑎𝑠𝑠/𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 (%𝑤/𝑣) = × 100
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
With dilute solutions, their percentage concentrations are low. So, instead, the concentrations are expressed in other
ways:

Parts per Million: A concentration of a solution that contains 1 gram of solute and 1,000,000 millilitres of solution would
have a concentration of 1 part per million (1ppm).

1 ppm = 1 milligram per litre (1 mgL-1) = 1 microgram per millilitre (1 ugL-1)

Molarity: The molarity (M) of a solution is used to represent the amount of moles of solute per liter of the solution.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛)

𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑐) =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉) 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠

Molality: The molality (m) of a solution is used to represent the amount of moles of solute per kilogram of the solvent.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛)

𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦 (𝑐) =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉) 𝑖𝑛 𝑘𝑖𝑙𝑜𝑔𝑟𝑎𝑚𝑠
Dilution

Diluting a solution involves adding more solvent to is to lower its concentration. The opposite of dilution is
preconcentration, where some of the solvent is removed, perhaps by evaporation to increase the concentration of the
solution.

In both dilution and preconcentration, the amount of solute stays the same. The new solution volume or concentration
can be calculated. From the definition of molarity,

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛)

𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑐) =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉) 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠

To solve for the number of moles of solute:

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛) = 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑐) × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉) 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠

Because this quantity does not change before and after the change in concentration, the product (M x V) must be the
same before and after the concentration change.

Using numbers to represent the initial and final conditions:

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑐1) × 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉1) = 𝐹𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑐2) × 𝐹𝑖𝑛𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉2)

This can also be applied to other concentration values as long as the units are the same on each side of the formula. For
instance:

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑝𝑝𝑚 (𝑐1) × 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉1) = 𝐹𝑖𝑛𝑎𝑙 𝑝𝑝𝑚 (𝑐2) × 𝐹𝑖𝑛𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉2)

This is the dilution equation. The volumes must also be expressed in the same units.

Note that this equation gives only the initial and final conditions, not the change in concentration or volume. The
amount of change is determined by subtracting c2 from c1 or V2 from V1.
Calculating acidity and basicity

The pH of a solution is a way of assigning a simple numerical value to represent hydrogen ion concentration. The pH
scale has values between 0 and 14. Values that are between 0 and 7 represent acids and values between 7 and 17
represent bases. A pH value of 7 refers to a neutral solution that is neither acidic or basic.

The pH of a solution is calculated using the formula:

𝑝𝐻 = −log [𝐻+ ]

For example:

a) A 0.001 molL-1 solution of hydrochloric acid (HCl):

[H+] = [HCl] = 0.001 molL-1
pH = -log[H+] = -log(0.001) = 3

b) A 2.5 x 10-6 molL-1 solution of sulfuric acid (H2SO4):

[H+] = 2 x [H2SO4] = 2 x 2.5 x 10-6 = 5 x 10-6 molL-1
pH = -log[H+] = -log(5 x 10-6) = 5.3

When performing these calculations, it is always important to check the answer. If the solution is an acid, then its pH
must be between 0 and 7. If it is above 7, then something may be wrong.

To a very small extent, water dissociates into ions. In pure water, [H+] = 1.0 x 10-7 and [OH-] = 1.0 x 10-7. The ionisation
constant of water Kw, can be used to calculate the [H+] and [OH-] in solution:

𝐾𝑤 = [𝐻 + ] × [𝑂𝐻 − ] = 1.0 × 10−14

More examples:

c) A 8.34 x 10-4 molL-1 solution of aluminium hydroxide (Al(OH)3):

[OH-] = 3 x [Al(OH)3] = 3 x 8.34 x 10-4 = 0.0025 molL-1
[H+] = Kw / [OH-] = 1.0 x 10-14 / 0.0025 = 4 x 10-12 molL-1
pH = -log[H+] = -log(4 x 10-12) = 11.40

Might have to work backwards- Inverse log

Might have to find concentration of of a hydrogen ion. Work backwards using anoter known conc.
Gas calculations

At standard temperature and pressure (STP) (which is 0oC and 100 kPa pressure), the volume of 1 mole of any gas is
22.71 litres. This information can be used to determine the number of moles of gas at these conditions:

𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉) 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑎𝑠 𝑎𝑡 𝑆𝑇𝑃 (𝑛) =
22.71
The temperature and pressure conditions of a gas however may vary, and this formula can no longer be used for these
situations. A new formula is needed to determine the number of moles when there are differing conditions:

𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 (𝑃) 𝑖𝑛 𝑘𝑖𝑙𝑜𝑝𝑎𝑠𝑐𝑎𝑙𝑠 × 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑉) 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 (𝑛) =
𝑅 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 8.31𝐽𝐾 −1 𝑚𝑜𝑙−1 ) × 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 (𝑇) 𝑖𝑛 𝑘𝑒𝑙𝑣𝑖𝑛

To calculate temperature in kelvin, take the temperature in degrees Celsius and add 273. Kelvin is a commonly used unit
in chemistry.

𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 (𝐾) = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 (𝑑𝑒𝑔. 𝑐𝑒𝑙𝑐𝑖𝑢𝑠) + 273

Examples:

a) The number of moles of oxygen gas in 3 litres at STP:

n(O2) = V / 22.71 = 3 / 22.71 = 0.13 moles

b) The number of moles of methane in 5 litres of gas when the temperature is 27oC and the pressure is 125 kPa:
n(CH4) = (125 x 5) / (8.31 x (27 + 273)) = 625 / 2493 = 0.25 moles

Stoichiometry: Limiting reagents

Stoichiometry can be used to calculate quantities of products provided there is some information relating to the
reactants that can be used to calculate the number of moles.

In a typical chemical reaction, it is rare that the reactants that combine together to make products have the exact
amounts needed to react together. In almost all occasions, there is one reactant at the conclusion of the reaction that
has run out and an amount of the other is left over.

At the conclusion of a chemical reaction:

• The reactant that has run out is known as the limiting reagent (or reactant).
• The reactant that still has some left over that hasn’t reacted is known as the reagent in excess.

In the calculations involved with these reactions, there will be information provided that will allow you to calculate the
number of moles of each reactant. The reason behind this is because only the number of moles of the limiting reagent
can be used to calculate the moles of products.

To demonstrate how these calculations are to be conducted, the following example is provided. It still follows the typical
process of calculating these values, but there is a small change in that the limiting reagent must be determined.

EXAMPLE:

A sample of 2.6 grams of sodium carbonate is added to 40 millilitres of a 0.1 molL-1 solution of nitric acid. Calculate the
mass of sodium nitrate produced.

STEP 1: Identify the chemical reaction involved and balance it.

sodium carbonate + nitric acid → sodium nitrate + water + carbon dioxide

Na2CO3(s) + 2HNO3(aq) → 2NaNO3(aq) + H2O(l) + CO2(g)

STEP 2: Extract all information from the question.

m(Na2CO3) = 2.6 g c(HNO3) = 0.1 molL-1

M(Na2CO3) = (2 x Na) + C + (3 x O) V(HNO3) = 40 mL = 0.04 L

= (2 x 22.99) + 12 + (3 x 16)
= 105.98 gmol-1

STEP 3: Use the information you have to calculate the number of moles.

n(Na2CO3) =m/M = 2.6 g / 105.98 gmol-1 = 0.025 mol

n(HNO3) = c x V = 0.1 molL-1 x 0.04 L = 0.004 mol

Now, with this information we can determine the limiting reagent.

In the chemical equation:

Na2CO3(s) : 2HNO3(aq)
1 : 2 (This is called the stoichiometric ratio)

In the chemical reaction:

Na2CO3(s) : 2HNO3(aq)
0.025 : 0.004 Divide both values by the lowest (0.004)
6.25 : 1 (This is called the actual ratio)

By comparing the two ratios, the actual ratio shows that the moles of sodium carbonate is waaay above half of the
moles of nitric acid (which is what it should be).

Because of this, sodium carbonate is in excess and nitric acid is the limiting reagent. The number of moles of nitric acid
must be used to determine the number of moles of sodium nitrate.

STEP 4: Use molar ratios to determine the number of moles of the relevant product.

For every 2 mol of nitric acid that is consumed in the reaction, there is 2 mol of sodium nitrate that is produced.

n(NaNO3) = n(HNO3) x 2/2 = 0.004 mol x 2/2 = 0.004 mol

STEP 5: Use the number of moles of product to calculate the answer.

M(NaNO3) = Na + N + (3 x O)

= 22.99 + 14 + (3 x 16)

= 84.99 gmol-1

m(NaNO3) = n x M = 0.004 mol x 84.99 gmol-1 = 0.34 g

The chemical reaction produced 0.34 g of sodium nitrate.

