International Baccalaureate Chemistry Standard and

Higher Level 2014 Exam Revision Guide

Table of contents:

Topic 1: Quantitative chemistry

Topic 2: Atomic structure

Topic 12: Atomic structure (HL)

Topic 3: Periodicity
Topic 13: Periodicity (HL)

Topic 4: Bonding

Topic 14: Bonding (HL)

Topic 5: Energetics
Topic 15: Energetics (HL)

Topic 6: Kinetics

Topic 16: Kinetics (HL)

Topic 7: Equilibrium

Topic 17: Equilibrium (HL)

Topic 8: Acids and bases

Topic 18: Acids and bases (HL)

Topic 9: Oxidation and reduction

Topic 19: Oxidation and reduction (HL)

Topic 10: Organic chemistry

Topic 20: Organic chemistry (HL)

Option B: Human biochemistry

Option D: Medicines and drugs

Topic 1: Quantitative chemistry
1.1 The mole concept and Avogadro’s constant
1.1.1 Apply the mole concept to substances
1.1.2 Determine the number of particles and the amount of substance (in moles).

Moles
A mole (mol) of a substance:
 contains as many elementary entities (particles, atoms, molecules etc.) as there are atoms in 12
grams of pure carbon-12
 is the relative atomic (or molecular or formula) mass expressed in grams
 6.02 × 1023 elementary entities (Avogadro’s constant)

Molar mass
The molar mass (g mol-1) is the mass in grams of one mole of a substance.
Number of particles = number of moles × Avogadro’s constant

1.2 Formulas
1.2.1 Define the terms relative atomic mass (Ar) and relative molecular mass (Mr).
1.2.2 Calculate the mass of one mole of a species from its formula.
1.2.3 Solve problems involving the relationship between the amount of substance in moles, mass and molar mass.
1.2.4 Distinguish between the terms empirical formula and molecular formula.
1.2.5 Determine the empirical formula from the percentage composition or from other experimental data.
1.2.6 Determine the molecular formula when given both the empirical formula and experimental data.

Relative mass

Definitions

Relative atomic mass (Ar) – the relative atomic mass is the average mass of an atom,
taking into account the relative abundances of all the naturally occurring isotopes of the
element, relative to one atom of C-12. It is a relative term so it has no units.
Relative molecular mass (Mr) – the relative molecular mass is the average mass of a
molecule, calculated by adding the relative atomic masses of its constituent atoms. It is a
relative term so it has no units.

For formula units (the single units of ionic compounds), the term relative formula mass is used. The
mass of a mole of a species is the relative mass expressed in grams. The number of moles is given by:
Mass (g)
Moles (mol) =
Molar mass (g mol−1 )

Formulas
The molecular formula is the chemical formula of a substance showing the actual number of atoms of
each element in a molecule. The empirical formula is the formula in which the ratio is simplified into
the smallest integers.

Problem solving

Finding the empirical formula from percent composition:

 Just simplify to the smallest integer ratio
Finding the empirical formula from percent mass:
Divide the percentages by the relative atomic masses and then simplify to the smallest
integer ratio

Finding the molecular formula given the empirical formula and relative molecular
mass:
1. Use the empirical formula to find the empirical mass
2. Divide the molecular mass by the empirical mass, and round to an integer, n
3. Multiply the empirical formula by n

1.3 Chemical equations

1.3.1 Deduce chemical equations when all reactants and products are given.
1.3.2 Identify the mole ratio of any two species in a chemical equation.
1.3.3 Apply the state symbols (s), (l), (g) and (aq).

1.4 Mass and gaseous volume relationships in chemical reactions

1.4.1 Calculate theoretical yields from chemical equations.
1.4.2 Determine the limiting reactant and the reactant in excess when quantities of reacting substances are given.
1.4.3 Solve problems involving theoretical, experimental and percentage yield.
1.4.4 Apply Avogadro’s law to calculate reacting volumes of gases.
1.4.5 Apply the concept of molar volume at standard temperature and pressure in calculations.
1.4.6 Solve problems involving the relationship between temperature, pressure and volume for a fixed mass of an ideal gas.
1.4.7 Solve problems using the ideal gas equation, PV = nRT
1.4.8 Analyse graphs relating to the ideal gas equation.

Theoretical yield
Theoretical yields assume that the limiting reagent is 100% used up. The actual yield is called the
experimental yield.

experimental yield
Percentage yield (%) = × 100%
theoretical yield
Limiting and excess reactants

Problem solving

If A + B → C
1. Calculate how much of reactant B (in moles) is needed to react with the amount of
reactant A provided.
2. If the amount needed is less than that provided, B is in excess and vice versa. A is
therefore the limiting reagent.
3. The difference between the amount of B needed and the amount of B provided is
equivalent to the moles of excess B.
4. The amount of product formed if A reacts completely is the theoretical yield.
Avogadro’s law
Avogadro’s law states that equal volumes of all gases under identical conditions of pressure and
temperature contain the same number of molecules i.e. the molar volume of gas A is the same as that
of gas B if the conditions (pressure and temperature) are the same. Under standard conditions (273K
and 1.013 × 105 Pa or 1 atm) the volume per mole is 22.4 dm3.

Ideal gases
The ideal gas equation is:
𝑃𝑉 = 𝑛𝑅𝑇

Where R is the gas constant which has a value of 8.31 J K-1 mol-1
The ideal gas equation implies Avogadro’s law. We can also use it to derive laws for specific cases by
moving the variables to the left hand side and the constants to the right hand side.

Law Result Formula

𝑃𝑉 𝑃1 𝑉1 𝑃2 𝑉2
Combined gas law =𝑘 =
𝑇 𝑇1 𝑇2

𝑃 𝑃1 𝑃2
Gay-Lussac’s law =𝑘 =
𝑇 𝑇1 𝑇2

Boyle’s law 𝑃𝑉 = 𝑘 𝑃1 𝑉1 = 𝑃2 𝑉2

𝑉 𝑉1 𝑉2
Charles’s law =𝑘 =
𝑇 𝑇1 𝑇2

1.5 Solutions
1.5.1 Distinguish between the terms solute, solvent, solution and concentration (g dm-3 and mol dm-3).
1.5.2 Solve problems involving concentration, amount of solute and volume of solution.

Definitions

Solute – the solute is the substance dissolved in a solvent in forming a solution.

Solvent – the solvent is the liquid that dissolves another substance or substances to form a
solution.
Solution – a solution is a homogeneous mixture of a liquid (the solvent) with another
substance (the solute). There is usually some interaction between the solvent and solute
molecules.
Concentration – concentration is the amount of solute in a known volume of solution. It can
be expressed either as g dm-3 or as mol dm-3. Concentration in mol dm-3 is often represented
by square brackets around the substance.
𝑛
𝑐=
𝑉
Topic 2: Atomic structure
2.1 The atom
2.1.1 State the position of protons, neutrons and electrons in the atom.
2.1.2 State the relative masses and relative charges of protons, neutrons and electrons.
2.1.3 Define the terms mass number (A), atomic number (Z) and isotopes of an element.
2.1.4 Deduce the symbol for an isotope given its mass number and atomic number.
2.1.5 Calculate the number of protons, neutrons and electrons in atoms and ions from the mass number, atomic number and
charge.
2.1.6 Compare the properties of the isotopes of an element.
2.1.7 Discuss the uses of radioisotopes

Atomic structure
Protons and neutrons (nucleons) are found in the nucleus. Electrons are found in energy levels or
‘shells’ surrounding the nucleus.

relative relative
particle
mass charge
proton 1 +1
neutron 1 0
electron 5 × 10-4 -1

IB definitions

Mass number (A) – the mass number of an atom is the total number of protons plus
neutrons in its nucleus.
Atomic number (Z) – the atomic number of an atom is the number of protons in its nucleus.
It is also equal to the number of electrons it contains. The atomic number defines the
element and its position in the Periodic Table.
Isotopes – atoms of the same element (and so have the same atomic number, Z) but have
different numbers of neutrons (and so have different mass number, A).

Calculations
 Number of protons = atomic number
 Number of electrons = atomic number – charge e.g. O-2 → 8 – (-2) = 10 electrons
 Number of neutrons = mass number – atomic number

Properties of isotopes
Isotopes show the same chemical properties as neutrons do not participate in chemical reactions. A
larger relative atomic mass means a larger density and a slower movement of atoms for a given
temperature. These differences affect the melting and boiling points and can be used in separation of
isotopes

Uses of radioisotopes
Uses of radioisotopes include: nuclear power generation, the sterilisation of surgical instruments in
hospitals, crime detection, finding cracks and stresses in metals and the preservation of food,
specifically:
 Carbon-14 is used in carbon-dating.
 Cobalt-60 is used in radiotherapy.
 Iodine-131 is used as a tracer in medicine for treating and diagnosing illnesses
 Uranium-235 is used for nuclear fission in power plants.
 2.2 The mass spectrometer
2.2.1 Describe and explain the operation of a mass spectrometer.
2.2.2 Describe how the mass spectrometer may be used to determine relative atomic mass using the 12C scale.
2.2.3 Calculate non-integer relative atomic masses and abundance of isotopes from given data.

The mass spectrometer

A mass spectrometer is used to determine relative atomic masses.
The stages of operation are:
1. Vaporisation: a vaporised sample is injected into
the instrument; this allows individual atoms to be
analysed
2. Ionisation: atoms are bombarded with a stream of
high energy electrons, knocking off valence electrons
3. Acceleration: the positive ions are attracted by the
negatively charged plates; they are accelerated by the
electric field
4. Deflection: the ions are deflected by an external
magnetic field placed at right angles to their path; the
amount of deflection is proportional to the
charge/mass ratio.
5. Detection: ions of a particular mass/charge ratio
are detected and a signal is sent to a recorder; the
strength of the signal is a measure of the number of
ions

Calculating the Ar
Using a mass spectrum, we can find out the relative atomic mass. The relative atomic mass is equal to
the sum of the relative abundances multiplied by their respective masses divided by the sum of the
relative abundances (which should be 100 if you’re dealing with percentages):

∑(relative abundance × mass)

𝐴𝑟 =
∑ relative abundances

Problems on this subject are usually quite easy; however there is one case which is not immediately
obvious: working out the abundances of isotopes given that there are only two and that you know the Ar.
The trick is that if one isotope has an abundance x, then the other must have an abundance of 100 – x,
thus there is only one variable so the problem is capable of being solved.

Problem solving

Chlorine has two isotopes – 35Cl and 37Cl and a relative atomic mass of 35.5. What are the
abundances of the two isotopes?
Let x represent the abundance of 35Cl.

𝑥 × 35 + (100 − 𝑥) × 37
35.5 =
100
35.5 × 100 = 35𝑥 + 3700 − 37𝑥
2𝑥 = 150
𝑥 = 75%
 So the abundance of 35Cl is 75% and the latter is 25% abundant.

2.3 Electron arrangement

2.3.1 Describe the electromagnetic spectrum.
2.3.2 Distinguish between a continuous spectrum and a line spectrum.
2.3.3 Explain how the lines in the emission spectrum of hydrogen are related to electron energy levels.
2.3.4 Deduce the electron arrangement for atoms and ions up to Z = 20.

Students should be able to identify the ultraviolet, visible and infrared and variation of wavelength and
frequency across the spectrum:

A continuous spectrum shows an unbroken sequence of frequencies, such as the spectrum of visible
light. A line spectrum is an emission spectrum that has only certain frequencies of light. It is produced
by excited atoms and ions as they fall back to a lower energy level.
The Bohr model
According to the Bohr model, an electron moves into a higher energy level when it absorbs energy,
from the ground state to an excited state. This absorption produces the absorption lines. When the
electrons fall back to the ground state they emit energy, producing the emission lines. The fact that
only a few distinct colours can be observed shows there are only certain orbits in which an electron can
be placed.

∆𝐸electron = 𝐸photon = ℎ𝑓

The emission spectrum of hydrogen

The observed emission spectrum show above results from the energy differences between energy
levels that correspond to frequencies in the visible light region (the Balmer series). These are jumps
from higher energy levels to the second energy levels. Jumps to the first energy level (the ground state)
produce higher frequency emissions (ultraviolet) and jumps down to the third level produce lower
frequency infrared radiation. The lines converge at higher energies because the energy levels inside the
atoms become closer together.
Electron arrangement

Element Electron arrangement Element Electron arrangement

1H 1 11Na 2, 8, 1

2He 2 12Mg 2, 8, 2

3Li 2, 1 13Al 2, 8, 3

4Be 2, 2 14Si 2, 8, 4

5B 2, 3 15P 2, 8, 5

6C 2, 4 16S 2, 8, 6

7N 2, 5 17Cl 2, 8, 7

8O 2, 6 18Ar 2, 8, 8

9F 2, 7 19K 2, 8, 8, 1

10Ne 2, 8 20Ca 2, 8, 8, 2

Topic 12: Atomic structure (HL)

12.1 Electron configuration
12.1.1 Explain how evidence from first ionization energies across periods accounts for the existence of main energy levels and
sub-levels in atoms.
12.1.2 Explain how successive ionization energy data is related to the electron configuration of an atom.
12.1.3 State the relative energies of s, p, d and f orbitals in a single energy level.
12.1.4 State the maximum number of orbitals in a given energy level.
12.1.5 Draw the shape of an s orbital and the shapes of the p x, py and pz orbitals.
12.1.6 Apply the Aufbau principle, Hund’s rule and the Pauli exclusion principle to write electron configurations for atoms and
ions up to Z = 54.

first ionisation energy for the first twenty elements

2500
He Ne
first ionisation energy / kJ

2000 F
N Ar
1500 Cl
C P
mol -1

Be Si
1000 H O Mg
Ca
S
500 B
Li Na Al
0 K
0 5 10 15 20
atomic number

As you can see, the first ionisation energy increases across each period, however it drops from one
period to the next due to the electron being removed from a higher energy level, but also from the
second to the third element in each period (e.g. Be to B). This is because for Be, the electron is being
removed from the s-orbital, whereas for B it is being removed from the p-orbital which has a slightly
higher energy and this more than counteracts the increase in effective nuclear charge.

Sub-level s p d f
 Number of
1 3 5 7
orbitals

Relative energy lowest highest

log (ionisation energy) succesive ionisation energies of aluminium

the next eight are taken from the

the first second energy level
three the last two
electrons
are taken
are removed
from the from the
third energy first energy
level level

1 2 3 4 5 6 7 8 9 10 11 12 13

ionisation number

Energy of sub-levels

An energy level, n, can have 2n2 electrons, meaning it has n2 orbitals.

Shapes of s and p orbitals

Pauli’s Exclusion Principle

No more than two electrons can occupy any one orbital and if two electrons are in the same orbital they
must spin in opposite directions

Aufbau Principle
Electrons are placed into orbitals of lowest energy first
Hund’s Third Rule
Orbitals of the same sub-level are filled singly first, then doubly – if more than one orbital in a sub-level
is available, electrons occupy different orbitals with parallel spins

These rules can be used to complete the electron configuration

e.g. for Z = 23, the full electron configuration is 1s22s22p63s23p64s23d3

and the abbreviated electron configuration is [Ar]4s23d3 or [Ar]3d34s2

There are two exceptions:

1. Chromium: [Ar]3d54s1

2. Copper: [Ar]3d104s1

This occurs because the 3d and 4s sub-levels are similar in energy. Chromium’s configuration allows it
to have 6 half-filled orbitals, reducing electrostatic repulsion. This makes it a stable configuration. Half-
filled sub-levels are stable so copper also has a half filled 4s sub-level.

When positive ions are formed for transition metals, the outer 4s electrons are removed before the 3d
electrons.
Topic 3: Periodicity
3.1 The periodic table
3.1.1 Describe the arrangement of elements in the periodic table in order of increasing atomic number.
3.1.2 Distinguish between the terms group and period.
3.1.3 Apply the relationship between the electron arrangement of elements and their position in the periodic table up to Z = 20.
3.1.4 Apply the relationship between the number of electrons in the highest occupied energy level for an element and its
position in the periodic table.

The elements are arranged in the periodic table in increasing order of atomic mass from left to right.
Going down one row increase the number of electron shells by one. Going one column to the right
increases atomic mass by 1.

Group - a group is a vertical column of elements in the Periodic Table. The atoms of the elements in the
group all have the same outer shell structure but an increasing number of inner shells.
Period – a period is a horizontal row of elements in the Periodic Table. Within a period, the atoms of the
elements have the same number of shells but with an increasing number of electrons in the outer shell.

Before calcium (Z = 20),

 group number = number of valence electrons
 period number = number of electron shells

3.2 Physical properties

3.2.1 Define the terms first ionization energy and electronegativity.
3.2.2 Describe and explain the trends in atomic radii, ionic radii, first ionization energies, electronegativities and melting points
for the alkali metals (Li → Cs) and the halogens (F → I)
3.2.3 Describe and explain the trends in atomic radii, ionic radii, first ionization energies and electronegativities for elements
across period 3.
3.2.4 Compare the relative electronegativity values of two or more elements based on their positions in the periodic table.

IB definitions

First ionisation energy – the first ionization energy is the minimum energy required to
remove a mole of electrons from a mole of gaseous atoms to form a mole of univalent
cations in the gaseous state. It is the enthalpy change for the reaction:

X(g) → X + (g) + e−

Electronegativity – electronegativity is a measure of the tendency of an atom in a molecule

to attract a shared pair of electrons towards itself.

The atomic radius is defined as the distance from the nucleus to the outermost electron or, in practice,
half the distance between two bonded nuclei.
Trends of alkali metals
 atomic radius increases down the group as there are more electron shells
 ionic radius increases down the group as there are more electron shells
 first ionisation energy decreases down the group as the valence electron is further from the
nucleus so the electrostatic force of attraction is weaker, and also because there is more
shielding (intermediate shells decrease the force)
 electronegativity decreases because of increased distance and shielding
  melting points of alkali metals decrease as atoms become larger and therefore metallic bond
becomes weaker

Trends of halogens
Halogens exhibit the same trends except that melting points increase as the van der Waals’ force
becomes greater with more electrons.
Trends across period 3

Trend Explanation

Across the period the number of protons in

atomic and ionic radii the nucleus increases (so there is a greater
P3- S2- attractive force) but there is the same
Na Cl- number of intermediate shells so there is the
Mg
same amount of shielding. The effective
atomic radius

Al
nuclear charge therefore increases across
Si P S the period, pulling the energy levels closer.
Na+ Cl This means that atomic nuclei decrease
Mg2+ across the period. The same trend is
Al3+ observed with ionic radii except because the
Si4+ cations have 1 shell fewer they have a
smaller radius.
1 2 3 4 5 6 7 8
group number The graph shows the Si4+ ion (radius: 42),
the Si4- ion also exists with a radius of 271.

As mentioned previously, the effective

nuclear charge increases across the period.
Because of this, the first ionisation energies
Ar
first ionisation energies generally increase across the period.
Cl
first ionisation energy

There are, however, two decreases:

P
 From Mg to Al – electrons in p orbitals
Mg Si S are of higher energy and further away
from the nucleus, thus easier to
remove
Na Al  From P to S – an electron in a doubly
occupied orbital is repelled by its
partner and so is easier to remove
than an electron in a half-filled orbital
1 2 3 4 5 6 7 8 Mg: [Ne] 3s2
group number
Al: [Ne] 3s2 3p1
P: [Ne] 3s2 3px1 3py1 3pz1
S: [Ne] 3s2 3px2 3py1 3pz1
 The electronegativity increases across the
electronegativities period as the size of the atoms decreases
Cl
electronegativity

S
P
Mg Si
Al
Na

1 2 3 4 5 6 7 8
group number

Electronegativity across the periodic table

The following diagram shows how electronegativity changes across the periodic table. Fluorine is the
most electronegative element.

3.3 Chemical properties

3.3.1 Discuss the similarities and differences in the chemical properties of elements in the same group.
3.3.2 Discuss the changes in nature, from ionic to covalent and from basic to acidic, of the oxides across period 3.

