Topic 1: Quantitative Chemistry

1.1 Introduction to the particulate nature of matter and chemical change

1.1.1 Atoms of different elements combine in fixed ratios to form compounds, which have different properties from their
component elements
1.1.2 Mixtures contain more than one element and/or compound that are not chemically bonded together and so retain their
individual properties
1.1.3 Mixtures are either homogeneous or heterogeneous

1.1.4 Deduction of chemical equations when reactants and products are specified

1.1.5 Application of the state symbols (s), (l), (g), and (aq) in equations

1.1.6 Explanation of observable changes in physical properties and temperatures during changes of state

Particle Nature of Matter

 Matter is anything that takes up space
 Matter can either refers to the particles (pure substances) or combination of a substances (mixtures):

Pure Substances
 A pure substance has definite and constant composition
 For a pure substance, from a particle perspective all particles will look and remain the same

Definitions

Element – Atoms all having the same number of protons

Molecule – Two or more elements chemically join together
Compounds – Two or more different elements chemically joined together in a fixed ratio

 From their definitions: All compounds are molecules, but not all molecules are compounds
 When the elements are joined, the atoms lose their individual properties and have different properties from the elements
they are composed of

Mixtures
 Mixture: A combination of pure substances
 Mixtures contain more than one element and/or compound that are
not chemically bonded together, so retain their individual properties
 Mixtures are either homogeneous or heterogeneous:
 Homogeneous mixtures are the same mixture throughout
o They will have a uniform composition
 Heterogeneous mixtures have a different mixture throughout
o They will have visibly different substances or phases
throughout, a non-uniform composition

Chemical Equation
 Chemical Equation: Describes what happens during a chemical reaction
 A chemical reaction will always have reactants and products as well as some special reaction conditions if required
 Reactants are always on the left, and products are always on the right: 𝑅𝑒𝑎𝑡𝑎𝑛𝑡𝑠 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
 Chemical equations usually use state symbols to identify the state of the products and reactants
 State Symbols
 Reactants and products can be in one of four states
o (s): solid
o (l): liquid
o (g): gas
o (aq): aqueous solution (dissolved in a solvent)
 The changes of state are to the left:
 A heating curve is a graph showing the temperature of a
substance plotted against the amount of energy it has
absorbed

 Note, during a state change there will be no increase or decrease in temperature

 Adding temperature only increases the kinetic energy of the molecules, which will eventually break the bonds, then the
molecules will change state
 It also takes a higher temperature to turn a solid to a liquid, and an even greater temperature to turn a liquid to a gas

Physical and Chemical Changes

 In a physical change, no new substances are produced
o Example: The melting of ice is a physical change. It is being changed physically
 In a chemical change, new chemical substances are formed
o The atoms in the reactants are rearranged to form new products. It is being changed chemically

1.2 The mole concept and Avogadro’s Constant

1.2.1 The mole is a fixed number of particles and refers to the amount, n, of substance
12
1.2.2 Masses of atoms are compared on a scale relative to C and are expressed as relative atomic mass (Ar) and relative
formula/molecular mass (Mr)
-1
1.2.3 Molar mass (M) has the units g mol

1.2.4 Calculation of the molar masses of atoms, ions, molecules and formula units

1.2.5 Solution of problems involving the relationships between the number of particles, the amount of substance in moles and
the mass in grams
1.2.6 Interconversion of the percentage composition by mass and the empirical formula and molar mass

1.2.7 Determination of the molecule formula of a compound from its empirical formula and molar mass

1.2.8 Obtaining and using experimental data for deriving empirical formulas from reactions involving mass changes

The Mole
 Definitions

Mole – The amount of substance that contains the same number of specified particles as there are atoms in 12g of
Carbon-12

 When dealing with particles of the size of atoms and molecules, it becomes very difficult to do the calculations as they are
present in very large numbers. So to make these calculations simpler, answers are expressed in mol
 The mole is given by the symbol 𝑛
 The mole makes it possible to correlate the number of particles with the mass that can be measured
 The number of particles in 1 mole is given by Avogadro’s constant
o Avogadro’s constant (L): 1 mol = 6.02 x 1023 particles (atoms, molecules, ions)
 In order to calculate number of particles: 𝑁 = 𝑛 × 𝐿
o 𝑁: number of particles (atoms, molecules, ions)
o Atoms are simple elements, ions are elements with a charge, and molecules are more than one atom
o 𝑛: number of moles
o 𝐿: Avogadro’s number
𝑁
 We can also rearrange this formula if we want to find number of mols: 𝑛 = 𝐿

Mole question:

Calculate the number of O2 molecules in 1.5 mol of oxygen (O2)

𝑛(𝑂2 ) = 1.5𝑚𝑜𝑙
𝐿 = 6.02 × 1023
Therefore: 𝑁 = 𝑛 × 𝐿 => 𝑁 = 1.5 × 6.02 × 1023 = 9.0 × 1023

Mole relationships
 A chemical formula shows the mole relationship between the individual atoms that make up that molecule. Example:
o Methane gas is produced from the combination of 1 mol of carbon atoms and 4 mol of atoms
o 1 mol of C + 4 mol of H → 1 mol of CH4
 To find the number of mol of an element in a molecule multiply the number of that element in the molecule by the amount
of mol of that molecule:
𝑛(𝑋) = # × 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑜𝑙𝑠
 To find the number of atoms of an element in a molecule multiply the above equation by 𝐿
 To find the total number of atoms of a molecule multiply the amount in mol by the number of atoms in the molecule

Mole relationship question:

1. Calculate the number of mol of oxygen in 0.05 mol of O2 molecules

𝑁(𝑂) = 2 × 𝑛(𝑂2 ) note that there is a two because in one molecule of O2 there are two oxygen atoms ratio ∴ is
2:1
𝑁(𝑂) = 2 × 0.05
𝑁(𝑂) = 0.1𝑚𝑜𝑙
2. Calculate the number of mol of SO42- ions in a 2.39x10-3 mol sample of PbSO4
𝑛(𝑃𝑏𝑆𝑂4 ) = 2.39 × 10−3
𝑛(𝑆𝑂4 2− ) = 𝑛(𝑃𝑏𝑆𝑂4 ) It is equal because the ratios are equal
𝑛(𝑆𝑂4 2− ) = 2.39 × 10−3
The Mole Concept
 Masses of atoms are compared on a scale relative to 12C and are expressed as relative atomic and molecular mass

Definitions

1
Relative atomic mass (Ar) – The average mass of all isotopes of an element compared to 12 the mass of C12 atom
1
Relative molecular/formula mass (Mr) – The mass of a molecule compared to 12 the mass of C12 atom

 The relative molecular mass (Mr) also called the molar mass can be calculated from its chemical formula using the relative
atomic masses (Ar) of the elements from the periodic table
 Some elements will have a greater atomic mass than others despite their atomic number because they will either have a
greater proportion of heavier isotopes or they will have a greater number of neutrons
 Relative atomic and molecular mass are relative therefore it has no units
 Molar mass (M) has the units g mol-1

Relative molecular mass question:

Calculate the relative formula mass (molar mass) of Vitamin C: C6H8O6

𝑀𝑟 (𝑉𝑖𝑡𝑎𝑚𝑖𝑛 𝐶) = [6 × 𝐴𝑟 (𝐶)] + [8 × 𝐴𝑟 (𝐻)] + [6 × 𝐴𝑟 (𝑂)] Note the multiples because there is a # of atoms
𝑀𝑟 (𝑉𝑖𝑡𝑎𝑚𝑖𝑛 𝐶) = (6 × 12) + (8 × 1) + (6 × 16)
𝑀𝑟 (𝑉𝑖𝑡𝑎𝑚𝑖𝑛 𝐶) = 176
Therefore 𝑀𝑟 (𝑉𝑖𝑡𝑎𝑚𝑖𝑛 𝐶) = 176𝑔𝑚𝑜𝑙 −1

Amount of moles
𝑚
 In order to calculate number of moles: 𝑛 = 𝑀 where
o 𝑛: moles
o 𝑚: mass
o 𝑀: molar mass

Number of moles question:

Calculate the amount in mol of 1.2g of Nitric Oxide (NO)

𝑚 = 1.2 𝑀 = 14 + 16 = 30
𝑚 1.2
Therefore, since 𝑛 = 𝑀 → 𝑛 = 30
= 0.04 𝑚𝑜𝑙

Percentage Composition
 The values of molar masses of elements in compounds can be used to calculate the % compositions of a compound once its
formula is known
 This is given by the following equation:
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑥
% 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑏𝑦 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑

Question: Determine the % composition by mass of each element in potassium nitrate (KNO3)

39.10 3 × 16.00
%𝐾 = 101.11 × 100 = 38.67% %𝑂 = 101.11
× 100 = 47.47%

%𝑁 = 100 − 38.67 − 47.47 = 13.86%

 Empirical formula
 Empirical formula: The formula of a compound that shows the lowest whole number ratio of each type of atom
 To calculate the empirical formula of compounds we:
1. Write the elements present in the compound
2. Write each elements % composition or mass
3. Divide the % or mass by the relative atomic mass and calculate the ratio
4. Divide each ratio by the smallest ratio above to get a whole number ratio
5. Express as an empirical formula

Question: A compound consists of carbon 75% and hydrogen 25% by mass. Determine empirical formula

𝐶: 𝐻
75 25
:
12.01 1.01
6.24 24.8
∶
6.24 6.24
1: 4

Molecular formula
 Molecular formula: The formula of a compound that shows the actual number of each type of atom in the molecule
 A molecular formula gives the actual number of different atoms covalently bonded in one molecule
 The molecular formula is always a whole multiple of the empirical formula
 A molecular formula can be found is the molar mass is known

Question: Work out the molecular formula of CH2 (Mr = 70)

𝐸𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝐹𝑜𝑟𝑚𝑢𝑙𝑎: 𝐴𝑟 (𝐶) + 𝐴𝑟 (𝐻2 ) = 12 + 2 = 14

70 ÷ 14 = 5
𝐶𝐻2 × 5 = 𝐶5 𝐻10

Atom Economy
 The atom economy of a chemical reaction is a measure of the amount of starting materials that become useful products
 A high atom economy means that less waste is created and the reaction has a higher efficiency
 To calculate:
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝐴𝑡𝑜𝑚 𝑒𝑐𝑜𝑛𝑜𝑚𝑦 = × 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠/𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

1.3 Reacting masses and volumes

1.3.1 Reactants can either be limiting or excess

1.3.2 The experimental yield can be different from the theoretical yield

1.3.3 Avogadro’s law enables the mole ratio of reacting gases to be determined from volumes of the gases

1.3.4 The molar volume of an ideal gas is a constant at specified temperature and pressure

1.3.5 The molar concentration of a solution is determined by the amount of solute and the volume of solution

1.3.6 A standard solution is one of known concentration

1.3.7 Solution of problems relating to reacting quantities, limiting and excess reactants, theoretical, experimental and
percentage yield
1.3.8 Calculation of reacting volumes of gases using Avogadro’s law
1.3.9 Solution of problems and analysis of graphs involving the relationship between temperature, pressure and volume for a
fixed mass of an ideal gas
1.3.10 Solution of problems relating to the ideal gas equation

1.3.11 Explanation of the deviation of real gases from ideal behavior at low temperatures and high pressure

1.3.12 Obtaining and using experimental values to calculate the molar mass of a gas from the ideal gas equation

1.3.13 Solution of problems involving molar concentration, amount of solute and volume of solution

1.3.14 Use of the experimental method of titration to calculate the concentration of a solution by reference to a standard
solution

Limiting/Excess reactants
 Reactants can either be in limiting or excess:
o The limiting reactant is the reactant that will be used up first in a chemical reaction
o The excess reactant is the reactant that will be left over after the limiting reactant is used all up
 In order to determine limiting reactant, divide the moles by the leading coefficient
 The reactant with the lower number of moles is the limiting reactant

Question:

Sulfur hexafluoride (SF6) is a colorless, odorless, and extremely stable compound. It is formed by burning sulfur in
the atmosphere of fluorine. Suppose that 4 moles of S are added to 20 moles of F2. Which will be the limiting
reagent?
S + 3F2 → SF6
𝑛(𝑠) ÷ 1 = 4 𝑚𝑜𝑙 ÷ 1 = 4 Divided by 1 because coefficient is one
𝑛(𝐹2 ) ÷ 3 = 20 𝑚𝑜𝑙 ÷ 3 = 6.67 Divided by 3 because coefficient is three
Therefore, S is limiting and F2 is in excess

Percentage yield
 Experimental yield can be different from theoretical yield. The yield of a reaction is the actual mass of product obtained:
o Some of the reactants may remain unreacted when the reaction is complete
o Some of the product may be lost when liquids or solids are transferred from one container to another
o Some of the reactants may form other products
 A percentage yield is the amount of product produced experimentally compared to the theoretical amount
 In order to calculate percentage yield:
𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑦𝑖𝑒𝑙𝑑 (%) = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

Question:

10.00g of ethane (C2H4) will react with exactly 56.95g of bromine. The theoretical yield for this reaction is 66.95.
The experimental yield of C2H4Br2 prepared in an experiment was 50.00g. Calculate the percentage yield.
𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑦𝑖𝑒𝑙𝑑 (%) = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
50
× 100 = 74.68%
66.95
Therefore, percentage yield if 74.68%
Theory of an ideal gas
 The kinetic molecular theory is a model used to explain the behavior of gases. The essential ideas are:
o Gaseous particles are in continuous random motion, in straight lines not curved
o Perfect elastic collision
o Average kinetic energy is directly proportional to temperature
o Volume of gas is negligible
o No intermolecular forces (no attraction between particles)
 Note that no gas is perfectly ideal

Ideal Gas Equation

 Ideal gas equation: 𝑃𝑉 = 𝑛𝑅𝑇 where:
o P: Pressure in kilopascals (kPa) In IB convert to Pa
o V: Volume decimeters cubed (dm3) In IB convert to m3
o n: Number of moles
o T: Temperature in kelvin
o R: 8.31 (Universal gas constant)

Question:

0.25 mol of nitrogen is placed in a flask of volume 5.0dm3 at a temperature of 5°C. What is the pressure?
𝑃 = 𝑥, 𝑉 = 5.0 𝑑𝑚3 , 𝑛 = 0.25 𝑚𝑜𝑙, 𝑇 = 278𝐾, 𝑅 = 8.31
𝑛𝑅𝑇 0.25 × 8.31 × 278
Therefore: 𝑃(𝑁2 ) = 𝑉
= 5.0
= 116𝑘𝑃𝑎

Combined Gas Equation

 The three gas laws applied to a fixed mass of gas can be summarized:
1
o 𝑃∝ at constant temperature
𝑉
o 𝑉 ∝ 𝑇 at constant pressure
o 𝑃 ∝ 𝑇 at constant volume
𝑃1 𝑉1 𝑃2 𝑉2
 These three laws can combine to form the combined gas law: 𝑇1
= 𝑇2

Law Result Formula

Combined gas law 𝑃𝑉 𝑃1 𝑉1 𝑃2 𝑉2

=𝑘 =
𝑇 𝑇1 𝑇2

Gay-Lussacs’ law 𝑃 𝑃1 𝑃2
=𝑘 =
𝑇 𝑇1 𝑇2

Boyles’ law 𝑃𝑉 = 𝑘 𝑃1 𝑉1 = 𝑃2 𝑉2

Charles’s law 𝑉 𝑉1 𝑉2
=𝑘 =
𝑇 𝑇1 𝑇2

 An ideal gas will have the greatest volume at a high temperature and low pressure
 Question:

A balloon has a volume of 150L at a pressure of 101kPa and a temperature of 27°C. It rises to an altitude of 15km
where the temperature is -30°C and the pressure 12kPa.
What is the volume of the balloon at this altitude
𝑉1 = 150𝐿 𝑉2 = 𝑥
𝑃1 = 101𝑘𝑃𝑎 𝑃2 = 12𝑘𝑃𝑎
𝑇1 = 27 + 273𝐾 𝑇2 = −30 + 273𝐾
𝑃1 𝑉1 𝑇2 101×150×(273+27)
Therefore: 𝑉2 = 𝑇1 𝑃2
= (273−30)×12
= 1559𝐿