EXTENSION: Calculating the excess mass of sodium carbonate.

If there was 0.004 mol of sodium nitrate produced from the reaction, the number of moles of sodium carbonate that
reacted can be calculated:

n(Na2CO3) reacted = n(NaNO3) x ½ = 0.004 mol x ½ = 0.002 mol

m(Na2CO3) reacted = n x M = 0.002 mol x 105.98 gmol-1 = 0.21 g

The mass of sodium carbonate left over by subtracting the mass that has reacted from the total mass used in the
reaction (2.6 grams).

m(Na2CO3) in excess = 2.6 g – 0.21 g = 2.39 g

There will be 2.39 grams of sodium carbonate left over from the reaction.

1. Take the reaction:

4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

In an experiment, 3.25 g of NH3 are allowed to react with 3.50 g of O2. How many litres of NO are formed at
standard temperature and pressure?

n(NH3) = m / M = 3.25 / 17 = 0.191 mol

n(O2) = m / M = 3.50 / 32 = 0.109 mol

Stoichiometric ratio = 4:5 Actual ratio = 0.191:0.109

O2 is limiting, NH3 in excess

n(NO) = n(O2) x 4/5 = 0.109 x 4/5 = 0.0872 mol

n = V / 22.71 V = n x 22.71 = 0.0872 x 22.71 = 1.98 L

2. If 4.95 g of ethylene (C2H4) are combusted with 3.25 g of oxygen.

C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(g)

a. How many grams of CO2 are formed?

b. How much excess reactant is left over?

n(C2H4) = m/M = 4.95/28 = 0.178 mol

n(O2) = m/M = 3.25/32 = 0.102 mol

S.R. = 1/3 A.R. = 0.178/0.102 O2 is the limiting reagent

n(CO2) = n(O2) x 2/3 = 0.102 x 2/3 = 0.068 mol

m(CO2) = nxM = 0.068 x 44 = 2.992 g

n(C2H4 reacted) = n(CO2) x ½ = 0.068 x ½ = 0.034 mol

n(C2H4 excess) = 0.178 – 0.034 = 0.144 mol

m(C2H4 excess) = nxM = 0.144 x 28 = 4.032 g

3. 25 mL of a solution of 0.15 molL -1 calcium hydroxide was reacted with 50 mL of a solution of 0.2 molL -1
hydrochloric acid.
a. Calculate the mass of calcium chloride produced.
b. Calculate the pH of the final solution.

Ca(OH)2 + 2HCl → CaCl2 + 2H2O

n(Ca(OH)2) = c x V = 0.15 x 0.025 = 0.00375 mol

n(HCl) = c x V = 0.2 x 0.05 = 0.01 mol

S.R. = 2/1 A.R. = 0.01/0.00375 Ca(OH)2 is limiting

n(CaCl2) = n(Ca(OH)2 x 1/1 = 0.00375 mol

m(CaCl2) = n x M = 0.00375 x 110.98 = 0.416 g

n(HCl react) = n(CaCl2) x 2/1 = 0.00375 x 2 = 0.0075 mol

n(HCl excess) = 0.01 – 0.0075 = 0.0025 mol

c(HCl excess) = n/V = 0.0025/0.075 (75mL total volume) = 0.033 molL -1

c(H+) = c(HCl) = 0.033 molL-1

pH = -log[H+] = -log(0.033) = 1.4

Volumetric Analysis:
Volumetric analysis is a set of analytical procedures that use the volumes of reactants used in a chemical
reaction to calculate the concentrations of products. They are normally referred to as titrations
The four main types of volumetric analysis are:
• Redox (oxidation-reduction) titrations: involving a redox reaction
• Precipitation titrations: involving a precipitation titration
• Complexometric titrations: involving a reaction that results in the formation of a complex
• Acid-base titrations: involving a neutralisation reaction
Acid-base titrations are widely used in the food, geochemical, oil and gas and environmental industries.

