1: Stoichiometric relationships

IB SL/ HL Chemistry
Revision Session April 2019
1.1 Introduction to the particulate nature of
matter and chemical change
- A chemical element - denoted by chemical symbol
- Compounds
- Chemical equations
1.1 Introduction to the particulate nature of
matter and chemical change
- Mixtures
- Homogeneous
- Heterogeneous
- Temperature - measure of average
KE of energy of a substance
- KE = ½ mv^2
- Fluids - liquids and gases

- State symbols
- (l)
- (aq)
- G)
- (s)
1.1 Introduction to the particulate nature of
matter and chemical change
- a-b - vibrational energy of particles
increases, and so does temperature

- b-c - melting point - molecules move

away from their fixed positions

- c-d - particles ain more kinetic energy

- d-e - boiling point - inter-particle forces

break

- e-f - particles gain more kinetic energy

1.2 The mole concept

- Avogadro’s constant - the mole - 6.022E-23 - number of particles in one

mole of a substance
- N = nL
- Relative atomic mass (Ar)
- Relative mass formula (Mr)

- Molar mass - mass of one more of a

subatance
1.2 The mole concept

The fountain of matter

1.2 The mole concept

- The empirical formula - simplest

whole-number ratio of the
elements in a compound
- Can be found experimentally
- The molecular formula - all
atoms present in the molecule
1.2 The mole concept
 1.3 Reacting masses and volumes
- Chemical equations show reactants combining in a fixed molar ratio

- CH4 + 4O2 → CO2 + 2H2O Yields & Reactants

- 1 g CH4 (M = 16.05 g/mol) = 0.0623 mol - How to find the limiting reactant?
- Rato = 1CO2 : 1CH4 - Write the balanced equation and focus on the mole ratio
- 0.0623 mol CO2 (M = 44.01 g/mol) = 2.74 g of the reactants
- Convert any given masses to moles
The theoretical yield is the quantity of product that - Compare ratios of given reactants and equation reactants
can form from compete conversion of the limiting (putting them in the same order)
reactant. - If given ratio is bigger than theoretical the denominator is
Experimental yield is the quantity of product
obtained experimentally. limiting
Percentage yield = experimental / theoretical x 100 - If given ratio is smaller than theoretical the numerator is
limiting
1.3 Reacting masses and volumes

Avogadro's law
“Equal volumes of all gases, when measured at the same temperature and
pressure, contain an equal number of particles.”
- V propotional to n

- Molar volume - 1 mol (STP) = 22.7 dm^-3

- Number of moles of gas = volume / molar volume
1.3 Reacting masses and volumes

Ideal gas equation:

PV = nRT
1.3 Reacting masses and volumes

- Concentration (mol / dm^3)

- Standard solutions

- Dilution

- ppm:
1.3 Reacting masses
and volumes

Volumetric analysis
2(12) Atomic structure
2.1 The nuclear atom

- Elements & Compounds

- J.J Thomsons model of the atom
- Plum pudding
- Ernest Rutherford:
- Fired alpha particles at sheet of gold
foil
- Expected them to go right through
- Most went through but some
deflected
- Conclusion that atoms are mainly
empty space with massive nuclei
2.1 The nuclear atom

Bohr model: - Isotopes are atoms of the same element with

different mass number
- Total mass= ∑(%abundance of
isotope)(mass of isotope)
- Results from a mass
spectrometer are
presented in the form of
a mass spectrum
- Ions
- Cation
- Positive
2.2 Electron configuration

The electromagnetic spectrum

2.2 Electron configuration

ΔEelectron = Ephoton
Ephoton = hv
ΔEelectron = hv
2.2 Electron configuration

- Higher energy states converge

- Ionization energy
- The series
- Lyman
- Balmer
- Paschen
2.2 Electron configuration
2.2 Electron configuration

Pauli Exclusion Principle

2.2 Electron configuration

- Aufbau principle states that electrons are placed into orbitals of lowest energy first
- Hund's rule states if more than orbital in a sub level is available, electrons will occupy different
orbitals with parallel spins
2.2 Electron configuration

Ex: Kyrpton
1s22s22p63s23p63d104s24p
6
.
12.1 Electrons in atoms
12.1 Electrons in atoms
3: Periodicity
13: The Transition Elements (AHL)

IB SL/ HL Chemistry
Revision Session March 2019
3.1 The Periodic Table

● Elements are placed in order of

increasing atomic number, Z.
● S-block: valence electron(s) in the
s-orbital
● P-block: valence electron(s) in the
p-orbital
● D-block: valence electron(s) in the
d-orbital
● F-block: valence electron(s) in the
f-orbital
3.1 The Periodic Table

● Non-metals: upper right-hand side

of the p-block
○ Exception: Hydrogen
● Metals are on the left-hand side
● Group 1: Alkali metals
● Group 2: Alkali earth metals
● Group 17: Halogens
● Group 18: Noble gases
● F-block: Lanthanoids and
actinoids
3.1 The Periodic Table

Any questions regarding 3.1?

3.2 Periodic Trends

● Effective Nuclear Charge

○ Nuclear charge increases by
one across a period
○ Outer electrons are shielded
from the nucleus and repelled
by inner electrons
○ Zeff increases across a period
and remains approximately
the same down a group
3.2 Periodic Trends

● Atomic Radius
○ The atomic radius r is half the
distance between
neighbouring nuclei
○ Atomic radii increase down a
group and decrease across a
period
○ → adding electrons to the
same principal energy level
whilst increasing protons
3.2 Periodic Trends
○ 3) The ionic radii decrease from
● Ionic Radius Groups 1 to 14 for the positive ions.
○ 1) Positive ions are smaller than ○ 4) The ionic radii decrease from
their parent atoms Groups 14 to 17 for the negative ions.
○ 2) Negative ions are larger than ○ 5) The ionic radii increase down a
their parent atoms group
3.2 Periodic Trends

● Ionisation energies
○ Energy required to remove
one moles electrons from one
mole of gaseous atoms in
their ground state.
○ Increase across a period
○ Decrease down a group
○ Dips: evidence for division of
energy levels into sublevels
○ Opposite trend to the trend of
atomic radii
3.2 Periodic Trends

● Electron Affinity
○ First electron affinity (ΔHθea)
is the energy change when
one mole of electrons is
added to one mole of
gaseous atoms to form one
mole of gaseous ions
○ Exothermic process
○ Group 17 has the highest
electron affinity
○ Group 1 has the lowest
3.2 Periodic Trends

● Electronegativity
○ Electronegativity is the ability
of an atom to attract
electrons in a covalent bonds.
It’s related to ionisation
energy as it’s also a measure
of the attraction between the
nucleus and its outer
electrons.
○ Increase across a period
○ Decrease down a group
3.2 Periodic Trends

● Melting points
○ Melting points depend on
type of bonding and structure
○ Down Group 1 melting points
decrease
○ Down Group 17 melting
points increase
○ Melting points generally rise
across a period and reach a
maximum at Group 14
3.2 Periodic Trends

● Group 18: The Noble Gases

○ 1) They are colourless
○ 2) They are monoatomic: they
exist as single atoms
○ 3) They are very unreactive-
the least reactive elements in
the periodic table
○ High ionisation energies
○ Explains behaviour of other
elements in other Groups
3.2 Periodic Trends

● Group 1: The Alkali Metals

○ Reactivity increases down a
group
○ Produce hydrogen and a
metal hydroxide in water
○ Solution will be alkaline
3.2 Periodic Trends

● Group 17: The Halogens

○ Halogens form
halides with group 1
metals
○ In a displacement
reaction, the more
reactive halogen
displaces the ions of
the less reactive
halogen from its
compounds.
3.2 Periodic Trends
● Bonding of the Period 3 Oxides
○ The ionic character of a
compound depends on the
difference in electronegativity
between its elements
○ Oxides of the non-metals are
covalent and acidic
○ Amphoteric oxides show both
acidic and basic properties
○ Basic oxides react with an
acid to form a salt and water
3.2 Periodic Trends

Any questions regarding 3.2?