Real vs Ideal Gases:

 A gas behaves more like an ideal gas at a high temperature and lower pressure:
o High temperature: The potential energy due to intermolecular forces becomes less significant compared with the
particles kinetic energy
o Low pressure: The size of the molecules becomes less significant compared to the empty space between them

Real Gases Ideal Gases

Gas particles have volume Gas particles do not have volume

Particles have attractive forces No attractive forces between particles

Molar Volume
 The molar volume of an ideal gas is a constant at specified temperature and pressure
o Molar volume (Vm): The volume occupied by one mole of a substance (chemical element or chemical compound) at
a given temperature and pressure
 Avogadro’s law states 1 mol of any gas at STP will occupy 22.7dm3
o Standard temperature and pressure (STP) conditions are at 273K and 100kPa
 Avogadro’s law enables the mole ratio of reacting gases to be determined from volumes of the gases
𝑉𝑚
𝑛=
𝑉
 In order to calculate the volume of a gas at STP: 𝑉 = 𝑛 × 𝑉𝑚
o Where n: moles, V: volume of gas, Vm: molar volume of gas at STP

Question:

Determine the volume occupied by 16.g of oxygen gas (O2 at STP)

𝑚 16
𝑛= = = 0.55
𝑀𝑟 32
𝑉(𝑂2 ) = 𝑛 × 𝑉𝑚 = 0.500 × 22.7 = 11.4
Molar Concentrations

Definitions

Solute – The smallest component in a solution (what is being dissolved)

Solvent – The largest component of a solution (what is it being dissolved in) (Remember VENT)
Solution – The solute and solvent combined (A homologous mixture)
Concentration – A measure of solute (mol) per solution (dm-3)

𝑚𝑜𝑙𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛
 Concentration can be calculated by: 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑉

Question:

What is the concentration of sodium chloride in a saline solution if 200cm3 of the solution contains 0.010mol NaCL
𝑛 0.010
𝑐 = 𝑣 = 200/1000 = 0.050𝑀(𝑚𝑜𝑙 𝑑𝑚−3 ) Volume is divided because dm3 is needed

Addition of solutions
 Calculate the new amount of mols by adding the number of moles from each individual solution, then find the new volume

Question:

Calculate the final concentration of mol dm-3 of CaCl2 when 25cm3 of 0.40M CaCl2 added to 50cm3 of 1.2M CaCl2
𝑛(𝐶𝑎𝐶𝑙2 ) = 𝑐 × 𝑣 𝑛(𝐶𝑎𝐶𝑙2 ) = 𝑐 × 𝑣
𝑛(𝐶𝑎𝐶𝑙2 ) = 0.40 × 0.025 𝑛(𝐶𝑎𝐶𝑙2 ) = 0.40 × 0.050
𝑛(𝐶𝑎𝐶𝑙2 ) = 0.010𝑚𝑜𝑙 𝑛(𝐶𝑎𝐶𝑙2 ) = 0.060𝑚𝑜𝑙
Therefore, by adding both mols together we get 0.070mol. Now we need to calculate concentration:
𝑛 0.070
[𝐶𝑎𝐶𝑙2 ] = = = 0.93𝑀
𝑣 0.075

Dilution
 Dilution: The process of adding more solvent to a solution
 When a solution is diluted, the solute particles are more widely spread. There is a direct relationship between volume and
concentration
 The dilution formula is then: 𝐶1 𝑉1 = 𝐶2 𝑉2

Question:

Calculate the molarity of CalCl2 in 200cm3 of 0.40M CaCl2 diluted to 400cm3 of water
𝐶1 = 0.40𝑀 𝐶2 = 𝑥 𝑉1 = 200𝑐𝑚3 𝑉2 = 400𝑐𝑚3
𝐶1 𝑉1 0.40×0.200
Therefore: 𝐶2 = 𝑉2
= 0.40
= 0.20𝑀
Topic 2: Atomic Structure
2.1 The nuclear atom
2.1.1 Atoms contain a positively charged dense nucleus composed of protons and neutrons (nucleons)

2.1.2 Negatively charged electrons occupy the space outside the nucleus

2.1.3 The mass spectrometer is used to determine the relative atomic mass of an element from its isotopic composition

2.1.4 Use of the nuclear symbol notation 𝐴𝑍𝑋 to deduce the number of protons, neutrons and electrons in atoms and ions

2.1.5 Calculations involving non-integer relative atomic masses and abundance of isotopes from given data, including mass
spectra

Rutherford’s experiment
 Rutherford’s experiment revealed that atoms have a nucleus
 In his experiment, he shot alpha particles straight towards a sheet of
gold foil. Around this foil was a florescent screen that would flash when
alpha particles hit the screen
 It was predicted that these alpha particles would go straight through the
gold foil and not get deflected
 However, a small percentage of particles were deflected through angles
much larger than 90 degrees. Some particles even were scattered back
 This showed that:
o The atom was mostly empty space instead of a solid (plum pudding model)
o This also showed that atoms had a nucleus, as alpha particles would sometimes get deflected backwards when they
would hit the nucleus

Sub-Atomic Structure
 Atoms are made up of a nucleus containing a positively charged protons and neutral neutrons, with negatively charged
electrons moving around the nucleus in shells
 Electrons are assumed to be massless

Sub-atomic particle relative mass relative charge

proton 1 +1
neutron 1 0
1
electron -1
1836

Definitions

Mass number (A) – Sum of the number of protons and neutrons in the nucleus
Atomic number (Z) – The number of protons in the nucleus. Since atoms are electrically neutral, the number of
protons is also equal to the number of electrons
Isotope – Atoms of the same element with the same number of protons, but with a different number of neutrons

 Some isotopes may be heavier than other elements despite having a smaller proton count because the element may have a
greater proportion of heavier isotopes
Nuclear Notation
 Nuclear notation shows the mass number, atomic number and symbol to
represent a particular isotope. To find:
o Atomic Number: Number of protons
o Mass Number: Number of protons and neutrons
o Number of electrons = atomic number – charge

Properties of isotopes
 Chemical properties depend on the outer shell of electrons. Since isotopes still have the same number of electrons, these
properties will remain the same
 Physical properties depend on their nuclei. Since the number of neutrons changes, properties such as density, rate of
diffusion, melting and boiling change. The mass will also change

Uses of radioisotopes
 Many isotopes are radioactive because the nuclei are more prone to breaking down spontaneously. Radiation is emitted
when this happens. Radioisotopes can occur naturally or be man-made
 Uses of radioisotopes include:

Carbon-14
 Carbon-14 is used to estimate the age of organisms. This process is called radiocarbon dating
 Surprisingly, these isotopes are very penetrating and can be used to treat cancerous cells

Cobalt-60
 Cobalt-60 is a powerful gamma emitter, making it useful for the treatment of cancer
 It has also been used in recent times to stop the immune response to transplanted organs in the body
 It is also used in levelling devices and to sterlize foods and spices

Iodine-131/Iodine 125
 Iodine-131 releases both gamma and beta radiation
 It can be used to treat thyroid cancer, and detect if the thyroid is functioning correctly
 The thyroid will take up the iodine and then the radiation will kill part of it
 Iodine 125 is a gamma emitter and can treat prostate cancer and brain tumors. It is also taken up by the thyroid gland

Mass Spectrometry
 A mass spectrometer is an instrument that can be used to measure the individual masses of atoms
 A mass spectrometer separates individual isotopes from a sample of atoms and determines the mass of each isotope
 The operation of the mass spectrometer can be broken down into four stages:
1. Vaporization: The sample is heated and vaporized, and passed
through into an evacuated tube
2. This separates the particles
3. Ionization: The atoms/molecules are then bombarded by a
stream of high energy electrons, knocking electrons off the
particles, resulting in ions with a 1+ charge
4. Acceleration: The positively charged ions are then accelerated
along the tube by means of the attraction to negatively charged
plates. The ions pass through the slits, which control the
direction and velocity of their motion
5. Deflection: The ions are then passed into a very strong magnetic field, deflecting the ions in a curved path
6. Detection: The ions are detected electronically by a device that measures the location and the number of particles
  The deflection or path of an ion in a mass spectrometer depends on:
o Absolute mass of the ion
o Charge of the ion
o Strength of magnetic field
o Velocity (speed) of ions
 This information is presented as a mass spectrum. In a mass spectrum showing the number of isotopes of an element:
o The number of peaks indicates the number of isotopes
o The position of each peak in the horizontal axis indicates the relative isotopic mass
o The relative heights of the peaks correspond to the relative abundance of the isotopes

Calculating atomic mass

 As the relative atomic mass of an element is the weighted average of the relative masses of the isotopes of an element we
can calculate relative atomic mass using the following formula:
(𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑖𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠1 × %𝑎𝑏𝑢𝑛𝑑𝑎𝑛𝑐𝑒1 ) + (𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑖𝑠𝑜𝑡𝑜𝑝𝑖𝑐 𝑚𝑎𝑠𝑠2 × %𝑎𝑏𝑢𝑛𝑑𝑎𝑛𝑐𝑒2 ) + ⋯
𝐴𝑟 =
100

Problem solving

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

2.2 Electron configuration

2.2.1 Emission spectra are produced when photons are emitted from atoms as excited electrons return to a lower energy level

2.2.2 The line emission spectrum of hydrogen provides evidence for the existence of electrons in discrete energy levels, which
converge at higher energies
2
2.2.3 The main energy level or shell is given an integer number, n, and can hold a maximum number of electrons, 2n

2.2.4 A more detailed model of the atom describes the division of the main energy level into s, p, d and f sub-levels of
successively higher energies
2.2.5 Sub-levels contain a fixed number of orbitals, regions of space where there is a high probability of finding an electron

2.2.6 Each orbital has a defined energy state for a given electronic configuration and chemical environment and can hold two
electrons of opposite spin
2.2.7 Description of the relationship between color, wavelength, frequency and energy across the electromagnetic spectrum

2.2.8 Distinction between a continuous spectrum and a line spectrum

2.2.9 Description of the emission spectrum of the hydrogen atom, including the relationships between the lines and energy
transitions to the first, second and third energy levels
2.2.10 Recognition of the shapes of an s atomic orbital and the p x, px, and pz atomic orbitals

2.2.11 Applications of the Aufbau principle, Hund’s rule and the Pauli exclusion principle to write electron configurations for
atoms and ions up to Z = 36
Bohr’s Model
 Bohr used the term energy levels to describe orbitals of differing energy
 The Bohr Model supports four main ideas:
1. Electrons orbit the nucleus in ring like paths around the nucleus at fixed energy levels. The higher the energy level the
farther away the electron is from the nucleus and the higher the energy
2. Orbits further from the nucleus exist at higher energy levels
3. Bohr said that electrons are quantized, meaning electrons can only occur in one energy level or another but nothing in
between. The ground state is the energy level an electron normally occupies
4. Electrons can only move from one orbital to another orbital at one time. When electrons absorb energy they move up to
a higher energy level. This is called the excited state. When the electron returns to a lower energy level they emit
energy. These emissions are not always visible to the naked eye

 One weakness of Bohr’s model was that he could not offer a reason why only certain energy levels were allowed

Emission spectrums
 Emission spectra are produced when photons are emitted from atoms as excited electrons return
to a lower energy level
 Each electron transition from a higher energy level to a lower energy level corresponds to
radiation with a specific frequency or wavelength
 Emission (line) spectrums are produced by excited atoms as they fall back to a lower energy level
and only contain specific colors (wavelengths, frequencies) of visible light
 There are also several other types of spectrums:
o Line spectrum: Only sharp, discrete colors
o Continuous spectrum: All colors
 Note: The line emission spectrum of hydrogen provides evidence for the existence of electrons in discrete energy levels
 The energy of the lines on the emission spectrum of hydrogen corresponds to the difference in energies between energy
levels

 Every element has its own unique emission (line spectrum). Hence, an element can be identified from its emission spectrum
 For instance, the helium emission spectrum is different from hydrogen because of the differences in the energy levels
 The Balmer series is the name given to a series of spectral emission lines of the hydrogen atom that result from electron
transitions from higher levels down to the energy level where n=2
 Ultraviolet light is produced when electrons drop to the first energy level (Lyman series)
 Infrared is produced when electrons drop to the third energy level (Paschen series)
Electromagnetic Spectrum
 All electromagnetic waves travel at the same speed, but can be distinguished by their wavelengths
o A wavelength is the distance between two successive crests
 A smaller wavelengths has a higher frequency, so possess more energy
 A larger wavelength has a lower frequency, so posses less energy
 To sum, as energy increases so does the frequency. So red light has lower energy than violet light which is why UV light is so
damaging to the skin, since high energy is more dangerous than low energy
 The electromagnetic spectrum shows the range of all possible frequencies of electromagnetic radiation
 The order of the spectrum is radio, microwave infrared, visible, ultraviolet, x-ray and gamma ray
o An easy way to remember is Rabbits Mate In Very Unusual eXpensive Gardens

Orbitals
 Orbital: A region of space in which the probability of finding an electron is greater than or equal to 95%
 This is because the Heisenberg Uncertainty Principle states it is impossible to define the exact position of an electron
 Each orbital can hold a maximum of two electrons with opposite spin
 Orbitals can be represented as boxes with electrons depicted with arrows. Often an up-arrow and a down-arrow are used
to show that the electrons are different. The “spin” is shown by the direction the arrow is pointing
 Three rules control how electrons fill atomic orbitals:
o 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
o Aufbau Principle: Electrons are placed into orbitals of lowest energy first
o 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

S/P/D/F Sub-levels
 Each main energy level is divided into several sub-levels
 Sub-levels contain a fixed number of orbitals, regions of space where there is a high probability of finding an electron
o Sub-level: A group of orbitals with particular properties like shape and angular momentum
 Orbitals can take up to 4 different shapes
o s-orbitals take a spherical shape
o p-orbitals resemble a “dumbbell” shape
 The sub-levels s, p, d and f contain the following
number of orbitals respectively where every orbital can hold up to two electrons maximum
o s: 1 orbital, 2 electrons
o p: 3 orbitals, 6 electrons
o d: 5 orbitals: 10 electrons
o f: 7 orbitals, 14 electrons
  Each main energy level can hold a max of 2n2 electrons

Writing electron configurations/arrangement

 To write an electron configuration:
1. Determine the total number of electrons
2. Fill the lowest energy subshells first and then proceed to higher energy levels until
all electrons are used. The easiest way is to use the chart on the left
3. S-orbital can hold 2 electrons, each p-orbital can hold 6, each d-orbital can hold 10
and each f-orbital can hold 14
 Note: The 4s orbital is filled first before 3d, but is removed first before 3d
 To write a condensed electron configuration:
1. Write the symbol in square brackets ([X]) for the nearest, smaller noble gas (The square brackets represent the electron
configuration for the noble gas)
2. Write the electron configuration following the noble gas configuration
 The electronic configurations of the transition elements copper and chromium do not follow the expected patterns
o Chromium has the electron configuration: [Ar] 3d5 4s1
o Copper has the electron configuration: [Ar] 3d10 4s1
 Electron arrangement is the number of electrons per each main energy level (i.e., Level 1, 2, 3, 4 and 5)

12.1 Electrons in atoms

12.1.1 In an emission spectrum, the limit of convergence at higher frequency corresponds to the first ionization energy

12.1.2 Trends in first ionization energy across periods account for the existence of main energy levels and syb-levels in atoms

12.1.3 Successive ionization energy data for an element give information that shows relations to electron configuration

12.1.4 Solving problems using 𝐸 = ℎ𝑣

12.1.5 Calculation of the value of the first ionization energy from spectral data which gives the wave length of frequency of the
convergence limit
12.1.6 Deduction of the group of an element from its successive ionization energy data

12.1.7 Explanation of the trends and discontinuities in first ionization energy across a period

Definitions

First ionization energy – The minimum amount of energy required to remove one mole of electrons from one mole
+
of gaseous atoms. The formula for first ionization energy is: 𝑋(𝑔) → 𝑋(𝑔) + 𝑒−