Group 1 – the alkali metals

 they are very reactive metals
 they form ionic compounds with non-metals
 the elements further down the group are more reactive that the higher ones since the valence
electron is further from nucleus and has more shielding
 they react with water to form hydrogen and metal hydroxide alkaline solution
 they react with halogens to form ionic salts

Group 7 - halogens
 they are very reactive non-metals
 reactivity decreases down group
 they form ionic compounds with metals and covalent compounds with other non-metals
  higher halogens can displace lower ones from compounds

Reactions with water

The reactions specified by the syllabus are:
Na 2 O(s) + H2 O(l) → 2NaOH(aq)
MgO(s) + H2 O(l) → 2Mg(OH)2 (aq)
P4 O10 (s) + 6H2 O(l) → 4H3 PO4 (aq)
SO3 (l) + H2 O(l) → H2 SO4 (aq)

Acidity of oxides across period 3

Formula Na2O MgO Al2O3 SiO2 P4O10 (s) SO3 (l) Cl2O7 (l)
of oxide (s) (s) (s) (s) P4O6 (s) SO2 (g) Cl2O (g)

Acid-base
basic amphoteric acidic
character

Structure giant
giant ionic molecular covalent
covalent

Topic 13: Periodicity (HL)

13.1 Trends across period 3
13.1.1 Explain the physical states (under standard conditions) and electrical conductivity (in the molten state) of the chlorides
and oxides of the elements in period 3 in terms of their bonding and structure.
13.1.2 Describe the reactions of chlorine and the chlorides referred to in 13.1.1 with water.

Period 3 oxides

P4O10 / Cl2O7 /
Oxide Na2O MgO Al2O3 SiO2 SO3 / SO2
P4O6 Cl2O

Physical liquid /
solid liquid / gas
state gas

Electrical
conductivity
high very low none
in molten
state

 metal oxides are solid because they have strong ionic bonds and therefore form an ionic lattice
 sulphur dioxide is a macromolecular covalent structure like diamond
 the remaining three are molecular covalent
 ionic compounds conduct best because of the mobile charges in molten or aqueous phase

Period 3 chlorides

Formula of AlCl3 /
NaCl MgCl2 SiCl4 PCl5 / PCl3 S2Cl2 Cl2
oxide Al2Cl6

Physical solid /
solid solid / gas liquid liquid gas
state liquid

Oxidation +1 +2 +3 +4 +5 / +3 +1 0
 number

Electrical
conductivity
high poor none
in molten
state

Structure giant ionic molecular covalent

 the more polar the substance is the better it conducts; ionic compounds conduct well
 the ionic compounds have the strongest forces of attraction and are therefore solid
 the non-metal chlorides have dipole-dipole or van der Waals’ forces (depending on whether the
dipoles cancel)
 Cl2 is non-polar so the IMFs are weak, therefore it is a gas
Reactions of period 3 chlorides with water
Chlorine reacts in a reversible disproportionation (both reduced and oxidised) reaction, producing
hydrochloric acid and chloric(I) acid:

Cl2 (aq) + H2 O(l) ⇌ HCl(aq) + HOCl(aq)

The solution is acidic. This is why chlorine turns damp litmus paper red.
Ionic chlorides split into ions in solution, which get surrounded by water molecules (partially charged
oxygen to cation and partially charged hydrogen to anion). They become hydrated.
NaCl(s) → Na+ (aq) + Cl− (aq)
MgCl2 (s) → Mg 2+ (aq) + 2Cl− (aq)

The pH of aqueous magnesium chloride is slightly less than 7 because the Mg2+ ion is polarising.
Aluminium chloride dissociates into ions when added to water:

AlCl3 (s) → Al3+ (aq) + 3Cl− (aq)

The aluminium ion has a high charge density due to it having a 3+ charge and a small ionic radius. The
ion attracts water molecules which form dative (or coordinate) bonds with the ion to form an
octahedral complex ion, [Al(H2O)6]3+
The hydrated ion is acidic as the Al3+ ion attracts the electrons of the OH bond of the surrounding water
molecules, and releases the H+ ion to form an acidic solution.

[Al(H2 O)6 ]3+ (aq) ⇌ [Al(H2 O)5 OH]2+ (aq) + H + (aq)

This process can go on:

[Al(H2 O)5 OH]2+ (aq) ⇌ [Al(H2 O)4 (OH)2 ]+ (aq) + H + (aq)

Silicon and phosphorus react to form hydrochloric acid:

SiCl4 (l) + 2H2 O(l) → SiO2 (s) + 4HCl(aq)

PCl3 (l) + 3H2 O(l) → H3 PO3 (aq) + 3HCl(aq)

PCl5 (s) + 4H2 O(l) → H3 PO4 (aq) + 5HCl(aq)

In summary:

Formula of NaCl MgCl2 AlCl3 / SiCl4 PCl5 / PCl3 S2Cl2 Cl2

 oxide Al2Cl6

Acid-base weakly
neutral acidic
character acidic

13.2 First-row d-block elements

13.2.1 List the characteristic properties of transition elements.
13.2.2 Explain why Sc and Zn are not considered to be transition elements.
13.2.3 Explain the existence of variable oxidation number in ions of transition elements.
13.2.4 Define the term ligand.
13.2.5 Describe and explain the formation of complexes of d-block elements.
13.2.6 Explain why some complexes of d-block elements are coloured.
13.2.7 State examples of the catalytic action of transition elements and their compounds.
13.2.8 Outline the economic significance of catalysts in the Contact and Haber processes.

Properties of transition elements

 variable oxidation states
 formation of complex ions
 coloured complexes
 catalytic behaviour
 the normal metallic properties (good conductors, malleable etc.)

Scandium and zinc

A transition metal is defined as an element that possesses an incomplete, or partially filled, d sub-level
in one or more of its oxidation states. Scandium is not a typical transition metal as its common ion Sc3+
has no d electrons. Zinc is not a transition metal as it contains a full d sub-level in all its oxidation states.
Explanation of variable oxidation number of transition elements
The fact that transition metals can have various oxidation numbers has to do with ionisation energies.
The diagram below shows the difference between calcium and titanium’s ionisation energies.

12000
ionisation energy/ kJ mol-1

10000
8000
6000
Calcium
4000 Titanium
2000
0
0 1 2 3 4 5 6
ionisation number

The increase in ionisation energies for titanium is more gradual as the 3d and 4s orbitals are close in
energy level. Titanium can exist in +2, +3 and +4 oxidation states, but not +5 because the jump in
ionisation energies is too large. Students should know that all transition elements can show an oxidation
number of +2. In addition, they should be familiar with the oxidation numbers of the following: Cr (+3,
+6), Mn (+4, +7), Fe (+3) and Cu (+1).
 IB definitions

Ligand – an ion or molecule that donates a pair of electrons to a metal atom or ion in
forming a coordination complex. Ligands are Lewis bases e.g. H2O, CN-, Cl- and NH3

Complexes
Transition metal ions have relatively high charges and small sizes allowing them to attract ligands’ lone
pairs of electrons. The number of dative bonds from ligands to the central ion is called the coordination
number. Ligands can be exchanged.
Coloured complexes
In the free ion the five d orbitals are degenerate (of equal energy). However, in complexes the electric
field produced by the ligands’ lone pair of electrons causes the d orbitals to split into two levels. The
energy difference corresponds to a frequency of light. The complex absorbs, from all the frequencies
that make up white light, the frequency of light that promotes an electron from the lower to the higher
level (remember E = hf). The complexes therefore appear to be the colour complementary to the one
that is absorbed. If the d sub-level is full or empty this cannot occur e.g. Cu+, Zn2+.
Transition metals as catalysts
Transition metals act as catalysts in the following examples (specified by the syllabus):
 Iron in Haber process
 Vanadium(V) oxide in Contact process
 Nickel in hydrogenation reactions e.g. C2H4 + H2 → C2H6
 Manganese(IV) oxide (MnO2) with hydrogen peroxide (decomposition)
 Palladium (Pd) and platinum (Pt) in catalytic converters
 Co in vitamin B12 (needed for the production of red blood cells)

Catalysts are used in processes such as the Haber process and the Contact process to speed up
reactions and so that the same rate can be attained at a lower temperature thus saving energy and also
shifting the equilibrium to the products side (by lowering temperature).

Topic 4: Bonding
4.1 Ionic bonding
4.1.1 Describe the ionic bond as the electrostatic attraction between oppositely charged ions.
4.1.2 Describe how ions can be formed as a result of electron transfer.
4.1.3 Deduce which ions will be formed when elements in groups 1, 2 and 3 lose electrons.
4.1.4 Deduce which ions will be formed when elements in groups 5, 6 and 7 gain electrons.
4.1.5 State that transition elements can form more than one ion.
4.1.6 Predict whether a compound of two elements would be ionic from the position of the elements in the periodic table or
from their electronegativity values.
4.1.7 State the formula of common polyatomic ions formed by non-metals in periods 2 and 3.
4.1.8 Describe the lattice structure of ionic compounds.

Ionic bonding
Ionic bonding occurs between elements that have a large difference in electronegativity (typically larger
than 1.8). The atom with the low electronegativity (the metal) loses an electron and becomes a cation.
The atom with the high electronegativity (the non-metal) gains the electron and becomes an anion. As a
result there is an electrostatic attraction between the two ions.
In NaCl, for example, chlorine already has noble gas configuration (it is in the form of diatomic
molecules), but the energy given out when the ionic lattice is formed is sufficient to break the bond in
the chlorine molecule to give atoms. Each sodium atom gives an electron to a chlorine atom. In the
lattice each cation is surrounded by 6 anions and vice versa.
Common polyatomic ions
 hydroxide, OH-
 nitrate, NO3-
 carbonate, CO32-
 hydrogencarbonate, HCO3-
 ethanoate, CH3COO-
 sulphate, SO42-
 hydrogensulphate, HSO4-

4.2 Covalent bonding

4.2.1 Describe the covalent bond as the electrostatic attraction between a pair of electrons and positively charged nuclei.
4.2.2 Describe how the covalent bond is formed as a result of electron sharing.
4.2.3 Deduce the Lewis (electron dot) structures of molecules and ions for up to four electron pairs on each atom.
4.2.4 State and explain the relationship between the number of bonds, bond length and bond strength.
4.2.5 Predict whether a compound of two elements would be covalent from the position of the elements in the periodic table or
from their electronegativity values.
4.2.6 Predict the relative polarity of bonds from electronegativity values
4.2.7 Predict the shape and bond angles for species with four, three and two negative charge centres on the central atom using
the valence shell electron pair repulsion theory (VSEPR).
4.2.8 Predict whether or not a molecule is polar from its molecular shape and bond polarities.
4.2.9 Describe and compare the structure and bonding in the three allotropes of carbon (diamond, graphite and C60 fullerene).
4.2.10 Describe the structure of and bonding in silicon and silicon dioxide.
Covalent bonding
In a covalent bond, the electrons are shared and attracted electrostatically by both positive nuclei
resulting in a directional bond between the two atoms to form a molecule. Generally the difference in
electronegativity has to be less than 1.8 for covalent bonding.

Lewis structures
In Lewis structures, lone pairs of electrons can be depicted by two crosses, two dots or a line. A bond
can be shown as a line (or double line for double bonds).
Drawing Lewis structures
1. calculate the total number of valence electrons in the molecule by multiplying the group number
of each element by the number of atoms of the element in the formula and totalling these
2. draw the skeletal structure of the molecule to show how the atoms are linked to each other
3. use pairs of crosses, dots or a single line to show one electron pair and put a pair in each bond
between atoms
4. add more electrons pairs to complete the octets around the atoms (hydrogen only needs two,
other exceptions below)
5. if there are not enough electrons, form double or triple bonds

Exceptions to the octet rule

The exceptions to the octet rule are:
 small atoms like B and Be form stable molecules with fewer than eight electrons (an incomplete
octet)
 atoms of elements in the third period and below may expand their octet by using d orbitals in their
valence shell. This arrangement is possible because the d orbitals available in the valence shell
of these atoms have energy values relatively close to those of the p orbitals.

Polar bonds
When the atoms are different the more electronegative atom exerts a greater attraction for the electron
pair, becoming more electron rich resulting in a polar bond. Bigger difference in electronegativities
means a more polar bond.

Polar molecules
For a molecule to be polar:
 It must have at least one polar bond (e.g. HCl)
 The polar bonds must not cancel out (e.g. methane is not polar)

VSEPR theory
VSEPR (valence shell electron pair repulsion) theory states that pairs of electrons arrange
themselves so that they are as far apart from each other as possible.

Number Geometrical Number of

Number of Shape and
of charge arrangement of non-bonding
bonding pairs angle
centres charge centres pairs

linear
2 linear 2 0
180°
 trigonal
3 trigonal planar 3 0 planar
120°

v-shaped
3 trigonal planar 2 1
<120°

tetrahedral
4 tetrahedral 4 0
109.5°

pyramidal
4 tetrahedral 3 1
<109.5°

v-shaped
4 tetrahedral 2 2
<109.5°

Carbon allotropes, silicon and silicon dioxide

Diamond Graphite C60 fullerene

sp3 sp2 sp2

each C forms 4 single bonds each C forms 3 single bonds each C forms 2 single bonds and 1 double
tetrahedral structure parralel layers of hexagon one ‘ball’ contains 60 C atoms

Silicon Silicon dioxide

Bond length and strength
Bond length is a measure of the distance between two nuclei. Bond strength is described in terms of
bond enthalpy. Multiples bonds have a greater number of shared electrons and so have a stronger force
of electrostatic attraction between the bonded nuclei. Thus there is a greater pulling power on the
nuclei, bringing them closer together, resulting in bonds that are shorter and stronger than single bonds.

4.3 Intermolecular forces

4.3.1 Describe the types of intermolecular forces (attractions between molecules that have temporary dipoles, permanent
dipoles or hydrogen bonding) and explain how they arise from the structural features of molecules.
4.3.2 Describe and explain how intermolecular forces affect the boiling points of substances.

Van der Waals’ force

Electrons can at any one moment be unevenly spread. This produces temporary instantaneous dipoles.
These can induce another dipole in neighbouring molecules. This force is called the Van der Waals’
force and increases with mass.

Dipole-dipole force
Dipole-dipole occurs because polar molecules are attracted to each other by electrostatic forces. It is
stronger that Van der Waals’ but weaker than H-bonding.
Hydrogen bonding
Hydrogen bonding occurs when hydrogen is bonded directly to a small highly electronegative element,
such as fluorine, oxygen or nitrogen. As the electron pair is drawn from the hydrogen atom, it has a
small relative charge and therefore attracts a lone pair from a neighbouring molecule.
Strength of intermolecular forces
1. Hydrogen bonding
2. Dipole-dipole
3. Van der Waals’
IMFs and boiling points
The stronger the intermolecular forces, the harder it is to separate the molecules i.e. the more energy it
takes which corresponds to a higher temperature, so the stronger the IMFs, the higher the boiling point.

4.4 Metallic bonding

4.4.1 Describe the metallic bond as the electrostatic attraction between a lattice of positive ions and delocalised electrons.
4.4.2 Explain the electrical conductivity and malleability of metals.

Metallic bonding
In the metal, the valence electrons detached from atoms creating lattice of cations. A metallic bond is
the attraction that two neighbouring cations have for delocalised electrons between them.
Properties of metals
 Metals are good conductors because they contain mobile charges (free electrons)
 Metals are malleable and ductile because the layers of cations can slide over each other without
breaking more bonds than are made. Impurities reduce this.

4.5 Physical properties

4.5.1 Compare and explain the properties of substances resulting from different types of bonding.

Bonding Properties

Metallic bonding high melting point, good conductor, low volatility

Macromolecular covalent high melting point, poor conductor (except graphite), low volatility

Weak high volatility, low melting/boiling points

IMFs
Simple
covalent
Strong low volatility, higher melting/boiling points
IMFs

Some polar covalent molecules, however, in conditions where they can ionise will conduct electricity.
For example, HCl dissolved in water (hydrochloric acid) is an electrical conductor.
Solubility – like dissolves like
At the contact surface, partial charges in the water molecules are attracted to ions of opposite charge in
the lattice, which may cause them to dislodge from their position. Ions separated from the lattice in this
way become surrounded by water molecules and are said to be hydrated.
Non-polar substances (e.g. O2, N2, hydrocarbons) are not very soluble in water. Non-polar substance
can, however, dissolve in non-polar solvents owing to their ability to interact by van der Waals’ forces,
for example the halogens are readily soluble in paraffin oil.
Topic 14: Bonding (HL)
14.1 Shapes of molecules and ions
14.1.1 Predict the shape and bond angles for species with five and six negative charge centres using the VSEPR theory.

No. of No. No. non-

Bond
charge Geometry bonding bonding Shape
angles
centres pairs pairs

90° trigonal
5 0
120° bipryramidal

90° unsymmetrical
4 1 tetrahedron
trigonal < 120° aka see saw
5
bipryramidal

3 2 90° T-shaped

2 3 180° linear

6 0 90° octahedral

6 octahedral square
5 1 90°
pyramidal

4 2 90° square planar

14.2 Hybridisation
14.2.1 Describe σ and π bonds.
14.2.2 Explain hybridisation in terms of the mixing of atomic orbitals to form new orbitals for bonding.
14.2.3 Identify and explain the relationships between Lewis structures, molecular shapes and types of hybridization (sp, sp 2 and
sp3).

Sigma (σ) bonds

Sigma bonds result from axial (head-on) overlap of s, p and hybrid orbitals in different combinations.
Pi (π) bonds
Pi bonds result from sideways overlap of parallel p orbitals and consist of two regions of electron density
(two overlaps). Pi bonds are weaker than sigma bonds as their electron density is further from the
positive charge of the nucleus.

Double and triple bonds

Double bonds consist of one sigma bond and one pi bond. Triple bonds consist of one sigma and two pi
bonds.
Hybridisation
Hybridisation is the process whereby unequal atomic orbitals within an atom mix to form new hybrid
atomic orbitals which are the same as each other, but different from the original orbitals. Hybrid orbitals
form stronger bonds by allowing greater overlap.
sp3 hybridisation
When carbon forms four single bonds (e.g. CH4), it undergoes sp3 hybridisation:

sp2 hybridisation
When carbon forms a double bond (e.g. C2H4), it undergoes sp2 hybridisation:
sp hybridisation
When carbon forms a triple bond (e.g. C2H2), it undergoes sp hybridisation:

Hybridisation and molecular shape

The shape of a molecule can be used to determine the type of hybridisation that has occurred:
 tetrahedral arrangement ↔ sp3 hybridised
 planar triangular arrangement ↔ sp2 hybridised
 linear arrangement ↔ sp hybridised

14.3 Delocalisation of electrons

14.3.1 Describe the delocalization of π electrons and explain how this can account for the structures of some species.

Delocalisation is a characteristic of pi bonds where there is more than one possible position for a double
bond within a molecule (when there are resonance structures).

Properties caused by delocalisation

 intermediate bond lengths and strengths (between single and double)
 greater stability: delocalisation spreads electrons as far from each other as possible making the
molecule more stable
 electrical conductivity in metals and graphite
Topic 5: Energetics
5.1 Exothermic and endothermic reactions
5.1.1 Define the terms exothermic reaction, endothermic reaction and standard enthalpy change of reaction (ΔH⦵).
5.1.2 State that combustion and neutralisation are exothermic processes.
5.1.3 Apply the relationship between temperature change, enthalpy change and the classification of a reaction as endothermic
or exothermic.
5.1.4 Deduce, from an enthalpy level diagram, the relative stabilities of reactants and products, and the sign of the enthalpy
change for the reaction.