13.1 First-row d-block elements

● First-row d-block elements show a

‘lull’ in periodic table patterns
○ They are all relatively similar
to one another
● Small decrease in atomic radii
across the first d-block row
○ Small increase in effective
nuclear charge experienced
by outer 4s electrons
13.1 First-row d-block elements

● Physical properties
○ High electrical and thermal conductivity
○ High melting point
○ Malleable
○ High tensile strength
○ Ductile
○ Iron, cobalt, & nickel are ferromagnetic
● Chemical properties
○ Form a variety of coloured compounds
with more than one oxidation number
○ Act as catalysts
13.1 First-row d-block elements

● Zinc is not a transition metal

○ Does not have multiple
oxidation states (only +2)
○ Does not form coloured
compounds
● Scandium
○ Sc3+ is colourless in aqueous
solution (no d-electrons)
○ Sc2+ (not common) exists
with a single d-electron
13.1 First-row d-block elements

● Variable oxidation states

can be explained through
the closeness of the 3d
and 4s orbitals in energy
○ Successive ionisation
energies increase
more gradually
13.1 First-row d-block elements

● Complex ions are formed when a

central ion is surrounded by
molecules or ions which possess
a lone pair of electrons
○ Surrounding species (ligands)
are attached via a coordinate
bond
○ Coordination number is the
number of coordinate bonds
from the ligands to the
central ion
13.1 First-row d-block elements

● Polydentate ligands are ligands

that have more than one lone pair
available to form a coordinate
bond
○ EDTA4- is a hexadentate
ligand
○ A chelate is a complex ion
containing at least one
polydentate ligand
13.1 First-row d-block elements

● Heterogeneous catalysts
○ Different state of matter than
the reactants
○ 3d and 4s electrons
○ Fe in the Haber Process
● Homogeneous catalysts
○ Same state of matter as the
reactants
○ Variable oxidation states
○ Fe2+ in haemoglobin
13.1 First-row d-block elements

● Diamagnetism is a property of all

materials and produces a very weak
opposition to an applied magnetic field
● Paramagnetism produces
magnetisation proportional to the
applied field and in the same direction.
● Ferromagnetism produces
magnetisations sometimes orders of
magnitude greater than the applied
field.
13.1 First-Row d-block elements

Any questions regarding 13.1?

13.2 Coloured Complexes

● Coloured complexes result from

incomplete d-orbitals
● Transition metals appear coloured
because they absorb visible light
● Transition metals absorb visible
light due to splitting in the d
orbital
○ Separation between orbitals:
ΔE
○ → ΔE = hv = hc/λ
13.2 Coloured Complexes

● Ligand strength: stronger ligands

= bigger split = higher energy light
● The identity of the central metal
ion: more protons = bigger split.
● Oxidation state: higher oxidation
state = bigger split.
13.2 Coloured Complexes

Any questions regarding 13.2?

13: Worked Example
13: Worked Example
13: Worked Example
4: Chemical Bonding and Structure
14: Chemical Bonding and Structure AHL

IB SL/ HL Chemistry
Revision Session March 2019
4.1 Ionic Bonding and Structure

● Ions are charged particles. ● Transition elements have variable

○ Loss of electrons (≥1) oxidation states
○ Cations = + ○ Small energy difference between
○ Anions = - the 3d and 4s subshells
● Recall: The group number relates
directly to the number of valence
electrons
● Metals generally become cations
● Non-metals generally become
anions
4.1 Ionic Bonding and Structure

● Exceptions to oxidation states:

○ Lead, Pb, Group 14: Pb2+
○ Tin, Sn, Group 14: Sn4+ or Sn2+
○ Silver, Ag: Ag+
○ Hydrogen, H: H- or H+
● Roman numerals:
○ eg, Cu+ → Copper (I) Oxide
● Polyatomic Ions
○ Ions made up of more than
one atom that have
experienced e- loss
4.1 Ionic Bonding and Structure

● Ionic compounds form when ● Ionic bond: the electrostatic attraction

oppositely charged ions attract. between oppositely charged ions.
● Ionisation: when electrons are ● Recall: there can never be a net loss
transferred between atoms or gain of electrons.
4.1 Ionic Bonding and Structure

● Ionic lattice: ions surround

themselves by ions of the
opposite charge.
● Coordination number: the number
of ions that a given ion is
surrounded by in an ionic lattice.
● Formula unit: The simplest ratio
(empirical formula) of ions in an
ionic lattice.
4.1 Ionic Bonding and Structure

Physical Properties of Ionic Compounds:

● High melting and boiling points

● Low volatility
● Solubility trends depend on the
similar chemical nature of the solute
and the solvent
● Bad conductors of electricity unless
molten or in solution (aqueous)
4.1 Ionic Bonding and Structure
Ionic Character:

● Recall: Electronegativity decreases down a group and increases across a period.

● The strongest ionic bond will form between the most electronegative and the
least electronegative element
● We can use differences in electronegativity to look at ionic character

Type of Bond Difference in electronegativity of the two elements in the compound

Pure Covalent < 0.4

Polar Covalent Between 0.4 and 1.8

Ionic > 1.8

4.1 Ionic Bonding and Structure

Any questions regarding 4.1?

4.2 Covalent Bonding

● When two nonmetals react ● A covalent bond is the electrostatic

together, each wants to achieve attraction between a pair of electrons
the electron configuration of a and positively charged nuclei
noble gas
○ → They share an electron pair
○ → It is concentrated in the
region between nuclei and
attracted to both
○ → It holds the atoms together
by electrostatic attraction
4.2 Covalent Bonding

● Molecules can form more than one

shared bond between them
Cl2 bond length 199pm

● Bonds are characterised by 2 things

○ Bond Strength (Enthalpy) Br2 bond length 228pm
○ Bond length
○ → As atomic radius increases,
molecules have longer bonds
4.2 Covalent Bonding

● Polarity is the result of unequal

sharing of electrons
○ Dipole
○ → δ + (less electronegative)
○ → δ - (more electronegative)
○ → ↦ (dipole notation)
● In a covalent bond, the greater the
difference in the electronegativity
values of the atoms, the more polar
the bond.
4.2 Covalent Bonding

Any questions regarding 4.2?

4.3 Covalent Structures
4.3 Covalent Structures

● Dative/ coordinate bonds are

formed when both electrons in a
shared pair come from the same
atom.
● Their characteristics do not differ
from regular covalent bonds.
4.3 Covalent Structures

● There are exceptions to the octet

rule. Small atoms such as Beryllium
(Be) and Boron (B) form stable
molecules in which the central atom
has less than eight electrons in its
valence shell. This is known as an
incomplete octet.
● These molecules are said to be
electron deficient and have a
tendency to accept an electron pair
from a molecule with a lone pair.
4.3 Covalent Structures

● VSEPR theory: Valence Shell Electron Pair Repulsion theory

● The total number of electron domains around the central atom determines the
geometrical arrangement
● Lone pairs have a higher concentration of charge because they are not shared
between two atoms, hence they cause more repulsion
○ lone pair - lone pair > lone pair - bonding pair > bonding pair - bonding pair
Number of 2 3 3 4 4 4
electron
domains

Electron Linear Triangular Triangular Tetrahedral Tetrahedral Tetrahedral

Domain Planar Planar
Geometry

Number of 0 0 1 0 1 2
lone pairs

Number of 2 3 2 4 3 2
Bonded pairs

Molecular Linear Triangular Bent / Tetrahedral Trigonal Bent/

Geometry Planar V-Shaped Pyramidal V-Shaped

Bond Angles 180° 120° ~ 117° / 109.5° ~ 107° 105°

< 120°
4.3 Covalent Structures

● Molecules with polar bonds are not

always polar
○ Symmetry
○ Equal polarity
○ → Both yes, then the molecule
is nonpolar
○ → Either one no, then the
molecule is polar
○ Net dipole moment
4.3 Covalent Structures

● In some molecules electrons are

delocalised. This means they spread
out and give greater stability to the
molecule or ion.
● Resonance occurs when there are
multiple, equally valid Lewis
structures for a molecule
● O3
● [CO3]2-
● C 6H 6
● RCOO-
4.3 Covalent Structures