 In an emission spectrum, the limit of convergence at higher frequency corresponds to the first ionization energy
First ionization energy factors
 Factors that influence ionization energy:

Size of the nuclear charge

 As the atomic number (number of protons) increases, the nuclear charge increases
 The larger the positive charge, the greater the attractive electrostatic force between the nucleus and all the electrons
 So, a larger amount of energy is needed to overcome these attractive forces and remove an electron
 As the proton number increases, ionization energy increases: First ionization energy increases across each period

Distance of outer electrons from the nucleus

 The force of electrostatic attraction between positive and negative charges decreases rapidly as the distance between them
increases
 Hence electrons in shells (main energy levels) further away from the nucleus, are more weakly attracted to the nucleus than
those closer to the nucleus
 The further the outer electron shell is from the nucleus, the lower the ionization energy
 Thus, ionization energies tend to decrease down a group of the periodic table

Shielding effect
 Since all electrons are negatively charged, they repel each other
 Electrons in full inner shells repel electrons in outer shells
 The full inner shells of electrons prevent the full nuclear charge being experienced by the
outer electrons. This is known as shielding
 The greater the shielding of outer electrons by the inner electron shells, the lower the
electrostatic attractive forces between the nucleus and the outer electrons
 The ionization energy is lower as the number of full electron shells between the outer
electrons and the nucleus increases

First ionization energy trends

 The general trend is that first ionization energies increase from left to
right across a period
 The increase in nuclear charge across a period causes an increase in
the attraction between the outer electrons and the nucleus makes the
electrons more difficult to remove
 However, 1st IE sometimes drops between elements in periods, (Be to
B). This is because Beryllium has the electronic structure 1s2 2s2 and
the boron atom has the electronic structure 1s2 2s2 2p1.
 1st IE will decrease as the electron is being removed from the s-orbital
in Be whereas for B it is being removed from the p-orbital which has a slightly higher energy and this counteracts the
increase in effective nuclear charge
o The greater the nuclear charge on the atom the harder it is to remove an electron
o Sub-levels are more stable when they are empty, half-full or full
o Electrons prefer to be unpaired if possible as pairing of electrons creates repulsion

Successive ionization energies

 Additional evidence of electron configuration in atoms comes from looking at patterns of successive ionization energies
 The second and third ionization energies are described as:
2+
o 𝑋 + (𝑔) → 𝑋(𝑔) + 𝑒−
3+
o 𝑋 2+ (𝑔) → 𝑋(𝑔) + 𝑒−
 Successive ionization energies increase for all atoms because as more electrons are removed the remaining electrons
experience an increasing effective nuclear charge and are held closer to the nucleus and hence more tightly
 The large increases (jumps) in ionization energy correspond to a change to a new inner shell, closer to the nucleus, with
the electrons held more strongly

Lines of convergence
 The separate lines in a series become closer together as their wavelength decreases (as their frequency and energy
increases). At these high energies the lines form a continuum
 The start of the continuum, beyond which separate lines cannot be distinguished is called the convergence limit
 We can use the ionization energy data to determine the wavelength of frequency of convergence
 This can be calculated by:
o 𝑐 = 𝑣𝜆
o 𝐸 = ℎ𝑣
 Where:
o Planck’s constant = 6.63 × 10−34 𝐽𝑠
o Speed of light = 3.00 × 108 𝑚𝑠 −1
Topic 3: Periodicity
3.1 Periodic Table
3.1.1 The periodic table is arranged into four blocks associated with the four sub-levels – s, p, d, and f

3.1.2 The periodic table consists of groups (vertical columns) and periods (horizontal rows)

3.1.3 The period number (n) is the outer energy level that is occupied by electrons

3.1.4 The number of the principal energy level and the number of the valence electrons in an atom can be deduced from its
position on the periodic table
3.1.5 The periodic table shows the position of metals, non-metals and metalloids

3.1.6 Deduction of the electron configuration of an atom from the element’s position on the periodic table, and vice versa

Periodic Table Arrangement

 The periodic table is arranged into 4 blocks associated with their last orbital: s, p, d and f
 Elements in the periodic table are arranged by increasing atomic number
 Group: A vertical column of elements
o Group number is the same as the number of valence electrons
 Period: A horizontal row of elements
o Period number is the same number of shells in the atom
o All shells except the outer shell will be full
 There is a division between metals and non-metals. Metals are on the left and non-metals are on the right
 The farther sub-level occupied is found by the location of the element (which block it is in):

 The location of the following families of the periodic table must be known: alkali metals, alkali earth metals, halogens, noble
gases, transition metals, lanthanides and actinoids

3.2 Periodic trends

3.2.1 Vertical and horizontal trends in the periodic table exist for atomic radius, ionic radius

3.2.2 Trends in metallic and non-metallic behavior are due to the trends above

3.2.3 Oxides change from basic through amphoteric to acidic across a period

3.2.4 Prediction and explanation of the metallic and non-metallic behavior of an element based on its position in the periodic
table
3.2.5 Discussion of the similarities and differences in the properties of elements in the same group, with reference to alkali
metals and halogens
 Definitions

Atomic Radius – The distance from the nucleus to the outermost electron
Ionic Radius – The distance from the nucleus to the outermost electrons in an ion
First ionization energy – The energy required to remove one mole of electrons from one mole of gaseous atoms.
+
This is shown by: 𝑋(𝑔) → 𝑋(𝑔) + 𝑒−

Electron affinity – The energy released when one mole of an electron is added to one mole gaseous atoms. This is
−
shown by: 𝑋(𝑔) + 𝑒 − → 𝑋(𝑔)

Electronegativity – A measure of the attraction an atom has for a shared pair of electrons in a covalent bond

Trends in the Periodic Table

 Periodicity refers to repeating trends or patterns of physical and chemical properties in elements

Atomic Radius
 Atomic radius increases down a group as the number of electron shells increases
 Atomic radius decreases across a period
o This is because electrons are added to the same main energy level (n=3) the nuclear
charge also increases
o The attraction between the nucleus and the outer electrons increases resulting in a
smaller radius

Ionic Radius
 Ionic radius of positive ions decrease across a period as the number of protons in the nucleus increases but the number of
electrons remain the same
 Ionic radius of negative ions decrease across a period as the number of protons in the nucleus increases but the number of
electrons remains the same

Ionization energy
 Ionization energy increases across a period
 The increase in nuclear charge across a period causes an increase in the attraction between
the outer electrons and the nucleus makes the electrons more difficult to remove
 Ionization energy decreases down a group
 The electron being removed is from the energy level furthest from the nucleus so it gets
easier to remove valence electrons as atomic radius increases down a group
o Valence Electrons: The outermost electrons of an atom

Electron affinity
 Generally, metals have a low EA and non-metals have a higher EA
 The greater the distance between the nucleus and the outer energy level, the weaker the electrostatic attraction and the
less energy is released when an electron is added to the atom

Electronegativity
 Metals have low electronegativities because they lose electrons easily
 Non-metals have high electronegativities as they gain electrons to complete their outer shell
 Generally, electronegativity tends to increase across a period and decrease down a group
Melting points
 Melting points generally increase across a period until group 14, then they decrease
 This depends on the type of bonding (covalent, ionic or metallic), structure (ionic lattice, molecular covalent, giant covalent,
or metallic structures), and strength of metallic bond

Metallic Character
 Metallic character: How easily an atom can lose electrons
 Metallic character is displayed by metals, which are all on the left-hand side of the periodic table including alkali metals,
alkalie earth metals, tarnsition metals the lanthanide and actinides, and the basic metals
 Metallic character increases down a group
 Metallic character decreases across a period

Trends Across: Group 1 – The Alkali Metals

 Atomic/Ionic radius increases down the group as there are more electron shells
 First ionization energy decreases down the group as the valence electron is further from the nucleus so its easier to remove
 Electronegativity decreases because of increased distance and shielding
 Melting points decrease as atoms become larger and therefore metallic bonds becomes weaker
 Reactivity increases down the group as the valence electron is easier to lose, due to shielding

Trends Across: Group 7 – Halogens

 Same trends as alkali metals except melting points increase as Van der Waal forces becomes greater with more electrons
 Reactivity decreases down group as with each consecutive element the outer shell gets further from the nucleus. So the
attraction between the nucleus and electrons gets weaker, so an electron is less easily gained.

Trends Across: period 3

 In period 3, sodium, magnesium and aluminum are metals located on the left of period 3
o Metals are shiny solids that are excellent thermal and electrical conductors. They are ductile and malleable
o Metals are reducing agents and form cations. Their oxides and hydroxides behave like bases and neutralize acids
 Aluminum oxide, however is insoluble in water and amphoteric
 Phosphorus, sulfur, chlorine and argon are non-metals located on the right of period 3
o Non-metals can be solids, liquids are gas
o Non-metals tend to be oxidizing agents and form anions. Their oxides tend to be acidic and are neutralized by bases
 All period three oxides will react with water to form either an acidic or alkali (basic) solution:

Group 1 2 13 14 15 16 17 18

Element Na Mg Al Si P S Cl Ar

Structure of element
Giant
Giant Metallic Simple Covalent
Covalent
Structure of Oxide

P4O10 SO3 Cl2O7

Formula of oxide Na2O MgO Al2O3 SiO2
P4O6 SO2 Cl2O

Acid-Base character
Basic Amphoteric Acidic No oxide
of oxide
13.1 First row d-block elements
13.1.1 Transition elements have variable oxidation states, form complex ions with ligands, have colored compounds, and display
catalytic and magnetic properties
13.1.2 Zn is not considered to be a transition element as it does not form ions with incomplete d-orbitals

13.1.3 Transition elements show an oxidation state of +2 when the s-electrons are removed

13.1.4 Explanation of the ability of transition metals to form variable oxidation states from successive ionization energies

13.1.5 Explanation of the nature of the coordinate bond within a complex ion

13.1.6 Deduction of the total charge given the formula of the ion and ligands present

13.1.7 Explanation of the magnetic properties in transition metals in terms of unpaired electrons

Transition metals
 Transition metals: Elements whose atoms have incomplete d-orbitals or can form positive
ions with an incomplete d sub-level
o Zinc is not considered a transition element as it does not have an incomplete d orbital
 Transition metals have variable oxidation states, display catalytic and magnetic properties,
form complex ions with ligands and have colored compounds (13.2)

Oxidation states
 All the d-block elements (except scandium and zinc) can exist in more than one oxidation state
 There is no increase in successive ionization energies in transition metals. There is only a
slightly higher effective nuclear charge so there are no great jumps in successive
ionization energies. So, ions can lose varying numbers of electrons with the same relative
ease, depending on the oxidative nature of the surrounding environment.
 All transition elements can form ions with an oxidation number of +2 (by losing the 2e-
from the 4s shell). So, transition elements show an oxidation state of +2 when the
s-electrons are removed
 In addition, each element can form a number of ions with different oxidation numbers
 In order to form ions:
o Electrons in the 4s subshell have less energy than the 3d subshell
o Ions are formed as the electrons are lost from the 4s and 3d subshell’s
o Electrons are removed from the valence shell (4s) before the 3d subshell

Properties of transition metals

Physical properties Chemical properties

 High electrical and thermal conductivity  Variable oxidation states

 High melting point  Formation of complex ions
 High tensile strength  Colored compounds
 Malleable (Can be beaten into shape)  Catalytic behavior
 Ductile (Can be drawn into wires) o Fe in the Haber process
o V2O5 in the Contact process
o Fe2+
 Metal complexes
 Transition metals and transition metal complexes may be classified as diamagnetic, paramagnetic or ferromagnetic
 Any unpaired electrons will cause metals to be paramagnetic. And the more unpaired electrons there are, the stronger it
becomes. This is because the unpaired electron (which is negatively charged and spinning) creates a small magnetic field
itself
 If all the electrons are paired, the effect of the spinning is cancelled out – so the small magnetic field is not created

Diamagnetic
 No unpaired electrons. Weakly repelled in an external magnetic field

Paramagnetism
 One or more unpaired d-orbital electrons. Attracted by an external field
 Paramagnetism increases with the number of unpaired electrons

Ferromagnetism
 Only occurs in iron, cobalt and nickel. The attraction to a magnetic field is much stronger
 In these metals large numbers of unpaired electrons line up in the regions called domains

Ligands
 Ligands are molecules or ions with a lone pair of electrons (or more) that form coordinate covalent bonds with a central
metal ion
 Ligands such as H2O and CN- are known as monodentate ligands as they use just one lone pair of electrons to form a
coordinate covalent bond to a central metal ion
 Polydentate ligands are species that have more than one lone pair of electrons to
form coordinate covalent bonds to a central metal ion
 Example: H2O and NH3 are both ligands because they have a lone pair of electrons

Question: Deduce the charge on the central metal ion given the formula of the ion and the ligands present

[𝐶𝑜(𝐻2 𝑂)6 ]2+

H2O is a neutral molecule (No charge). The charge on the complex ion is 2+ ∴oxidation state is 2+

13.2 Colored complexes

13.2.1 The d sub-level splits into two sets of orbitals of different energy in a complex ion

13.2.2 Complexes of d-block elements are colored, as light is absorbed when an electron is excited between the d-orbitals

13.2.3 The color absorbed is complementary to the color observed

13.2.4 Explanation of the effect of the identity of the metal ion, the oxidation number of the metal and the identity of the ligand
on the color of transition metal ion complexes
13.2.5 Explanation of the effects of different ligands on the splitting of the d-orbitals in transition metal complexes and color
observed using spectrochemical series
13.2.6 Construction of equations to explain the pH changes for reactions of Na 2O, MgO, P4O10 and the oxides of nitrogen and
sulfur with water
Complex ions
 A complex is formed when ligands dative covalently (coordinate bond) bond to a central metal ion
(or atom) by donating a pair of electrons
 Ligands can be replaced by other ligands and the complexes will have different colours
 The number of lone pairs bonded to the metal ion is known as the coordination number
 In this example H2O is the ligand as it surrounds a central metal ion and it has a coordination number
of 6

Colored Compounds
 Compounds of group 1, 2 and 3 are typically white. Similarly compounds of zinc, one of the d-block elements not classified as
a transition metal is also white
 Complexes of d-block elements are colored, as light is absorbed when an electron is excited between the d-orbitals:
o As the ligand approaches the metal to form a complex ion the non-bonding pairs of electrons on the ligand will repel
the d orbital causing the five d orbitals to split: 3 to lower energy and two to higher energy

o The energy gap between the two levels correspond to the wavelength of visible light
o Electrons can transition from the lower to a higher set of d orbitals by absorbing certain wavelengths of light. The
complementary color of the color that is absorbed is transmitted
 The greater the oxidation state the greater the split between the d-orbitals
 There are four factors that affect the color of a transition metal:
o Nature of the transition element
o The identity of the metal ion
o The identity of the ligand
o Oxidation State

The Spectrochemical series

 The spectrochemical series arranges ligands in order of their ability to split d-orbitals in an octahedral complex ion

 Iodine ions cause the smallest splitting while the carbonyl group, while CO causes the largest splitting
Topic 4: Bonding
4.1 Ionic bonding and structure
4.1.1 Positive ions (cations) form by metals losing valence electrons

4.1.2 Negative ions (anions) form by non-metals gaining electrons

4.1.3 The number of electrons lost or gained is determined by the electron configuration of the atom

4.1.4 The ionic bond is due to electrostatic attraction between oppositely charged ions

4.1.5 Under normal conditions, ionic compounds are usually solids with lattice structures

4.1.6 Deduction of the formula and name of an ionic compound from its component ions, including polyatomic ions

4.1.7 Explanation of the physical properties of ionic compounds (volatility, electrical conductivity and solubility) in terms of their
structure

Ions
 Atoms have a neutral charge as their negative electrons and positive protons balance out
 However, ions are formed when atoms gain or lose electrons
 The charge is changed by adding or removing electrons from an atom
 Cations are atoms that lose electrons and therefore have a positive net charge
 Therefore, positive ions are called cations
 Anions are atoms that gain electrons and therefore have a negative net charge
 Therefore, negative ions are called anions