Procedure:
1. An accurate volume of sample solution (say 20 or 25 ml) is pipeted carefully into the colonical flaslk.
2. 3 drops of indicator are added to the solution
3. The standard solution is used to rinse the burrete and is then filled. Then the volume is recorded as the
initial volume
4. Whilst mixinf the sample solution the standard solution is added dropwise until the colour of the
sample solution is changed. Thw colume of the standard solution is then measured and it is noted as
the final volume
5. The difference in volumes is calculated and recorded as the titre
*The procedure is repeated until volumes are within +/- 0.2ml
*Reading from top or bottom of miniscuss has no effect on calculations aslong as you consistently read
from 1 direction
Standard solutions: produced from a primary standard which is a solute that:
• can be obtained pure
• relatively high formula mass
• stable in air
• hygroscopic/anhydrous
Standardising a solution is important as having moistuew and impurities will make the mass larger
than it actually is but have less of the actual substance. This will lead to a consistently higher that
expected value for the concentration of the acid being calculated.
What is a primary standard?: A solid material used to make a solution of accurate concentrations

Examples of appropriate primary standards: sodium carbonate, oxalic acid, potassium hydrogen phthalate.
If the solution produced from a primary standard is used to find the concentration of another solution, then
that solution is a secondary standard.
How to prepare a primary standard:
1. Weigh out primary standard.
2. Dissolve primary standard in a certain volume of water (that doesn't exceed the volule you intend to
use).
3. Rinse the solution into a volumetric flask.
4. Invert the solution a number of times so it is well mixed.
5. Use the mass to calculate the concentration of the primary standard to 4 significant figures.
6. Label the solution with its name, chamical formula and concentration, using appropriate units of
measurement.

Secondary standard is a substance whose concentration have been found by comparison against a
primary standard. However this is unreliable.
End point: the end point of a titration is when the
indicator changes colour or the observable result is
achieved.
Equivalence point: the equivalence point of a titration
is when the amount of titrant (moles) is chemically
equivalent to the analyte/sample. When enough
titrant has been added to neutralise the sample
(analyte solution)
The end point always comes after the equivalence
point and is dependent on the titrator's technique and
the pH range of the indicator.

Titration calculation

Minimising errors in titration

Titration curves: Strong acid/Strong base

Phenolphthalein indicator range

Bromothymol blue indicator range

Methyl red indicator range

Neutral salt

HCl(aq) + NaOH(aq) à NaCl(aq) + H2O(l)

Titration curves: Weak acid/Strong base

Phenolphthalein indicator range

Bromothymol blue indicator range

Methyl red indicator range

Basic salt

CH3COOH(aq) + NaOH(aq) à NaCH3COO(aq) + H2O(l)

Titration curves: Strong acid/Weak base

Phenolphthalein indicator range

Bromothymol blue indicator range

Methyl red indicator range

Acidic salt

HCl(aq) + NH3(aq) à NH4Cl(aq)

Titration curves: Weak acid/Weak base

Phenolphthalein indicator range

Bromothymol blue indicator range

Methyl red indicator range

Neutral salt

CH3COOH(aq) + NH3(aq) à NH4CH3COO(aq)

More Titrations stoichiometry
A chemist collected samples of seawater in order to determine its chloride concentration.
They transferred 15 millilitres of seawater to a flask and added distilled water to make the final volume up to
100 millilitres. The chemist ended the 20 million little portion of the dilute seawater and placed in a colonial
flask to this day added 20 millilitres of 0.100 moles per litre silver nitrate solution. Excess of nitrate was added
to ensure the all of the chloride ions would be percipitated. The mass of solid silver chloride was determined
to be 0.264 grams.

A) Edit calculate the concentration of chloride ions in seawater in moles per liter

B) calculate the concentration of silver ions in solution X (see diagram)

Redox reactions/ Oxidation-reduction reactions
• Oxidation: loss of electrons.
• Reduction: gain of electrons.

Zn + CuSO4 → ZnSO4 + Cu
Zn (0) + Cu2+ (2) → Zn2+ (2) + Cu (0)
OXIDATION HALF EQUATION: Zn → Zn2+ + 2e

REDUCTION HALF EQUATION: Cu2+ - 2e → Cu

Zn is the reductant, Cu2+ is the oxidant
ALWAYS CHECK IF BOTH SIDES HAVE THE SAME REACTANTS

CH4 + 2O2 → CO2 + 2H2O

(-4)(+1) (0) (+4)(-2) (+1)(-2)

Carbon is being oxidized and oxygen is being reduced

Oxidation numbers
Each element in a redox reaction is assigned a oxidation number. So we can work out which species is oxidized
and which is reduced. It can be thought of as the charge of something if it were an ion.
Rules
• Any species in its elemental state has an oxidation number of zero
• Monatomic ions have an oxidation number equal to the charge on the ion
• Hydrogen atoms have an oxidation number of 1+ (except hydroxides which are -1)
• Oxygen atoms have an oxidation number of -2 (except peroxides which are -1)
• The sum of the oxidation numbers of the elements involved in a polyatomic ion equal the charge on
that ion.
Galvanic cells
This type of electrochemical cell Is commonly called a battery. In all of the batteries which are used to power
items of equipment, there is a redox reaction occurring.
Galvanic cells are devices that use a chemical reaction to produce an electric current.
A standard galvanic cell can be put together by setting up some laboratory equipment as follows.