Allotrope Graphite Diamond Fullerene Graphene

● Allotropes are different
forms of an element in
Structure Each C Each C Each C Each C
the same physical state, atom atom atom atom
such as Oxygen and bonded to bonded to bonded to bonded to 3
3 others. 4 others. 3 others. others.
Ozone, which both exist
as gases. Different Electrical Good Non- Semi- Very good
Conductor conductor conductor conductor conductor
bonding within these
structures gives rise to Thermal Bad Efficient Bad Best thermal
Conductor conductor conductor conductor conductor
distinct forms with
different properties. Special Soft and Hardest Very light Thinnest
● 4 allotropes of carbon properties slippery substance and strong material
4.3 Covalent Structures

Graphite Diamond C60 Fullerene

Sheets of
Graphene
4.3 Covalent Structures

● Silicone Dioxide, SiO2, commonly

known as silica or quartz, also
forms a giant covalent structure
based on tetrahedral arrangement.
● Each Si atom is covalently bonded
to four O atoms, and each O to two
Si atoms.
● The formula SiO2 refers to the ratio
of atoms within the giant molecule
4.3 Covalent Structures

Any questions regarding 4.3?

4.4 Intermolecular Forces

● Intermolecular forces are forces

that act between molecules, as
opposed to intramolecular forces,
which act within molecules.
● London (dispersion) forces
○ No permanent dipole
○ → Temporary dipole
○ → Induced dipole
○ Weakest IMF
○ Strength increases with
increasing # of electrons
4.4 Intermolecular Forces

● Dipole-dipole attractions
○ Permanent dipole
○ Neighbouring molecules attract
each other by oppositely
charged ends
○ Generally stronger than LDF
● Van der Waal’s forces
○ Umbrella term
○ Entails dipole-dipole attraction,
London forces, and less
common forms of IMF.
4.4 Intermolecular Forces

● Hydrogen Bonding
○ When H is bonded directly to
N, O, F
○ Strongest IMF
○ Water can form a tetrahedral
arrangement
○ Hydrogen bonding can also
occur within large molecules,
such as DNA
4.4 Intermolecular Forces

Non-polar Polar Molecules

molecules molecules with H-O,
H-N, or H-F
London
Dispersion
Forces
van der
Waal’s
forces
✓ ✓ ✓
Dipole-dipole
attractions
✓ ✓
Hydrogen
Bonding
✓
4.4 Intermolecular Forces

● The physical properties of covalent

compounds are largely a result of
their intermolecular forces
● Melting and Boiling Points
○ Changing state by melting or
boiling separates particles and
their IMF. Hence more IMF =
higher melting/boiling points.
○ Covalent molecules have higher
melting and boiling points than
ionic molecules
4.4 Intermolecular Forces

● Solubility
○ Non-polar substances are generally
able to dissolve in non-polar
solvents by the formation of LDS
between solute and solvent
○ Polar substances are generally able
to dissolve in water through dipole
interactions and hydrogen bonding
○ Solubility is reduced in larger
molecules
4.4 Intermolecular Forces

● Electrical Conductivity
○ Covalent compounds do not contain ions and are thus not able to conduct
electricity in the solid or liquid state. Some polar covalent molecules,
however, can conduct electricity, such as HCl or graphite.
4.4 Intermolecular Forces

Any questions regarding 4.4?

4.5 Metallic Bonding

● Metals have few electrons in their outer

shell, generally have low first ionisation
energies, and tend to react by losing
their valence electrons
● Hence, when no other element is
present, those outer electrons tend to
delocalise
● The metal atoms form a lattice of
positive ions surrounded by and
electrostatically attracted to a pool of
delocalised electrons
4.5 Metallic Bonding

● The strength of a metallic bond is 1+, Group 1 2+, Group 2

determined by:
○ The number of delocalised
electrons
○ The charge on the cation
○ The radius of the cation DOWN THE GROUP
● The greater the number of delocalised
electrons and the smaller the cation,
the greater the binding force between
them
● Strength decreases down a group
4.5 Metallic Bonding

● Alloys are solid solutions of metals

with enhanced properties,
containing more than one metal
and held together by metallic
bonding
● Alloys are often more chemically
stable, stronger, and more resistant
to corrosion
● This is due to the layers in the
lattice not being able to slide over
each other as easily
4.5 Metallic Bonding

Any questions regarding 4.5?

4: Worked Example
4: Worked Example
4: Worked Example

Which statement best explains why alloys tend to be less malleable than pure
metals?

A. The added metal has more valence electrons so increases the amount of
delocalisation
B. The added metal prevents the layers from being drawn out into a wire
C. The added metal disturbs the lattice so the layers are less able to slide over
each other
D. The added metal acts as an impurity and so lowers the melting point
4: Worked Example

1. State and explain which of propan-1-ol, CH3CH2CH2OH, and methoxyethane,

CH3OCH2CH3, is more volatile.
2. Propan-1-ol, CH3CH2CH2OH, and hexan-1-ol, CH3(CH2)4CH2OH, are both
alcohols. State and explain which compound is more soluble in water.
3. Graphite is used as a lubricant and is an electrical conductor. Diamond is hard
and does not conduct electricity. Explain these statements in terms of the
structure and bonding of these allotropes of carbon.
4: Worked Example
1. Methoxyethane, CH3OCH2CH3, is more volatile, because it does not have hydrogen bonding (unlike
the alcohol) and the strongest intermolecular attraction is dipole-dipole.

2. Propan-1-ol, CH3CH2CH2OH, is more soluble in water, as the nonpolar carbon chain is shorter.

3. Graphite forms a layer of hexagonal rings, and each C atom is bonded to three other C atoms.
Layers are held by weak attractive forces and so can slide over each other with delocalised
electrons between the layers (which also makes graphite a good electrical conductor). Diamond has
all C atoms bonded to four other C atoms. It is a giant tetrahedral structure with strong covalent
bonds and no delocalised electrons.
14.1 Further aspects of covalent bonding

● Some molecules contain a central

atom with an expanded octet
● This is possible because the d
orbitals available in the valence
shell of these atoms have energy
values relatively close to those of
the p orbital, so promotion is
relatively easy and will allow
additional electron pairs to form
14.1 Further aspects of covalent bonding

● Molecular geometry determines

molecular polarity
● If there are no lone pairs and all the
atoms attached to the central atom
are the same, the molecules are
nonpolar
● If the atoms attached to the central
atom are not all the same, there
may or may not be a net dipole
depending on the symmetry
14.1 Further aspects of covalent bonding

● Recall that resonance occurs when

a molecule allows for more than
one valid Lewis structure to be
drawn
● In order to determine the most
stable structure we use the concept
of formal charge. It treats covalent
bonds as if they were purely
covalent with equal electron
distribution
14.1 Further aspects of covalent bonding
Preferred structure ↴
● Low formal charge means that less
charge transfer has taken place in
forming a structure from its atoms
○ The preferred structure is the one
with the formal charge that is equal
to the overall charge of the molecule
● If there are multiple lowest formal
charges, the preferred structure is the
Preferred structure ↴
one with the negative number(s)
assigned to the more electronegative
element
 14.1 Further aspects of covalent bonding

● Ozone, O3, has two resonance structures and δ+

a bond angle of ~ 117°. Its resonance hybrid

δ-
is pictured here. δ-
● Ozone is polar due to its formal charges
● Ozone is an essential component of the
lower part of the stratosphere
● O・denotes a free radical that has an
unpaired electron and so is highly reactive
● Oxygen contains stronger bonds than ozone,
and so is dissociated by a shorter
wavelength of light
14.1 Further aspects of covalent bonding

● Ozone absorbs radiation

of wavelengths in the
range 200 - 315 nm
○ UV-B and UV-C →
Damage to living
tissue
○ Source of heat in the
stratosphere
14.1 Further aspects of covalent bonding

● Ozone’s ability to absorb UV

radiation also means that it is
unstable and reacts easily with
compounds found in the
stratosphere
○ Nitrogen oxides, NOx
○ Chlorofluorocarbons, CFCs
○ → Produce highly reactive
free radicals that catalyse
the decomposition of ozone
to oxygen
14.1 Further aspects of covalent bonding

● Chlorofluorocarbons were widely

used partially due to low toxicity
in the troposphere
○ → When they enter the
stratosphere, the higher UV
radiation breaks them down
○ → This releases Chlorine
free radicals
● The chlorine radicals catalyse
the decomposition of ozone
● → Cl・acts as a catalyst
14.1 Further aspects of covalent bonding

● A bond forms when two atomic

orbitals, each containing one
electron, overlap to form a new
molecular orbital that is at lower
energy
● The sigma (σ) bond
○ All single covalent bonds
are sigma bonds
○ Sigma bonds form by the
overlap of orbitals along the
bond axis
14.1 Further aspects of covalent bonding

● The pi (π) bond

○ Caused by the sideways overlap
of p orbitals
○ The electron density is
concentrated in two regions,
above and below the plane of
the bond axis
○ Double covalent bonds contain
one sigma and one pi bond.
Triple covalent bonds contain
one sigma and two pi bonds
14.1 Further aspects of covalent bonding

Any questions regarding 14.1?