IB definitions

Exothermic reaction – An exothermic reaction is one that releases heat to the surroundings
as a result of forming products with stronger bonds than the reactants. Exothermic reactions
have a negative ΔH value.
Endothermic reaction – An endothermic reaction is one that absorbs heat from the
surroundings as a result of forming products with weaker bonds than the reactants.
Endothermic reactions have a positive ΔH value.
Standard enthalpy change of reaction – Standard enthalpy change is the heat transferred
during a reaction carried out under standard conditions:
 pressure 100 kPa
 temperature 298 K
 all substances pure and in their standard state

Combustion and neutralisation are exothermic processes.

Temperature changes and enthalpy changes
 a decrease in temperature of the system means that energy is absorbed in the reaction which
means it is endothermic
 an increase in temperature of the system means that the reaction gives out energy which means
it is exothermic
Enthalpy level diagrams

5.2 Calculation of enthalpy changes

5.2.1 Calculate the heat energy change when the temperature of a pure substance is changed.
5.2.2 Design suitable experimental procedures for measuring the heat energy changes of reactions.
5.2.3 Calculate the enthalpy change for a reaction using experimental data on temperature changes, quantities of reactants and
mass of water.
5.2.4 Evaluate the results of experiments to determine enthalpy changes.
Temperature change of pure substances
𝑄 = 𝑚𝑐∆𝑇

Where: Q = energy, m = mass, c = specific heat capacity and ΔT = temperature change

Enthalpy experiments

Measuring enthalpy of
Measuring enthalpy of combustion
neutralisation

Enthalpy calculations
𝑄 𝑚𝑐∆𝑇
∆𝐻 = =
𝑛 𝑛
Where n is the number of moles reacted (in the combustion experiment this can be calculated from the
change in mass of the fuel burner)
Determining temperature change from graphs
You need to extrapolate backwards in order to compensate for the heat loss.

5.3 Hess’s law

5.3.1 Determine the enthalpy change of a reaction that is the sum of two or three reactions with known enthalpy changes.

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 the reactants and products, are the same.
This means that you can work out the enthalpy of a reaction by adding and reversing several reactions.

Problem solving

Using the equations below:

C(s) + O2 (g) → CO2 (g) ∆𝐻 = −390 kJ mol−1
 Mn(s) + O2 (g) → MnO2 (s) ∆𝐻 = −520 kJ mol−1
What is the enthalpy change for the following reaction?
MnO2 (s) + C(s) → Mn(s) + CO2 (g)
As you can see, if you reverse the second reaction (and change the sign of the enthalpy), it
cancels to give the above reaction, therefore the enthalpy change is -390 + 520 = 130 kJ
mol-1.

5.4 Bond enthalpies

5.4.1 Define the term average bond enthalpy.
5.4.2 Explain, in terms of average bond enthalpies, why some reactions are exothermic and others are endothermic.

IB definitions

Average bond enthalpy - The average bond enthalpy is the energy required to break a
mole of covalent bonds in the reactant, all reactants and products being in the gaseous state.
For example, X2(g) → 2X(g)
It is an average value because it takes account of the different energies in a bond between
the same atoms in different molecules.
Average bond enthalpy can also be defined as the energy released on forming a mole of
covalent bonds in the products, all reactants and products being in the gaseous state.

Bond enthalpies and reaction enthalpies

 If the sum of the bond enthalpies in the reactants is greater than in the products then the reaction
is exothermic.
 If it is less, the reaction is endothermic
Bond-breaking is an endothermic process; bond-making is an exothermic process

Topic 15: Energetics (HL)

15.1 Standard enthalpy changes of reactions
15.1.1 Define and apply the terms standard state, standard enthalpy change of formation and standard enthalpy change of
combustion
15.1.2 Determine the enthalpy change of a reaction using standard enthalpy changes of formation and combustion.

IB definitions

Standard state – the pure form of the substance under standard conditions of 298K (25°C)
 and 1.00 × 105 Pa.
Standard enthalpy change of formation – the standard enthalpy of formation of a
substance is the enthalpy change that occurs when one mole of the substance is formed
from its elements in their standard states under standard conditions of 298K (25°C) and 1.00
× 105 Pa.
Standard enthalpy change of combustion – the standard enthalpy of combustion of a
substance is the enthalpy change that occurs when one mole of the substance burns
completely under standard conditions of 298K (25°C) and 1.00 × 105 Pa.

The standard conditions for enthalpy changes are:

 RTP
 solutions of 1M
 all substances in their standard states
Hess’s law
Using Hess’s law we can find the enthalpy change of a reaction using combustion or formation data.

Using formation data Using combustion data

⊖
∆𝐻reaction = ∑ ∆𝐻𝑓⊖ (products) − ∑ ∆𝐻𝑓⊖ (reactants) ∆𝐻 = ∑ ∆𝐻𝑐⊖ (reactants) − ∑ ∆𝐻𝑐⊖ (products)

15.2 Born-Haber cycle

15.2.1 Define and apply the terms lattice enthalpy and electron affinity.
15.2.2 Explain how the relative sizes and the charges of ions affect the lattice enthalpies of different ionic compounds.
15.2.3 Construct a Born–Haber cycle for group 1 and 2 oxides and chlorides, and use it to calculate an enthalpy change.
15.2.4 Discuss the difference between theoretical and experimental lattice enthalpy values of ionic compounds in terms of their
covalent character.

IB definitions

Lattice enthalpy – the enthalpy change that occurs when one mole of a solid ionic
compound is separated into gaseous ions under standard conditions.
Electron affinity – the enthalpy change that occurs when one mole of gaseous atoms
attracts one mole of electrons

The first electron affinity is exothermic as the electron is attracted to the positively charged nucleus. The
second, however, is endothermic as an electron is being added to an already negative atom.
Factors affecting lattice enthalpies
The energy needed to separate the ions depends on the product of the ionic
charges and the sum of the ionic radii Tip: think of the
Coulomb law
 an increase in the ionic radius of one of the ions decreases the attraction equation:
between the ions 𝑞1 𝑞2
𝐹=𝑘
 an increase in the ionic charge increases the ionic attraction between ions 𝑟2

Born-Haber cycles

Oxides Chlorides

Theoretical and actual lattice enthalpy values

Theoretical lattice enthalpy values are calculated by assuming the crystal is made up from perfectly
spherical ions. This ionic model assumes that the only interaction is due to electrostatic forces between
ions.
The larger the difference between the theoretical and real lattice enthalpies, the larger the covalent
character of the substance, for example in sodium iodide, the Na+ is small and the I- is large and
‘squashy’ meaning the Na+ ion can polarise the anion giving the substance more covalent character.
The covalent character increases down the halogen group when bonded to sodium since the ions are
larger
Theoretical scenario Actual scenario
 15.3 Entropy
15.3.1 State and explain the factors that increase the entropy in a system.
15.3.2 Predict whether the entropy change (ΔS) for a given reaction or process is positive or negative.
15.3.3 Calculate the standard entropy change for a reaction (ΔSƟ) using standard entropy values (SƟ).

Factors that increase the entropy of a system (ΔS > 0)

 mixing different types of particles
 a change in state where the distance between the particles increases
 the increased movement of particles
 increasing the number of particles
 the greatest increase is usually found where the number of particles in the gaseous state
increases
∆𝑆 ⊖ = ∆𝑆 ⊖ (products) − ∆𝑆 ⊖ (reactants)
 15.4 Spontaneity
15.4.1 Predict whether a reaction or process will be spontaneous by using the sign of ΔGƟ.
15.4.2 Calculate ΔGƟ for a reaction using the equation ΔGƟ = ΔHƟ - TΔSƟ and by using values of the standard free energy change of
formation, ΔGfƟ.
15.4.3 Predict the effect of a change in temperature on the spontaneity of a reaction using standard entropy and enthalpy changes
and the equation ΔGƟ = ΔHƟ - TΔSƟ

Gibbs’ free energy

The sign of ΔG must be negative for a process or reaction to be spontaneous.

𝛥𝐺 ⊖ = 𝛥𝐻 ⊖ − 𝑇𝛥𝑆 ⊖

The fact that we use standard conditions implies that the temperature is 298K.

Calculating ΔG

⊖
∆𝐺reaction = ∑ ∆𝐺𝑓⊖ (products) − ∑ ∆𝐺𝑓⊖ (reactants)

Depending on the values of ΔH and ΔS, a reaction might become spontaneous at a certain temperature.

ΔH⊖ ΔS⊖ T ΔG Spontaneity

not
positive positive low positive ≈ ∆𝐻⊖
spontaneous
positive positive high negative ≈ −𝑇∆𝑆 ⊖ spontaneous
not
positive negative low positive ≈ ∆𝐻⊖
spontaneous
not
positive negative high positive ≈ −𝑇∆𝑆 ⊖
spontaneous
negative positive low negative ≈ ∆𝐻⊖ spontaneous
negative positive high negative ≈ −𝑇∆𝑆 ⊖ spontaneous
negative negative low negative ≈ ∆𝐻⊖ spontaneous
not
negative negative high positive ≈ −𝑇∆𝑆 ⊖
spontaneous
Topic 6: Kinetics
6.1 Rates of reaction
6.1.1 Define the term rate of reaction.
6.1.2 Describe suitable experimental procedures for measuring rates of reactions.
6.1.3 Analyse data from rate experiments.

IB definitions

Rate of reaction – the rate of increase of concentration of one of the products or the rate of
decrease of concentration of one of the reactants

Kinetics experiments
Rates of reaction can be measured by:
1. Change in volume of gas produced e.g. Mg + 2HCl → MgCl2 + H2
2. Change in mass (if a gas is produced) – same example as previous
3. Colourimetry/spectrophotometry e.g. 2HI (colourless) → H2 (colourless) + I2 (coloured)
4. Change in concentration measured using conductivity
5. Clock reactions e.g. sodium thiosulphate + hydrochloric acid

6.2 Collision theory

6.2.1 Describe the kinetic theory in terms of the movement of particles whose average energy is proportional to temperature in
Kelvin.
6.2.2 Define the term activation energy, Ea.
6.2.3 Describe the collision theory.
6.2.4 Predict and explain, using the collision theory, the qualitative effects of particle size, temperature, concentration and
pressure on the rate of a reaction.
6.2.5 Sketch and explain qualitatively the Maxwell–Boltzmann energy distribution curve for a fixed amount of gas at different
temperatures and its consequences for changes in reaction rate.
6.2.6 Describe the effect of a catalyst on a chemical reaction.
6.2.7 Sketch and explain Maxwell–Boltzmann curves for reactions with and without catalysts.

Kinetic theory
The essence of kinetic-molecular theory is that particles in a substance move randomly as a result of
the kinetic energy that they possess.
𝑇Kelvin ∝ 𝑣particle

IB definitions

Activation energy – the minimum energy required for a chemical reaction to take place

Collision theory
According to collision theory, for a reaction to occur three criteria must be met:
 the particles must collide
  they must collide with the appropriate geometry or orientation so that the reactive parts of the
particles come into contact
 they must collide with sufficient energy (the activation energy)

Effect of increasing
Quantity Explanation
quantity

The greater the particle size, the smaller the exposed surface
area. Reactions require collisions for reactions to occur, so if
particle size decreases rate
the surface area is smaller, fewer collisions will occur per unit
time

As the temperature increases, a greater proportion of the

particles have the activation energy (see Maxwell-Boltzmann
temperature increases rate energy distribution). The particles are also moving faster (see
kinetic theory above), therefore more collisions occur per unit
time.

Increasing the concentration increases the frequency of

concentration increases rate collisions which increases the frequency of successful
collisions too, thus increasing the rate.

Higher pressure compresses the gas, effectively increasing the

pressure increases rate concentration, so increasing the frequency of collisions and
therefore the rate too.

The Maxwell-Boltzmann distribution

 Increasing the temperature lowers the peak of the curve and moves it to the right, more particles
have enough energy to react
 Adding a catalyst reduces the activation energy, more particles have enough energy to react

Topic 16: Kinetics (HL)

 16.1 Rate expression
16.1.1 Distinguish between the terms rate constant, overall order of reaction and order of reaction with respect to a particular
reactant.
16.1.2 Deduce the rate expression for a reaction from experimental data.
16.1.3 Solve problems involving the rate expression.
16.1.4 Sketch, identify and analyse graphical representations for zero-, first- and second-order reactions.

Rate expression
𝐴 + 𝐵 → products

rate = 𝑘[𝐴]𝑚 [𝐵]𝑛

The rate constant (k) is the constant of proportionality in the rate expression. It has a specific value for
a specific reaction at a specific temperature. The units vary depending on the expressions.
The overall order of the reaction is m + n
The order with respect to a reactant is the power it is raised to in the rate expression
Initial rates method
This method involves comparing the factor by which the concentration is changed to the factor by which
the rate changes in order to determine the order with respect to the reactant
concentration multiplier order with respect to reactant = rate multiplier

So, for example, if the concentration of a reactant is doubled and the rate becomes eight times greater,
the order with respect to the reactant is 3.

Units of rate constant

Zero order First order Second order Third order

Rate = k[A]3 or
Rate = k[A]2 or
Rate = k Rate = k[A] Rate = k[A][B]2 or
Rate = k[A][B]
Rate = k[A][B][C]

mol dm−3 s−1 mol dm−3 s−1 mol dm−3 s−1

units of rate mol dm−3 (mol dm−3 )2 (mol dm−3 )3
= mol dm−3 s−1 = s−1 = mol−1 dm3 s−1 = mol−2 dm6 s−1

First, second and third order reactions

The concentration vs. time graphs for first and second orders look quite similar however, first order
reactions have a constant half-life, whereas with second order reactions each half-life is twice the
preceding one.

16.2 Reaction mechanism

16.2.1 Explain that reactions can occur by more than one step and that the slowest step determines the rate of reaction (rate-
determining step).
16.2.2 Describe the relationship between reaction mechanism, order of reaction and rate determining step.

Most reactions that occur at a measurable rate occur as a series of simple steps. The sequence of
steps is known as the reaction mechanism. The individual steps (elementary steps) usually cannot
be observed directly. Intermediates are substances that are made in one step and used up in another.
The sum of the elementary steps should cancel to give the original equation. The term molecularity is
used in reference to an elementary step to indicate the number of reactant species involved. If a
reaction has three, four or more species combining, it is likely that it can be split into steps.
The rate-determining step
The rate equation can be known by knowing the reaction mechanism, specifically the slowest step,
which acts as a limit on the rate and is therefore called the rate-determining step.
The rate equation is also equal to the rate constant (k) multiplied by the concentrations of the
substances raised to the power of their respective coefficients in the rate-determining step.
aA + bB → products (slowstep)

rate = 𝑘 [A]a [B]b

Problem solving

A noteworthy example is the following (page 226 in HL book)

Step 1: NO(g) + NO(g) → N2 O2 (g) fast

Step 2: N2 O2 (g) + O2 (g) → 2NO2 (g) slow: the rate-determining

step

Overall: 2NO(g) + O2 (g) → 2NO2 (g)

rate = 𝑘[N2 O2 ][O2 ]

But
NO(g) + NO(g) → N2 O2 (g)
therefore:
rate = 𝑘[NO]2 [O2 ]

If a species is both on the reactant and product side of the overall equation, it is probably a catalyst.
 16.3 Activation energy
16.3.1 Describe qualitatively the relationship between the rate constant (k) and temperature (T).
16.3.2 Determine activation energy (Ea) values from the Arrhenius equation by a graphical method.

The rate of reaction increases with temperature (we know this already because of collision theory). A
common relationship is that 10°C increase doubles the rate. Looking back at the Maxwell-Boltzmann
distribution curve, an increase in temperature means that more particles have an energy greater or
equal to the activation energy. This means that the value of the activation energy will determine
temperature’s effect. When the Ea is larger a temperature rise will make a larger difference, and when
the Ea is smaller the temperature change will have a less significant effect.

The Arrhenius equation

𝐸𝑎
𝑘 = 𝐴𝑒 −𝑅𝑇

A = the Arrhenius constant

𝐸𝑎
ln 𝑘 = − + ln 𝐴
𝑅𝑇
The Arrhenius plot

Topic 7: Equilibrium
7.1 Dynamic equilibrium
7.1.1 Outline the characteristics of chemical and physical systems in a state of equilibrium.

Feature of equilibrium state Explanation

Equilibrium is dynamic The reaction has stopped but both

1 forward and backward reactions are
still occurring at the same rate

Equilibrium is achieved in a closed A closed system prevents exchange of

system matter with the surroundings, so
2 equilibrium is achieved where both
reactants and products can react and
recombine.

The concentrations of reactants and They are being produced and

3 products remain constant at destroyed at an equal rate.
equilibrium

At equilibrium there is no change in Colour and density do not change as

4
macroscopic properties these depend on the concentrations.

5 Equilibrium can be reached from The reaction can be started with all
 either direction reactants, all products or a mixture.

7.2 The position of equilibrium

7.2.1 Deduce the equilibrium constant expression (KC) from the equation for a homogeneous reaction.
7.2.2 Deduce the extent of a reaction from the magnitude of the equilibrium constant.
7.2.3 Apply Le Chatelier’s principle to predict the qualitative effects of changes of temperature, pressure and concentration on
the position of equilibrium and on the value of the equilibrium constant.
7.2.4 State and explain the effect of a catalyst on an equilibrium reaction
7.2.5 Apply the concepts of kinetics and equilibrium to industrial processes.

Equilibrium constant
Given a reversible reaction,
aA + bB ⇌ cC + dD

The equilibrium expression is the concentration of the products raised to the coefficients in the balanced
equation over those of the reactants:
[𝐶]𝑐 [𝐷]𝑑
𝐾𝐶 =
[𝐴]𝑎 [𝐵]𝑏

A rule of thumb is:

𝐾𝐶 >> 1 → reaction nearly goes to completion
𝐾𝐶 << 1 → reaction hardly proceeds at all
10-2 < 𝐾𝐶 < 102 → both reactants and products present in noticeable amounts

Le Chatelier’s principle
If any change is imposed on a system that is in equilibrium then the system tends to adjust to a new
equilibrium counteracting the change.
 In an exothermic reaction heat can be considered a product, so increasing the temperature will
shift the equilibrium towards the reactants, and decreasing the temperature will shift it to the
products
 In an endothermic reaction heat can be considered a reactant
 Increasing pressure shifts the equilibrium to the side with fewer moles of gas, so as to decrease
the pressure
 Decreasing pressure shifts it to the side with more moles of gas
 Increasing concentration shifts it to the side with fewer moles of solute
 Decreasing concentration shifts it to the side with more
 A catalyst speeds up the reaction but does not affect the value of the equilibrium constant
Only temperature affects the value of the equilibrium constant
The Haber process
The Haber process is the process used to produce ammonia, NH3
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ∆𝐻 = −93kJ mol−1

Conditions:

Reason (if ideal ≠

Ideal conditions Actual conditions
actual)

high pressure 250 atm -

 low temperature 450°C faster rate of reaction

catalyst iron -

The Contact process

The Contact process is the process used to produce sulphuric acid, H2SO4
2SO2 (g) + O2 (g) ⇌ 2SO3 (g) ∆𝐻 = −197kJ mol−1

Conditions:

Reason (if ideal ≠

Ideal conditions Actual conditions
actual)

99% yield, higher

high pressure 2 atm
pressure is unnecessary

low temperature 450°C faster rate of reaction

catalyst Vanadium(V) oxide -

Topic 17: Equilibrium (HL)

17.1 Liquid-vapour equilibrium
17.1.1 Describe the equilibrium established between a liquid and its own vapour and how it is affected by temperature changes.
17.1.2 Sketch graphs showing the relationship between vapour pressure and temperature and explain them in terms of the
kinetic theory.
17.1.3 State and explain the relationship between enthalpy of vaporisation, boiling point and intermolecular forces.
evaporation
Condensed form (l) ⇌ evaporated form (g)
condensation

Equilibrium of this sort requires a closed system. The liquid evaporates and the condensation rate
increases (due to more collisions on surface). When the opposite rates are equal, equilibrium is
reached.
Vapour pressure
Vapour pressure is the pressure exerted by a vapour on its liquid; however the term usually refers to
the equilibrium vapour pressure. High vapour pressure means the equilibrium lies to the right and vice
versa.
 temperature
 nature of substance
Temperature
For an explanation of why the vapour pressure changes with temperature, we must return to the
Maxwell-Boltzmann distribution:

Nature of the substance

Substances with stronger intermolecular forces have a larger minimum escape energy as more energy
is needed to make the molecules separate. When applied to a mole of a substance, the “minimum
escape energy” is called the enthalpy of vaporisation.