Ionic Bonding
 Ionic bonds form as a result of the electrostatic attraction between oppositely charged ions
o An electrostatic attraction is the attraction of oppositely charged of particles/objects
 This bond only occurs between metals and non-metals
 The metal will have a positive charge, while the non-metal will have a negative charge
 The opposite charges create an electrostatic attraction between the ions, causing them to form a neutral lattice
 The charge of the ions will cancel each other out

Formation of an ionic compound

 When metals react with non-metals electrons are transferred from the metal to the non-metal forming an ion
 Ionic compounds are balanced as the negative and positive charges balance each other out
 The formation of an ionic compound can be represented using
electron shell diagrams
 Example: When sodium and chlorine react together to form
sodium chloride the electron that a sodium atom loses to form a
stable sodium ion is gained by a chlorine atom to for a stable
chlorine ion

Chemical Charge
 Remember, noble gas configuration is the most stable so most elements will try
to reach it by either losing or gaining electrons
 To find the ionic charge of an element the periodic table can be used:
 Group 1, 2, 3 elements form ions with charges of 1+, 2+ and 3+ respectively
 Group 15, 16, 17 elements form ions with charges of 3-, 2-, 1- respectively
 Elements in group 14 can lose 4 electrons but can also gain 4 electrons
 Physical Properties of Ionic Compounds
 The electrostatic force of attraction between oppositely charged ions arrange in a 3D structure called a lattice
 This is possible because the ions are held together by their opposite charges, and each ion will be surrounded
by 6 other different ions
 For the most stable arrangement positively charged ions are packed as closely as possible to the negative
charged ions, while ions of the same charge are as far apart as possible. This maximizes electrostatic attraction between the
ions, while minimizing repulsion
 Under normal conditions, ionic compounds are usually solids with lattice structures
 The lattice structure of an ionic compound can be used to explain their physical properties

Volatility
 Volatility: The tendency of a substance to vaporize
 Ionic compounds have ionic bonds which are very strong meaning that a lot of energy is needed to break its bonds. Thus at
room temperature there isn’t enough energy to break the lattice.
 Example: If you leave salt in a room for 100 years it will be the same, it won’t turn into a gas because it’s non-volatile
 Therefore ionic compounds can be described as having a low volatility or being non-volatile

High melting temperatures

 As mentioned before ionic bonds are very strong and a lot of energy is needed to break its bond
 Hence ionic compounds have high melting temperatures
 Therefore Ionic compounds are solid at room temperature
 Melting point: Solid -> Liquid
 Boiling point: Liquid -> Gas

Electric conductivity
 When ionic compounds are solid the ions are not free to move as there are held in fixed
positions so the ionic compound cannot conduct electricity when solid
 When ionic compounds melt however, the ions are free to move as they are no longer
held in the crystal, therefore melted ionic compounds can conduct electricity

Solubility
 Water is a covalent polar compound (has positive and negative poles) therefore can break molecules off the lattice structure
 Therefore, the ions from the lattice structure can be separated by polar water molecules
 So, ionic compounds are soluble in polar solvents
 However not all ionic compounds are soluble

4.2 Covalent bonding

4.2.1 A covalent bond is formed by the electrostatic attraction between a shared pair of electrons and the positively charged
nuclei
4.2.2 Single, double and triple covalent bonds involve one, two and three shared pairs of electrons respectively

4.2.3 Bond length decreases and bond strength increases as the number of shared electrons increases

4.2.4 Bond polarity results from the difference in electronegativities of the bonded atoms

4.2.5 Deduction of the polar nature of a covalent bond from electronegativity values
 Covalent bonds
 A covalent bond is formed by the electrostatic attraction between a shared pair of electrons and the positively charged
nuclei. This type of bonding occurs between two atoms of the same elements or close elements on the periodic table.
 Covalent bonds generally occur between non-metals only
 If atoms have similar electronegativities (the same affinity for electrons), they are likely to form a covalent bond
 This is because both atoms have the same affinity for electrons and neither has a tendency to donate them, therefore they
must share electrons in order to achieve octet configuration and become more stable

Double/Triple Covalent Bond

 A double covalent bond is formed when two atoms shared 2 electron pairs (4 electrons)
 A triple covalent bond is formed when two atoms share 3 electron pairs (6 electrons)

Bond Length/Strength
 Bond length: A measure of the distance between the two bonded nuclei
 Bond strength: A measure of the energy required to break the bond. Described in terms of bond enthalpy
 Bond length decreases as the number of electron pair increases because there will be a greater attractive force between
the two nuclei
 Bond strength increases as the number of electron pair increases as more energy is required to break them

Non-polar covalent bond

 When electronegativities are not equal, electrons are not shared equally and a partial ionic charge develops
 To find the most ionic bond compare the electronegative differences of each bond against the Pauling Scale
 The greater the electronegative difference the more ionic the bond is
 Bonds that are partially ionic are called polar covalent bonds, this also means
the most polar bonds with have the highest electronegative value
 Non-polar covalent bonds have equal sharing of bond electrons

4.3 Covalent structures

4.3.1 Lewis (electron dot) structures show all the valence electrons in a covalently bonded species

4.3.2 The “octet rule” refers to the tendency of atoms to gain a valence shell with a total of 8 electrons

4.3.3 Some atoms, like Be and B, might form stable compounds with incomplete octets of electrons

4.3.4 Resonance structures occur when there is more than one possible position for a double bond in a molecule

4.3.5 Shapes of species are determined by the repulsion of electron pairs according to VSEPR theory

4.3.6 Carbon and silicon form giant covalent/network covalent structures

4.3.7 Explanation of the physical properties of ionic compounds (volatility, electrical conductivity and solubility) in terms of their
structure
4.3.8 Deduction of Lewis (electron dot) structure of molecules and ions showing all valence electrons for up to four electron
pairs on each atom
4.3.9 The use of VSEPR theory to predict the electron domain geometry and the molecular geometry for species with two, three
and four electron domains
4.3.10 Prediction of bond angles from molecular geometry and presence of non-bonding pairs of electrons

4.3.11 Prediction of molecular polarity from bond polarity and molecular geometry
2-
4.3.12 Deduction of resonance structures, examples include but are not limited to C 6H6, CO3 and O3

4.3.13 Explanation of the properties of giant covalent compounds in terms of their structures
Covalent Compounds
 A covalent compound is formed when two or more non-metal atoms bond by sharing valence electrons
o Non-metals are types of elements that lack metallic characteristics
 This bonding occurs primarily between non-metals however it can also be observed between non-metals and metals
 The number of covalent bonds that will form depends directly on the number of electrons it needs to fill its valence shell
 The “octet rule” refers to the tendency of atoms to gain a valence shell with a total of 8 electrons
 Electron shell diagrams, known as Lewis or electron dot structures, can be constructed for covalently bonded molecules
 All valence electrons are drawn, as these are the electrons that can take part in bonding

Lewis Structure
 Lewis Structure: A diagram of molecules or other covalent species in which the outer shell (valence) electrons of the atom
are represented dots or crosses and the sharing of electrons to form a covalent bond is shown. To draw Lewis Diagrams:
1. Count all the valence electrons
2. Determine the central atom (the least electron negative which is the furthest away from Florine)
3. Draw single bonds to the central atom
4. Put all remaining valence electrons on atoms as lone pairs
5. Turn lone pairs into double or triple bonds to give every atom an octet
See resonance structure in 14.1
 Boron and beryllium are exceptions to the octet rule
 Atoms of elements in period 3 and below may expand their octet by using d-orbital’s in their valence shell

Electron domain
 Electron domain: Describes the number of electrons in the valence shell. They may be occupied by lone pairs, single, double
or triple bonds
 Molecular geometry: Explains the 3D shape of a molecule. That is the position of the electrons in the outer shell where they
experience the maximum repulsion
 The number of electron domains determines the shape of the covalent molecule each covalent molecule shape is a result of
electron repulsion. Each pair of electrons will be repelled from others as far as possible in three dimensions as each negative
charge center carrier a negative charge
 Electron repulsion decreases in the following order:
lone pair – lone pair > lone pair – bonding pair > bonding pair – bonding pair
 The arrangement of atoms in space is the molecular geometry

VSEPR Diagram
 We can predict molecular geometry using the VSEPR model (Exceptions to VSEPR in 14.1)
1. Sketch the Lewis structure of the ion or molecule
2. Find the number of bonding pairs and non-bonding pairs surrounding the central molecule (double bonds and triple bonds
count as a bonding pair)
3. Use the table below to calculate the shape
 Some are some important exceptions to the octet rule
 Two conditions must apply if a molecule is to be a dipole (polar)
o It must have polar bonds
o The partial charges must be distributed asymmetrically across the molecule (the molecule must not be symmetrical)
 A molecule that contains polar covalent bonds will form a dipole
 A polar molecule must have dipoles distributed so overall there is a positive and negative end of the molecule
Electron
Geometric Arrangement Bonding pairs Lone pairs angle
domains

2 linear 2 0 180°

trigonal planar 3 0 120°

Bent 2 1 <120°

tetrahedral 4 0 109.5°

4
Trigonal pyramidal 3 1 <109.5°

Bent 2 2 <109.5°

trigonal bipyramid
5 0 90°
120°

see saw
5 trigonal bipyramid 4 1 90°
< 120°

T-shaped
3 2
90°

octahedral
6 0 90°
90°

6 square pyramidal
5 1 90°
90°

square planar
4 2 90°
90°
Covalent structures
 Covalent compounds have two types of structures: simple covalent and giant covalent (network covalent) structures

Simple covalent structures

 These contain only a few atoms held together by strong covalent bonds such as carbon dioxide where one atom of carbon is
covalently bonded with two atoms or oxygen
 Molecular covalent substances have low boiling points and are usually liquids and gases, due to the weak intermolecular
forces (not intramolecular)
 These structures are also non-conductive. This is because they do not have any free electrons or an overall electric charge

Giant covalent structures

 Giant covalent structures contain a lot of non-metal atoms, each joined to adjacent atoms by covalent bonds
 Example: Silicon and carbon form giant covalent structures
 The atoms are usually arranged into giant regular lattices, which are extremely strong structures because of the many bonds
involved (such as graphite or diamond)
 Giant covalent structures have very high melting points because a lot of strong covalent bonds must be broken
 Giant covalent structures also vary in conductivity, as some contain free electrons while some do not

Allotropes of carbon
 Carbon can be found in three forms. All of these forms contain carbon only but vary in their structure
 They are called allotropes of carbon

Graphite
 Graphite has a hexagonal layer structure, and although it has
covalent bonds between the carbon atoms, it has weak Van Der
Waals forces between the layers themselves, allowing the bonds to
be shattered easily and the layers to slide over each other easily
o The covalent bonds within the layers are very strong
o The dispersion forces between the layers are weak
 The structure of graphite is described as a covalent layer lattice
 Graphite has good conductivity as there are delocalized electrons between the hexagonal layers and electrons are free to
move parallel

Diamond
 In diamond, each carbon atom is joined to four other carbon atoms, forming a giant covalent structure
 Diamond has a tetrahedral structure held together with strong covalent bonds
 There are no weak links to these lattices
 As a result, diamond is very hard and has a high melting point
 Diamond has bad conductivity as there are no delocalized electrons as the outer shell electrons are used for covalent bonds

C60 Fullerenes
 60 carbon atoms form a sphere in which each atom is covalently bonded to three others
 Fullerene is a semiconductor that is very strong and light. It is used in the medical field for the
transportation of medicines in the body.
 Structure: Spheres made of atoms arranged in hexagons (not a lattice)

Silicon
 Silicon is a member of group four of the periodic table and so is able to form 4 covalent bonds with other silicone atoms to
form network covalent structure
4.4 Intermolecular forces
4.4.1 Intermolecular forces include London (dispersion) forces, dipole-dipole forces and hydrogen bonding

4.4.2 The relative strengths of these interactions are London (dispersion) forces < dipole-dipole forces < hydrogen bonds

4.4.3 Deduction of the types of intermolecular force present in substances, based on their structure and chemical formula

4.4.4 Explanation of the physical properties of covalent compounds (volatility, electrical conductivity and solubility) in terms of
their structure and intermolecular forces

Intermolecular forces
 Intermolecular forces are the forces that exist between molecules
 Intramolecular forces are the forces that exist between atoms (ionic and covalent)
 There are three main types of intermolecular forces:

London Dispersion Forces

 The London dispersion force is the weakest intermolecular force
 The London dispersion force is a temporary attractive force that results when the electrons in two adjacent atoms occupy
positions that make the atoms form temporary dipoles. This force is sometimes called an induced dipole-induced dipole
attraction
 London dispersion forces are the attractive forces that cause non-polar substances to condense to liquids and to freeze into
solids when the temperature is lowered sufficiently

Dipole-Dipole
 A dipole is a molecule that has both positive and negative regions
 A dipole-dipole force is when the positive side of a polar molecular attracts the negative
side of another polar molecule
 The strength of this attraction will depend on the distance and orientation of the dipoles
 The molecules need to be very close to each other like a liquid in order to work

Hydrogen Bonds
 Hydrogen bond is an attraction between a slightly positive hydrogen on one molecule and a slightly negative atom on
another molecule
 Hydrogen bonds are a type of dipole-dipole force
 The most electronegative elements are all found in the top right corner of the periodic table
 The large electronegativity difference between hydrogen atoms and fluorine, oxygen and nitrogen causes hydrogen bonds
to be the strongest of all intermolecular forces
 The relative strength of intermolecular bonding is:
o London Dispersion Forces < dipole-dipole forces < hydrogen bonds

4.5 Metallic bonding

4.5.1 A metallic bond is the electrostatic attraction between a lattice of positive ions and delocalized electrons

4.5.2 The strength of a metallic bond depends on the charge of the ions and the radius of the metal ion

4.5.3 Alloys usually contain more than one metal and have enhanced properties

4.5.4 Explanation of electrical conductivity and malleability in metals

4.5.5 Explanation of trends in melting points of metals

4.5.6 Explanation of the properties of alloys in terms of non-directional bonding

Metallic bonding
 A metallic bond is the electrostatic attraction between a lattice of positive ions and delocalized electrons
 The strength of a metallic bond depends on the charge of the ions and the result of the metal ion
 Metals conduct electricity because they have mobile delocalized electrons. When a potential is applied to a piece of metal,
the mobile electrons move through the metallic structure and carry an electric current.
 Metals are malleable and ductile
 This is because the layers of metals can slide over each other
when metals are bent, hammered or stretched without
breaking the metallic bond
 Characteristics of metals are:
o They are good conductors of heat and electricity
because of the delocalized electrons in their structures
o Have highest conductivity when they are aqueous or melted and the lowest conductivity when they are gases
o Shiny, the delocalized electrons in the metallic structure reflect light
 Since metals have low electronegativity values, they can lose electrons easily to form positive ions
 Since non-metals have high electronegativity values they can gain electrons to form negative ions

Alloys
 Different metals are often melted together, mixed and then allowed to cool
 The resultant solid is called an alloy
 Alloys usually contain more than one metal and have enhanced properties
 The properties of a metal can be significantly altered by adding small amounts of another substance, usually another metal
 The production of alloys is possible because of the non-directional nature of the delocalized electrons, and the fact that the
lattice can accommodate ions of different sizes
 Alloys are usually more stronger than regular metals. This is because if different atoms are present, the regular network of
positive ions will be disturbed
 The atoms of a different size make it harder for layers of positive ions to slide over each other and thus prevent bending or
denting of the metal.