14.2 Hybridisation

● The formation of covalent bonds often

starts with the excitation of atoms. Eg,
Carbon
○ Ground state electrons change
during bonding
○ Excitation occurs when an electron
is promoted within the atom from
the 2s to a vacant 2p orbital
○ The atom now has four singly
occupied orbitals available for
bonding
 14.2 Hybridisation

Different types of hybrid orbitals:

sp3: one s orbital + three p orbitals

sp2: one s orbital + two p orbitals

sp: one s orbital + one p orbital

● Hybridisation is the process where atomic orbitals within an atom mix to

produce hybrid orbitals of intermediate energy (degenerate orbitals). The
atom is able to form stronger covalent bonds using these hybrid orbitals.
14.2 Hybridisation

● sp3 hybridisation
○ The orbitals orientate
themselves at 109.5°,
forming a tetrahedron
○ Each hybrid orbital
overlaps with the atomic
orbital of another atom,
forming four sigma
bonds
○ eg, methane, CH4 →
14.2 Hybridisation

● sp2 hybridisation
○ When a double bond is formed,
the atom undergoes sp2
hybridisation in order to leave
one p-orbital unhybridised to
allow for a regular pi bond
○ The orbitals orientate
themselves at 120°, forming a
triangular planar shape, and
three sigma bonds are formed
14.2 Hybridisation

● sp hybridisation
○ When a triple bond is
formed, the atom
undergoes sp hybridisation,
leaving two p orbitals
unhybridised for the
formation of two pi bonds.
○ The orbitals orientate
themselves at 180°, giving
a linear shape
14.2 Hybridisation

Any questions regarding 14.2?

14: Worked Example
14: Worked Example
14: Worked Example
14: Worked Example
5(15) Energetics and
thermochemistry
5.1 Measuring energy changes

- Energy is a measure of the ability to do work

- Energy is conserved in chemical reactions
- Heat - energy transfer
- The system
- Open
- Closed
- Isolated
- Surroundings
5.1 Measuring energy changes

- Enthalpy (H) - a measure of the amount of heat

energy contained in a substance. It is stored in
the chemical bonds and intermolecular forces as
potential energy.
- Exothermic Reactions
- ΔH is negative
- Products are more energetically stable
- Heat is given out by the system
- Endothermic Reactions
- ΔH is positive
- Reactants are more energetically stable
- Energy transfer from system to
surroundings
-
5.1 Measuring energy changes

- Standard enthalpy changes

- The standard conditions:
- 100 kPa
- 1 mol/dm^3 for all solutions
- Standard states at 298 K
- Q = mcΔT
5.1 Measuring energy
changes
- Standard enthalpy of combustion
5.1 Measuring energy changes

- Enthalpy changes of reaction in solution

- Carrying out the reaction in an
isolated system
- Measure the temperature change
- Account for error
- Calculate energy released
- Divide by moles of limiting reaction
5.1 Measuring energy changes

Any questions?
5.2 Hess’s Law

Hess's law states that the enthalpy change for

any chemical reaction is independent of the
route, provided the starting conditions and final
conditions , and reactants and products, are the
same.
5.2 Hess’s Law

- Standard enthalpy of formation ΔHf𝛳, of a

substance is the enthalpy change that
occurs when one mole of the substance is
formed from its elements in their standard
states.
- Breaking bonds is endothermic
- Making bonds is exothermic
- Average bond enthalpy
5.2 Hess’s Law

Any questions?
5.3 Bond enthalpies

- Breaking bonds is an endothermic process

- Bond enthalpy & average bond enthalpy
- The average bond enthalpy is the energy
needed to break one mole of bonds in
gaseous molecules under standard
conditions averaged over similar
compounds.
- Making bonds is an exothermic process
- Bond enthalpies can be used to calculate
the enthalpy changes of reaction
5.3 Bond enthalpies
5.3 Bond Enthalpies

Any questions?
15.1 Energy cycles
Definitions to know:

- First ionization energy - minimum energy required to remove one mole of electrons from one
mole of gaseous atoms - endothermic
- First electron affinity - enthalpy change when one mole of gaseous electrons is added to one
mole of gaseous atoms - exothermic
- The lattice enthalpy is the enthalpy change that occurs when one mole of a solid ionic
compound is separated into gaseous ions under standard conditions.
- Hydration enthalpy is the change in enthalpy associated with 1 mole of gaseous ions
dissolving in water to form a solution
- The enthalpy change of solution is the enthalpy change when one mole of solute is dissolved
in a solvent to infinite dilution under standard conditions.
- The enthalpy of atomization is the enthalpy change that occurs when one mole of gaseous
atoms is formed from the element in its standard state
15.1 Energy cycles

The Born-Haber cycle

15.1 Energy cycles

- Theoretical lattice enthalpies can be

calculated from the ionic model
- Ionic model:
- Only interaction between ions
is due to electrostatic forces
between ions
- Increase in ionic radius - decrease in
attraction
- Increase in ionic charge - increase in
attraction
15.1 Energy cycles

- Enthalpies of solution
- The enthalpy change of hydration of an ion
is the enthalpy change that occurs when
one mole of gaseous ions is dissolved to
form an infinitely dilute solution of one
mole of aqueous ions under standard
conditions of temperature and pressure
- The enthalpy change of solution is related
to the lattice enthalpy and the hydration
enthalpies of the constituent ions
15.1 Energy cycles
Please don't have any

Any questions?
15.2 Entropy and spontaneity

- Entropy (S) refers to the distribution of

available energy among the particles.
- Second law of thermodynamics states the
total entropy of an isolated system can never
decrease over time
- Changing from an ordered state to a more
disordered increases entropy
15.2 Entropy and spontaneity

- Gibbs free energy is a measure of the

energy which is free to do useful work
rather than leave the system
- ΔG < 0 - spontaneous
- ΔG > 0 - non spontaneous
- At low temperature: ΔG = ΔH, all
exothermic reactions can occur at low
temperatures
- At high temperatures: ΔG = -TΔS, all
reactions which have positive ΔS value are
feasible at high temperatures even if
they're endothermic.
- Gibbs free energy and equilibrium
6: Chemical Kinetics
16: Chemical Kinetics (AHL)

IB SL/ HL Chemistry
Revision Session March 2019
6.1 Collision Theory and Rates of Reaction

● The reaction mechanism is a

sequence of making and breaking
bonds
● Rate of a reaction: rate of change
in concentration per unit time (s-1)
● Rate depends on how quickly the
concentration of product or
reactant changes with respect to
time
● Units molldm-3s-1
6.1 Collision Theory and Rates of Reaction

● Gradient of a curve is used to

measure rate
● Gradient is not constant
○ Concentration of reactants is
greatest at the start
○ Rate is greatest at the start
● Initial Rate
○ Take the tangent of the curve
at t=0
6.1 Collision Theory and Rates of Reaction