Strong High Low vapour High

→ → →
IMFs ΔHvap pressure boiling pt.
Weak Lower High vapour Low
→ → →
IMFs ΔHvap pressure boiling pt.

17.2 The equilibrium law

17.2.1 Solve homogeneous equilibrium problems using the expression for Kc.

1. Write the balanced equation

2. Under the equation write in the values of the concentrations of each component using three rows:
initial, change and equilibrium
 Initial represents the concentration originally placed in the flask; it is assumed to be 0 if not
stated otherwise
 Change represents the amount that reacts to reach equilibrium. The changes that occur
must be in the same ratio as the coefficients in the balanced equation, so if we know one
of these values we can deduce the others.
 Equilibrium is the concentration present in the equilibrium mixture = initial + change
3. Write the expression for KC from the balanced equation. Substitute the values for equilibrium
concentration and calculate KC.

Problem solving

Calculating the equilibrium concentrations given KC and initial conditions

The equilibrium constant KC for the reaction
SO3 (g) + NO(g) ⇌ NO2 (g) + SO2 (g)
was found to be 6.78 at a specified temperature. If the initial concentrations of NO and SO 3
were both 0.03 mol dm-3, what would be the equilibrium concentration of each component?
Solution
SO3(g) + NO(g) ⇌ NO2(g) + SO2(g)

Initial 0.03 0.03 0.00 0.00

Change -x -x x x
 Equilibrium 0.03 - x 0.03 - x x x
[NO2 ][SO2 ] 𝑥2
𝐾𝐶 = = = 6.78
[SO3 ][NO] (0.03 − 𝑥)2

Solving a quadratic gives the value of x.

Calculating equilibrium concentrations when KC is very small
This situation allows us to make the following approximation:
[reactant]initial ≈ [reactant]equilibrium

The thermal decomposition of water has a very small value of KC. At 1000°C, KC = 7.3 × 10-
18 for the reaction

2H2 O(g) ⇌ 2H2 (g) + O2 (g)

A reaction is set up at this temperature with an initial H2O concentration of 0.10 mol dm-3.
Calculate the H2 concentration at equilibrium.
Solution
2H2O(g) = 2H2(g) + O2(g)

Initial 0.10 0.00 0.00

Change -2x +2x +x

Equilibrium 0.10 -
2x x
2x

We will use the aforementioned approximation to give:

[H2 ]2 [O2 ] 2𝑥 2
𝐾𝐶 = = = 7.3 × 10−18
[H2 O] 0.102

The rest is simple arithmetic.

Effect on equilibrium
Effect on KC
expression

reversing the reaction inverts the expression KC-1

doubling the reaction coefficients squares expression KC2

halving the reaction coefficients square roots expression KC1/2

adding together two reactions multiplies two expressions KC × KC ’

Topic 8: Acids and bases
8.1 Theories of acids and bases
8.1.1 Define acids and bases according to the Brønsted–Lowry and Lewis theories.
8.1.2 Deduce whether or not a species could act as a Brønsted–Lowry and/or a Lewis acid or base.
8.1.3 Deduce the formula of the conjugate acid (or base) of any Brønsted–Lowry base (or acid).

IB definitions

Brønsted–Lowry acid – a proton (H+) donor

Brønsted–Lowry base – a proton (H+) acceptor
Lewis acid – an electron pair acceptor
Lewis base – an electron pair donor

Lewis acids
Lewis acids include BF3, AlCl3, and transition metal ions in aqueous solution which accept a pair of
electrons from each of the six surrounding water molecules. This makes ligands Lewis bases.

Conjugate acid-base pairs

HA + B ⇌ A− + BH +

Conjugate Brønsted–Lowry acid-base pairs differ by just one proton.

8.2 Properties of acids and bases

8.2.1 Outline the characteristic properties of acids and bases in aqueous solution.

Properties of acids Properties of bases

 pH below 7
 react with hydroxides to form a salt
and water
 react with metal oxides to form a salt  pH above 7
and water  alkalis are bases that dissolve in water
 react with ammonia to form a salt  turns litmus blue
 react with metals to form a salt and
hydrogen gas
 react with carbonates forming a salt,
water and carbon dioxide
 turns litmus pink

8.3 Strong and weak acids and bases

8.3.1 Distinguish between strong and weak acids and bases in terms of the extent of dissociation, reaction with water and
electrical conductivity.
8.3.2 State whether a given acid or base is strong or weak.
8.3.3 Distinguish between strong and weak acids and bases, and determine the relative strengths of acids and bases, using
experimental data.

Strong and weak acids and bases

A strong acid or base dissociates completely into its ions in aqueous solution (the dissociation reaction
goes to completion)
A weak acid or base only dissociates partially (the dissociation reaction is an equilibrium that lies to the
left)
Strong acids and bases conduct electricity better in solution and react more vigorously than weak acids
and bases.
Examples

Strong acid Strong base

hydrochloric acid, HCl sodium hydroxide, NaOH

nitric acid, HNO3 potassium hydroxide, KOH

barium hydroxide,
sulphuric acid, H2SO4
Ba(OH)2

Weak acid Weak base

ethanoic acid, CH3COOH ammonia, NH3

carbonic acid, H2CO3 aminoethane, C2H5NH2

8.4 The pH scale

8.4.1 Distinguish between aqueous solutions that are acidic, neutral or alkaline using the pH scale.
8.4.2 Identify which of two or more aqueous solutions is more acidic or alkaline using pH values.
8.4.3 State that each change of one pH unit represents a 10-fold change in the hydrogen ion concentration [H+(aq)].
8.4.4 Deduce changes in [H+(aq)] when the pH of a solution changes by more than one pH unit.

Acids have a pH below 7. Neutral substances have a pH of exactly 7. Bases have a pH greater than 7.
The greater the pH the more alkaline a substance and the lower the pH the more acidic it is.
pH = − log[H + ]

This means that decreasing one pH unit represents a ten-fold increase in hydrogen ion concentration
and increasing one unit represents a ten-fold increase. A two unit change represents a one hundred-fold
change and so on.

Topic 18: Acids and bases (HL)

18.1 Calculations involving acids and bases
18.1.1 State the expression for the ionic product constant of water (Kw).
18.1.2 Deduce [H+(aq)] and [OH-(aq)] for water at different temperatures given KW values.
18.1.3 Solve problems involving [H+(aq)], [OH-(aq)], pH and pOH.
18.1.4 State the equation for the reaction of any weak acid or weak base with water, and hence deduce the expressions for Ka
and Kb.
18.1.5 Solve problems involving solutions of weak acids and bases using the
expressions: Ka × Kb = KW
pKa + pKb = pKW
pH + pOH = pKW
 18.1.6 Identify the relative strengths of acids and bases using values of Ka, Kb, pKa and pKb.

Ionic product constant of water

H2 O(l) ⇌ H + (aq) + OH − (aq)
[H+ ][OH − ]
𝐾𝑐 =
[H2 O]

𝐾𝑤 = 𝐾𝑐 [H2 O] = [H + ][OH − ]

At room temperature, KW has a value of 1.00 × 10-14

pH and pOH
pH = − log[H + ]

pOH = − log[OH − ]

pH + pOH = p𝐾𝑊 (= 14 at 25°C)

Weak acids
A weak acid dissociates partially in water:

HA(aq) + H2 O(l) ⇌ H3 O+ + A− (aq)

From this we can work out an equilibrium expression:

[H3 O+ ][A− ] [H3 O+ ][A− ]
𝐾𝑐 = → 𝐾𝑎 = 𝐾𝑐 [H2 O] =
[H2 O][HA] [HA]

Weak bases
Weak bases also dissociate partially. This can be expressed as:

B(aq) + H2 O(l) ⇌ BH + (aq) + OH − (aq)

This gives the expression:

[BH + ][OH − ] [BH + ][OH − ]
𝐾𝑐 = → 𝐾𝑏 = 𝐾𝑐 [H2 O] =
[B][H2 O] [B]

Ka, Kb, pKa and pKb

Strong acid Weak acid Strong base Weak base

high Ka low pKa high Kb low pKb

low Ka high pKa low Kb high pKb

Since weak acids and bases only dissociate slightly they have low Ka or Kb respectively (remember that
if the equilibrium lies to the left, Kc << 1). Since strong acids and bases dissociate fully, they will have
larger Ka or Kb respectively (remember if equilibrium lies to right, Kc >> 1).

18.2 Buffer solutions

18.2.1 Describe the composition of a buffer solution and explain its action.
18.2.2 Solve problems involving the composition and pH of a specified buffer system.

A buffer solution is resistant to changes in pH on the addition of small amounts of strong acid or alkali.
They are a mixture of two solutions such that it contains the two species of a conjugate acid-base pair.
Acidic buffers maintain the pH below 7 and basic buffers maintain it above 7.
Factors that affect buffers
  Dilution changes the buffering capacity. This depends on the molar concentrations of its
components, so decreases as they are lowered by dilution.
 Temperature affects the Ka and Kb values
Calculating the pH (or pOH) of a buffer
Step 1: Write both dissociation equations:
HA ⇌ H + + A−
MA → M + + A−

Step 2: Make the following assumptions:

[HA]initial = [HA]equilibrium

[MA]initial = [A− ]equilibrium

Step 3: Write the equilibrium expression and rearrange depending on what you want to find:

[H + ][A− ] 𝐾𝑎 [HA]
𝐾𝑎 = → [𝐻 + ] =
[HA] [A− ]

Step 4: Implement the assumptions:

[H + ][MA]initial 𝐾𝑎 [HA]initial
𝐾𝑎 = 𝑜𝑟 [H + ] =
[HA]initial [MA]initial

The same procedure can be done with pOH and Kb.

The Henderson-Hasselbalch equations

[salt] [salt]
pH = p𝐾𝑎 + log & pOH = p𝐾𝑏 + log
[acid] [base]

18.3 Salt hydrolysis

18.3.1 Deduce whether salts form acidic, alkaline or neutral aqueous solutions.

The pH of a salt solution depends on whether and to what extent its ions react with water and hydrolyse
it, releasing H+ or OH- ions.
Anion hydrolysis
The anion is the conjugate base of the parent acid. When the acid is weak, this conjugate is strong
enough to hydrolyse water:
A− (aq) + H2 O(l) ⇌ HA(aq) + OH − (aq)

The release of OH- ions causes the pH of the solution to increase.

Cation hydrolysis
When a base is weak and the conjugate cation (M+) is a non-metal e.g. NH4+
M + (aq) + H2 O(l) ⇌ MOH(aq) + H + (aq)

Release of H+ ions makes the pH decrease.

A metal ion can hydrolyse water if it has a high charge density (i.e. a small ionic radius and a large
charge). Such ions include Be2+, Al3+ and transition metal ions most notably Fe3+. More than one water
molecule can be hydrolysed within the complex.
[Al(H2 O)6 ]3+ (aq) ⇌ [Al(H2 O)5 OH]2+ (aq) + H + (aq)

18.4 Acid-base titrations

18.4.1 Sketch the general shapes of graphs of pH against volume for titrations involving strong and weak acids and bases, and
 explain their important features.

Strong acid + Strong base Weak acid + Strong base

e.g. HCl + NaOH e.g. CH3COOH + NaOH

 The leftmost and rightmost points represent the pH of the acid and base respectively
 the big vertical jump is the point of inflection
 the equivalence point is where the solutions neutralise
 pH = pKa or pOH = pKb at the half-equivalence point

Strong acid + Weak base Weak acid + Weak base

e.g. HCl + NH3 e.g. CH3COOH + NH3

 when a weak acid is added to a weak base, it is difficult to determine the equivalence point.
Instead other techniques are used.

18.5 Indicators
18.5.1 Describe qualitatively the action of an acid–base indicator.
18.5.2 State and explain how the pH range of an acid–base indicator relates to its pKa value.
18.5.3 Identify an appropriate indicator for a titration, given the equivalence point of the titration and the pH range of the
indicator.

Indicators are weak acids or weak bases in which the undissociated and dissociated forms have
different colours.
HIn(aq) ⇌ H + (aq) + In− (aq)

colour A colour B
Le Chatelier’s principle
Increasing the H+ concentration moves the equilibrium to the left
Increasing the OH- concentration moves the equilibrium to the right
Colour change
Indicators change colour when the pH is equal to their pKa, at the midpoint in the equilibrium, so that
[HIn] = [In-]
[H+ ][In− ] [H + ][In− ]
𝐾𝑎 = = → p𝐾𝑎 = pH
[HIn] [HIn]

This is known as the change point or the end point of the indicator. At this point, the addition of a very
small volume of acid or base will shift the equilibrium as described above, and so cause the indicator to
change colour.
Choosing the appropriate indicator
An indicator will be effective in signalling the equivalence point of a titration when its end point coincides
with the pH at the equivalence point.

Reactants in titration pH range at equivalence

strong acid + strong base 3 -11

weak acid + strong base 7 – 11

strong acid + weak base 3–7

no significant change in pH at
weak acid + weak base
equivalence

The problem with indicators

Our eyes are able to identify the distinct colour of one form of an indicator when the ratio to its other
form is 10:1. So for a transition to be observed from colour A to colour B these concentrations must
change from 10:1 to 1:10. This corresponds to a range of 2 pH units. This is why there is a range of ±1
pH unit on either side of the pKa value. This is given as the end point range.

Topic 9: Oxidation and reduction

9.1 Introduction to oxidation and reduction
9.1.1 Define oxidation and reduction in terms of electron loss and gain.
9.1.2 Deduce the oxidation number of an element in a compound.
9.1.3 State the names of compounds using oxidation numbers.
9.1.4 Deduce whether an element undergoes oxidation or reduction in reactions using oxidation numbers.

IB definitions

Oxidation – the loss of an electron, the gain of oxygen, the loss of hydrogen or the increase
in oxidation number
Reduction – the gain of an electron, the loss of oxygen, the gain of hydrogen or the
decrease in oxidation number

9.2 Redox equations

9.2.1 Deduce simple oxidation and reduction half-equations given the species involved in a redox reaction.
 9.2.2 Deduce redox equations using half-equations.
9.2.3 Define the terms oxidizing agent and reducing agent.
9.2.4 Identify the oxidizing and reducing agents in redox equations.

Writing half-equations
1. Balance the atoms other than H and O
2. Balance each half-equation for O by adding H2O as needed.
3. Balance each half-equation for H by adding H+ as needed.
4. Balance each half-equation for charge by adding electrons to the sides with the more positive
charge.
Writing the redox equation
5. Equalize the number of electrons in the two-half equations by multiplying each appropriately.
Add the two half-equations together, cancelling out anything that is the same on both sides, which
includes electrons.

IB definitions

Oxidising agent – a substance that readily oxidizes other substances. Oxidizing agents are
thus reduced
Reducing agent – a substance that readily reduces other substances. Reducing agents are
thus oxidized.

9.3 Reactivity
9.3.1 Deduce a reactivity series based on the chemical behaviour of a group of oxidizing and reducing agents.
9.3.2 Deduce the feasibility of a redox reaction from a given reactivity series.

More reactive metals are stronger reducing agents than less reactive metals. A more reactive metal is
able to reduce the ions of a less reactive metal. More reactive non-metals are stronger oxidising agents
than less reactive non-metals. A more reactive non-metal is able to oxidise the ions of a less reactive
non-metal.

9.4 Voltaic cells

9.4.1 Explain how a redox reaction is used to produce electricity in a voltaic cell.
9.4.2 State that oxidation occurs at the negative electrode (anode) and reduction occurs at the positive electrode (cathode).

If zinc is placed in a copper (II) sulphate solution, electrons are transferred spontaneously from the zinc
to copper and energy is released as heat. Instead of being lost as heat, the energy can be available as
electrical energy by separating the two half-reactions into half-cells and allowing the electrons to flow
through a circuit. This is known as an electrochemical, galvanic or voltaic cell.
Half cells generate electrode potentials: when a metal is placed in a solution containing its ions, an
equilibrium forms between the oxidised and normal forms. As atoms become ions they leave their
electrons behind them creating a charge separation or electrode potential, the size of which is
determined by the position of the equilibrium. In general, the more reactive a metal, the more negative
its electrode potential in its half-cell. Half-cells connected by a wire are called electrodes. Oxidation
always occurs at the anode; reduction always occurs at the cathode. In the voltaic cell, the anode has
a negative charge and the cathode has a positive charge. Electrons flow from the anode to cathode. A
salt bridge is a glass tube that contains an aqueous solution of ions that enables negative charge to be
carried in the opposite direction to that of the electrons (from cathode to anode). This ion movement
neutralises any build up of charge and maintains the pd.
Notation
The notation used for describing electrochemical cells is:

9.5 Electrolytic cells

9.5.1 Describe, using a diagram, the essential components of an electrolytic cell.
9.5.2 State that oxidation occurs at the positive electrode (anode) and reduction occurs at the negative electrode (cathode).
9.5.3 Describe how current is conducted in an electrolytic cell.
9.5.4 Deduce the products of the electrolysis of a molten salt.

An electrolytic cell uses an external source of voltage to bring about a redox reaction that would
otherwise be non-spontaneous. The reactant is known as the electrolyte – a molten liquid or aqueous
solution of an ionic compound. As the electric current passes through it, redox reactions occur at the
electrodes, removing the charges of the ions or ‘discharging’ them. Oxidation occurs at the positive
electrode (anode) – anions lose electrons - and reduction occurs at the negative electrode (cathode) –
positive ions gain electrons.

The current is not passed through the electrolyte by electrons but by the ions as they are mobile.

Topic 19: Oxidation and reduction (HL)

19.1 Standard electrode potentials
 19.1.1 Describe the standard hydrogen electrode.
19.1.2 Define the term standard electrode potential (E⊖)
19.1.3 Calculate cell potentials using standard electrode potentials.
19.1.4 Predict whether a reaction will be spontaneous using standard electrode potential values.

Standard hydrogen electrode

 the electrode is coated in very fine platinum (also known as platinum black)
 the large surface area makes the reaction happen readily
 platinum is also fairly inert and can also catalyse the proton reduction
Standard electrode potential
When the standard hydrogen electrode is connected to another standard half-cell by an external circuit
with a high resistance voltmeter and a salt bridge, the emf generated is known as the standard
electrode potential of the half-cell.

𝐸 ⊖ cell = 𝐸 ⊖ half−cell where reduction occurs − 𝐸 ⊖ half−cell where oxidation occurs

The values inserted into this equation must be reduction potentials. The stoichiometry of the equation
does not matter.
If 𝐸 ⊖ cell is positive, the reaction is spontaneous as written; if 𝐸 ⊖ cell is negative, the reaction is non-
spontaneous and in fact the reverse reaction is spontaneous.

19.2 Electrolysis
19.2.1 Predict and explain the products of electrolysis of aqueous solutions.
19.2.2 Determine the relative amounts of the products formed during electrolysis.
19.2.3 Describe the use of electrolysis in electroplating.

Predicting the products of electrolysis

The products of electrolysis are influenced by various factors:
1. the relative E⊖ values of the ions
At the cathode the cation with the higher E⊖ is value preferentially reduced.
At the anode the anion with the lower E⊖ is value is preferentially oxidised.
2. the relative concentrations of the ions in the electrolyte
At the anode, if the anion which would be preferentially oxidised (e.g. Cl - in NaCl solution) has a low
concentration the hydroxide ion will be oxidised (unless of course the hydroxide ion is the ion
preferentially discharged already).
3. the nature of the electrode
Electrolysis of copper (II) sulphate solution: when carbon (neutral) electrodes are used, electrolysis
occurs as you would expect. With copper electrodes, at the cathode Cu 2+ ions are discharged (becomes
Cu). At the anode the copper electrode is oxidised, supplying electrons. So the net movement of Cu 2+
ions is from the anode to the cathode. The anode shrinks and the cathode swells.