A galvanic cell also known as an electrochemical so harness is the electron transfer over redox reaction to
produce an electrical current. It does this by preventing direct contact between the oxidising agent and the
reducing agent. To get from the reducing agent to the oxidising agent electrons are forced to flow between
two electrodes from anode to the cathode via an external circuit.
A salt bridge allows ions to move between the oxidising and reducing agents. If the external circuit is
disconnected the redox reaction in the cell stops

• When this equipment is set up, electric currents starts to flow from the zinc to the copper (which you
can read from the voltmeter). The zinc metal starts to dissolve, forming zinc ions and copper ions in
solution start to build additional copper on the copper rod.
o SO the beaker with the zinc is where oxidation is occurring and the beaker with the copper rod
is where reduction is occurring.
In electrochemical cells, the electrons move FROM the anode TO the cathode.
THE PART OF A GALVANIC CELL WHERE OXIDATION OCCURS IS CALLED THE ANODE
THE PART OF A GALVANIC CELL WHERE REDUCTION OCCURS IS CALLED THE CATHODE
Definitions
• Anode- Oxidation occurs here. This electrode makes contact with the reducing agent. Labelled
negative.
• Cathode- Reduction occurs here. This electrode makes contact with the oxidising agent. Labelled
positive.
• Electrolyte- Electrodes immersed in an electrolyte solution. Can conduct charge
• Salt bridge- Contains a non reactive electrolyte solution. Prevents direct contact of both oxidizing and
reducing agents while still permitting ions to flow through it. Anions flow through bridge to anode
while cations flow towards cathodes
• Oxidation half-cell- Part of cell where oxidation occurs. Consists of anode plus surrounding electrolyte
• Reduction half-cell- Part of cell where reduction occurs. Consists of cathode plus surrounding
electrolyte
Measuring the strength of oxidizing agents
The voltage produced by a galvanic cells is a measure of the driving force of the redox reation occuring in a
cell. It reflects the combined strength of the oxidizing and reducing agents involved. The stronger these are
the greater tendency for the reaction to occur, the higher the cell voltage. This ranks the strength of different
oxidizing agents, we use the table of standard reduction potentials to measure this.
This data is obtained by measuring ability of a substance to be reduced by hydrogen gas
The standard substance, Hydrogen gas, along with its oxidation product, Hydrogen ion is placed into the left
half of a galvanic cell. The right half contains the test substance which reduction potenitial is being measured
with its reduction product.
The more positive, the greater tendency for it to be reduced or to oxidise other substances

Using the SRP table

For oxidation half equations, you must read the half equation from right to left. This means you must flip the E o value.

• Strongest oxidising agent- TOP LEFT

• Strongest reducing agent- BOTTOM RIGHT
• Weakest oxidising agent- BOTTOM LEFT
• Weakest reducing agent- TOP RIGHT
Limitations of the SRP Data- It doesn’t tell anything about rate, only spontaneity. So having a large positive Eo
may have such a high en, that at normal conditions, it is still very slow. The SRP data is also at specific
conditions so changing it, makes data useless (25 degrees, 1 molL, 100 kPa for gas)
Defining Eo –
The Eo of a cell is given by the standard reduction potential of the cathode minus the standard reduction
potential of the anode.

As the value of the - Eo reduction anode is equvilent to the value for the oxidation potential for the half
reaction pccuring at the anode, the Eo can be given as