● Techniques for measuring rate of

reaction
○ 1) Change in volume
○ 2) Change in mass
○ 3) Change in transmission of light
○ 4) Change in concentration
measured using titration
○ 5) Change in concentration
measured using conductivity
○ 6) Non-continuous methods of
detecting a change during a reaction
6.1 Collision Theory and Rates of Reaction

● Particles in a substance move randomly as a result of the kinetic energy that

they possess
● Temperature in Kelvin is proportional to the average kinetic energy of the
particles in a substance
6.1 Collision Theory and Rates of Reaction

● Maxwell-Boltzmann distribution curve

○ The probability of a certain value
occuring plotted against kinetic
energy
○ Area under the curve: total
number of particles in the sample
● How do reactions happen?
○ Kinetic energy of particles causes
them to collide
○ ‘Successful’ collision: formation
of products
6.1 Collision Theory and Rates of Reaction

● Energy of Collision
○ Activation Energy,
Ea, is the minimum
value of kinetic
energy which
particles must have
before they are able
to react
● Geometry of Collision
○ Orientation of
particles
6.1 Collision Theory and Rates of Reaction

● 1) Temperature
○ Increasing temperature increases
average kinetic energy of the
particles
○ More particles collide
successfully
● 2) Concentration
○ Increasing concentration
increases rate of reaction
○ Frequency of (successful)
collisions increases
6.1 Collision Theory and Rates of Reaction

● 3) Particle Size
○ Decreasing particle size
increases rate of reaction
○ Heterogeneous reactions:
Surface area
● 4) Pressure
○ Reactions involving gases
○ Increasing pressure increases
concentration
○ Increases probability of
successful collisions
6.1 Collision Theory and Rates of Reaction

● 5) Catalyst
○ A catalyst is a substance that
increases the rate of a chemical
reaction without itself undergoing
permanent chemical change.
○ Most catalysts work by providing
an alternate route for the reaction
pathway that has a lower
activation energy.
○ Biological catalyst: Enzyme
6.1 Collision Theory and Rates of Reaction

Any questions regarding 6.1?

6:Worked Example
6:Worked Example
6:Worked Example
6:Worked Example
6:Worked Example

(i)

(ii) The minimum energy required for the reaction to proceed.

(iii) Increases the rate of reaction by lowering the activation energy.

16.1 Rate Expression and Reaction Mechanism

● The rate law for a reaction is derived

empirically

reaction rate ∝ [C60O3]

reaction rate = k [C60O3]

● k is the rate constant

● Orders of a reaction
○ The rate is proportional to the product
of the concentrations of the reactants,
each raised to a power
16.1 Rate Expression and Reaction Mechanism

● Units of k depend on the order of the reaction

● The value of k can be calculated from the rate expression when the
concentrations of reactants and the corresponding rate are known
16.1 Rate Expression and Reaction Mechanism
16.1 Rate Expression and Reaction Mechanism
16.1 Rate Expression and Reaction Mechanism
16.1 Rate Expression and Reaction Mechanism
16.1 Rate Expression and Reaction Mechanism

● If a reactant has a
constant half-life, then
the reaction must be first
order with respect to that
reactant
● The shorter the value of
the half-life, the faster the
reaction
● Radioactive decay
reactions follow
first-order kinetics
16.1 Rate Expression and Reaction Mechanism

● Initial rates method:

● Changing [A] → no effect on
rate → zero order with respect
to A
● Changing [A] → directly
proportional change to rate →
first order with respect to A
● Changing [A] → square of that
change in rate → second
order with respect to A rate = k [A] [B]2
16.1 Rate Expression and Reaction Mechanism

● Reaction mechanism: sequence

of steps of a reaction
● Elementary steps: individual
steps in the reaction mechanism
● Intermediates: products of a
single step that are used in a
subsequent step
● Molecularity: indicates the
number of reactant species
involved
16.1 Rate Expression and Reaction Mechanism

● The overall rate of reaction is

determined by the slowest step
in the sequence
○ Rate-determining step
● Products of the reaction can only
appear as fast as the products of
this elementary step
● The rate expression for an
overall reaction is determined by
reaction mechanism
16.1 Rate Expression and Reaction Mechanism

Any questions regarding 16.1?

16.2 Activation Energy

● The Arrhenius Equation:

● Take the natural logarithm of both

sides of the equation:

● Finding k given two temperatures:

16.2 Activation Energy

Any questions regarding 16.2?

16: Worked Example
7: Equilibrium
17: The Equilibrium Law (AHL)

IB SL/ HL Chemistry
Revision Session March 2019
7.1 Equilibrium

● Physical Systems
○ Equilibrium: when the rate of
the forwards and the reverse
reaction are equal →
● Chemical Systems
○ 2HI (g) ⇌ H2 (g) + I2 (g) ⤵
7.1 Equilibrium

● Constant concentrations ≠
equal concentrations
● Equilibrium mixture: the
proportion of reactants
and products at
equilibrium
● Predominantly Products:
‘lie to the right’
● Predominantly Reactants:
‘lie to the left’
7.1 Equilibrium

● The equilibrium constant

Kc can be predicted from a
reaction’s stoichiometry
● The equilibrium constant
Kc has a fixed value for a
certain reaction at a
specified temperature.
● Every reaction has its own
particular value of Kc
7.1 Equilibrium

● The magnitude of Kc gives information on the extent of reaction

● If Kc ≫ 1, the reaction is considered to almost go to completion
● If Kc ≪ 1, the reaction is considered to hardly proceed
7.1 Equilibrium

● The reaction quotient, Q,

enables us to predict the Q > Kc ≡ Products are greater, so
direction of a reaction
the reverse reaction is favoured
● It is measured the same way
as Kc, except when the Q = Kc ≡ The reaction is at
reaction is not at equilibrium
● It is a measure of the equilibrium
relative amounts of Q < Kc ≡ Reactants are greater,
reactants and products
present in a reaction at a so the forwards reaction is favoured
particular time
7.1 Equilibrium

Change in Equation Expression of Kc Effect on Kc

Reversing the reaction Inverts the expression 1/Kc or Kc-1

Doubling coefficients Squares expression K c2

Halving coefficients Root of expression √Kc

Adding reactions Multiplies expression Kc = Kc1 × Kc2 …..

7.1 Equilibrium

● Le Châtelier’s Principle
states that a system at
equilibrium when subjected
to a change will respond in
such a way as to minimise
the effect of that change.
● 1) Changes in concentration
○ Does not affect Kc
○ The reaction will shift in
the direction where a
substance is removed
7.1 Equilibrium

● 2) Changes in Pressure ● 3) Changes in Temperature

○ Does not affect Kc ○ If the temperature is increased, the
○ There is only an effect if reaction will shift towards the
all molecules are in the endothermic (+ΔH) direction
gaseous phase ○ This does affect the equilibrium
○ At increased pressure, constant.
the reaction will shift
towards the side with
the least gaseous
molecules
7.1 Equilibrium

● 4) Addition of a
catalyst
○ Adding a catalyst
does not change
the position of
equilibrium and
the value of Kc
for that reaction
○ It only lowers
activation energy
7.1 Equilibrium
7.1 Equilibrium

● Haber Process
○ Reactants
N2(g) + 3H2(g) ⇌ 2NH3(g)
and Products
are all
gaseous Nitrogen + Hydrogen ⇌ Ammonia
○ There are less gas gas gas
gaseous
moles in the
products ΔH = -93 kJ/mol
7.1 Equilibrium

● The Contact Process

○ i) Combustion of sulphur
to form sulphur dioxide
○ ii) Oxidation of sulphur
dioxide to sulphur trioxide
○ iii) Combination of sulphur
trioxide with water to
produce sulphuric acid
● Rate of the process depends
on step (ii)
7.1 Equilibrium

Any questions regarding 7.1?