Carbon electrodes Copper electrodes

Determining the relative amounts of products

The relative amounts of products depend on the stoichiometry of the equation e.g.
2H2 O(l) → 2H2 (g) + O2 (g)

In this electrolysis of water, twice the number of moles (and because of Avogadro’s law, twice the
volume too) of hydrogen will be produced than of oxygen.
Determining the actual amounts of product*
This isn’t actually on the syllabus. The yield depends on three quantities
 charge of the ion
 the current
 duration (time)
Charge is the product of current and time:
𝑄 =𝐼∙𝑡

1 mole of electrons has a charge of 96,500 coulombs. To calculate the yield:

Current × time = charge
1 mol e−
Charge × = moles of electrons
96500C
moles of product
moles of electrons × = moles of product
moles of electrons

Problem solving

If a current of 2.00 amps is passed through a solution of CuSO4 for 10 minutes, how many
moles of Cu are formed?
 60s 1mol(e− ) 1mol(Cu)
10min × × 2.00A × × = 0.00622 (3 significant figures)
1min 96500C 2mol(e− )

Electroplating
Electroplating is the process of using electrolysis to deposit a layer of
a metal on top of another metal or other conductive substance. An
electrolytic cell used for electroplating has the following features:
 an electrolyte containing the metal ions to be deposited
 the object to be plated as the cathode
 sometimes the anode is made of the same metal which is to be
coated because it may be oxidised to replenish the supply the
ions in the electrolyte
Electroplating can be used for various purposes:
 decorative purposes
 corrosion control e.g. zinc is deposited on iron or steel in a process called galvanisation. This is
called sacrificial protection.
 improvement of function e.g. electroplating of chromium on steel improves the wear on steel
parts such as hand tools or crankshafts

Topic 10: Organic chemistry

10.1 Introduction
10.1.1 Describe the features of a homologous series.
10.1.2 Predict and explain the trends in boiling points of members of a homologous series.
10.1.3 Distinguish between empirical, molecular and structural formulas.
10.1.4 Describe structural isomers as compounds with the same molecular formula but with different arrangements of atoms.
10.1.5 Deduce structural formulas for the isomers of the non-cyclic alkanes up to C6.
10.1.6 Apply IUPAC rules for naming the isomers of the non-cyclic alkanes up to C6.
10.1.7 Deduce structural formulas for the isomers of the straight-chain alkenes up to C6.
10.1.8 Apply IUPAC rules for naming the isomers of the straight-chain alkenes up to C6.
10.1.9 Deduce structural formulas for compounds containing up to six carbon atoms with one of the following functional groups:
alcohol, aldehyde, ketone, carboxylic acid and halide.
10.1.10 Apply IUPAC rules for naming compounds containing up to six carbon atoms with one of the following functional groups:
alcohol, aldehyde, ketone, carboxylic acid and halide.
10.1.11 Identify the following functional groups when present in structural formulas: amino (NH 2), benzene ring and esters
(RCOOR)
10.1.12 Identify primary, secondary and tertiary carbon atoms in alcohols and halogenoalkanes.
10.1.13 Discuss the volatility and solubility in water of compounds containing the functional groups listed in 10.1.9.

Homologous series
The main features of a homologous series are:
1. Successive members of a homologous series differ by one CH2 group
2. All members of a homologous series can be expressed by the same general formula
3. Successive members show a gradation in physical properties
4. The different members have similar chemical properties
The boiling points increase as the chain gets longer as the van der Waals forces get stronger.
Formulas
The empirical formula shows the simplest ratio of atoms in a compound.
The molecular formula shows the actual number of atoms in a compound.
The structural formula is a representation of a molecule showing how the atoms are bonded together.

Full structural Condensed Stereochemical

formula structural formula formula
H O
∣ ∥
H−C −C−O−H CH3COOH
∣ ∥
H O

Structural isomers
Structural isomers are compounds with the same molecular formula but with different arrangements of
atoms, for example the isomers of hexane are:
hexane 2-methylpentane 3-methylpentane

2,2-dimethylbutane 2,3-dimethylbutane

Nomenclature for organic compounds: the IUPAC system

Rule 1: Identify the longest straight chain of carbon atoms
Rule 2: Identify the functional group, which gives the suffix (ending).
Rule 3: Identify the side chains or substituent groups, which give the prefix.
IUPAC
The name is in the form:
Prefix – Parent – Suffix

Homologous Functional
Prefix Suffix
series group

alkane - alkyl- -ane

 alkene alkenyl- -ene

alcohol −OH hydroxy- -anol

amine −NH2 amino- -anamine

aldehyde oxo- -anal

ketone -oyl- -one

carboxylic acid carboxy- -oic acid

amide carboxamido- -anamide

ester alkoxycarbonyl- -anoate

nitrile cyano- -anenitrile

fluoro-, chloro,
Halogen alkane C−X
bromo-, iodo-

acid halide

Primary, secondary and tertiary carbon atoms

A primary carbon atom is attached to the functional group and also to at least two hydrogen atoms.
A secondary carbon atom is attached to the functional group and also to one hydrogen atoms and two
alkyl groups.
A tertiary carbon atom is attached to the functional group and is also bonded to three alkyl groups and
so has no hydrogen atoms.

Primary Secondary Tertiary

Volatility
We can summarise the effect on volatility of the different functional groups as follows.
 most volatile least volatile
alkane > halogenoalkane > aldehyde > ketone >
alcohol > carboxylic acid
van der Waals’ → dipole-dipole → hydrogen bonding
increasing strength of molecular attraction →
increasing boiling point →

Solubility
Molecules with functional groups that enable hydrogen bonds to form with water include the alcohols,
the carboxylic acids and the amines. So the smaller members of these series are readily soluble in
water. Aldehydes, ketones, amides and esters are less soluble, while halogenoalkanes, alkanes and
alkenes are insoluble.

10.2 Alkanes
10.2.1 Explain the low reactivity of alkanes in terms of bond enthalpies and bond polarity.
10.2.2 Describe, using equations, the complete and incomplete combustion of alkanes.
10.2.3 Describe, using equations, the reactions of methane and ethane with chlorine and bromine.
10.2.4 Explain the reactions of methane and ethane with chlorine and bromine in terms of a free-radical mechanism.

Low Reactivity of Alkanes

Alkanes contain only C-C and C-H bonds. These are both strong bonds (bond enthalpies of 348 and
412 kJ mol-1 respectively) so alkanes are quite stable. They will only react when there is a strong source
of energy. Alkanes are also non-polar, so are not susceptible to attack by most common reactants.
Combustion
Alkanes undergo complete combustion to give CO2 and H2O:
C3 H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2 O

When the oxygen supply is limited, alkanes undergo incomplete combustion, to produce carbon
monoxide and water or carbon and water if the supply is even more limited:
2C3 H8 (g) + 7O2 (g) → 6CO(g) + 8H2 O(g)
C3 H8 (g) + 2O2 (g) → 3C(s) + 4H2 O(g)

Reactions with Cl and Br

Alkanes undergo halogen substitution or halogenation in the presence of UV light e.g.
CH4 (g) + Cl2 (g) → CH3 Cl(g) + HCl(g)

The UV light is needed to break the covalent bond in the chlorine molecule. This creates two free
radicals i.e. two chlorine atoms each with an unpaired electron. This is the start of a reaction described
by a reaction mechanism.
1. Initiation
The homolytic fission of the chlorine molecule:
UV light
Cl2 → 2Cl ∙
2. Propagation
For example:
Cl ∙ +CH4 → CH3 ⋅ +HCl
CH3 ∙ +Cl2 → CH3 Cl + Cl ∙
CH3 Cl + Cl ∙ → CH2 Cl ∙ +HCl
CH2 Cl ∙ +Cl2 → CH2 Cl2 + Cl ∙

These reactions are called propagation because they both use and produce free radicals.
3. Termination
Cl ∙ +Cl ∙ → Cl2
CH3 ∙ +Cl ∙ → CH3 Cl
 CH3 ∙ +CH3 ∙ → C2 H6

10.3 Alkenes
10.3.1 Describe, using equations, the reactions of alkenes with hydrogen and halogens.
10.3.2 Describe, using equations, the reactions of symmetrical alkenes with hydrogen halides and water.
10.3.3 Distinguish between alkanes and alkenes using bromine water.
10.3.4 Outline the polymerization of alkenes.
10.3.5 Outline the economic importance of the reactions of alkenes.

Alkenes have the general formula CnH2n

They are unsaturated hydrocarbons containing a carbon-carbon double bond
Addition reactions of alkenes
The π bond is weaker than the σ and so it breaks.

With hydrogen
Hydrogenation occurs in the presence of a nickel catalyst at 150°C e.g.
H H H H H H
Ni catalyst
∣ ∣ ∣ 150°C
∣ ∣ ∣
H − C − C = C − H + H2 → H− C−C −C −H
∣ ∣ ∣ ∣ ∣ ∣
H H H H H H
propene + hydrogen → propane
With halogens
Dihalogeno compounds are produced in the reactions between halogens and alkenes. These reactions
happen quickly at room temperature accompanied by the loss of colour of the halogen e.g.
H H H H H H
∣ ∣ ∣ fffffffff ∣ ∣ ∣
H − C − C = C − H + Br2 → H− C − C − C −H
∣ ∣ ∣ ∣ ∣ ∣
H H H H Br Br
propene + bromine → 1,2-dibromopropane
With hydrogen halides
The hydrogen halide (HX) with the weaker bond reacts faster. This means the reaction rate increases
down the group. This takes place rapidly at room temperature e.g.
H H H H H H
∣ ∣ ∣ fffffffff ∣ ∣ ∣
H − C = C − C − H + HCl → H−C − C − C−H
∣ ∣ ∣ ∣ ∣ ∣
H H H H Cl H

The halide bonds to the carbon with fewer hydrogens bonded to it.
With water
Hydration is the reaction that converts an alkene into an alcohol. Conditions: heat with steam and
catalyst of concentrated sulphuric acid.

Test to distinguish alkanes and alkenes

We can distinguish between alkanes and alkenes in terms of their chemical properties. Alkenes will
react with bromine water, decolourising it, whereas alkanes will only do this in the presence of UV light.
Since alkenes have a higher carbon to hydrogen ratio, they contain much more unburned carbon than
alkanes when they burn, giving a smokier, dirtier flame.

Polymerisation
Alkenes (the monomers) can join together to produce long chains called polymers by addition.

The hydration of ethene is of industrial significance because ethanol is a very important solvent and so
is manufactured on a large scale. The hydrogenation reaction is used in the margarine industry to
saturate oil compounds, making the liquid solid. Polymers have many uses, for example:
Polymer Example of uses
polythene plastic bags
polychloroethene
water pipes
(PVC)
polypropene ropes
polystyrene packaging and insulation
Teflon
non-stick frying pans
(polytetrafluoroethene)
nylon tents
clothing (especially mixed
terylene
with cotton)

10.4 Alcohols
10.4.1 Describe, using equations, the complete combustion of alcohols.
10.4.2 Describe, using equations, the oxidation reactions of alcohols.
10.4.3 Determine the products formed by the oxidation of primary and secondary alcohols.

Combustion
When alcohols undergo complete combustion (when oxygen is plentiful), the products are water and
carbon dioxide:
2CH3 OH(l) + 3O2 (g) → 2CO2 (g) + 4H2 O(g)

The longer the chain the greater the ∆H

When oxygen is less plentiful, the combustion will produce water and carbon or carbon monoxide.
2CH3 OH(l) + O2 (g) → 2C(s) + 4H2 O(g)

CH3 OH(l) + O2 (g) → CO(g) + 2H2 O(g)

Oxidation
Combustion involves the complete oxidation of the alcohol molecules, but it is also possible for them to
react with oxidising agents which selectively oxidise the carbon atom attached to the OH group, keeping
the carbon skeleton intact, so that useful compounds can be made. In the lab, acidified potassium
dichromate(VI) is used as the oxidising agent. Owing to the Cr(VI), this solution is bright orange. When
the mixture is heated, the colour changes to green as the Cr(VI) is reduced to Cr(III). The oxidising
agent is usually represented by +[O].
Primary alcohols
Primary alcohols are oxidised in a two-step reaction, first forming the aldehyde and then the carboxylic
acid:

H H H O H O
∣ ∣ +[O], heat ∣ ∥ +[O], heat ∣ ∥
H − C − C − OH → H− C −C −H → H − C − C − OH
∣ ∣ ∣ ∥ reflux ∣ ∥
H H H O H O

ethanol → ethanal → ethanoic acid

If you want to obtain the aldehyde, it is possible to remove it by distillation (since the aldehyde is the
only of the three that does not have H-bonding). To obtain the carboxylic acid, on the other hand, a
reflux condenser is used.

Secondary alcohols
Secondary alcohols are oxidised to the ketone:
H H H H H H
∣ ∣ ∣ +[O], heat ∣ ∣ ∣
H− C− C −C −H → H− C − C − C −H
∣ ∣ ∣ reflux ∣ ∥ ∣
H OH H H O H
propan-2-ol → propanone
Tertiary alcohols
Tertiary alcohols are not readily oxidised under similar conditions, as this would involve breaking the
carbon skeleton of the molecule, which requires significantly more energy: no colour change.

10.5 Halogenalkanes
10.5.1 Describe, using equations, the substitution reactions of halogenoalkanes with sodium hydroxide.
10.5.2 Explain the substitution reactions of halogenoalkanes with sodium hydroxide in terms of S N1 and SN2 mechanisms.

Substitution
In a halogenoalkane, the C-X bond is polar because the halogen is more electronegative. As a result
the halogen gains a partial negative charge (δ-), whereas the carbon gains a partial positive charge (δ+)
and is said to be electron deficient. Nucleophiles are reactants that are themselves electron rich (they
have a lone pair of electrons or they are anions) such as H2O, OH-, NH3 and CN-. SN stands for
nucleophilic substitution.
Primary halogenoalkanes: SN2 mechanism
Primary halogenoalkanes have at least two hydrogen atoms attached to the carbon with the C-X bond
e.g.
H
∣
H − C − Cl
∣
H
The overall reaction with NaOH is:
CH3 Cl + OH − → CH3 OH + Cl−

As the hydrogen atoms are so small, the carbon atom is relatively open to attack by the nucleophile. An
unstable transition state is formed in which the carbon is weakly bonded simultaneously to both the
halogen and the nucleophile. The C-X bond breaks heterolytically, releasing X- and forming the product.

This is known as a bimolecular reaction because the rate is dependent on both the concentration of the
halogenoalkane and of the hydroxide ion. It is called SN2: substitution nucleophilic bimolecular.

Tertiary halogenoalkane: SN1 mechanism

Tertiary halogenoalkanes have three alkyl groups attached to the carbon with the C-X bond e.g.
CH3
∣
CH3 − C − Cl
∣
CH3

The overall reaction that occurs with NaOH is:

CH3 C(CH3 )ClCH3 + OH − → CH3 C(CH3 )OHCH3 + Cl−

The presence of the alkyl groups around the carbon of the C-X bond causes steric hindrance, meaning
that these bulky groups make it difficult for an incoming group to attack this carbon atom. The first
reaction involves the C-X bond breaking heterolytically. The carbon is left with a positive charge. It is
called a carbocation. This is then attacked by the nucleophile in the second step.

A factor which favours this mechanism in tertiary halogenoalkanes is that the carbocation is stabilised
by the presence of the three alkyl groups, as each of these has an electron-donating or positive
inductive effect, shown by the blue arrows in the diagram above. This stabilising effect helps the
carbocation to persist for long enough for the second step to occur.
This is a unimolecular reaction.
Secondary halogenoalkanes
Secondary halogenoalkanes undergo both SN1 and SN2 mechanisms.

10.6 Reaction pathways

10.6.1 Deduce reaction pathways given the starting materials and the product.

See reaction pathways in higher level organic chemistry.

Topic 20: Organic chemistry (HL)
20.1 Introduction
20.1.1 Deduce structural formulas for compounds containing up to six carbon atoms with one of the following functional groups:
amine, amide, ester and nitrile.
20.1.2 Apply IUPAC rules for naming compounds containing up to six carbon atoms with one of the following functional groups:
amine, amide, ester and nitrile.

See section 10.1.

20.2 Nucleophilic substitution reactions

20.2.1 Explain why the hydroxide ion is a better nucleophile than water.
20.2.2 Describe and explain how the rate of nucleophilic substitution in halogenoalkanes by the hydroxide ion depends on the
identity of the halogen.
20.2.3 Describe and explain how the rate of nucleophilic substitution in halogenoalkanes by the hydroxide ion depends on
whether the halogenoalkane is primary, secondary or tertiary.
20.2.4 Describe, using equations, the substitution reactions of halogenoalkanes with ammonia and potassium cyanide.
20.2.5 Explain the reactions of primary halogenoalkanes with ammonia and potassium cyanide in terms of the S N2 mechanism.
20.2.6 Describe, using equations, the reduction of nitriles using hydrogen and a nickel catalyst.

Water vs. the hydroxide ion

Water can be used as the nucleophile in a hydrolysis reaction instead of NaOH(aq), but H2O is a weaker
nucleophile than the OH- ion as it does not have a negative charge, just a δ-. The reaction will be slower,
except for the SN1 mechanism (unimolecular).

The effect of the halogen on the rate

1. The polarity of the C-X bond – as the electronegativity of the halogens decreases down the
group, the C in the C-X bond become less electron deficient and so less vulnerable to
nucleophilic attack.
2. The strength of the C-X bond – the C-X bond decreases in strength from fluorine to iodine. The
weaker the bond, the faster the reaction.
The data suggest that the strength of the bond is the dominant factor, thus:
iodoalkanes > bromoalkanes > chloroalkanes > fluoroalkanes
The effect of the mechanism
Since SN1 reaction give the fastest rate. Reactions with tertiary alkanes happen fastest (S N1) then
secondary (SN1 and SN2) then primary (SN2).

Conversion into amines

Ammonia, NH3, is a nucleophile on account of the lone pair of electrons on the N. When reacted with a
halogenoalkane, the substitution yields an amine in which the halogen is replaced by the amine group.

H H H H
∣ ∣ ∣ ∣
H − C − C − Br + NH3 → H − C − C − NH2 + HBr
∣ ∣ ∣ ∣
H H H H

This reaction is usually carried out using concentrated ammonia solution in a sealed tube that raises
the pressure. Because amines, like ammonia, have a lone pair of electrons, they can also behave as
nucleophiles and so react to form further substituted products. Increasing the concentration of the
ammonia will, however, decrease the amounts of these other products.
Conversion into nitrile
The cyanide ion contains a lone pair of electrons and a negative charge on the carbon atom:
[× × −
×C ≡ N× ]

The reactions take place when the halogenoalkane is heated under reflux with a solution of
potassium cyanide in ethanol. The alcohol acts as a solvent for both the polar and non-polar
components of the reaction mixture.

When the substitution reaction occurs, the compound gains a carbon atom. This is therefore one of the
most convenient methods for increasing the chain length. Reduction of this group using hydrogen and a
metal catalyst such as nickel converts it into a primary amine.
Ni
C2 H5 CN + 2H2 → C2 H5 CH2 NH2

20.3 Elimination reactions

20.3.1 Describe, using equations, the elimination of HBr from bromoalkanes.
20.3.2 Describe and explain the mechanism for the elimination of HBr from bromoalkanes.

Elimination
An elimination reaction involves the removal of a small molecule from a larger molecule. It results in the
formation of a C=C bond.
X Y
∣ ∣ ∣ ∣
−C−C− → −C = C− + X−Y
∣ ∣ ∣ ∣
X Y

The reaction is usually carried out in the presence of a hot alcoholic solution of a base such as sodium
hydroxide.
alcoholic solvent
CH3 CH2 CH2 Br + NaOH → CH3 CH = CH2 + NaBr + H2 O

E2 mechanism
This proceeds by the OH- ion acting as a base and accepting a proton, H+, from the bromopropane. The
carbon-bromine bond splits heterolytically with both the electrons going to the bromide ion. The
electrons from the carbon-hydrogen bond form the new bond of the double bond.