Types of Bond comparison

Type of bonding Ionic Metallic Simple Covalent Giant Covalent

Very high
Very high
Medium to high Low
Requires a large
Melting point Requires a large
Depends on size and Weak bond between amount of energy to
amount of energy to
charge of ions molecules break all covalent
break bond
bonds

Low Usually low High

Low
Solid at room Solid at room Easy to break the
Volatility temperature, high Usually solids at room
temperature due to weak intermolecular
boiling point temperature and high
high boiling point. forces between
boiling points
Difficult to vaporize (Mercury is a liquid) molecules

All conduct
Conduct electricity electricity in solid Delocalized electrons
when in liquid state state Polar molecules form in graphite
Electrical conductivity Ions are free to move Delocalized ions when they Others do not have
and are not held in a electrons allow dissolve free particles or
lattice electrical current to electrons
be conducted
 Some will dissolve in a
polar solvent Polar molecules
The attraction to the Some metals react dissolve in polar
Do not dissolve in any
Solubility solvent must be with water to make substances, non-polar
solvents
greater than the alkaline solutions molecules dissolve in
attraction to other non-polar substances
ions

14.1 Further aspects of covalent bonding and structure

14.1.1 Covalent bonds result from the overlap of atomic orbitals. A sigma bond is formed by the direct head-on/end-to-end
overlap of atomic orbitals, resulting in electron density concentrated between the nuclei of the bonding atoms. A pi bond
is formed by the sideways overlap of atomic orbitals, resulting in electron density above and below the plane of the nuclei
of the bonding atoms
14.1.2 Formal charge (FC) can be used to decide which Lewis (electron dot) structure is preferred from several. The FC is the
charge an atom would have if all atoms in the molecule had the same electronegativity. FC = (Number of valence
electrons) – ½ (Number of bonding electrons) – (Number of non-bonding electrons). The Lewis (electron dot) structure
with the atoms having FC values closest to zero is preferred
14.1.3 Exceptions to the octet rule include some species having incomplete octets and expanded octets

14.1.4 Delocalization involves electrons that are shared by/between all atoms in a molecule or ion as opposed to being localized
between a pair of atoms
14.1.5 Resonance involves using two or more Lewis (electron dot) structures to represent a particular molecule or ion. A
resonance structure is one of two or more alternative Lewis (electron dot) structures for a molecule or ion that cannot be
described fully with one Lewis (electron dot) structure alone
14.1.6 Prediction whether sigma (σ) or pi (π) bonds are formed from the linear combination of atomic orbitals.

14.1.7 Deduction of the Lewis (electron dot) structures of molecules and ions showing all valence electrons for up to six electron
pairs on each atom
14.1.8 Application of FC to ascertain which Lewis (electron dot) structure is preferred from different Lewis (electron dot)
structures
14.1.9 Deduction using VSEPR theory of the electron domain geometry and molecular geometry with five and six electron
domains and associated bond angles
14.1.10 Explanation of the wavelength of light required to dissociate oxygen and ozone

14.1.11 Description of the mechanism of the catalysis of ozone depletion when

catalyzed by CFCs and NOx.

Overlapping Orbitals
 Covalent bonds are formed from the overlap of atomic orbitals
o Two orbital’s from different atoms, each containing one unpaired electron, can merge in the region of space
between the two atoms
 This overlapping of two orbitals creates a bonding orbital between the two atoms
 π-bonds are formed by the sideway overlap of orbitals resulting in electron
density above and below the plane of the nuclei of the bonding atom
 A sigma bond is formed by the direct head-on/end-to-end overlap of orbitals
resulting in electron density concentrated between the nuclei of the bonding
atoms
 Double bonds consist of one sigma bond and one pi bond
 Triple bonds consist of one sigma and two pi bonds
 Resonance Structure
 Electrons have no fixed position in molecules but can be found in certain spaces (orbitals)
 Resonance structures do not change the relative positions of the atoms, but instead the electron locations
 Instead of being combined to one location electrons have a tendency to be shared between more than one bonding
position, and therefore are said to be delocalized
 Delocalization involves electrons that are shared
by/between more than one pair in a molecule or ion
as opposed to being localized between a pair of atoms
(There is more than one location for a pair of electrons)
 The electrons from the double bond have delocalized
and spread themselves equally between both possible bonding positions

Formal Charge (FC)

 Therefore, when drawing Lewis (electron dot diagrams) it is often possible to come up with multiple possible structures
 Formal charge allows us to calculate which of these structure is the most stable. To calculate formal charge:
1
𝐹𝐶 = 𝑉 − ( 𝐵 + 𝐿)
2
 Where:
o V=Valence electrons, B=# of bonding electrons, L= # of lone pair electrons
 The most stable structure is the molecule that:
o Formal charge value closest to 0
o The negative charges located on the most electronegative atom

14.2 Hybridization
14.1.1 A hybrid orbital results from the mixing of different types of atomic orbitals on the same atoms
3 2
14.1.2 Explanation of the formation of sp , sp and sp hybrid orbitals in methane, ethane and ethyne

14.1.3 Identification and explanation of the relationships between Lewis (electron dot) structures, electron domains, molecular
geometries and types of hybridization

Hybridization
 A hybrid orbital results because of the mixing of different types of atomic orbitals on the same atom
 We write hybridization as a mix of the two combined levels
 To find hybridization, we can look at the Lewis structure
 Generally speaking:
o If there are four electron domains around the central atom, the hybridization will be sp3
o If there are three electron domains, the hybridization will be sp2
o If there are two electron domains the hybridization will be sp
Topic 5: Energetics
5.1 Measuring energy changes
5.1.1 Heat is a form of energy

5.1.2 Temperature is a measure of the average kinetic energy of the particles

5.1.3 Total energy is conserved in chemical reactions

5.1.4 Chemical reactions that involve transfer of heat between the system and the surroundings are described as endothermic
or exothermic
The enthalpy change (ΔH) for chemical reactions is indicated in kJ mol
-1
5.1.5

5.1.6 ΔH values are usually expressed under standard conditions, given by ΔH° including standard states

5.1.7 Calculations of the heat change when the temperature of a pure substance is changed using 𝑞 = 𝑚𝑐∆𝑇

5.1.8 A calorimetry experiment for an enthalpy of reaction should be covered and the results evaluated

Heat and Temperature

 Energetics is the study of heat changes in chemical reactions
o Heat is a form of energy
 Energy can neither be created nor destroyed. Total energy is always conserved and can only be transferred
 Heat energy always flows from a higher temperature object to a lower temperature object
 The Kelvin scale is based on kinetic energy, so 0K means that there is no kinetic movement at all

Definitions

Heat – A measure of the total kinetic energy of particles in a substance

Temperature – A measure of the average kinetic energy of particles in a substance

Enthalpy (H)
 Enthalpy (H): The amount of heat energy contained in a substance
 Enthalpy is stored in the chemical bonds as potential energy
 When substances react, the total enthalpy of a system cannot be measured (due to loss of heat), but it is possible to
measure the difference in the enthalpy between the reactants and products
 Enthalpy is denoted as H, however heat change is denoted as ΔH
 The enthalpy change for chemical reactions is denoted kJ mol-1
 The reaction mixture is called the system (the chemical reaction), which gives
heat to or takes heat from the surroundings (anything around the system)
 Chemical reactions that involve transfer of heat between system and the
surroundings are described as exothermic and endothermic

Exothermic: Heat is Released

 In exothermic reactions heat is released to the surroundings
o This is because more heat energy is released than what is added
o So, the overall heat energy is released from the system, causing the surroundings to become hotter
 Exothermic reactions have negative ΔH values, because heat is released (thus enthalpy decreases, -ΔH)
 In an exothermic reaction, the products are more stable than the reactants as they have a lower enthalpy
o Less heat means more stable
 This means the reaction is downhill in terms of heat energy
 Exothermic reactions release energy (as heat)
 Examples include:
o Bond forming: Removing heat brings atoms closer together, forming bonds
o When chemical bonds are formed, heat is released (See 5.3)
o Gas -> Liquid -> Solid: Heat is removed, thus these are exothermic reactions
o Rain: The condensation of water vapor into rain releases energy in the form of heat
o Combustion: The burning of carbon compounds uses oxygen from air, and produces CO2, H2O and lots of heat

Endothermic: Heat is Absorbed

 In endothermic reactions heat is absorbed from the surroundings
o This is because more heat energy is added than what is released
o So, the overall heat energy is absorbed by the system, causing the surroundings to become cooler.
 Endothermic reactions have positive ΔH values, because heat is absorbed (thus, enthalpy increases +ΔH)
 In an endothermic reaction, the produces are less stable than the reactants as they have a higher enthalpy
o More heat means less stable
 This means the reaction is uphill in terms of heat energy
 Exothermic reactions require energy (through heat)
 Examples include:
o Bond breaking: Adding heat separates atoms, breaks bonds (See 5.3)
o Photosynthesis: Plants absorb heat energy from sunlight to convert CO2 and water into glucose and oxygen
o Solid -> Liquid -> Gas: Heat is added, so the reactions are endothermic

Energy Diagrams: Endothermic and Exothermic Reaction

Enthalpy

Enthalpy

Reaction Pathway Reaction Pathway

Standard Enthalpy change: ∆𝑯𝜽𝒙

 Standard enthalpy change of reaction: The enthalpy change of a reaction carried out under standard with everything in its
standard state
 Only ∆𝐻 𝜃 can be measured, not 𝐻
 Standard enthalpy change is measured in kJ mol-1

∆𝐻𝑥𝜃
a) ∆𝐻: Refers to Enthalpy change
A positive value indicates an endothermic reaction while a negative value indicates an exothermic reaction
b) 𝜃: Refers to standard conditions where 289K, 101.3 kPa, 1 mol dm-3
Standard conditions are necessary as enthalpy changes will have different values depending on the conditions under which
they are measured. Therefore, all enthalpy changes are performed under standard conditions
c) 𝑥: Refers to the type of enthalpy change
Sometimes, bond enthalpies are average values/differ (slightly) from one compound to another so the standard enthalpy will
not be the same value in the data booklet
Standard Enthalpy of Formation: ∆𝑯𝜽𝒇
 The standard enthalpy change of formation (∆𝐻𝑓𝜃 ): The energy change when one mole of a compound is formed from its
elements in their standard states under standard conditions
 To calculate enthalpy change from formation:

∆𝐻 𝜃 = ∑ ∆𝐻𝑓𝜃 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ ∆𝐻𝑓𝜃 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

 ∆𝐻𝑓𝜃 values are found in the data booklet (remember to include coefficients) (Elements have a ∆𝐻𝑓𝜃 value of zero)

Standard Enthalpy of Combustion: ∆𝑯𝜽𝒄𝒐𝒎𝒃

 The standard enthalpy change of combustion (∆Hc°): The energy released when one mole of a compound is completely
burned in excess oxygen under standard conditions with no change in pressure
 Combustion reactions always produce CO2 and H2O
 All combustion reactions are exothermic (always negative) as heat is released during combustion process
 To calculate enthalpy change from combustion:

𝜃 𝜃
∆𝐻 𝜃 = ∑ ∆𝐻𝑐𝑜𝑚𝑏 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) − ∑ ∆𝐻𝑐𝑜𝑚𝑏 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠)

Thermochemical equations
 Thermochemical equations give the balanced equation with an enthalpy charge
 State symbols must be shown, as ∆𝐻 𝜃 depends on the state of the reactants or products
 In order to calculate energy changes for a specific amount of a substance using the thermochemical equation:

Question

Calculate the energy released, in kJ, when 0.500kJ SO3 reacts with water
𝑆𝑂3 + 𝐻2 𝑂 → 𝐻2 𝑆𝑂4 ∆𝐻 𝜃 = −129.6 𝑘𝐽 𝑚𝑜𝑙−1
Step 1: Calculate how many moles of SO3 there are:
1000𝑔
𝑛(𝑆𝑂3 ) = = 12.49𝑚𝑜𝑙
80.07
Step 2: Compare to thermochemical equation:
1 mol of SO3 releases 129.6 kJ, therefore 12.5 mol of SO3 releases − 𝑥 kJ
Step 3: Use ratios:
1 −129.6
= = −1618 𝑘𝐽
12.5 𝑥

Heat changes calculations

 Heat changes (enthalpy) can be calculated from the temperature changes:
𝑞 = 𝑚𝑐∆𝑇
 𝑞: heat change
 𝑚: mass (Use the mass of water unless specified)
 𝑐: specific heat capacity
o Specific heat capacity (c): The energy required to raise the temperature of 1g of substance by 1K
 ∆𝑇: Temperature change
o If the temperature of the compound increased, then the reaction is endothermic and 𝑞 must be positive
o If the temperature of the compound decreased, then the reaction is exothermic and 𝑞 must be negative
 For calorimetry experiments take the absolute value of ∆𝑇 then:
o If the temperature of the water INCREASED, then the reaction is exothermic and 𝑞 must be negative
o If the temperature of the water DECREASED, then the reaction is endothermic and 𝑞 must be positive

Enthalpy Change
 To calculate enthalpy change (∆𝐻), the equation below can be used:
𝑞 (𝑒𝑛𝑒𝑟𝑔𝑦, 𝑘𝐽)
∆𝐻 =
𝑛 (𝑚𝑜𝑙)
 However, ∆𝐻 can be either positive or negative. Simply add a positive or negative sign to 𝑄 when:
o The temperature of the substance INCREASED, then the reaction was endothermic and 𝑄 is positive
o The temperature of the substance DECREASED, then the reaction was exothermic and 𝑄 is negative

Standard Enthalpy of Neutralization: ∆𝑯𝜽𝒏𝒆𝒖𝒕

 The standard enthalpy change of neutralization (∆Hneut°): The enthalpy change when a strong acid and base react together to
form one mole of water under standard conditions
 Neutralization reactions are exothermic (always negative) as heat is released
 To calculate enthalpy change from combustion:
1. Calculate the number of moles of acid and base using 𝑛 = 𝑐𝑣
2. Determine the limiting reactant. This will tell you how many moles of water can be produced
3. Add the volumes of acid and base together (where 1cm3=1g) to get the mass
4. Use 𝑄 = 𝑚𝑐∆𝑇 to calculate enthalpy change
𝑄
5. Use ∆𝐻 = where 𝑛 is number of moles of water produced
𝑛

Calorimetry
 Calorimetry is the process of measuring the amount of heat released or absorbed during a chemical reaction
 When the reaction occurs, it is either going to give off or take in heat
 The change in heat can be measured by observing the temperature of water, as water can serve as the surroundings
 There are many ways to perform calorimetry, the most common is to use a bomb shell
 Calorimetry is performed many different ways:

 However, when using calorimetry several assumptions are made

 This is because heat loss and incomplete combustion can lead to systematic errors
in experimental results
 These assumptions are:
1. That all the heat is transferred to the water
(Some might be transferred to the metal or is still inside the system)
2. That all the solution has dissolved
3. The mass of the water remained constant
4. There was an unlimited oxygen source
5. The experiment was under standard conditions
  To compensate for heat lost by the water we can extrapolate the graph recorded
 By extrapolating the graph, the temperature rise that would have taken place had the reaction been instantaneous can be
calculated by taking 𝑇2 − 𝑇0

5.2 Hess’s Law

5.2.1 The enthalpy change for a reaction that is accrued out in a series of steps is equal to the sum of the enthalpy changes for
the individual steps
5.2.2 Application of Hess’s Law to calculate enthalpy changes

5.2.3 Calculation of ∆𝐻 reactions using ∆𝐻𝑓o data

5.2.4 Determination of the enthalpy change of a reaction that is the sum of multiple reactions with known enthalpy changes

Hess’s Law
 Hess’s Law states that regardless of the multiple stages or steps of a reaction, the total enthalpy change for the reaction is
the sum of all changes
 This means the enthalpy change going from A to B is the same whether the reaction
proceeds directly to A or whether it goes via A to C then B
 This is known as an energy diagram and can be written as two reactions that when
combined produce the overall equation: ∆H3 = ∆H1 + ∆H2

Question

Using the equation below:

𝐶 + 𝑂2 → 𝐶𝑂2 ∆𝐻 = −390 𝑘𝐽 𝑚𝑜𝑙−1
𝑀𝑛 + 𝑂2 → 𝑀𝑛𝑂2 ∆𝐻 = −520 𝑘𝐽 𝑚𝑜𝑙−1
Which is the enthalpy change for the following reaction?
𝑀𝑛𝑂2 + 𝐶 → 𝑀𝑛 + 𝐶𝑂2 ∆𝐻 = −390 𝑘𝐽 𝑚𝑜𝑙−1
As you can see, if we 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