7: Worked Example
7: Worked Example
 7: Worked Example
Ethanol is manufactured by the hydration of ethene according to the equation below.
C2H4 (g)+ H2O (g) ⇋ C2H5OH (g)
a) State the expression for the equilibrium constant, Kc , for this reaction.
b) Under certain conditions, the value of Kc for this reaction is 3.7 x 10-3. When the
temperature is increased the value is 4.9 x 10-4.
i) State what can be deduced about the position of equilibrium at the higher
temperature from these values of Kc .
ii) State what can be deduced about the sign of ΔH for the reaction, explaining
your choice.
c) The process used to manufacture ethanol is carried out at high pressure. State
two advantages of using high pressure.
 7: Worked Example
a) [C2H5OH ] a) Use the general formula.
[C2H4]x[H2O]
b) b)
i) It is shifted to the left. i) Q is less than Kc , therefore there are
more reactants.
ii) ΔH is negative. ii) The temperature was increased and the
reaction shifted towards the reactants,
meaning they must be the endothermic
side, so the forwards reaction is
exothermic.
c) - rate of reaction increased c) Recall Le Châtelier’s Principle
- increased collision frequency
- equilibrium shifted to right
- fewer moles of gas on the right
17.1 The Equilibrium Law

● RICE boxes consist of four 0.50 mol of I2 (g) and 0.50 mol of Br2 (g) are placed in a
elements: closed flask. The following equilibrium is established.

● 1) The Balanced Reaction I2 (g) + Br2 (g) ⇋ 2IBr (g)

● 2) Initial Concentrations
The equilibrium mixture contains 0.80 mol of IBr (g). What
● 3) Change in concentrations is the value of Kc?
● 4) Equilibrium concentrations
17.1 The Equilibrium Law
17.1 The Equilibrium Law

● When Kc < 10-3, you can approximate:

○ [reactant]initial = [reactant]equilibrium
17.1 The Equilibrium Law

● Different reactions have widely

differing values of Kc
● In some cases, such as the
ionisation of water, the
reaction barely takes place,
while in other reactions, such
as the combustion of
methane, it almost goes to
completion
17.1 The Equilibrium Law
17.1 The Equilibrium Law

● ΔGӨ = standard free energy change

● R = the gas constant 8.31JK-1mol-1
● T = the absolute temperature, in Kelvin
● ln K = the natural logarithm of Kc
17.1 The Equilibrium Law

● Kc for rusting of iron: 10261

● Concentration does not affect
Kc because the concentration
changes don’t affect the
values of the rate constants
● Adding a catalyst increases
the values of k and k’ by the
same factor so Kc is not
affected
● Kc increases as the
temperature increases
17.1 The Equilibrium Law

Any questions regarding 17.1?

8(18) Acids and Bases
8.1 Theories of acids and bases
- Lavoisier - oxygen + non-metal
- Arrhenius
- Acids: hydroxide + cations
- Bases: hydrogen ions + anions
- Brønsted-Lowey:
- A Bronsted-Lowry acid is a proton (H+) donor
- A Bronsted-Lowry base is a proton (H+) acceptor.
- The acid and base in a conjugate pair differ by just one
proton.
- An amphoteric substance is a substance than can act
as either an acid or base depending on what it is
reacting with.
- An amphiprotic substance is a substance that can act
as either a proton donor or a proton acceptor depending
on what it is reacting with.
8.1 Theories of acid and bases

Any questions?
8.2 Properties of acids and bases

- Alkalis are bases that dissolve in water to form the hydroxide

ion OH-

1. Acid + metal -> salt + hydrogen

2. Acid + base -> salt + water

- Enthalpy of neutralization

3. Acid + carbonate -> salt + water + carbon dioxide

8.2 Properties of acids and bases

- Acids and bases can be distinguished using indicators

- Acid-base titrations are based on neutralization reactions

8.2 Properties of acids and bases

Any questions?
8.3 The pH scale

- Measuring pH
- Indicator
- pH meter

The ionization of water

8.3 The pH scale

Any questions?
 8.4 Strong and weak acids and bases

- The strength of an acid or base depends on

its extent of ionization

Distinguishing between strong and

weak:
1. Electrical conductivity
2. Rate of reaction
3. pH
8.4 Strong and weak acids and bases

Any questions?
18.1 Lewis acids and bases

- A Lewis acid is a lone pair acceptor

- A Lewis base is a lone pair donor

- A nucleophile is an electron-rich species that

donates a lone pair to form a new covalent
bond in a reaction

- An electrophile is an electron deficient

species that accepts a lone pair from another
reactant to form a new covalent bond.
18.1 Lewis acids and bases

Any questions?
18.2 Calculations involving acids and bases
18.2 Calculations involving acids and bases
18.2 Calculations involving acids and bases

Acid dissociation constant (Ka)

Base dissociation constant (Kb)

18.2 Calculations involving acids and bases
18.2 Calculations involving acids and bases

Any questions?
18.3 pH curves
18.3 pH curves

- Making buffer solutions:

- pH depends on:
- pKa or pKb Factors influencing buffers
- Ratio of acid:salt or base:salt - Dilution
- Acid or base must have pKa or pKb - Temperature
values as close to pH or pOH of buffer
- Mixing with salt
- Neutralization
 18.3 pH curves
- Salt hydrolysis

- Salt of strong acid and strong base -

no hydrolysis
- pH approx. 7
- Salt of weak acid and strong base -
anion hydrolysis
- pH > 7
- Salt of strong acid and weak base -
cation hydrolysis
- pH < 7
- Salt of weak acid and weak base -
¯\_(ツ)_/¯
18.3 pH curves

Strong acid and strong base Weak acid and strong base
18.3 pH curves

Strong acid and weak base Weak acid and weak base
18.3 pH curves
- Indicators signal the change in pH
18.3 pH curves

Any questions?
8.5 Acid deposition

- Rainwater is naturally acidic due to

dissolved CO2. rain water with a pH < 5.6 is
known as acid rain

- Wet acid deposition: rain, snow, sleet, hail,

fog, mist, dew
- Dry acid deposition: acidifying particles,
gases fall to ground as dust and smoke,
later dissolve in water to form acids
8.5 Acid deposition
Sulfur oxidizes Nitrogen oxides
8.5 Acid deposition

Effects of acid deposition - Plant life

- Materials - Leaching of Mg2+, Ca2+, and K2+
- Marble & limestone - Release of Al3+
- Stomata

- Water
- Lowers pH
- Release of Al3+
- Eutrophication
- Metals (Iron & Aluminium)
- Human health
- Inhaling of sulfate and nitrate
particles
- Irritation to eyes
- Leaching of toxic metal ions such as
Al3+, Pb2+ and Cu2+
8.5 Acid deposition

Responses to acid deposition - Reduction of NOx emissions

- Catalytic converters in vehicles
- Reduction of SO2 emission
- Pre Combustion methods
- Hydrodesulfurization - Lower temperature combustion
- Post-combustion methods
- Flue gas desulfurization - Other options
- Lowering demand for fossil fuels
- Restoration of ecosystems damaged
by acid rain
- Use of CaO or Ca(OH)2
8.5 Acid deposition

Any questions?
9: Redox Processes

IB SL/ HL Chemistry
Revision Session March 2019
9.1 Oxidation and Reduction

● Half-equations show what

happens to each reactant in
terms of electrons
● Magnesium is gaining
electrons in both reactions
● Oxidation is the loss of
electrons, reduction is the gain
of electrons
○ Mnemonic: OIL RIG
9.1 Oxidation and Reduction

● Oxidation state is a value

assigned to each atom in a
compound (apparent charge)
○ The sign: ‘+’ means the
atom has lost electron
control, ‘-’ means it has
gained electron control
○ Its value: refers to the
number of electrons over
which control has been
changed
9.1 Oxidation and Reduction

● A redox reaction is a chemical

reaction in which changes in the
oxidation state occur. Oxidation
occurs when there is an increase in
oxidation state of an element,
reduction occurs when there is a
decrease in oxidation state of an
element.
● IUPAC nomenclature uses roman
numerals to indicate oxidation
state
9.1 Oxidation and Reduction
9.1 Oxidation and Reduction
9.1 Oxidation and Reduction

● In a redox reaction, the

substance that is reduced is
the oxidising agent and the
substance that is oxidised is
the reducing agent
9.1 Oxidation and Reduction

● More reactive metals are

stronger reducing agents
● The comparison of different
displacement reactions is the
origin of the activity series:
9.1 Oxidation and Reduction

● More reactive non-metals are stronger

oxidising agents
● The comparison of different displacement
reactions is the origin of the activity series:
9.1 Oxidation and Reduction

● The titration is based on a redox reaction between the two reactants and finds
the equivalence point where they have reacted by transferring electrons
● Carried out in the same way as acid-base titrations, but sometimes an
indicator isn’t needed due to a colour change within the redox reaction itself
9.1 Oxidation and Reduction

● Te redox titration uses

KMnO4 in an acidic solution
as the oxidising agent
● It’s accompanied by a colour
change from deep purple to
colourless
● The liberated iodine is then
titrated with sodium
thiosulphate using starch as
an indicator
● Deep blue to colourless
9.1 Oxidation and Reduction

● The biological oxygen

demand, or BOD, is the
quantity of oxygen needed to
oxidise organic matter in a
sample of water over a
five-day period at a specified
temperature
● The Winkler method
calculates BOD from
sequences of steps and
redox titrations
9.1 Oxidation and Reduction

Any questions regarding 9.1?