This mechanism proceeds as a concerted one-step mechanism, and is bimolecular. E2 means

elimination bimolecular.

E1 mechanism
An alternate mechanism would involve the ionisation of the halogenoalkane by loss of the halide ion
occurring as the first slow step in a two-step process. This is followed by loss of the proton and
formation of the double bond in a second, faster step.

H H H H H H
∣ ∣ ∣ slow ∣ ∣ ∣
H− C − C − C −H → H − C − C − C − H + Br −
⤹∣⤸ ⤹∣⤸ ⤹∣⤸ ∣ ∣ +
H H Br H H ∣

H H H H H H
∣ ∣ ∣ fast ∣ ∣ ∣
H− C − C − C −H → H − C − C = C − H + H+
∣ ∣ + ∣ ∣ ∣
H H ∣ H H H

The rate only depends on the halogenoalkane concentration. E1 is elimination unimolecular.

Nucleophilic substitution is favoured by NaOH in warm, aqueous solution where OH - behaves as a
nucleophile. The elimination reaction is favoured by NaOH in hot alcohol. In reality, both reactions
occur.

20.4 Condensation reactions

20.4.1 Describe, using equations, the reactions of alcohols with carboxylic acids to form esters, and state the uses of esters.
20.4.2 Describe, using equations, the reactions of amines with carboxylic acids.
20.4.3 Deduce the structures of the polymers formed in the reactions of alcohols with carboxylic acids.
20.4.4 Deduce the structures of the polymers formed in the reactions of amines with carboxylic acids.
20.4.5 Outline the economic importance of condensation reactions.

A condensation reaction occurs when two molecules react to form a product with the loss of a small
molecule.
Esters
Carboxylic acids and alcohols condense to form esters (this is called esterification)

Carboxylic acid + alcohol ⇌ ester + water

The name of the ester takes the name of the alkyl portion of the alcohol followed by the name of the
acid salt (e.g. methanol + ethanoic acid gives methyl ethanoate, if you can’t remember that, then recall
that sodium hydroxide + ethanoic acid gives sodium ethanoate). This reaction is usually carried out by
warming a mixture of the carboxylic acid and alcohol in the presence of concentrated sulphuric acid.
Esters have no hydrogen bonding and so are more volatile and less soluble in water than the parent
acid and alcohol. Many esters have sweet, fruity smells and are used in food flavourings and perfumes.
Some are used as plasticisers, helping to soften plastics and make them more flexible.
O
H2 SO4 (conc)
∥
X − COOH + HO − Y → X − C − O − Y + H2 O
∥
O

Polyesters
The product of a diacid (two OH groups) and a dicarboxylic acid (two COOH groups) is a polyester.

O O
∥ ∥
𝑛 × HOOC − X − COOH + 𝑛 × HO − Y − OH → −X − C − O − Y − O − C − + 𝑛H2 O
∥ ∥
( O O )𝑛

Amides
Carboxylic acids and amines condense to form amides.

O O
∥ ∥
X − COOH + H2 N − Y → X − C − N − Y + H2 O
∥ ∣
O H

Polyamides
The product of diamines and diacids is a polyamide.

O O O O
∥ ∥ ∥ ∥
𝑛 × HOOC − X − COOH + 𝑛 × H2 N − Y − NH2 → −X − C − N − Y − N − C + 𝑛H2 O
∥ ∣ ∣ ∥
( O H H O) 𝑛

Many synthetic polyamides have been produced such as Kevlar. They are widely used in the textiles
industry for clothing and carpets, as well as machine parts, tyre cords, and ropes.

20.5 Reaction pathways

20.5.1 Deduce reaction pathways given the starting materials and the product.
20.6 Stereoisomerism
20.6.1 Describe stereoisomers as compounds with the same structural formula but with different arrangements of atoms in
space.
 20.6.2 Describe and explain geometrical isomerism in non-cyclic alkenes.
20.6.3 Describe and explain geometrical isomerism in C3 and C4 cycloalkanes.
20.6.4 Explain the difference in the physical and chemical properties of geometrical isomers.
20.6.5 Describe and explain optical isomerism in simple organic molecules.
20.6.6 Outline the use of a polarimeter in distinguishing between optical isomers.
20.6.7 Compare the physical and chemical properties of enantiomers.

Stereoisomerism
Stereoisomers differ from each other in the spatial arrangement of their atoms. There are two types of
stereoisomerism in the IB: geometric (cis-trans) and optical isomerism.

Geometric (cis-trans) isomers

When there is some constraint in a molecule that restricts the free rotation of bonded groups, they
become fixed in space relative to each other. This restriction can be caused by a double bond or a
cyclic structure. The double bond is made of a σ and a π bond. Rotating would break the π bond. For
cyclic molecules, the substituted groups do not have to be on adjacent carbon atoms – only their
position relative to the plane matters.

Physical properties
The physical properties depend on various factors, including:
 the polarity of the molecules
 the shape or symmetry of the molecules

cis-1,2- trans-1,2-
dichloroethene dichloroethene
net dipole non-polar molecule
boiling point 60°C boiling point 48°C
melting point -80°C melting point -50°C

The boiling point of the cis isomer is higher because the molecule has dipole-dipole forces of attraction
as well as van der Waals’. The melting point is generally more influenced by the symmetry of the
molecules as this affects the packing in the solid state, therefore the trans isomers has the higher
melting point.

cis-butenedioic acid trans-butenedioic acid

melting point 139°C melting point 287°C
intramolecular h-bonding intermolecular h-bonding

Chemical properties
The chemical properties of geometric isomers are usually very similar. An exception is butenedioic acid.

When the trans isomer is heated it sublimes, but does not react chemically.

Optical isomers
A carbon atom bonded to four different atoms or groups is known as asymmetric or chiral. Optical
isomers are non-superimposable mirror images of a molecule. A mixture containing equal amounts of
the two enantiomers is known a racemic mixture.

Optical isomers have identical chemical and physical properties with two exceptions:
 optical activity
 reactivity with other chiral molecules

Optical activity
Ordinary light consists of electromagnetic waves that oscillate in an infinite number if planes at right
angles to the direction of travel. When passed through a polariser, only the light waves oscillating in a
single plane pass through. This is plane-polarised light. The amount and direction of rotation can be
measured with a polarimeter. The light that comes out of the solution passes through a second polariser
called an analyser, which is rotated until the maximum amount of light passes through. In order to
compare different solutions, the concentrations, the wavelength of light used and the sample path-
length must all be kept the same.
Optical isomers rotate plane-polarised light in equal amounts but in opposite directions. A racemic
mixture is optically inactive.

Reactivity with other chiral molecules

When a racemic mixture is reacted with a single enantiomer of another chiral compound, the two
components of the mixture, the (+) (rotates clockwise) and (-) (anticlockwise), react to produce different
products, having different chemical and physical properties which allow them to be separated, by a
process called resolution
Topic 11: Measurement and data processing
11.1 Uncertainty and error in measurement
11.1.1 Describe and give examples of random uncertainties and systematic errors.
11.1.2 Distinguish between precision and accuracy.
11.1.3 Describe how the effects of random uncertainties may be reduced.
11.1.4 State random uncertainty as an uncertainty range (±).
11.1.5 State the results of calculations to the appropriate number of significant figures.

Accuracy and Precision

Accuracy is an indication of how close a measurement is to the accepted value (a measure of
correctness).
Precision is an indication of the agreement among a number of measurements made in the same way
(a measure of exactness).

Random and systematic errors

A random uncertainty is produced by unknown and unpredictable variations in the experimental
situation, such as temperature fluctuations and estimations when reading instruments. They affect the
precision of the results and can be reduced but not eliminated by repeating trials. They appear as error
bars on a graph.
A systematic error is an error associated with a particular instrument or experimental technique that
causes the measured value to be off by the same amount each time. They affect the accuracy of the
results and can be mitigated by fixing source of error. They appear as a non-zero y-intercept.

Significant figures and Decimal Places

The result of addition (or subtraction) is quoted to the same number of decimal places as the input
value with the fewest. The result of multiplication (or division) is quoted to the same number of
significant figures.

11.2 Uncertainties in calculated results

11.2.1 State uncertainties as absolute and percentage uncertainties.
11.2.2 Determine the uncertainties in results.

Given a measurement 5 ± 1,
 the absolute uncertainty is ± 1
 the percentage uncertainty is 20%
Calculating uncertainties
When adding or subtracting, the uncertainties are added together.

𝐴+𝐵 = 𝐶 → ∆𝐶 = ∆𝐴 + ∆𝐵

When multiplying or dividing, percentage uncertainties are added and the result is multiplied by the
value to get the absolute uncertainty.

∆A ∆𝐵
𝐴 ×𝐵=𝐶 → ∆𝐶 = 𝐶 × ( + )
𝐴 𝐵

11.3 Graphical techniques

11.3.1 Sketch graphs to represent dependences and interpret graph behaviour.
 11.3.2 Construct graphs from experimental data.
11.3.3 Draw best-fit lines through data points on a graph.
11.3.4 Determine the values of physical quantities from graphs.

-
Option B: Human biochemistry
B1 Energy
B.1.1 Calculate the energy value of a food from enthalpy of combustion data.

Bomb calorimeter

The energy released can be calculated by:

𝑄 = 𝑚𝑐∆𝑇
When done accurately, the calculation must include a factor known as the ‘bomb factor’ which allows for
the temperature rise in the metal bomb parts and must also make a small correction to account for the
electrical energy input and the burning fuse.

B2 Proteins
B.2.1 Draw the general formula of 2-amino acids.
B.2.2 Describe the characteristic properties of 2-amino acids
B.2.3 Describe the condensation reaction of 2-amino acids to form polypeptides.
B.2.4 Describe and explain the primary, secondary (α-helix and β-pleated sheets), tertiary and quaternary structure of proteins.
B.2.5 Explain how proteins can be analysed by chromatography and electrophoresis.
B.2.6 List the major functions of proteins in the body.

Structure of 2-amino acids

Amino acids are the monomers that make up proteins.

They are called 2-amino acids because the chain is numbered starting with the carboxylic acid group.
The amino group is therefore attached to carbon 2.
Properties of 2-amino acids
Amino acids are crystalline compounds with high melting points, usually above 200 °C, and have much
greater solubility in water than in non-polar solvents. These properties are typical of ionic compounds
and suggest that amino acids exist as dipolar ions (having both positive and negative charges on the
same group of atoms) known as zwitterions. The fact that amino acids usually move in an electric field
is further evidence of the existence of charges within their structure.

Since they contain both acid and base groups, amino acids are amphoteric.
As an acid, donating H+,

As a base, accepting H+,

They can therefore act as buffers.

At the isoelectric point, with no net charge at this pH, amino acids will not move in an electric field. Also
at this point, the molecules will have minimum mutual repulsion and so be the least soluble.

Condensation reactions of amino acids

Amino acids can link to form a dipeptide, then a tripeptide and eventually a polypeptide. The bond
between amino acids is an amide link also known as a peptide bond.

Primary structure of proteins

The primary structure of a protein refers to the number and sequence of amino acids in its polypeptide
chain

Secondary structure of proteins

The secondary structure refers to folding of the polypeptide chain as a result of hydrogen bonding
between peptide groups along its length. Hydrogen bonds can form between the C=O group of one
peptide bond and the N-H group of another peptide bond further along the chain which will cause the
chain to fold.
α-helix
The α-helix is a regular coiled configuration of the polypeptide chain resulting from hydrogen bonds
forming between two peptide bonds four amino acid units apart. This twists the chain into a tightly coiled
helix.
β-pleated sheets
The β-pleated sheet is a structure composed of ‘side by side’ polypeptides which are in extended form,
that is, not tightly coiled as in the α-helix. The polypeptides are arranged in pleated sheets that are
cross-linked by inter-chain hydrogen bonds

Tertiary structure of proteins

The tertiary structure refers to the further twisting, folding and coiling of the polypeptide chain as a result
of interactions between the R groups, known as side chains. The structure that results will be a very
specific compact three-dimensional structure, known as the protein’s conformation.
The interactions which stabilise this conformation are:
a. Hydrophobic interactions – between non-polar side chains (van der Waals’ forces)
b. Hydrogen bonding – between polar side chains.
c. Ionic bond – between side chains carrying a charge.
d. Disulphide bridges – between sulphur atoms in the amino acid cysteine. These are covalent
bonds and hence the strongest of these interactions.
These interactions can be upset by changes in medium (pH and temperature). When a protein loses its
tertiary structure it is denatured.
Quaternary structure of proteins
Some proteins comprise more than one polypeptide chain and in these cases the association between
these chains is known as the quaternary structure.

Analysis of proteins
The first step in protein analysis is hydrolysing the protein into its component amino acids. This is not
the same as the primary structure as you will not know the sequence of the amino acids.
Chromatography
The procedure is simple to run. A small sample of the amino acid mixture is spotted near the bottom of
some chromatographic paper and this position, known as the origin, clearly marked (in pencil so as not
to interfere with the experiment). The paper is then suspended in a chromatographic tank containing a
small volume of solvent, ensuring that the spot is above the level of the solvent.
As the solvent rises up the paper by capillary action it will pass over the spot. Amino acids in the spot
will distribute themselves between two phases – the stationary phase (the water in the paper) and the
mobile phase (the solvent) to different extents and so move up the paper at different speeds. They will
therefore become spread out according to their different solubilities.
When the solvent reaches almost to the top of the paper, its final position is marked and is known as the
solvent front. The paper is removed from the tank and developed by spraying it with the locating
reagent ninhydrin.
From the results you can calculate the Rf value (retention factor).
distance moved by amino acid
Rf =
distance moved by solvent

Electrophoresis
Electrophoresis is a technique for the analysis and separation of a mixture based on the movement of
charged particles in an electric field. As we learned earlier, amino acids carry different charges
depending on the pH and so can be separated by this means when placed in a buffered solution.
In gel electrophoresis, the medium is a gel, typically made of polyacrylamide. The amino acid mixture is
placed in wells in the centre of the gel and an electric field is applied. Depending on the pH of the buffer
used, different amino acids will move at different rates towards the oppositely charged electrodes. At
their isoelectric point, amino acids will not move as they carry no net charge. When separation is
complete they can be detected by a stain or made to fluoresce under UV light and identified from their
position using data tables.
Electrophoresis can also be used to separate and identify intact proteins according to their different
rates of migration towards the poles.

Functions of proteins in the body

1. Structural – bones, muscles, collagen
2. Enzymes – biological catalysts
3. Transportation – haemoglobin
4. Protection - antibodies

B3 Carbohydrates
B.3.1 Describe the structural features of monosaccharides.
B.3.2 Draw the straight-chain and ring structural formulas of glucose and fructose.
B.3.3 Describe the condensation of monosaccharides to form disaccharides and polysaccharides.
 B.3.4 List the major functions of carbohydrates in the human body.
B.3.5 Compare the structural properties of starch and cellulose, and explain why humans can digest starch but not cellulose.
B.3.6 State what is meant by the term dietary fibre.
B.3.7 Describe the importance of a diet high in dietary fibre.

Structure of monosaccharides
All carbohydrates have the general formula Cx(H2O)y. Monosaccharides have the empirical formula
CH2O (x = y). They contain a carbonyl group (C=O) and at least two OH groups. The large number of
polar groups makes them readily soluble in water.

Straight-chain vs. ring structure of C6H12O6

Straight-chain Ring

The ring structure restricts rotation and allows for geometric (cis-trans) isomers known as α-glucose and
β-glucose.

Condensation reactions of monosaccharides

When two monosaccharides react a water molecule is eliminated and a glycosidic bond is formed.

Starch
Starch is a polymer of α-glucose, used as the main storage carbohydrate in plants. Starch is a mixture of
amylase (1-4 linked α-glucose molecules) and amylopectin (1-4 and 1-6 linked α-glucose molecules).
Starch is a spiral structure.

Glycogen
Glycogen is like amylopectin but with many more 1-6 glycosidic branches.
Cellulose
Cellulose is a polymer of β-glucose molecules. It has 1-4 links called β-glycosidic links. These position
the sugars at a different angle from the α-glycosidic links found in amylase and amylopectin so the
cellulose chain forms an uncoiled linear structure with alternate glucose monomers ‘upside down’ with
respect to each other.

Starch vs. cellulose

Starch Cellulose
made from α-glucose made from β-glucose
spiral structure uncoiled linear structure

Functions of carbohydrates
 glucose and fructose are the main substrates for respiration
 they are also used in the synthesis of larger molecules (e.g. fats, nucleic acids, amino acids)
 glycogen is used for energy storage in the liver and muscles
 cellulose makes up dietary fibre

Dietary fibre
The human body produces the enzymes to hydrolyse starch and cellulose. The enzyme needed to
break down the β-glycosidic links (cellulose) found in cellulose are not produced by the body. Cellulose
makes up dietary fibre. Dietary fibre is needed for the health of the large intestine. The cellulose fibrils
abrade the wall of the digestive tract and stimulate the lining to produce mucus. This helps in the
smooth passage of undigested food through the gut and so helps to reduce conditions such as
constipation and the related conditions hemorrhoids (bleeding of the wall of the rectum) and irritable
bowel syndrome. There is also evidence that it may be helpful in preventing the development of
colorectal cancer.
B4 Lipids
B.4.1 Compare the composition of the three types of lipids found in the human body.
B.4.2 Outline the difference between HDL and LDL cholesterol and outline its importance.
B.4.3 Describe the difference in structure between saturated and unsaturated fatty acids.
B.4.4 Compare the structures of the two essential fatty acids linoleic (omega–6 fatty acid) and linolenic (omega–3 fatty acid) and
state their importance.
B.4.5 Define the term iodine number and calculate the number of C=C double bonds in an unsaturated fat/oil using addition
reactions.
B.4.6 Describe the condensation of glycerol and three fatty acid molecules to make a triglyceride.
B.4.7 Describe the enzyme-catalysed hydrolysis of triglycerides during digestion.
B.4.8 Explain the higher energy value of fats as compared to carbohydrates.
B.4.9 Describe the important roles of lipids in the body and the negative effects that they can have on health.
Triglycerides
Triglycerides are the major constituent of fats and oils. They are esters formed by
condensation reactions between glycerol (propane-1,2,3-triol) and three fatty acids.
Each glycerol condenses with three fatty acids and eliminates three water molecules.

Phospholipids
Phospholipids are like triglycerides but the third -OH position of the glycerol has,
instead, condensed with a phosphate group. Different phospholipids vary in their fatty
acid chains and in the group attached to the phosphate.

Phospholipids are characterized by having a polar, or hydrophilic ‘head’ (the phosphate group) and two
non-polar, or hydrophobic ‘tails’ (the hydrocarbon chains of the fatty acids). As a result they will
spontaneously form a phospholipid bilayer which maximizes the interactions between the polar
groups and water, while creating a non-polar, hydrophobic, interior.

Steroids
Steroids are lipids with a structure consisting of four fused rings e.g. cholesterol:

HDL and LDL cholesterol

Cholesterol is transported in the blood by lipoproteins. The main types are LDL (low density lipoprotein
or ‘bad cholesterol’) and HDL (high density lipoprotein or ‘good cholesterol’). High levels of LDL
cholesterol are associated with increased deposition in the walls of the arteries, while high levels of HDL
cholesterol seem to protect against heart attack. It is believed that HDL tends to carry cholesterol away
from the arteries, thus slowing its build-up.

Saturated and unsaturated fatty acids

Saturated fatty acids contain all single carbon–carbon bonds; unsaturated fatty acids contain one or
more double carbon–carbon bond in the hydrocarbon chain. One double bond makes it
monounsaturated and several make it polyunsaturated. Saturated fatty acids have 109.5° bond
angles allowing the molecules to pack closely together and have strong IMFs. They form saturated
triglycerides which are solid at room temperature and are known as fats.