5.3 Bond enthalpies

5.3.1 Bond-forming releases energy and bond-breaking requires energy

5.3.2 Average bond enthalpy is the energy needed to break one mol of a bond in a gaseous molecule averaged over similar
compounds
5.3.3 Calculations of the enthalpy changes from known bond enthalpy values and comparison of these to experimentally
measured values
5.3.4 Sketching and evaluation of potential energy profiles in determining whether reactants or products are more stable and if
the reaction is exothermic or endothermic
5.3.5 Discussion of the bond strength in ozone relative to oxygen in its importance to the atmosphere

Bond enthalpy
 Average bond enthalpy: The energy required to break one mole of the same type of
bond in the gaseous state averaged over a variety of similar compounds
 Energy is released through the formation of chemical bonds
o Bond forming: Removing heat brings atoms closer together, forming bonds
o Releases energy, ∆𝐻 negative therefore exothermic
 Energy is required when breaking chemical bonds
o Bond breaking: Adding heat separates atoms, breaks bonds (See 5.3)
 o Requires energy, ∆𝐻 positive therefore endothermic

 The enthalpy of reaction (∆𝐻 𝜃 ) can be calculated using bond enthalpies

 Since there are average bond enthalpies, the calculation gives only an approximate result. To calculate:

∆𝐻 𝜃 = Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛) − Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑)

 𝐸 represents the bond energy per mol of bonds (see data booklet)
 When Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛) > Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑) the reaction is endothermic
 When Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑) > Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛) the reaction is exothermic

Question

Calculate the enthalpy of reaction of methane: 𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 3𝐻2 𝑂

𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛) − Σ𝐸(𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑)
𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (4(C − H) + 2(O = O)) − (2(C = O) + 6(H = O))
𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (4 × 414 × +2 × 498) − (2 × 804 + 6 × 463)
𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = −1734 kJ mol−1

 However, bond enthalpies can only be used by themselves if all the reactants and products are in the gaseous state

Ozone depletion
 Oxygen is present in the atmosphere in two forms:
o Normal oxygen: O2
o Ozone: O3
 Much of the harmful UV radiation is absorbed by the ozone layer
 The ozone layer forms a protective screen which absorbed the UV light to ensure that the radiation that reaches the surface
of the Earth is different from the emitted by the Sun
o Without the ozone layer the UV radiation would have caused damage to living tissue
 The bond in oxygen and ozone are both broken when they absorb UV radiation of sufficient energy
 However, both oxygen and ozone are broken by UV light of different wavelengths
 This is because the bonds in oxygen, O2, are stronger than those in ozone, O3
 The stronger double bond in O2 requires higher energy UV radiation (Shorter wavelength) to break
 The wavelengths of light needed to break the bonds in ozone are calculated using a modified Planck’s equation:
ℎ×𝑐
E𝑝ℎ𝑜𝑡𝑜𝑛 =
𝜆

Ozone depletion question:

The bond energy in ozone is 363 𝑘𝐽 𝑚𝑜𝑙 −1. Calculate the wavelength of UV radiation needed to break the bond
One mole of photons are needed to break one mole of bonds. The energy of a mole of photos is the energy of one
photon multiplied by Avogadro’s number (𝐿)
𝐿 × E𝑝ℎ𝑜𝑡𝑜𝑛 = 363 000 𝐽
363 000
E𝑝ℎ𝑜𝑡𝑜𝑛 =
6.02 × 1023
We want to find wavelength, 𝜆, so by rearranging Planck’s equation:
ℎ×𝑐
𝜆=
E𝑝ℎ𝑜𝑡𝑜𝑛

𝜆 = 330𝑛𝑚
Any radiation in the UV region with a wavelength smaller than 330nm breaks the bond in ozone
  The bonds in O3 are broken by UV radiation with a wavelength of <330nm
 The bond in O2 is broken by UV radiation with a wavelength of <242nm

The Ozone-Oxygen Cycle

 The ozone–oxygen cycle is the process by which ozone is continually
regenerated in Earth's stratosphere
 It describes how ozone is both formed and depleted by natural processes
in the atmosphere (diagram on right)
 In the atmosphere, high-energy UV breaks the strong bonds in O2 so
that O3 can be formed. Lower-energy UV breaks the weaker bonds in O3
 This cycle of reactions is significant because dangerous ultraviolet light
has been absorbed and the stratosphere has become warmer

15.1 Enthalpy cycles

15.1.1 Representative equations can be used for enthalpy/energy of hydration, ionization, atomization, electron affinity, lattice,
covalent bond and solution
15.1.2 Enthalpy of solution, hydration enthalpy and lattice enthalpy are related in an energy cycle

15.1.3 Construction of Born-Haber cycles for group 1 and 2 oxides and chlorides

15.1.4 Construction of energy cycles from Born-Haber or dissolution energy cycles

15.1.5 Relate size and charge of ions to lattice and hydration enthalpies

15.1.6 Perform lab experiments which could include single replacement reactions in aqueous solutions

Born-Haber Cycle
 Born-Haber cycles are energy cycles describing the formation of ionic compounds
 Lattice enthalpy cannot be measured because gaseous ions do not combine directly to form a compound
 The Born-Haber cycle allows the experimental lattice enthalpy to be calculated from other enthalpy changes
o Hess’s law can be used to find any missing value from a Born Haber cycle, not just a lattice enthalpy
 Remember the following:

Energy cycle Definition Equation

The energy required to remove 1 mole of an electron from 1

Ionization enthalpy ∆𝑯𝜽𝒊
mole of an atom in gaseous state* 𝑋(𝑔) → 𝑋 + (𝑔) + 𝑒 −
First ionization energy
Since ionization always requires energy, it is always endothermic

The energy required to remove 1 mole of an electron from 1 mole

Second ionization energy 𝑋 + (𝑔) → 𝑋 2+ (𝑔) + 𝑒 −
of an ion in its gaseous state*

Electron affinity enthalpy ∆𝑯𝜽𝒆 The energy change when 1 mole of an electron is added to 1
𝑋(𝑔) + 𝑒 − → 𝑋 − (𝑔)
First electron affinity mole of an atom in its gaseous state*

The energy required when 1 mole of an ionic compound is

Lattice Enthalpy ∆𝑯𝜽𝒍𝒂𝒕 𝑋 + (𝑔) + 𝑌 − (𝑔) → 𝑋𝑌(𝑠)
formed from its gaseous ions*

The energy change to make 1 mole of gaseous atoms from its

Atomization Enthalpy ∆𝑯𝜽𝒂𝒕𝒐𝒎 𝑋(𝑠) → 𝑋(𝑔)
elements*
 * “under standard conditions” with regarding enthalpy
 The Born-Haber cycle will contain all enthalpy cycles listed above
 By rearranging this formula, we can solve for lattice energy (Hess’s Law)

Energy Cycle: Enthalpy of solution, hydration and lattice enthalpy

 Other energy cycles include the one between enthalpy of solution, hydrate and lattice enthalpy
𝜃
o Enthalpy of solution (∆𝐻𝑠𝑜𝑙 ): The enthalpy change when one mole of an ionic compound is dissolved in water to
infinite dilution
𝜃
o Enthalpy of Hydration (∆𝐻ℎ𝑦𝑑 ): The enthalpy change when one mole of gaseous ions dissolve to give an infinitely
dilute solution
 The enthalpy of solution is found by (Hess’s Law):
𝜃 𝜃 𝜃
∆𝐻𝑠𝑜𝑙 = ∆𝐻𝑙𝑎𝑡 + ∆𝐻ℎ𝑦𝑑
𝜃
 First the solid ionic compound is broken down into its gaseous ions (∆𝐻𝑙𝑎𝑡 )
𝜃
 Then the gaseous ions are then hydrated by water molecules (∆𝐻ℎ𝑦𝑑 )

15.2 Entropy and spontaneity

15.2.1 Entropy (S) refers to the distribution of available energy among the particles. The more ways the energy can be distributed
the higher the entropy
15.2.2 Gibbs free energy (G) relates the energy that can be obtained from a chemical reaction to the change in enthalpy (∆𝐻),
change in entropy (∆𝑆), and absolute temperature (T)
15.2.3 Entropy of gas > liquid > solid under same conditions

15.2.4 Prediction of weather a change will result in an increase or decrease in entropy by considering the states of the reactants
and products
15.2.5 Calculations of entropy changes (∆𝑆) from given standard entropy values (𝑆 𝑜 )

15.2.6 Application of ∆𝐺° = ∆𝐻° − 𝑇∆𝑆° in predicting spontaneity and calculation of various conditions of enthalpy and
temperature that will affect this
16.2.7 Relation of ∆𝐺 to position of equilibrium

Entropy
 Entropy (S) refers to the distribution of available energy among the particles in a system
o The more ways the energy can be distributed the higher the energy
 Entropy is sometimes referred to as a measure of disorder of a system
 The change in the disorder of a system is known as the entropy change, ∆𝑆
 The more disordered a system becomes the more positive the value of ∆𝑆 becomes
 Systems which become more ordered will have decreasing ∆𝑆 values
 Standard entropy: The entropy content of one mole of substance under a standard state
 Factors that increase the entropy of a system include:
1. Changes of state, gas has the most entropy, solids have the least (account for coefficients)
o Solids have low entropy values
o Gas molecules have a high entropy value
2. Increased number of particles (Example, increasing concentration)
3. Increased temperature (which increases movement of particles)
4. More complicated structure (or more atoms attached)
5. Dissolution (dissolving) of an ionic compound
 Unlike enthalpy, absolute values of entropy can be measured
 The standard entropy change for a reaction can be determined by (account for coefficients):

∆𝑆 𝜃 = 𝑆 𝜃 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑆 𝜃 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
 Entropy question:

Calculate the standard entropy for the formation of ammonia:

3𝐻2 + 𝑁2 ⇌ 2𝑁𝐻3
Step 1: Calculate the standard entropies of each molecule/compound (account for coefficients)
The standard entropies of hydrogen, nitrogen and ammonia are 131, 192 and 192 kJ mol-1 respectively
∴ ∆𝑆 𝜃 = 𝑆 𝜃 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑆 𝜃 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 2 × 192 − [(3 × 131) + 192] = −201 𝑘𝐽−1

𝑞
 ∆𝑆 can also be calculated in a reversible process by: ∆𝑆 = 𝑇
 The second law of thermodynamics states that the entropy of a spontaneous reaction (when not in equilibrium) will increase
over time. When the system is at equilibrium will have 0 entropy

Spontaneity
 A reaction is said to be spontaneous if the system moves from a less stable to a more stable state
 Spontaneity depends both upon the enthalpy change and the entropy change
 These two factors are combined and expressed as the Gibbs energy change ∆𝐺, often called “free energy change”
 The standard free energy change ∆𝐺 𝜃 is defined as:

∆𝐺 𝜃 = ∆𝐻 𝜃 − 𝑇∆𝑆 𝜃
 A spontaneous reaction is one that releases free energy, so ∆𝐺 must be negative if the reaction is spontaneous
a. If ∆𝐺 𝜃 < 0 the reaction is spontaneous
b. If ∆𝐺 𝜃 = 0 the reaction is at equilibrium
c. If ∆𝐺 𝜃 > 0 the reaction is not spontaneous
 Some reactions will always be spontaneous depending on ∆𝐻 𝜃 , 𝑇 and ∆𝑆 𝜃
 ∆𝐻 and ∆𝑆 can be either positive or negative, while 𝑇 can either be a low or high value. The spontaneity can then be:

∆𝑯 ∆𝑺 −𝑻 ∆𝑮 Spontaneity

Low + Not Spontaneous

+ +
High - Spontaneous

+ - Low/High + Not spontaneous

- + Low/high - Spontaneous

Low - Spontaneous
- -
High + Non spontaneous

 Spontaneity can also be found by substituting values into: ∆𝐺 𝜃 = ∆𝐻 𝜃 − 𝑇∆𝑆 𝜃

1. Substitute 100 for ∆𝐻 and ∆𝑆
2. Substitute 0.1 for a low temperature, and 10 for a high temperature
3. If ∆𝐺 is negative the reaction is spontaneous. If ∆𝐺 is positive, the reaction is not spontaneous
Topic 6: Kinetics
6.1 Collision theory and rates of reactions
6.1.1 Species react as a result of collisions of sufficient energy and proper orientation

6.1.2 The rate of reaction is expressed as the change in concentration of a particular reactant/product per unit time

6.1.3 Concentration changes in a reaction can be followed indirectly by monitoring changes in mass, volume and color

6.1.4 Activation energy (Ea) is the minimum energy that colliding molecules need in order to have successful collisions leading to
a reaction
6.1.5 By decreasing Ea a catalyst increases the rate of a chemical reaction, without itself being permanently chemically changed

6.1.6 Descriptions of the kinetic theory in terms of the movement of particles whose average kinetic energy is proportional to
temperature in Kelvin
6.1.7 Analysis of graphical and numerical data from rate experiments

6.1.8 Explanation of the effects of temperature, pressure/concentration and particle size on rate of reaction

6.1.9 Construction of Maxwell-Boltzmann energy distribution curves to account for the probability of successful collisions and
factors affecting these, including the effect of a catalyst
6.1.10 Investigation of rates of reaction experimentally and evaluation of the results

6.1.11 Sketching and explanation of energy profiles with and without catalysts

Collision Theory
 For a reaction between two particles to occur three conditions must be met
o The particles must collide
o They must collide with the appropriate geometry or orientation
o They must collide with sufficient energy to bring about the reaction
 The minimum amount of energy required is known as the activation energy

Factor Effect of increasing factor Explanation

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

As the temperature increases, the particles will move faster so there will be
more collisions per second. However, the main reason why an increase in
Temperature Increases rate temperature increases the rate is that more of the colliding particles will
possess the necessary activation energy resulting in more successful collisions.
Generally, an increase of 10°C doubles the rate of a chemical reaction

Increasing the concentration increases the frequency of collisions which

Concentration Increases rate
increases the frequency of successful collisions too, thus increasing the rate.

Higher pressure compresses the gas, effectively increasing the concentration, so

Pressure Increases rate
increasing the frequency of collisions and therefore the rate too.