9.2 & 19.1 Electrochemical cells

- Half-cells generate electrode potential

- The more reactive the metal the more
negative the electrode potential
9.2 & 19.1 Electrochemical cells

- Two connected half-cells make a voltaic

cell
- Electrons flow from anode to cathode
- Redcat, anox
- Salt bridge completes the circuit
- Anode - negative
- Cathode positive
- A salt bridge completes the circuit

- Cell
Diagram
convention:
9.2 & 19.1 Electrochemical cells
Summary:
- Electrons flow from anode to cathode through the external circuit
- Anions migrate from cathode to anode through salt bridge
- Cations migrate from anode to cathode through salt bridge
9.2 & 19.1 Electrochemical cells

- Electromotive force - potential

generated between two half cells
- Electrode potential (E)
- Standard hydrogen electrode is
assigned an electrode potential value
of 0V
- Conditions to measure standard
electrode potential:
- All solutions must have concentration of 1
-3
mol dm
- All gases must be at pressure 100 kPa
- All substances must be pure
- Temperature is 298 K
- If half-cell does not include a solid metal,
platinum is used as the electrode
9.2 & 19.1 Electrochemical cells

- Using the standard electrode potential data:

- Ecell = Ered - Eox (*dont invert, multiply or
alter values)
- Ecell Is positive for all spontaneous
reactions

- Electrode potential and free energy (ΔG)

- When Ecell is positive, ΔG is negative -

reaction is spontaneous
- When Ecell is negative, ΔG is positive -
reaction is nonspontaneous
- When Ecell is 0, ΔG is 0 - reaction is at
equilibrium
9.2 & 19.1 Electrochemical cells

- External source drives non-spontaneous

reactions
- Electrolyte is the solution
- Electrodes immersed in electrolyte
- Electric wires connect the electrodes

- Redox reactions occur at the electrodes

- Cathode:

- Anode:
9.2 & 19.1 Electrochemical cells
- Electrolysis of molten salts
- No solvents so only ions of salt are present
- Electrolysis of aqueous solutions
- At the cathode H2O reduced to H2

- At the anode, H2O can be oxidized to O2

- Considering a solute M+A= is in aqueous solution

- At the anode: A- or H2O can be oxidized
- At the cathode: M+ or H2O can be reduced
- Selective discharge:
- Relative E values of ions
- At cathode - less negative one
- At anode - less positive one
- Relative concentrations of the ions
- If [ion].25% its favoured
- Nature of the electrode
- If metal used is oxidizable, it will do that instead of ions
9.2 & 19.1 Electrochemical cells

Factors affecting the amount of product in electrolysis:

- Current
- Duration of electrolysis
- Charge on ions
9.2 & 19.1 Electrochemical cells

- Electroplating - using electrolysis to

deposit a layer of a metal on top of
another metal or conductive object
- An electrolyte containing the metal ions to
be deposited
- Cathode made of the object to be plates
- Anode is same metal which is to be coated
- Purposes:
- Decorative
- Corrosion control - rion with a layer of zinc
(galvanized tion) as zinc is preferentially
oxidized
- Improvement of function - e.g.
electroplating with chromium improves
wear on steel parts
9.2 & 19.1 Electrochemical cells

Any questions?
10: Organic Chemistry
20: Organic Chemistry (AHL)

IB SL/ HL Chemistry
Revision Session March 2019
10.1 Fundamentals of Organic Chemistry

● Homologous series
○ 1) Successive members
in a homologous series
differ by a -CH2- group
○ 2) Members can be
represented by the
same general formula
○ 3) Gradation in physical
properties
○ 4) Similar chemical
properties
10.1 Fundamentals of Organic Chemistry

Stereochemical
10.1 Fundamentals of Organic Chemistry
10.1 Fundamentals of Organic Chemistry
10.1 Fundamentals of Organic Chemistry
10.1 Fundamentals of Organic Chemistry

● Structural isomers are

molecules that have the
same molecular formula but
different arrangements of
the atoms ↑ Structural isomers of C4H10 ➝

↑ Structural isomers of C5H10 ↑

10.1 Fundamentals of Organic Chemistry

● Primary carbon atom: attached

to the functional group and also
at least two H atoms → Primary
molecules
● Secondary carbon atom:
attached to the functional group
and also one H atom and two
alkyl groups
● Tertiary carbon atom: attached
to the functional group, zero H
atoms, and three alkyl groups
10.1 Fundamentals of Organic Chemistry

● Kekulé’s proposed structure:

● Delocalisation causes electron

density to be in donut shapes Modern benzene model
above and below the plane of
the ring
10.1 Fundamentals of Organic Chemistry
10.1 Fundamentals of Organic Chemistry

● Parts that influence the physical properties of an organic molecule:

○ The Hydrocarbon skeleton
○ The Functional Group
10.1 Fundamentals of Organic Chemistry

Any questions regarding 10.1?

10.2 Functional Group Chemistry

Complete combustion:
● Combustion of alkanes:
● Complete: CO2 and H2O
● Incomplete: CO and H2O
● Extreme O2 limitation: C and H2O Incomplete combustion:
● Carbon monoxide: combines
irreversibly with haemoglobin in
blood
● Unburned carbon: contributes to In extreme O2 limitation:
global dimming
● Carbon dioxide: contributes to
global warming
10.2 Functional Group Chemistry

● Substitution reactions of alkanes:

● 1) Initiation (Cl2 → 2 Cl・ by
photochemical homolytic fission)
● 2) Propagation (uses and
produces radicals → chain rxn)
● 3) Termination ↓
10.2 Functional Group Chemistry

● Hydrogenation of alkenes:
● Nickel catalyst & 150°C
● Margarine industry: saturate oils
that contain unsaturated
hydrocarbon chains
● Addition of halogens:
● Produce dihalogeno compounds
● Loss of colour of the original
reacting halogen
● Reactions like this happen at
room temperature
10.2 Functional Group Chemistry

● Addition of halogen halides:

● Produces halogenoalkanes
● Room temperature
● Reactivity increases down Group
17 due to weaker H-X bonds
● Addition of water (hydration):
● conc. H2SO4 used as a catalyst
● Intermediate is involved
● Alcohols are formed from the
reaction of water to alkenes
10.2 Functional Group Chemistry

● Polymerisation of alkenes:
● Alkenes readily undergo addition
reactions
○ They can join together to form
addition polymers
○ Single unit: monomer
● Structures are shown using a
repeating unit
● Other polymers: PVC
(polychloroethene), and PTFE
(polytetrafluoroethene), or Teflon ®
10.2 Functional Group Chemistry
10.2 Functional Group Chemistry

● Combustion of alcohols:
● Produce CO2 and H2O
● Energy released per mol
increases up the homologous
series
10.2 Functional Group Chemistry

Oxidation of Alcohols:

● Potassium dichromate (VI) is a

common oxidising agent
○ Orange Cr (VI) is reduced to
green Cr (III)
○ Oxidising agent shown as [O]
● Primary alcohols
○ Aldehyde ➝ Carboxylic acid
○ eg, Ethanol ➝ Ethanal ➝
Ethanoic acid
10.2 Functional Group Chemistry

Oxidation of Alcohols:

● Secondary alcohols
○ Ketones
○ eg, Propan-2-ol ➝
Propanone
● Tertiary alcohols
○ No reaction
○ There is no hydrogen
attached to the carbon to
which the functional
group is attached
10.2 Functional Group Chemistry

● Esterification reaction:
● Alcohol + carboxylic acid ⇌
ester + water
● Nomenclature: prefix of the
alcohol + -yl & prefix of the
carboxylic acid + -anoate
10.2 Functional Group Chemistry

● Nucleophilic substitution of halogenoalkanes:

● Nucleophiles are species that are electron-rich and thus attracted to parts of
molecules that are electron-deficient
○ The halogen is replaced by the nucleophile in nucleophilic substitution
10.2 Functional Group Chemistry

● Benzene does not readily

undergo addition reactions
● Electrophiles are species
that have a positive/ partial
positive charge and are
electron deficient
● This leads to electrophilic
substitution reactions
10.2 Functional Group Chemistry

Any questions regarding 10.2?

10: Worked Example

Two compounds, A and D, each have the formula C4H9Cl.

Compound A is reacted with dilute aqueous sodium hydroxide to produce compound B with a formula of
C4H10O. Compound B is then oxidised with acidified potassium manganate (VII) to produce compound C
with a formula of C4H8O. Compound C resists further oxidation by acidified potassium manganate (VII).

Compound D is reacted with dilute aqueous sodium hydroxide to produce compound E with a formula of
C4H10O. Compound E does not react with acidified potassium manganate (VII).

Deduce the structural formulas for compounds A, B, C, D, and E.

10: Worked Example Solution Explanation

What are we given? What can we deduce?

A: C4H9Cl A is a halogenoalkane, and so is D. C is oxidised from the

B: C4H10O = C4H9OH alcohol B but cannot be oxidised further. This means that
C: C4H8O B must be a secondary alcohol and C must be a ketone.
D: C4H9Cl Therefore A is a secondary halogenoalkane.
E: ? → does not oxidise
D must also be a halogenoalkane from its given formula.
A + NaOH → B With NaOH it must therefore undergo a substitution
reaction like A, and hence E must be an alcohol. Since the
B → C (oxidation reaction) alcohol cannot be oxidised, it must be a tertiary alcohol.
So, D must be a tertiary halogenoalkane.
D + NaOH → E (does not oxidise further)
10: Worked Example Solution

A: B: C:

D: E:
O

C 3
20.1 Types of Organic Reactions

● Nucleophiles: electron rich

species
● Electrophiles: electron
deficient species
● SN = substitution
nucleophilic
● Polar C-X bond causes
carbon to be electron
deficient
● Bond breaks heterolytically
due to a nucleophile
20.1 Types of Organic Reactions

● Hydrogen atoms are small →

unstable transition state is
formed
○ Carbon is weakly bonded to
the nucleophile and the
halogen
● SN2: substitution nucleophilic
bimolecular
● Inversion → SN2 is
stereospecific
● Favoured by aprotic solvents
20.1 Types of Organic Reactions

● Alkyl groups cause steric

hindrance
● The halogenoalkane ionises by
breaking the C-X bond
● Carbocation intermediate
● Alkyl groups have a positive
inductive effect
● SN1: substitution nucleophilic
unimolecular
● The SN1 mechanism favours
protic solvents
20.1 Types of Organic Reactions

● Factors that affect the rate of

nucleophilic substitution
reactions:
● 1) Effect of the mechanism
● 2) The influence of the leaving
group
○ (a) Polarity of the C-X bond
○ (b) Strength of the C-X
bond
● 3) Choice of solvent
20.1 Types of Organic Reactions
20.1 Types of Organic Reactions

● Ethene & Bromine

● 1) Br is a non-polar molecule →
it becomes polarised by
electron repulsion
● 2) the Br atom nearest the
double bond gains a δ+ charge
and acts as the electrophile.
The bromine molecule splits
heterolytically, forming Br一 and
Br+
20.1 Types of Organic Reactions

● Ethene & Hydrogen

Bromide
● Hydrogen Bromide splits
heterolytically, into Br一
and H+, which is the
electrophile
● The carbocation forms
and then reacts with the
Br一 to form bromoethane
20.1 Types of Organic Reactions

● Unsymmetric addition:
● The electrophile attacks the
carbon with the most stable
carbocation (the one with the
most positive inductive effects
from the alkyl groups)
● Markovnikov’s rule: the
electrophilic portion of the
reagent adds to the carbon that
is bonded to the greater
number of hydrogen atoms
20.1 Types of Organic Reactions
20.1 Types of Organic Reactions

● Electrophilic substitution
reactions of benzene
● Loss of an H+ ion from the
intermediate leads to the
electrically neutral substitution
product as two electrons from
the C-H bond move to
regenerate the aromatic ring.
As a result, the product is more
stable.
20.1 Types of Organic Reactions

● The nitration of benzene is the

substitution of 一H by 一NO2 to
form nitrobenzene, C6H5NO2
● The electrophile, NO2+, is
generated by using a nitrating
mixture at 50°C
● NO2+ is a strong electrophile
and reacts with the π electrons
of the benzene ring to form the
carbocation intermediate.
20.1 Types of Organic Reactions

● Reduction of carbonyl
compounds
● Use of lithium aluminium
hydride, LiAlH4 →
○ Conditions: heat with
LiAlH4 in dry ether.
● Use of sodium borohydride,
NaBH4 →
○ Conditions: heat with
NaBH4 (aq)
20.1 Types of Organic Reactions
20.1 Types of Organic Reactions

Any questions regarding 20.1?

20.2 Synthetic Routes
20.2 Synthetic Routes

● The series of discrete steps involved in

creating reactions where the product
of one is the reactant of the next is
known as a synthetic route
● Retrosynthetic analysis: backwards
approach in which the functional
groups of target molecules are studied
and broken down into progressively
smaller fragments- precursors.
20.2 Synthetic routes

Any questions regarding 20.2?

20.3 Stereoisomerism

● Stereoisomerism is a type of
isomerism that has molecules
with atoms attached in the same
order, but which differ from each
other in their spatial arrangement
or three-dimensional
arrangement.
● Unlike structural isomers,
stereoisomers require
three-dimensional representation
20.3 Stereoisomerism

● When there is some constraint in a

molecule that restricts the free
rotation of substituted groups, they
become fixed in space relative to
each other
● Cis refers to the isomer that has
the same groups on the same side
of the double bond or ring, while
trans is the isomer that has the
same groups on opposite sides or
across the reference place
20.3 Stereoisomerism
20.3 Stereoisomerism

● E/Z isomerism is based on the

Cahn-Ingold-Prelog rules of priority
● Rule 1: the atom with the higher
atomic number has higher priority
● Rule 2: if the atoms are the same,
apply Rule 1 to the next atom
● Z-isomer: priority groups on the
same side
● E-isomer: priority groups on
opposite sides
20.3 Stereoisomerism

● A carbon atom attached to four

different atoms or groups is
known as a chiral, asymmetric, or
as a stereocentre
● Optical isomerism: the two mirror
images of this chiral
● Enantiomers: the two
non-superimposable forms
● A mixture containing equal
amounts of the two enantiomers:
racemic/ racemate
20.3 Stereoisomerism

● Diastereomers:
when molecules
have different
configurations at
one or more, but
not all, chiral
centres
○ Not mirror
images
20.3 Stereoisomerism

● The two enantiomers of a chiral compound rotate plane-polarised light in

equal and opposite directions.
20.3 Stereoisomerism

● When a racemic mixture is

reacted with a single
enantiomer of another chiral
compound, the two
components of the mixture
react to produce different
products
● The manufacture of a single
enantiomer using a chiral
catalyst is known as
asymmetric synthesis
20.3 Stereoisomerism

Any questions regarding 20.3?

20: Worked example
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