The 120° bond angles caused by the C=C bonds create kinks in the chain, making them pack less
densely. Unsaturated triglycerides have weaker IMFs and are liquids at room temperature, known as
oils. There is a strong correlation between diets rich in saturated fats and elevated levels of LDL.

Essential fatty acids

The human body is unable to synthesise two polyunsaturated fatty acids: linoleic acid (omega-6-fatty
acid) and linolenic acid (omega-3-fatty acid). The terms omega-6 and omega-3 fatty acids refer to the
position of the first double bond in the molecule relative to the terminal CH3 group. They are called
‘essential fatty acids’ because they must be obtained from the diet. They are obtained from plant and
fish sources, for example, shellfish, leafy vegetables, canola oil and flaxseed oil. They play a role in
lowering LDL cholesterol and hence help to protect against heart disease.
Iodine number

IB definitions

The iodine number of a fat is defined as the number of grams of iodine which reacts with 100
g of fat.

Unsaturated fatty acids undergo addition reactions with iodine, adding an iodine atom to each of the two
carbons in the C=C bond.
 I I
∣ ∣ ∣ ∣
− C = C − + I2 → − C − C −
∣ ∣ ∣ ∣
X Y

Problem solving

Question: what is the iodine number of linoleic acid, C18H32O2?

If we take the carboxylic acid group (COOH) off, we are left with C17H31. One of those
hydrogens comes from the fact that the terminal carbon has three Hs bonded to it. So the
remaining 30 hydrogens are distributed among 17 carbons. If there were no double bonds,
the 17 carbons would require 34 hydrogens. Each C=C takes off two hydrogens. So to get
from 34 hydrogens to the 30 required there must be 2 double bonds.
Therefore two moles of I2 react with one mole of linoleic acid.
The Mr of linoleic acid = 280 g mol-1
The Mr of iodine = 254 g mol-1
Therefore 280 grams of linoleic acid react with 508 grams of iodine.
508 g I2
100g × = 181 g
280 g linoleic acid

Answer: the iodine number of linoleic acid is 181 grams.

Digestion of fats
Fats and oils are insoluble therefore must be broken down into their component molecules in the gut
during digestion. This involves hydrolysis reactions involving water and lipases.

Carbohydrates vs. lipids

Lipids contain stored energy that can be released when they are broken down in the reactions of
respiration in cells. The reactions involve a series of oxidation steps, ultimately yielding CO2 and H2O.
As noted above, lipids are less oxidized than carbohydrates and so can effectively undergo more
oxidation and so release more energy per unit mass when used as a respiratory substrate.

Roles of lipids in the body

 releasing energy in respiration
 storing energy in the adipose tissue
 fat tissue protects organs such as the kidneys
 fat tissue provides insulation

B5 Micronutrients and macronutrients

B.5.1 Outline the difference between micronutrients and macronutrients.
B.5.2 Compare the structures of retinol (vitamin A), calciferol (vitamin D) and ascorbic acid (vitamin C).
B.5.3 Deduce whether a vitamin is water- or fat-soluble from its structure.
B.5.4 Discuss the causes and effects of nutrient deficiencies in different countries and suggest solutions.

Micro vs. macro

Micronutrients are those needed in extremely small amounts, generally less than 0.005% of body
mass, used to produce enzymes, hormones and other essential substances, e.g. vitamins and trace
minerals like Fe, Cu, Zn, I, Se, Mn, Mo… Macronutrients are those nutrients needed in relatively large
amounts. They are used to provide energy in the body and to build and maintain its structure, e.g. lipids,
carbohydrates, proteins and some minerals such as calcium.

Vitamins
Vitamins with many polar bonds are water soluble e.g. vitamin C. Those which are more non-polar are
fat soluble e.g. vitamin A and D.

Nutrient deficiencies

Nutrient Role of nutrient Effects and symptoms Solutions

anaemia (fatigue, brittle iron fortification with
Iron haemoglobin nails, poor endurance cereal flours and milk
and lowered immunity) products
goitre (swelling of
synthesis of thyroxine
Iodine thyroid gland), mental adding it to salt
hormone
retardation in children
healthy skin (acne
adding to margarine
treatment), good xerophthalmia (dry eyes
Retinol (vitamin A) (since it is fat soluble):
eyesight, antioxidant and night blindness)
‘vitamin A fortification’
(protects against toxins)
pellagra (dermatitis,
Niacin (vitamin B3) - diarrhoea and -
dementia)
beriberi (weight loss,
Thiamin (vitamin B1) - -
fatigue and swelling)
- cofactor in some
enzymic
reactions scurvy (bleeding gums,
Ascorbic acid (vitamin - important in tissue lowered resistance to
eating citrus fruit
C) regeneration following infections and dark
injury spots on skin)
- helps give resistance
to some diseases
stimulates uptake of
calcium ions by cells
rickets (softened and
Calciferol (vitamin D) and so is important in -
deformed bones)
the health of bones and
teeth
marasmus (weight loss
Protein see functions of protein and emaciation) and -
kwashiorkor

General solutions:
• providing food rations that are composed of fresh and vitamin- and mineral-rich foods
• adding nutrients missing in commonly consumed foods
• genetic modification of food
• providing nutritional supplements
• providing selenium supplements to people eating foods grown in selenium-poor soil.

B6 Hormones
B.6.1 Outline the production and function of hormones in the body.
B.6.2 Compare the structures of cholesterol and the sex hormones.
B.6.3 Describe the mode of action of oral contraceptives.
B.6.4 Outline the use and abuse of steroids.

Hormones are chemical messengers. They are secreted directly into the blood by endocrine glands.
Endocrine gland Hormone Functions
increase uptake of water, so raises the concentration of
anti-diuretic hormone
pituitary gland urine; important in the control of osmotic potential of the
(ADH)
blood
regulation of the basal metabolic rate, growth and
thyroid gland thyroxine
development
increases uptake of Na+ by the kidneys and so
adrenal cortex aldosterone important in the control of Na+ and K+ ratios in fluids;
raises blood pressure
raises blood glucose level, increases rate and force of
adrenal medulla adrenaline heartbeat and increases blood supply to heart and
skeletal muscles
decreases blood glucose level by increasing uptake
pancreas insulin and utilisation by cells; increases glucose to glycogen
conversion in the liver
oestrogen and development of secondary female characteristics,
ovary
progesterone menstrual cycle
testes testosterone development of secondary male characteristics

Cholesterol and the sex hormones

Cholesterol and the sex hormones are steroid-based (they have four fused carbon rings). They have
different chains and functional groups.
Oral contraceptives
The oral contraceptive contains oestrogen and progesterone which suppresses the secretion of FSH
(follicle stimulating hormone) and LH (luteinising hormone), in effect simulating pregnancy, and
therefore prevents ovulation.

Uses and abuses of steroids

 oral contraceptives
 alleviating the symptoms of menopause: HRT (hormone replacement therapy) – the hormones
replace those secreted prior to menopause
 testosterone is used in the treatment of disorders of the testes and breast cancer
 synthetic anabolic steroids are used to help gain weight after debilitating diseases
 Modified synthetic forms of these anabolic steroids have been used by athletes to build up body
muscles and increase endurance.
 Anabolic steroids can cause many changes in secondary sexual characteristics resulting from
systemic hormone imbalances. Changes in hair distribution, sexual desire and fertility are
common.
 These hormones are toxic to the liver and have an associated increased risk of liver cancer.

B7 Hormones
B.7.1 Describe the characteristics of biological catalysts (enzymes).
B.7.2 Compare inorganic catalysts and biological catalysts (enzymes).
B.7.3 Describe the relationship between substrate concentration and enzyme activity.
B.7.4 Determine Vmax and the value of the Michaelis constant (Km) by graphical means and explain its significance.
B.7.5 Describe the mechanism of enzyme action, including enzyme substrate complex, active site and induced fit model.
B.7.6 Compare competitive inhibition and non-competitive inhibition.
B.7.7 State and explain the effects of heavy metal ions, temperature changes and pH changes on enzyme activity.

Characteristics of enzymes
Enzymes are proteins, typically containing several hundred amino acids. They have a well-defined
tertiary structure and so are globular proteins, soluble in water.

Organic vs. inorganic catalysts

Feature Enzyme Inorganic catalyst

structure proteins varied e.g. metal ions, complex
 molecules
mode of action lowers activation energy lowers activation energy
specificity highly specific much less specific
saturation enzymes become saturated most do not
phase homogeneous homogeneous or heterogeneous
speed faster slower
regulation by inhibitors and activators usually not
chemicals
sensitivity to sensitive not sensitive
temperature

Substrate concentration and enzyme activity

The maximum rate (Vmax) varies from one enzyme to another and depends on the temperature and pH
conditions. It has the units of rate.
The Michaelis constant (Km) is the substrate concentration at which the rate is ½ its maximum value. It
has the units of concentration. It varies with pH and temperature. The value of Km gives information
about the affinity of the enzyme for its substrate. It is an inverse relationship - a low value of Km means
that the reaction is going quickly even at low substrate concentrations. A higher value means that the
enzyme has a lower affinity for its substrate

Enzyme-substrate complex
Enzymes are biological catalysts that increase the rate of reaction without themselves being affected, by
offering an alternative reaction pathway. The substrate binds to the enzyme at the active site to form an
enzyme substrate complex. This depends on the compatibility of the R groups at the active site. The
interactions involve hydrophobic interactions, dipole-dipole attractions, hydrogen bonds and ionic
attractions. The binding in the complex puts a strain on the substrate molecule, and so facilitates the
breaking and the forming of bonds.

Induced-fit mechanism
This suggests that in the presence of the substrate, the active site undergoes some conformational
changes, shaping itself to allow a better fi t. So instead of the substrate fitting into a rigid active site, this
is a more dynamic relationship in which the amino acid R groups at the active site change into the
precise positions that allow the binding to occur.
Temperature

Increasing the temperature increases the frequency of collisions and therefore increases the rate. After
a certain point, the effect of the increase in kinetic energy is to change the conformation of the protein
by disrupting the bonds and forces responsible for holding it in its tertiary structure. This is
denaturation. Lowering the temperature causes deactivation, but this is usually reversible.

pH
Changes in pH represent changes in the hydrogen ion concentration, and this affects the equilibrium
positions of ionization reactions. When these reactions involve the R groups of amino acids in the
enzyme structure, the change in ionic charge alters the attractive forces stabilizing the molecule, and
hence its shape and its ability to bind substrate. The specific effect of pH depends on the pKa and pKb
values of the R groups of the amino acids, especially those at the active site, and so is different for each
enzyme.

Heavy-metal ions
Heavy-metal ions cause non-competitive inhibition.
Inhibitors
 competitive inhibitors bind reversibly to the active site
 non-competitive inhibitors bind reversibly away from the active site

Competitive inhibitors
These block the active site making the enzyme unable to catalyse the reaction.

Increasing the concentration of substrate reduces the extent of inhibition as relatively fewer of the
inhibitor molecules are able to bind. In this type of inhibition, Vmax is not altered as there is still a
substrate concentration where full activity of the enzyme can be achieved. But as it takes a higher
substrate concentration to reach this rate, Km is increased.

Non-competitive inhibitors
The binding of this type of inhibitor causes a conformational change in
the protein structure that alters the active site, inhibiting its ability to bind
to the substrate. Increasing the concentration of substrate does not
reduce the extent of this type of inhibition as the enzymes have
effectively been decommissioned by the inhibitor and are unavailable.
Vmax is decreased and cannot be restored no matter how high the
substrate concentration. The value of Km is unchanged because the
uninhibited enzymes are perfectly functional.

B8 Nucleic acids
B.8.1 Describe the structure of nucleotides and their condensation polymers (nucleic acids or polynucleotides).
B.8.2 Distinguish between the structures of DNA and RNA.
B.8.3 Explain the double helical structure of DNA.
B.8.4 Describe the role of DNA as the repository of genetic information, and explain its role in protein synthesis.
B.8.5 Outline the steps involved in DNA profiling and state its use.

Structure of nucleotides
Nucleotides have three components:
1. A pentose (C5) sugar; in DNA it is deoxyribose (left); in RNA it is ribose (right)
 2. A phosphate group PO43-

3. A nitrogenous base

A, G and C are found in both DNA and RNA, but T is only in DNA and U only in RNA.
The complete nucleotide looks like this:

Polynucleotides
The condensation reaction involves the phosphate group on 5’ and the OH group on 3’
Double helical structure of DNA
In DNA, two polynucleotide strands are coiled around the same axis forming a double helix with the
sugar–phosphate backbone on the outside and the nitrogenous bases on the inside. The two strands
are held together by hydrogen bonds that form between bases on each strand. Due to the chemistry of
the bases and the conformation of the helix, only certain base pairings involving one purine with one
pyrimidine are possible: adenine always forms a pair with thymine; guanine always forms a pair with
cytosine.

DNA vs. RNA

DNA RNA
deoxyribose sugar ribose sugar
thymine, T, nitrogenous
uracil, U, nitrogenous base
base
double helix single-stranded structure
RNA is also less stable and more short-lived in the cell. RNA is able to cross the nuclear membrane.
Genetic information
DNA is the genetic material containing all the information for the development of the individual coded in
the base sequences along its length. This code is built from four ‘letters’ and directs the synthesis of
proteins by determining the sequence of their amino acids (i.e. their primary structure). Essentially, this
means that the four-letter code of bases in DNA must be translated into a code to account for all 20 of
the amino acids found in proteins.
Transcription
DNA is confined to the nucleus, but protein synthesis occurs on ribosomes in the cytoplasm of the cell.
So DNA must allow a copy to be made of the relevant part of its information; this copy is in the form of
mRNA. The mRNA then moves to the ribosome.
The synthesis of mRNA from DNA is known as transcription. It occurs when the two strands of DNA
separate by breaking the hydrogen bonds between the paired bases, a process often referred to as
unzipping. Each strand of DNA can then act as a template for the assembly of a complementary strand
of mRNA from ribonucleotides.

Once formed, the mRNA detaches from its DNA template and leaves the nucleus for the ribosome. The
DNA remains in the nucleus and reforms the double helix.
Translation
At the ribosome, the sequence of bases in mRNA is used to determine the sequence of amino acids in
a polypeptide. This is known as translation and involves the use of another RNA species, tRNA, which
works like an adaptor. One end of the tRNA molecule recognizes a specific triplet of bases in the mRNA
known as a codon. The other end of the tRNA recognizes a corresponding amino acid. As codons in
the mRNA are read sequentially, successive tRNA molecules bring the appropriate amino acids into
position, where they link together by peptide bonds to form a polypeptide
Hence the sequence of bases in the DNA, via RNA, determines the sequence of amino acids in the
protein. The specifi c relationship between the bases and amino acids is known as the genetic code.
As we have just seen, it is a triplet code with three bases specifying each amino acid.
DNA profiling
1. DNA is extracted
2. It is cut into small pieces using restriction enzymes. This is
because the easiest place to detect the unique nature of individual
DNA is in regions where short sequences of bases are repeated a
variable number of times. These are known as short tandem repeats
(STRs).
3. A technique known as the polymerase chain reaction (PCR) is
used to amplify these regions in the DNA by making multiple copies.
4. The DNA fragments that result are then separated and detected
using gel electrophoresis. Due to its phosphate groups, DNA carries a
negative charge. So, the fragments move towards the positive terminal
by a distance that corresponds to their molecular size: shorter
fragments move further than longer fragments. The nitrocellulose sheet
used in the electrophoresis is treated with radiation, for example 32P,
and exposed using X-ray film.
Uses
 To identify victims whose bodies are not recovered from the
scene of an accident or crime.
 To identify a suspect in forensic cases.
 To confirm biological relationships e.g. paternity tests
 To determine the relationships between populations in the study
of evolution, migration and ecology.

B9 Respiration
B.9.1 Compare aerobic and anaerobic respiration of glucose in terms of
oxidation/reduction and energy released.
B.9.2 Outline the role of copper ions in electron transport and iron ions in oxygen
transport.

Respiration
Respiration is the process of chemical breakdown of energy rich
molecules in cells with the release of energy. It takes place in all living
cells all the time. Respiration occurring in the absence of oxygen is
known as anaerobic respiration, while that using oxygen is known as
aerobic respiration.
Respiration begins with the anaerobic process of glycolysis
In glycolysis, a glucose molecule is converted into two pyruvate
molecules, C3H4O3. During glycolysis, the partial oxidation of glucose is
accompanied by the reduction of a coenzyme, a dinucleotide called
NAD+, as shown below.
The fate of pyruvate in anaerobic conditions
In order to allow the reactions of glycolysis to continue, the co-enzyme must be re-oxidised. This is
achieved by reducing the pyruvate - to lactate in human cells such as active muscles, and to ethanol
and carbon dioxide in plants or micro-organisms such as yeast.

When oxygen is present, further reactions oxidize the pyruvate in a sequence of steps which ultimately
yield carbon dioxide and water. Along the way, other reactants are successively reduced and re-
oxidized, but ultimately oxygen acts as the terminal electron acceptor and is reduced to water.

Electron transport carriers

These proteins are embedded in a membrane where they become successively reduced and then re-
oxidized as they in turn accept and pass on the electrons. The carriers are organized in sequence
corresponding to their electrode potentials so that the electrons effectively flow down an electrochemical
gradient. The terminal electron carrier, cytochrome oxidase, contains Cu. The Cu changes its oxidation
state between +1 and +2 as electrons flow through it.

Haemoglobin
In hemoglobin and myoglobin, the uptake of oxygen is not accompanied by a change in the oxidation
number of the Fe which remains in the +2 state. Instead, the oxygen is bound in molecular form, O 2, in
the structure in a complex way that involves a conformational shift of the protein. For this reason, we
refer to these molecules as becoming oxygenated when they gain oxygen, as they are not oxidized in
the chemical sense.
Option D: Medicines and drugs
D1 Pharmaceutical products
D.1.1 List the effects of medicines and drugs on the functioning of the body.
D.1.2 Outline the stages involved in the research, development and testing of new pharmaceutical products.
D.1.3 Describe the different methods of administering drugs.
D.1.4 Discuss the terms therapeutic window, tolerance and side-effects.

Drugs and medicines

A drug is a chemical that affects how the body works.
A medicine is a substance that improves

Effects of medicines and drugs on the body

Generally, a medicine or drug is any chemical that does one or more of the following.
 Alters the physiological state, including consciousness, activity level or coordination
 Alters incoming sensory sensations
 Alters mood or emotions
The placebo effect
The placebo effect is when patients gain therapeutic effect from their belief that they have been given a
useful drug, even when they have not.

Research and development

Thalidomide
Thalidomide a sedative and anti-inflammatory medication and later prescribed to pregnant women in
many countries to help reduce ‘morning sickness’ in their early months of pregnancy. The drug had a
side effect on the development of the foetus leading to malformed limbs.

Administering drugs
 oral – taken by mouth
 inhalation – vapour breathed in; smoking; treatment of respiratory conditions
 skin patches; absorbed directly from the skin into the blood e.g. nicotine patches
 suppositories – inserted into the rectum; haemorrhoids
 eye or ear drops – treatment of infections in those areas
 parenteral (by injection)
Tolerance
When a person is given repeated doses of a drug, it sometimes happens that tolerance develops, that
is a reduced response to the drug. So higher doses are needed to produce the same effect and this
increases the chances of there being toxic side-effects.
Side effects
Side effects are physiological effects which are not intended and vary greatly from one drug to another,
and with the same drug in different people. Some side effects are beneficial e.g. aspirin, taken for pain
relief, helps protect against heart disease. Other drugs e.g. thalidomide have negative side effects.
Therapeutic window
The therapeutic window is the range of a drug’s concentration in the blood between its therapeutic level
and its toxic level. Within the therapeutic window the drug is both safe and effective.