Rate of reaction
 Chemical kinetics is the study of the factors affecting the rate of a chemical reaction
 The rate of a chemical reaction can be defined as the change in concentration of the products/reactants per unit time or
Increase/decrease in concentration of product/reacts per unit time
 Concentration changes in a reaction can be indirectly monitored by monitoring :
o Change in volume of a gas, mass, concentration through titration, gas pressure or electrical conductivity
o Calorimetry and light absorbance
 The results obtained is usually then plotted in a graph of concentration against time
 The rate at any point in time is the gradient of the graph at that time
∆𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
 Thus, find the gradient at 𝑡 by using 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = ∆𝑡𝑖𝑚𝑒

 The rate of reaction (gradient) will generally be the steepest at the start of the curve
o This is because a high concentration of reactant particles, therefore a high frequency of successful collisions
 The rate of reaction (gradient) decreases over time as time as the concentration of reactant particles decreases, thus the
frequency of successful collisions also decreases
 Hence, the rate of reaction can also be defined as:

The Rate of Disappearance of Reactants The Rate of Formation of Products

∆[𝑹] ∆[𝑃]
𝑹𝒂𝒕𝒆 = − 𝑅𝑎𝑡𝑒 =
∆𝑻 ∆𝑇
Since Rate of Disappearance of Reactants is This is the rate of which the products are formed
decreases over time, the negative sign counteracts
this effect

 Where ∆[𝑅] means the change in the concentration of 𝑅, and ∆[𝑃] means the change in the concentration of 𝑃
 The units for rate of reactions are 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1

Maxwell-Boltzmann distribution curve

 The Maxwell-Boltzmann curve shows the distribution of kinetic energy for a reaction
 Only a small proportion of particles at a given temperature will have sufficient kinetic energy to overcome its Ea
 Activation energy (Ea): The minimum amount of energy required for a reaction to occur
 As temperature increases, the area under the curve does not change as the total number of particles remains constant.
 Instead more particles have a very high velocity resulting in an increase in the average kinetic energy which leads to a
broadening of the curve, however still has same activation energy
 Adding a catalyst reduces the activation energy, more particles have enough energy to react
o If a species is both on the reactant and product side of the overall equation, it is probably a catalyst
16.1 Rate expression and reaction mechanism
16.1.1 Reactions may occur by more than one step and the slowest step determines the rate of reaction

16.1.2 The molecularity of an elementary step is the number of reactant particles taking part in that step

16.1.3 The order of a reaction can be either integer or fractional in nature. The order of a reaction can describe, with respect to a
reactant, the number of particles taking part in the rate-determining step
16.1.4 Rate equations can only be determined experimentally

16.1.5 The value of the rate constant (k) is affected by temperature and its units are determined from the overall order of the
reaction
16.1.6 Catalysts alter a reaction mechanism, introducing a step with lower activation energy

16.1.7 Deduction of the rate expression for an equation from experimental data and solving problems involving the rate
expression
16.1.8 Sketching, identifying, and analyzing graphical representations for zero, first and second order reactions

16.1.9 Evaluation of proposed reaction mechanisms to be consistent with kinetic and stoichiometric data

Rate Expression
 The rate of reaction between two reactants, A and B, can be followed experimentally
 The mathematical relationship of reaction rate with reactant concentration can be expressed as a rate expression
For the following hypothetical reaction: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶
The Rate Law can be expressed as: 𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦
 The proportionality constant, 𝑘, is known as the rate constant
 The rate constant is different for each reaction and is changed by temperature
 The overall order of a reaction is: 𝑜𝑟𝑑𝑒𝑟 = 𝑥 + 𝑦
 For example, take: 𝑟𝑎𝑡𝑒 = 𝑘[𝐴][𝐵]2 . This reaction is third-order overall, first-order in A, and second order in B
 However, the order of a reaction and the rate expression can only be determined experimentally. They cannot be decuded
from the balance equation
 Generally, reaction orders can be classified as zero-order, first-order, second-order and third-order:

Order: Zero order First order Second order Third order

The rate is directly The rate is proportional

The rate does not proportional to to the square of the If the concentration
Description depend on concentration concentration doubles, the rate
concentration If concentration If the concentration increases eight times
doubles, rate doubles doubles, rate quadruples

2
Rate = k[A]3 or
Rate Rate = k[A] or
Rate = k Rate = k[A] Rate = k[A][B]2 or
Expression 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 s −1 mol dm−3 (mol dm−3 )2 (mol dm−3 )3
= s −1 = mol−1 dm3 s −1 = mol−2dm6 s−1
 When graphed, reactions orders will be graphed as:

16.2 Activation energy

16.2.1 The Arrhenius equation uses the temperature dependence of the rate constant to determine the activation energy

16.2.2 A graph of 1/T against ln(k) is a linear plot with gradient –Ea/R and intercept, lnA

16.2.3 The frequency factor (or pre-exponential factor) (A) takes into account the frequency of collisions with proper orientations
−𝐸𝑎
16.2.4 Analyzing graphical representation of the Arrhenius equation in its linear form 𝑙𝑛𝑘 = 𝐴𝑒 𝑅𝑇 + 𝑙𝑛𝐴
−𝐸𝑎
16.2.5 Using the Arrhenius equation 𝑘 = 𝐴𝑒 𝑅𝑇
Describing the relationships between temperature and rate constant; frequency factor and complexity of molecules
16.2.6
colliding

16.2.7 Determining and evaluating values of activation energy and frequency factors from data

Reaction Mechanisms
 Many reactions do not go in one step. This is particularly true when there are more than two reactant molecules as the
chances of a successful collision between three or more particles is extremely small. Where there is more than one step then
each step will proceed at its own rate. No matter how fast the other steps are the overall rate of reaction will depend only
upon the rate of the slowest step
 The step with the highest activation energy will act as the rate determining step, which acts as a limit on the rate of reaction

Arrhenius equation
 The rate constant for a reaction is only constant if the temperature remains constant. As the temperature increases the
reactants possess more energy and the rate constant increases
 The relationship between rate constant and absolute temperature is given by the Arrhenius equation:
𝐸𝑎
𝑘 = 𝐴𝑒 −𝑅𝑇
k: rate constant/A: Arrhenius constant/Ea: Activation energy/R: Gas constant/T: Temperature
 A graph of the Arrhenius equation allows us to calculate the activation energy of a reaction. We used the integrated version
of the equation to simply the graph into a linear expression (𝑦 = 𝑚𝑥 + 𝑐)
𝐸𝑎 1
𝑙𝑛𝑘 = − + 𝑙𝑛𝐴
𝑅𝑇
 The equation can be used to determine both the frequency factor and the activation energy for a reaction
Topic 7: Equilibrium
7.1 Equilibrium
7.1.1 A state of equilibrium is reached in a close system when the rates of forward and reverse reactions are equal

7.1.2 The equilibrium law describes how the equilibrium constant (Kc) can be determined for a particular chemical reaction

7.1.3 The magnitude of the equilibrium constant indicates the extent of a reaction at equilibrium and is temperature dependent

7.1.4 The reaction quotient (Q) measures the relative amount of products and reactants present during a reaction at a particular
point in time. Q is the equilibrium expression with non-equilibrium concentrations. The position of the equilibrium
changes with changes in concentration, pressure, and the temperature
7.1.5 A catalyst has no effect on the position of equilibrium or the equilibrium constant

7.1.6 The characteristics of chemical and physical systems in a state of equilibrium

7.1.7 Deduction of the equilibrium constant expression (Kc) from an equation for a homogeneous reaction

7.1.8 Determination of the relationship between different equilibrium constants (K c) from an equation for a homogeneous
reaction
7.1.9 Determination of the relationship between different equilibrium constants (K c) for the same reaction at the same
temperature
7.1.10 Application of Le Chatelier’s principle to predict the qualitative effects of changes of temperature, pressure and
concentration on the position of equilibrium and one the value of the equilibrium constant

Dynamic equilibrium
 Chemical equilibrium is a state in which the rate of the forward reaction equals the rate of the backward reaction
 In other words the forward and reverse reactions will continue to occur, but the concentration will stay the same
 Such a system is said to be in a state of dynamic equilibrium. Characteristics of equilibrium include:

Feature of equilibrium state Explanation

The reaction has stopped but both forward and backward reactions are
1 Equilibrium is dynamic
still occurring at the same rate

A closed system prevents exchange of matter with the surroundings, so

2 Equilibrium is achieved in a closed system equilibrium is achieved where both reactants and products can react and
recombine.

The concentrations of reactants and

3 They are being produced and destroyed at an equal rate.
products remain constant

There is no change in macroscopic

4 Color and density do not change as these depend on the concentrations.
properties

Equilibrium can be reached from either

5 The reaction can be started with all reactants, all products or a mixture.
direction (products or reactants)

 Example: In a closed container, liquid bromine is in a dynamic equilibrium with its vapor. There will always be both liquid and
gas bromine in the flask. This state is described as a dynamic equilibrium. Vaporization and condensation are both happening
simultaneously in the flask. Liquid bromine is in dynamic equilibrium with bromine vapour. This can be presented as:
𝐵𝑟2 (𝑙) ⇄ 𝐵𝑟2 (𝑔)
 Dynamic equilibrium can only be established in a closed system where reactants and products cannot escape
Equilibrium Constant: Kc
 An equilibrium reaction can be represented as 𝑎𝐴 + 𝑏𝐵 ⇄ 𝑐𝐶 + 𝑑𝐷
 Lower case letters represent the number of moles (coefficient), the uppercase letters represent the molecule itself
 The equilibrium constant of concentration gives the ratio of concentrations of products over reactants for a reaction that is
at equilibrium. The equilibrium constant expression is written as 𝐾𝑐 and is represented as:
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 [𝐶]𝑐 [𝐷]𝑑
𝐾𝑐 = =
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 [𝐴]𝑎 [𝐵]𝑏
 The value of 𝐾𝑐 represents the position of the equilibrium as equilibrium can either be near the products or reactants
o If 𝐾𝑐 > 1 then equilibrium favors the products
o If 𝐾𝑐 < 1 then equilibrium favors the reactants
 The value of 𝐾𝑐 will remain constant as the system will adjust to keep the concentrations at equilibrium despite its
environment

Le Châtelier’s principle
 Le Châtelier’s principle states that if a dynamic equilibrium is disturbed by changing the conditions the position of
equilibrium shifts to counteract the change to re-establish an equilibrium:

Condition Effect

Increasing concentration shifts the equilibrium to the side with fewer moles of solute
Concentration
Decreasing concentration shifts the equilibrium to the side with more moles of solute

Increasing pressure shifts the equilibrium to the side with fewer moles of gas
Pressure
Decreasing pressure shifts the equilibrium to the side with more moles of gas

 In order to find how temperature change affects equilibrium conditions the sign of the reaction enthalpy must be known to
determine whether the reaction is exothermic or endothermic
 Temperature is the only condition that can change the value of 𝑲𝒄 and the position of the equilibrium

In an exothermic reaction heat can be considered a product, so increasing the temperature will shift the
equilibrium towards the reactants,
Temperature
In an endothermic heat can be considered as a reactant, so decreasing the temperature will shift the
equilibrium towards the products

 A catalyst will lower the activation energy an equal amount for both the forward and reverse reaction
 Therefore catalysts have no effect on the equilibrium constant

Manipulation of Kc
Condition Effect on 𝑲𝑪

Inverse Reaction 1 [𝐴]𝑎 [𝐵]𝑏

𝐾𝑐′ = =
𝐾𝐶 [𝐶]𝑐 [𝐷]𝑑

Multiple of a reaction [𝐶]2𝑐 [𝐷]2𝑑

𝐾𝑐𝑥 =
[𝐴]2𝑎 [𝐵]2𝑏

Adding two reactions 𝐾𝑐1 × 𝐾𝑐2

 Reaction Quotient
 The reaction quotient (𝑄) measures the relative amounts of products and reactants present during a reaction at a particular
point in time. The 𝑄 value can be compared to the Equilibrium Constant, 𝐾𝑐 , to determine the direction of a reaction
o If 𝐾𝐶 = 𝑄 the reaction is at equilibrium
o If 𝐾𝐶 > 𝑄 then Q will increase and produce more products
o If 𝐾𝐶 < 𝑄 then Q will decrease and therefore create more reactants
 The main difference between 𝐾𝑐 and 𝑄 is that 𝐾𝑐 describes a reaction that is at equilibrium, whereas 𝑄 describes a reaction
that is not at equilibrium. To determine 𝑄, the concentrations of the reactants and products must be known:
 A system not at equilibrium can be described as “lying to the left”, indicating that there is a greater amount of reactants or
“lying to the right”, indicating that there is a greater amount of products
 As time passes and the reaction continues, the concentrations of all reaction components change and eventually reach the
equilibrium concentrations. In other words, the value of Q will eventual become 𝐾𝑐

17.1 The equilibrium law

17.1.1 Le Chatelier’s principle for changes in concentration can be explained by the equilibrium law

17.1.2 The position of equilibrium corresponds to a maximum value of entropy and a minimum of the Gibbs free energy

17.1.3 The Gibbs free energy changes of a reaction and the equilibrium constant can both be used to measure the position of an
equilibrium reaction and are related by the equation, ∆𝐺 = −𝑅𝑇𝑙𝑛𝐾
17.1.4 Solution of homogeneous equilibrium problems using the expression for K c

17.1.5 Relationship between ∆𝐺 and the equilibrium constant

17.1.6 Calculations using the equation ∆𝐺 = −𝑅𝑇𝑙𝑛𝐾

Equilibrium calculations
 The equilibrium law can be used either to find the value of the equilibrium constant or to find the value of an unknown
equilibrium constant. The easiest approach for calculating equilibrium concentrations is to use an ICE table, which is an
organized method to track which quantities are known and which need to be calculated. ICE stands for:
o I: The initial concentration or amount
o C: The change in concentration from the initial state to equilibrium
o E: The equilibrium concentration

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 SO3 were both 0.03 mol
dm-3, what would be the equilibrium concentration of each component?

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.

 Make sure the volume of the vessel is 1. Otherwise divide the equilibrium
Gibbs free energy and Equilibrium
 Equilibrium occurs when the reaction is at a minimum value of Gibbs free energy and a maximum value of entropy
 The formula for Gibbs free energy is:

∆𝐺 𝜃 = 𝑅𝑇 ln 𝐾
Topic 8: Acids and bases
8.1 Theories of acids and bases
+ +
8.1.1 A Brønsted-Lowry acid is a proton/H donor and a Brønsted-Lowry base is a proton/H acceptor

8.1.2 Amphiprotic species can act as both Brønsted-Lowry acids and bases

8.1.3 A pair of species differing by a single proton is called a conjugate acid-base pair

8.1.4 Deduction of the Brønsted-Lowry acid and base in a chemical reaction

8.1.5 Deduction of the conjugate acid or conjugate base in a chemical reaction

Brønsted-Lowry theory
 According to the Brønsted-Lowry theory, a substance behaves as an acid when it donates a proton to a base. A
substance behaves as a base when it accepts a proton from an acid. Thus:
o A Brønsted-Lowry acid is a proton (H+) donor
o A Brønsted-Lowry base is a proton (H+) acceptor
 Acids can be a combination of hydrogen ions (𝑯+ ) and an anion. Examples include: 𝐻𝐶𝑙, 𝐻𝑁𝑂3 , 𝐻𝐶2 𝐻3𝑂2
 Bases can be a combination of hydroxide ions (𝑶𝑯− ) and metal cations. Examples include: 𝑁𝑎𝑂𝐻, 𝐾𝑂𝐻
o However, sometimes a hydrogen next to a metal signifies a base such as 𝑁𝑎𝐻
 Acid-Base Conjugate Pairs: A conjugate pair is two species which differ by a single proton:
o The acid will become the conjugate base
o The base will become the conjugate acid

Conjugate-Base Pair Question:

Label the conjugate acid-base pairs in the following reactions:

CH3 COOH + H2 O(g) ⇌ CH3 𝐶𝑂𝑂− + H3 O+
Conjugate pair 1: CH3 COOH/CH3 𝐶𝑂𝑂−
𝐶𝐻3 𝐶𝑂𝑂𝐻 is the acid because it donates a H+ , so CH3 𝐶𝑂𝑂− is conjugate base
Conjugate pair 2: H2 O/H3 O+
H2 O is the base because it accepts a H+ , so H3 O+ is the conjugate acid

 To find the conjugate acid of a species, add one H+

 To find the conjugate base of a species, takeaway one H+
 Before the Brønsted-Lory theory acids and bases were distinguished by their taste, acids tasted sour

Amphiprotic
 Some substances can behave as either acids and bases, depending on what they react with, and can therefore donate or
receive protons. Such substances are said to be amphiprotic
o Amphiprotic: A chemical species capable of accepting and donating protons, thus able to act as a Brønsted-
Lowry acid and a base
 This means the species must be able to accept or donate a proton to another species
 H2O is amphiprotic as it is able to donate a proton to form a OH− or accept a proton
to form H3 O+ therefore acting as a Brønsted-Lowry acid or base

Amphiprotic Species Question:

Write an equation to show hydrogen phosphate acting as and an acid and a base in water
Acting like an Acid: HPO42− + H2 O(g) ⇌ PO43− + H3 O+
Acting like a Base: HPO4 2− + H2 O(g) ⇌ HPO4 − + OH−
 Amphoteric
 Amphoteric: A species that can act as an acid or base, including reactions that do not involve a proton
 Amphiprotic specifically relates to the Brønsted-Lowry acid-base theory, where the emphasis is on the transfer of a
proton. Amphoteric is a more general term that isn’t just confined to proton transfer
 All amphiprotic species are also amphoteric but not all amphoteric species are amphiprotic