FIRST STEP IS TO IDENTIFY REDUCTION OR OXIDATION HALF EQUATIONS. THEN LOOK AT SRP TABLE. FIND
THE EQUATION AND IF ITS NOT IN THE SAME FORMAT AS THE HALF EQUATION, FLIP IT AND FLIP THE
POSITIVE OR NEGATIVE ASWELL.
Predicting changes in a galvanic cell
SRP data can predict chemical changes likely to occur in a galvanic cell.
• Of all species in a galvanic cell, the one most likely to be reduced will be the oxidizing agent with the
greatest Eo reduction potential.
• Of all species in a galvanic cell, the one most likely to be oxidised will be the reducing agent with the
greatest Eo oxidation potential
This the redox reaction occuring in the cell combine strongest oxidizing with strongest reducing agent. The
max voltage available from the cell is the Eo cell values for this redox reaction.
Electrolytic cells
Electrolytic cells have various uses such as electroplating objects and in producing elemental substances that
are difficult to obtain in nature.
Electrolytic cells are devices that use electric current to get a reaction going that wouldn’t normally occur
Electrolysis can be conducted on
• Molten salts
• Aqueous solutions
Electrolysis of molten salts
When electrolysis is conducted on a molten salt, the salt breaks up into its anion and cation and those ions are
then chemically converted into their elemental form. The electrodes that are used for these processes are
made of some type of inert substance such as platinum, graphite or steel.

Electrolysis of aqueous solutions

The electrolysis of aqueous solution can be somewhat difficult because as well as the ions in the electrolyte
water is also present and could be electrolyzed instead of the ions. Because the competing reactions occuring
care must be taken to identify the correct reactions occuring at the anode and cathode.

Factors that affect which reaction occurs are

1. The nature of the electrolyte: if water is this over used to prepare the solution there is a
possibility that it may be electrolysed rather than the ions. The oxidation and reduction half
equations for electrolysis of water are.
Oxidation 2H2O → O2 + 4H+ + 4e- Eo= -1.23V
Reduction 2H2O + 2e- → H2 + 2OH- Eo= -0.83V
In the electrolysis of an aqueous solution, if the Eo value for the oxidation of ions is more
negative than -1.23 volts, then water will be electrolysed rather than the ions. If the Eo
value for the reduction of ions is more negative that -0.83 volts, than water will be
electrolysed rather than ions.

E.g A solution of copper (II) chloride, and the electrodes used are made of graphite
There are 2 potential oxidation reactions
Cl- → Cl2 + 2e- Eo=-1.36V
2H2O → O2 + 4H+ + 4e- Eo= -1.23V
There are 2 potential reduction reactions
Cu2+ + 2e- → Cu Eo= +0.34V
2H2O + 2e- → H2 + 2OH- Eo= -0.83V
The preferred reactions are the ones that are the least negative
2H2O → O2 + 4H+ + 4e- Eo= -1.23V
Cu2+ + 2e- → Cu Eo= +0.34V
Cu + 2H2O → Cu + O2 + 4H
2+ + Eo TOTAL= -0.89V
(not balanced ?)

2. Concentration
In a situation where the difference between the Eo value of the ions and the Eo value of
the water electrolyzing is very small, then there is a chance that concentration can have
 an effect. Dilute solutions contain more water so there is a greater chance of the water
electrolyzing than in a concentrated solution.

E.g In a concentrated solution for the same reaction above (A solution of copper (II)
chloride, and the electrodes used are made of graphite)

In concentrated solution, the anode reaction will

be
Cl- → Cl2 + 2e- Eo=-1.36V
In a dilute solution, the anode reaction will be
2H2O → O2 + 4H+ + 4e- Eo= -1.23V

In the concentrated solution, bubbles of Cl2 will

form and in dilute, bubbles of O2

3. The nature of the electrodes

If in a electrode such as graphite platinum are used then there's a high chance of water
electrolyzing however more reactive metal is used then it may add additional reactions
at the anode or cathode
E.g When electrolysing copper chloride copper electrodes can be used, when this occurs
there is an extra reaction that can occur at the anode. The chloride can be oxidised, the
water can be oxidised and the copper electrode can be oxidised.
At the cathode, the standard reactions occur with copper or water would be reduced

Oxidation:
Cu→ Cu2+ + 2e- Eo= -0.34V
Cl- → Cl2 + 2e- Eo=-1.36V
2H2O → O2 + 4H+ + 4e- Eo= -1.23V

Reduction:
Cu2+ + 2e- → Cu Eo= +0.34V
2H2O + 2e- → H2 + 2OH- Eo= -0.83V

The preffered reactions are least negative so:

ANODE OX: Cu→ Cu2+ + 2e- Eo= -0.34V
CATHODES OX: Cu2+ + 2e- → Cu Eo= +0.34V
Cu + Cu → Cu + Cu
2+ 2+ EO= 0.0V

Because the overall voltage is 0, any voltage can be applied for the reaction to occur.
The copper anode will decrease in mass whilst the copper cathode will increase in mass.