D2 Antacids
D.2.1 State and explain how excess acidity in the stomach can be reduced by the use of different bases.

Antacids
Antacids are usually weakly basic compounds, often metal oxides or hydroxides, carbonates or
hydrogencarbonates, which react with the acid to produce a salt and water e.g.
Al(OH)3 (s) + 3HCl(aq) → AlCl3(aq) + 3H2 O(l)

Mg(OH)2 (s) + 2HCl(aq) → MgCl2 (aq) + 2H2 O(l)

Some antacids use carbonates, which produce carbon dioxide during neutralization, which can cause
stomach bloating and flatulence. To avert this antifoaming agents are added such as dimethicone.
Some antacids also contain alginates which float to the top of the stomach, forming a ‘raft’ which acts as
a barrier preventing reflux into the oesophagus (heart burn).
 D3 Analgesics
D.3.1 Describe and explain the different ways that analgesics prevent pain.
D.3.2 Describe the use of derivatives of salicylic acid as mild analgesics, and compare the advantages and disadvantages of using
aspirin and paracetamol (acetaminophen).
D.3.3 Compare the structures of morphine, codeine and diamorphine (heroin, a semi-synthetic opiate).
D.3.4 Discuss the advantages and disadvantages of using morphine and its derivatives as strong analgesics.

Mild analgesics
Mild analgesics, including aspirin and non-steroidal anti-inflammatory drugs (NSAIDs) such as
ibuprofen, function by intercepting the pain stimulus at the source, often by interfering with the
production of substances (for example, prostaglandins) that cause pain, swelling or fever. They don’t
affect the function of the brain so are non-narcotics.

Strong analgesics
Strong analgesics, , work by temporarily bonding to receptor sites in the brain, preventing the
transmission of pain impulses without depressing the central nervous system. They affect the function of
the brain so are narcotics.

Salicylic acid
Salicylic acid (left) is an analgesic that comes from the bark of the willow tree. However, it tastes shit
and induces vomiting. To remedy this the OH group was replaced with an ester group and the
compound creates is aspirin (right). Aspirin has been found to be useful in preventing the recurrence of
heart attacks and strokes. The disadvantages of aspirin include ulceration and stomach bleeding,
allergic reactions and Reye’s syndrome in children (a potentially fatal liver and brain disorder).
Paracetamol is very safe in the correct dose but can, in rare cases, cause blood disorders and kidney
damage. Overdosage can lead to serious liver damage, brain damage and even death.

Aspirin vs. paracetamol

Aspirin Paracetamol

Analgesic (painkiller) yes yes

Antipyretic (reduces fever) yes yes

Reduces inflammation yes no

Side-effects stomach wall irritant, blood anti-coagulant does not irritate stomach wall

Severe side-effects (over-dosage) Reye’s syndrome in children serious kidney, liver and brain damage

Synergistic effect with alcohol increased risk of stomach bleeding toxic side-effects can be increased

Allergic reactions relatively common rare

Recommended use for children no; can cause Reye’s syndrome (although yes
 ‘baby aspirin’ is available)

Strong analgesics

Codeine Morphine Diamorphine (heroin)

Structure

Functional  benzene ring

 benzene ring  benzene ring
groups  ether
 ether  ether
 alkene  alkene  alkene
 alcohol  alcohol  ester – ethanoate
 tertiary amine  tertiary amine  tertiary amine

Side-effects of strong analgesics

 constipation
 suppressing cough reflex
 constriction of pupil in eye
Narcotic effects
Short term:
 feeling of well-being and contentment
 euphoria
 dulling of pain, fear and tension

Long term:
 constipation
 loss of libido
 loss of appetite
 poor nutrition
 dependence
 withdrawal symptoms: cold sweats and anxiety
 crime
 HIV and hepatitis from sharing needles

The conversion of morphine into heroin involves replacing both OH groups with less polar ester groups.
This makes heroin more lipid-soluble, so it crosses the blood-brain barrier more quickly.

D4 Depressants
D.4.1 Describe the effects of depressants.
D.4.2 Discuss the social and physiological effects of the use and abuse of ethanol.
D.4.3 Describe and explain the techniques used for the detection of ethanol in the breath, the blood and urine.
D.4.4 Describe the synergistic effects of ethanol with other drugs.
D.4.5 Identify other commonly used depressants and describe their structures.
Depressants
Depressants are drugs that act on the brain and spinal cord (known as the central nervous system or
CNS). The action of these drugs changes the communication between brain cells by altering the
concentration or the activity of chemicals called neurotransmitters. As a result they cause a
depression, or a decrease in brain activity that in turn influences the functioning of other parts of the
body, such as the heart and the mechanisms determining breathing rate.
Effects of depressants

Dosage Low to moderate High dose Extremely high

effect dose doses
slurred speech
calmness staggering gait respiratory
relief from anxiety altered depression
very relaxed perception coma/death
muscles sleep induced
Description: tranquiliser sedative hypnotic

increasing
dosage

Alcohol abuse
Short-term effects:
 loss of self-restraint, concentration and insight are impaired
 loss of balance and judgement
 violent behaviour associated with domestic abuse and family breakdown
 risk-taking behaviour
 dehydration caused by increased urine output leading to ‘hangover’ and loss of productivity
 at high doses, can cause vomiting, loss of consciousness, coma and death
Long-term effects:
 alcoholism, withdrawal symptoms
 liver diseases e.g. cirrhosis and liver cancer
 coronary heart disease
 high blood pressure
 foetal alcohol syndrome
 permanent brain damage
Detection of alcohol in breath
An equilibrium forms in the lungs between alcohol and the exhaled air. There is a specific value of KC for
a specific temperature, so measurement of alcohol in exhaled air can be used to determine the blood-
alcohol level.
Breathalyser
The breathalyser contains potassium dichromate(VI) crystals which are orange, but are changed to
green chromium(III) ions. The extent of colour change can be measured using a photocell. This test is
not very accurate.

Infrared spectroscopy
This analysis is done with an intoximeter. The principle here (Chapter 12) is that different molecules
cause different absorption bands in the infrared part of the spectrum, as a result of vibrations of their
particular bonds and functional groups. Hence ethanol has a characteristic absorption band at 2950 cm-
1 owing to its C-H bonds. The O-H bond cannot be used because it is also present in water vapour. The

size of the peak can be used to measure ethanol concentration, when compared with a reference taken
from the ambient air.

Ethanol analysis of blood and urine

In gas-liquid chromatography, blood or urine is vaporised and injected into a stream of inert gases
(the mobile phase) over the surface of a non-volatile liquid (the stationary phase). The components of
the vapour, including ethanol gas, move at different rates depending on their boiling points and relative
solubility in the two phases. As a result, each leaves the column holding the liquid phase after a specific
interval of time known as its retention time. So a peak at the retention time corresponding to ethanol
can be used to confirm its presence in the vapour. The area under the peak is a measure of ethanol
concentration relative to a known standard in the mixture such as propan-1-ol.

Synergy
The synergy of ethanol means it increases the activity of other drugs. Some examples are:
 with aspirin, ethanol can cause increased bleeding of the stomach lining and increased risk of
ulcers
 with other depressants such as barbiturates, including sleeping pills, ethanol can induce heavy
sedation, possibly leading to coma
 with tobacco, ethanol appears to increase the incidence of cancers, particularly of the intestines
and liver
 with many other drugs, ethanol can interfere with their metabolism by the liver, which can cause
greater and more prolonged drug effects.
Other depressants
The benzodiazepines are a major group of depressants which depress activity in the part of the brain
that controls emotion and so are used as tranquilizers in the treatment of anxiety disorders and related
insomnia. As well as being the most commonly used class of sleeping pill, they are also used as muscle
relaxants.
A widely used anti-depressant drug is fluoxetine hydrochloride, marketed as Prozac. It functions by
increasing the levels of serotonin – an important neurotransmitter in the brain. It is used in the treatment
of depression, as well as eating and panic disorders.

D5 Stimulants
D.5.1 List the physiological effects of stimulants.
D.5.2 Compare amphetamines and epinephrine (adrenaline).
D.5.3 Discuss the short- and long-term effects of nicotine consumption.
D.5.4 Describe the effects of caffeine and compare its structure with that of nicotine.

Physiological effects of stimulants

 They can help to facilitate breathing by causing relaxation of the air passages and are used in the
treatment of respiratory infections such as severe bronchitis.
 They may reduce appetite and so have been used as part of a treatment for obesity.
 They may cause palpitations or tremors to occur.
 When used in excess, they can cause extreme restlessness, sleeplessness, fits, delusions and
hallucinations.
Amphetamines
Amphetamines mimic and have similar structures to adrenaline.

They both have the phenyl-ethyl-amine structure.

Because of their role in stimulating the sympathetic nervous system, the amphetamines are called
sympathomimetic drugs. In small doses, amphetamines increase mental alertness and physical
energy. Side-effects include dilation of the pupils of the eyes and decreased appetite, as well as
possible blurred vision and dizziness. Regular use of these drugs leads to the rapid development of
both tolerance and dependence, coupled with serious long-term effects such as severe depression and
reduced resistance to infection.
Nicotine
As a lipid-soluble molecule, nicotine is able to cross the blood–brain barrier bringing about rapid effects
on brain activity. Its action is to increase the levels of adrenaline as well as to alter the concentrations of
certain neurotransmitters in the brain.
 Short-term effects Long-term effects
 high blood pressure
 increases concentration
 increases risk of heart disease
 relieves tension and boredom
including angina
 helps to counter fatigue
 coronary thrombosis
 increases heart rate and blood
 increases the level of fatty acids
pressure
in the blood which can lead to
 decreases urine output
atherosclerosis and stroke
 over-stimulation of stomach
acids which can lead to
increased risk of peptic ulcers

Caffeine

Note that, like nicotine, caffeine contains heterocyclic rings (containing both carbon and nitrogen) and a
tertiary amine group. In addition, caffeine contains two amide groups.
Effects of caffeine

Consumption of caffeine in small Consumption of caffeine in large

amounts amounts
 enhancement of mental  can cause anxiety, irritability
energy, alertness and ability and insomnia
to concentrate  can cause dependence; side-
 acts as a diuretic, increasing effects on withdrawal include
the volume of urine; can headaches and nausea
cause dehydration

D6 Antibacterials
D.6.1 Outline the historical development of penicillins.
D.6.2 Explain how penicillins work and discuss the effects of modifying the side-chain.
D.6.3 Discuss and explain the importance of patient compliance and the effect of penicillin overprescription.

History of penicillin
 Alexander Fleming noticed that a fungus or mould known as Penicillium notatum produced a
chemical which inhibited bacterial growth.
 Howard Florey and Ernst Chain isolated penicillin as the antibacterial agent.
  Large-scale production methods were developed using deep fermentation tanks containing corn
steep liquor through which sterile air was forced.

How penecillins work

Its core structure is a four-membered ring consisting of one nitrogen and three carbon atoms and known
as beta-lactam, which is responsible for the antibacterial properties. By acting as an irreversible inhibitor
of an enzyme, it prevents the development of cross-links in bacterial cell walls, so weakening the walls
and causing the bacteria to rupture and die during their reproductive phase.

Modifying side chains

A disadvantage of penicillin G is that it is broken by stomach acid and has to be injected into the blood.
Bacterial resistance occurs because of genetic mutation. Resistant bacteria produce an enzyme,
penicillinase, which can open penicillin’s beta-lactam ring and render it inactive. The problem is
compounded by the wide use of penicillins in animal feeds to lower the incidence of disease. This has
caused the antibiotics to enter the human food chain and hence increase the proportion of resistant
bacteria.
The issue can be addressed in the following ways:
 modifying the side chains
 making penicillins prescription-only drugs; encouraging doctors not to over-prescribe
 encouraging patients to complete the full course of treatment (known as patient compliance)

Over-prescription
• Leads to greater immunity of bacteria to penicillin, since the strongest and most resistant strains
survive.
• Greater doses of penicillin are required to be effective
• Danger of developing super bacteria
• Kill beneficial bacteria as well as harmful bacteria

D7 Antivirals
D.7.1 State how viruses differ from bacteria.
D.7.2 Describe the different ways in which antiviral drugs work.
D.7.3 Discuss the difficulties associated with solving the AIDS problem.

Viruses vs. bacteria

 Bacteria are larger
 Bacteria have a cell wall and a nucleus
 Bacteria reproduce by cell division, whilst viruses insert genetic material into cells
 Bacteria feed, excrete and grow whereas viruses do not
The action of antiviral drugs
 block enzyme activity within host cell/block reverse transcriptase;
 alter host cell's genetic material;
 prevent virus from multiplying/replicating;
  alter virus’s binding site on cell wall/prevent virus binding with cell wall;
 prevent virus from entering/leaving cell;

Difficulties of solving AIDS problem

 HIV virus mutates rapidly;
 HIV metabolism linked to that of host cell/HIV uses host cell;
 Drugs harm host cell as well as HIV/ difficult to target HIV without damaging host cell;
 The control and treatment of HIV is exacerbated by the high price of anti-retroviral agents and
socio-cultural issues.

D8 Drug action
D.8.1 Describe the importance of geometrical isomerism in drug action.
D.8.2 Discuss the importance of chirality in drug action.
D.8.3 Explain the importance of the beta-lactam ring action of penicillin.
D.8.4 Explain the increased potency of diamorphine (heroin) compared to morphine.

Geometrical isomerism
Many anti-cancer drugs function by targeting DNA to stop the division of cells. An example is cisplatin,
Pt(NH3 )2 Cl2 . It has a square planar geometry and therefore exhibits cis-trans isomerism.

In the body, the neutral complex exchanges one or both of its negative chloride groups with neutral
water ligands and so forms reactive positively charged species.

This positive species binds strongly to DNA by exchanging the water and chloride ligands for bonds
between platinum and nitrogen atoms in adjacent molecules of the base guanine (G) in the double helix.

The trans isomer cannot bond in this way so cannot be used for chemotherapy.

Chirality
When drugs are synthesised, both of the optical isomers are made. With thalidomide, one isomer
induced sleep and calmness in pregnant women and the other produced severe foetal abnormalities.
Beta-lactam ring
The bond angles in this ring are reduced to about 90°, despite the fact that, because they have sp 2 and
sp3 hybridized atomic orbitals, the atoms in the ring seek to form bonds with angles of 120° and 109.5°
respectively. This puts a strain on the bonds, effectively weakening them.
The action of these beta-lactam antibiotics is to disrupt the formation of cell walls of bacteria by
inhibiting a key bacterial enzyme, transpeptidase. As the drug approaches the enzyme, the high
reactivity of the amide group in the ring causes it to irreversibly bind near the active site of the enzyme
as the ring breaks

Heroin vs. morphine

To make heroin, the OH groups in morphine are replaced with ester groups. This makes the molecule
less polar, making it able to cross the (non-polar) blood-brain barrier more easily. Heroin reaches the
brain cells faster and in higher concentration.

D9 Drug design
D.9.1 Discuss the use of a compound library in drug design.
D.9.2 Explain the use of combinatorial and parallel chemistry to synthesize new drugs.
D.9.3 Describe how computers are used in drug design.
D.9.4 Discuss how the polarity of a molecule can be modified to increase its aqueous solubility and how this facilitates its
distribution around the body.
D.9.5 Describe the use of chiral auxiliari

The first step in developing a drug is to identify the molecular target; this is usually an enzyme, a
receptor or DNA.

Finding a lead compound

Traditionally, a large collection of related compounds are synthesized individually and evaluated for
biological properties. This approach is time-consuming and expensive.

Combinatorial chemistry
Combinatorial chemistry is a process used to synthesize a large number of compounds, called
combinatorial libraries. The reactions involved usually occur on insoluble resin beads, a technique
known as solid-phase chemistry.

Different molecules can be made using the mix and split method:

Subsequent screening of the products for the desired activity will hopefully identify a useful lead
compound
The IB mark scheme gives the following as acceptable answers to the question explain what is meant
by combinatorial chemistry:
Any three of the following.
 process used to synthesize a large number of compounds / OWTTE;
 compounds are structurally related;
 repetitive/computerized technique;
 screen them for biological activity / OWTTE;
 produces a library/database of different compounds / OWTTE;

Parallel synthesis
Parallel synthesis produces libraries that are more focused and less diverse than those from
combinatorial techniques. Parallel synthesis usually involves the synthesis of a highly reactive
intermediate via a series of simple steps, then its subsequent reactions with a number of different
reagents. One of the popular means of achieving this is known as the teabag procedure in which
porous bags of resins are suspended in reagents. Automated or semi-automated synthesizers can yield
up to 144 structures in separate reaction tubes.

Computer-aided design
Three-dimensional models of drugs can be created in silico and molecular modelling software can be
used for the virtual development and evaluation of new drugs. Molecular-modelling software analyses
the interaction between the drug and its receptor site, helping to design molecules that give an optimal
fit. The part of the drug molecule that permits the specifi c binding and is responsible for the activity is
called the pharmacophore. Even when the exact structure of the receptor site is not known, a process
called pharmacophore mapping can derive a model called a 3-D pharmacophore. This is done by
analysing the molecules that bind to the receptor, searching for their common features and using
software to predict the most likely three-dimensional structure. Computers should reduce the number of
candidate molecules that must be tested, and means fewer molecules have to be tested in vivo (in living
organisms).

Modification of drug structure

Reaction of –COOH to form ionic salt
Aspirin contains an ester group and a carboxylic acid group attached to a benzene ring. When it is
reacted with a strong alkali, it forms a salt in which the carboxylic acid group is converted into its
conjugate base, the acid anion, as shown below. This increases the aqueous solubility of the
compound; formulations containing the salt of the acid are known as soluble aspirin.

Reaction of –NH2 to form ionic salt

The amine group can be reacted with HCl to form the chloride salt. This contains the conjugate acid, the
basic cation.

Chiral auxiliary
A chiral auxiliary is used to convert a non-chiral molecule into just the desired enantiomer, thus avoiding
the need to separate enantiomers from a racemic mixture. This is a chiral molecule which binds to the
reactant, physically blocking one reaction site through steric hindrance, so ensuring that the next step in
the reaction can only take place from one side. This effectively forces the reaction to proceed with a
specified stereochemistry. Once the specific enantiomer of the new product has been set, the auxiliary
can be taken off and recycled.

D10 Mind-altering drugs

D.10.1 Describe the effects of lysergic acid diethylamide (LSD), mescaline, psilocybin and tetrahydrocannabinol (THC).
D.10.2 Discuss the structural similarities and differences between LSD, mescaline and psilocybin.
D.10.3 Discuss the arguments for and against the legalisation of cannabis.
 Name Structure Effects
 potent hallucinogen that creates
distortions of the body and crawling
geometric patterns
 causes impaired judgment,
hypertension, dilated pupils, and
LSD
changes to body temperature and
heart rate
 can cause unpredictable mood swings
from euphoria (a ‘good trip’) to
depression and panic (a ‘bad trip’)
 about 1000–3000 times less potent
than LSD; causes subjective
hallucinations dependent on the
individual
Mescaline  effects include anxiety, static tremors,
and psychic disturbances with vivid
visual hallucinations
 abdominal pain, nausea and diarrhoea
are also common
 produces subjective hallucinations
similar to mescaline but milder
 some people experience a pleasant
mood, others become apprehensive
Psilocybin  compulsive movement and
inappropriate laughter may occur; also
vertigo and dizziness
 numbness, muscle weakness and
drowsiness are also common
 depresses the central nervous system
and causes mental relaxation and
euphoria
 loss of inhibitions
 alteration of perception of time and
space
 Palpitations, loss of concentration,
THC
light-headedness, weakness and a
sense of floating
 At high doses, the drug can cause
depression of respiration and can lead
to collapse
 withdrawal symptoms, including
insomnia, anxiety and restlessness

Legalisation of cannabis
 Arguments for legalization include the ability of cannabis to offer relief from certain diseases.
 Arguments against legalization include the possible harmful effects and the possibility of
cannabis users moving on to harder drugs.