8.2 Properties of acids and bases

8.2.1 Most acids have observable characteristic chemical reactions with reactivate metals, metal oxides, metal hydroxides,
hydrogen carbonates and carbonates
8.2.2 Salt and water are produced in exothermic neutralization reactions

8.2.3 Balancing chemical equations for the reaction of acids

8.2.4 Identification of the acid and base needed to make different salts

Neutralization Reactions
 Neutralization: A chemical reaction where a base and an acid react to form a salt and water
o Salt: An ionic Compound
 Acid base reactions will always produce a salt and water
 Salt and water are neither acidic nor basic. They are called neutral solutions
 Neutralization reactions are exothermic as heat is released
 There are different types of bases that acids react with to form salt:

Hydroxyl Base:
 Equation: 𝐴𝑐𝑖𝑑 + 𝐵𝑎𝑠𝑒 → 𝑆𝑎𝑙𝑡 + 𝑊𝑎𝑡𝑒𝑟
 To find the salt formula, take away the hydrogen from the acid and the hydroxyl group from the base (these will join
together to give 𝑊𝑎𝑡𝑒𝑟. Then join remaining terms (Ensure charge is the same, positive term is listed first)

Neutralization Reaction Question:

Write the equation for the reaction between hydrochloric acid (𝐻𝐶𝑙) and a solution of sodium hydroxide (𝑁𝑎𝑂𝐻)
to form a salt and water:
𝐻𝐶𝑙 + 𝑁𝑎𝑂𝐻 → 𝐻2 𝑂 + 𝑁𝑎𝐶𝑙
Take away 𝐻 + from 𝐻𝐶𝑙, and 𝑂𝐻− from 𝑁𝑎𝑂𝐻 to get 𝐻2 𝑂, then join last remaining pieces (positive ion listed first)

Carbonate Base
 Equation: 𝐴𝑐𝑖𝑑 + 𝐶𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 𝐵𝑎𝑠𝑒 → 𝑆𝑎𝑙𝑡 + 𝑊𝑎𝑡𝑒𝑟 + 𝐶𝑂2
 Metal carbonates include Na2CO3, MgCO3 and CaCO3
 To find the salt formula, perform the same steps as before, but account for CO2

Metal Reactions:
 Equation 𝐴𝑐𝑖𝑑 + 𝑀𝑒𝑡𝑎𝑙 → 𝑆𝑎𝑙𝑡 + 𝐻2
 Reactive metals include Ca, Mg, K and Zn but not Cu, Ag or Au
 To find the salt formula, perform the same steps as before, but account for H2

Acids and Metal Reactions Question:

Write the equation for the reaction when zinc is added to hydrochloric acid
2𝐻𝐶𝑙 + 𝑍𝑛 → 𝑍𝑛𝐶𝑙2 + 𝐻2
8.3 The pH scale
8.3.1 𝑝𝐻 = −log[𝐻 + (𝑎𝑞)] 𝑎𝑛𝑑 [𝐻 + ] = 10−𝑝𝐻

8.3.2 A change of one pH unit represents a 10-fold change in the hydrogen ion concentration [𝐻 + ]

8.3.3 pH values distinguish between acidic, neutral and alkaline solutions

8.3.4 The ionic product constant, 𝐾𝑤 = [𝐻 + ][𝑂𝐻 − ] = 10−14 at 298K

8.3.5 Solving problems involving pH, [𝐻 + ] and [𝑂𝐻 − ]

8.3.6 Students should be familiar with the use of a pH meter and universal indicator

Self-Ionization of Water
 Because of its amphoteric (or amphiprotic) nature, water does not always remain as H2 O molecules.
 Water will self-ionize, where it will exist in equilibrium between two water molecules and H3 O+ and OH−
2H2 O ⇌ H3 O+ + OH−
 K 𝑊 is the ionization constant of water:
K 𝑊 = [H+ ][OH− ] = (1.0 × 10−7 )(1.0 × 10−7 ) = 1.0 × 10−14

pH and pOH
 “𝑝” represents taking the negative logarithm of the value (p = −log) Therefore:
o pK𝑊 = pH + pOH = 14
o pH = − log[H+ ]
o pOH = − log[OH− ]
 The pH scale represents the concentration of 𝐻 +. The acidity of a solution is a measure of the
concentration of hydrogen ions present. Using pH + pOH = 14:
 When pH<7, the solution is acidic as [H+ ] > [OH− ]
 When pH=7, the solution is neutral as [H+ ] = [OH− ]
 When pH>7, the solution is basic as [H+ ] < [OH− ]
 Log laws allow us to find [H+ ] and [OH− ]:
o [OH− ] = 10−𝑝𝑂𝐻
o [H+ ] = 10−𝑝𝐻
 The pH scale is logarithmic, meaning that an increase or decreases of an integer value changes
the concentration by ten
 A two-unit change represents a one-hundred-fold change and so on
 There are no units for pH

Acid-Base Indicators
 Acid-Base Indicators (also known as pH indicators) are weak acids that indicate the concentration of H+ in a solution by
changing color
 base indicators undissociated and dissociated forms of acid-base indicators have different colors
 They exist as liquid types or dye-infused paper strips. In liquid form
indicators are directly added to solutions whereas paper form
indicators are dipped into solutions then removed
 Both liquid and paper form pH indicators are then compared against a
pH/color key to determine the solutions acidity or alkalinity
 Common indicators (In Data booklet):

Indicator Color in Acid Color in Alkali (Base)

Litmus Red Blue

Methyl Orange Red Yellow

Phenolphthalein Colorless Pink

 When titrating and acid against a base (or the other way), the indicator will change color at the equivalence point
 Using a titration curve, choose an indicator that changes color at the steepest part of the curve (equivalence point)
8.4 Strong and weak acids and bases
8.4.1 Strong and weak acids and bases differ in the extent of ionization

8.4.2 Strong acids and bases of equal concentrations have higher conductive than weak acids and bases

8.4.3 A strong acid is a good proton donor and has a weak conjugate base

8.4.4 A strong base is a good proton acceptor and has a weak conjugate acid

8.4.5 Distinction between strong and weak acids and bases in terms of the rates of their reactions with metals, metal oxides,
metal hydroxides, metal hydrogen carbonates and metal carbonates and their electrical conductivities for solutions of
equal concentrations

Strong and Weak Acids/Bases

 All acids and bases do not dissociate to the same extent. Not all acids and bases are of equal strength in producing [H+ ]
and [OH− ] in solution. The terms “strong” and “weak” give an indication of the strength of an acid/base

Strong acid Weak acid

Strong acids fully dissociate in solution (~100%) Weak acids partially dissociate in solution (<5%)

Form strong electrolytes when absorbed in Water Form weak electrolytes when absorbed in water

At the same concentration, strong acids will produce more [𝐇+ ] than weak acids

Examples: Examples

hydrochloric acid, HCl nitric acid, HNO3 ethanoic acid, CH3COOH carbonic acid, H2CO3

sulphuric acid, H2SO4 Propanoic Acid phosphoric acid, H3PO4

Strong bases Weak bases

Strong bases fully ionize in solution (~100%) Weak bases partially ionize in solution (<5%)

At the same concentration, strong bases will produce more [𝐎𝐇 − ] than weak acids

sodium hydroxide, NaOH ammonia, NH3

Examples: potassium hydroxide, KOH Examples

barium hydroxide, Ba(OH)2 Ethylamine, CH3CH2NH2

 When dealing with strong acids/bases use a single arrow as it will ionize completely
 When dealing with weak acids/bases use a double arrow as it will not ionize completely and exists in equilibrium
 A strong acid has a weak conjugate base while a strong base has a weak conjugate acid

Strong and Weak Acid and Bases Question:

Compare 1M CH3COOH vs 1M HCl

CH3COOH is a weak acid, while HCl is a strong acid
Therefore, HCl will fully ionize while CH3COOH will only partially ionize

Experimental techniques to determine acid or base strengths

 Conductivity: Strong acids and strong bases will be a better conductor
o At the same concentration of acids and bases, the concentration of hydrogen ions will be higher in a strong acid
than in a weak acid, and the concentration of hydroxide ions will be higher than in a weak base
o The more ions present, the more conductive a solution
o Conductivity can be measured with pH meter or an electrodes/conductivity meters
  pH: At the same concentration, strong acids have lower pH than weak acids, and strong bases have a higher pH than
weak bases
o Because pH is a measure of H+ concentration, the pH scale can be used directly to compare the strengths of
acids (provided they are of equal molar concentration)
o Remember, the higher the H+ concentraiton, the lower the pH value
o A universal indicator of a pH meter can be used to measure pH
 Rates of Reactions
o The reaction of acids depend on the concentration of H+ ions
o Reaction rate will be sped up with stronger acids
 Reactions with metals/carbonates: Strong acids will react more vigorously with metals/carbonates

8.5 Acid deposition

8.5.1 Rain is naturally acidic because of dissolved CO 2 and has a pH of 5.6. Acid deposition has a pH below 5.6

8.5.2 Acid deposition is formed when nitrogen or sulfur oxides dissolve in water to form HNO 3, HNO2, H2SO4 and H2SO3

8.5.3 Sources of the oxides of sulfur and nitrogen and the effects of acid deposition should be covered

8.5.4 Balancing the equations that describe the combustion of sulfur and nitrogen to their oxides and the subsequent formation
of H2SO3, H2SO4, HNO2 and HNO3
8.5.5 Distinction between the pre-combustion and post-combustion methods of reducing sulfur oxides emissions

8.5.6 Deduction of acid deposition equations for acid deposition with reactive metals and carbonates

Pollution
 Acid deposition: Process by which acid forming pollutants are deposited on the Earth’s surface
 Rain is naturally acidic because of dissolved CO2 and has a pH of 5.6. Acid deposition has a pH below 5.6.
o However, carbon dioxide itself is not responsible for acid rain since the pH of acid rain is around 5.6
 Acid deposition occurs when nitrogen or sulfur oxides dissolve in water to form HNO2, H2SO4 and H2SO3 (weak acids)
o Sulfur oxides can be formed from various natural processes, including the burning of sulfur containing fuels
o Nitrogen oxides can be produced in combustion (coal, gas, oil fueled power stations)

Sulfurous Acid: H2SO4 Nitrous Acid: HNO2 Carbonic Acid: H2CO3

Corrodes marble, limestone buildings Corrodes marble, limestone buildings Corrodes marble, limestone
and statues and statues buildings and statues

Leaching in soils Leaching in soils Acidification of lakes

Harms/Kills Plants Harms/Kills Plants

 Acid rain results when sulfur dioxide (SO2) and nitrogen oxides (NOX) are emitted into the atmosphere and transported
by wind and air currents. The SO2 and NOX react with water, oxygen and other chemical sot form sulfuric and nitric acids.
These then mix with water and other materials before falling to the ground
 Effects of Acid deposition on the environment
o Displaces metal ions from soil, and prevents the growth/development of plants
o Elevated acid levels in lakes and rivers, affect pH sensitive ecosystems
o Causes the poisoning of fish, eventually resulting in the uptake of poison and damage to human healthy
o Irritates mucous membrane causing respiratory illness (asthma)
 Methods to lower or counteract the effects of acid deposition:
1. Lower the amounts of NOX and SOX formed. This can be done by improved engine design, the use of catalytic
converts, and removing sulfur before, during and after combustion of sulfur containing fuels
2. Switch to alternative methods of energy (wind and solar power) and reduce the amount of fuel burned
3. Liming of lakes: Adding calcium oxide or calcium hydroxide (lime) neutralizes the acidity, increases the amount
of calcium ions and precipitates aluminum from solution. This has been shown to be effective in many, but not
all, lakes where it has been tried
18.1 Lewis acids and bases
18.1.1 A Lewis acid is a lone pair acceptor and a Lewis base is a lone pair donor

18.1.2 When a Lewis base reacts with a Lewis acid a coordinate bond is formed

18.1.3 A nucleophile is a Lewis base and an electrophile is a Lewis acid

18.1.4 Application of Lewis’ acid-base theory to inorganic and organic chemistry to identify the role of the reacting species

Lewis Acids & Bases

 A Lewis Acid is any species that can accept a pair of electrons
 A Lewis Base is any species that can donate a pair of electrons
 A coordinate covalent bond is formed when these two substances react
 All transition metals ions with ligands as Lewis acid and Lewis bases
 Electrophiles act as Lewis bases. Nucleophile act as Lewis acids

Brønsted-Lowry vs Lewis Theory

Theory Definition of acid Definition of base

Brønsted-Lowry Proton donor Proton acceptor

Lewis Electron acceptor Electron donor

 A Lewis base is also a Brønsted-Lory base, but not all Lewis acids are Brønsted-Lowry acids
o The term Lewis Acid is reserved for those acids which cannot donate a H+ ion (don’t have a hydrogen atom, but
can still donate accept a pair of electrons)
 Many reactions can be described as acid-base as a transfer of protons that take place. Lewis acid-base reactions take
place when no protons are transferred.

18.2 Calculations involving acids and bases

18.2.1 The expression for the dissociation constant of a weak acid (Ka) and a weak base (Kb)

18.2.2 For a conjugate acid base pair, 𝐾𝑎 × 𝐾𝑏 = 𝐾𝑤

18.2.3 The relationship between 𝐾𝑎 and 𝑝𝐾𝑎 is (𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎 ) and between 𝐾𝑏 and 𝑝𝐾𝑏 is (𝑝𝐾𝑏 = −𝑙𝑜𝑔𝐾𝑏 )

18.2.4 Solution of problems involving [𝐻 + (𝑎𝑞)], [𝑂𝐻 − (𝑎𝑞)], pH, pOH, 𝐾𝑎 , 𝑝𝐾𝑎 , 𝐾𝑏 and 𝑝𝐾𝑏

18.2.5 Discussion of the relative strengths of acids and bases using values of 𝐾𝑎 , 𝑝𝐾𝑎 , 𝐾𝑏 , and 𝑝𝐾𝑏

Weak Acids and Bases

 K 𝑎 is the equilibrium constant for an weak acidr reacting with water
 The partial dissociation of a weak acid 𝐻𝐴 in water can be written as: 𝐻𝐴 + 𝐻2 𝑂 ⇌ 𝐻 + + 𝐴−
o Where 𝐻𝐴 is the acid with hydrogen, and 𝐴− is the conjugate base taken away one hydrogen
 The equilibrium expression for this reaction is as follows where K 𝑎 is known as the acid dissociation constant
[H+ ][A− ]
K𝑎 =
[𝐻𝐴]
 K 𝑏 is the equilibrium constant for a weak base reacting with water
 The partial dissociation of a weak base can be written as: 𝐴− + 𝐻2 𝑂 ⇌ 𝑂𝐻− + 𝐻𝐴
 The equilibrium expression for this reaction is as follows where K 𝑏 is known as the base dissociation constant
[OH− ][HA]
K𝑏 =
[𝐴− ]
[H+ ][A− ] [OH− ][HA]
 Therefore: K a × K b = [𝐻𝐴]
× [𝐴− ]
= [H+ ][OH− ] = K W
 Therefore: K W = K a × K b . This can also be expressed as: pK a + pK b = 14
o pKa = −logK a
o pKb = −logK b
18.3 pH curves
18.3.1 The characteristics of the pH curves produced by the different combinations of strong and weak acids and bases

18.3.2 An acid-base indicator is a weak acid or a weak base where the components of the conjugate acid-base pair have different
colors
18.3.3 The relationship between the pH range of an acid-base indicator, which is a weak acid, and its 𝑝𝐾𝑎 value

18.3.4 The buffer region on the pH curve represents the region where small additions of acids or base result in little or no change
in pH
18.3.5 The composition and action of a buffer solution

18.3.6 The general shapes of graphs of pH against volume for titrations involving strong and weak acids and bases with an
explanation of their important features
18.3.7 Selection of an appropriate indicator for a titration, given the equivalence point of the titration and the end point of the
indicator
18.3.8 While the nature of the acid-base buffer always remains the same, buffer solutions can be prepared by either mixing a
weak acid/base with a solution of a salt containing its conjugate, or by partial neutralization of a weak acid/base with a
strong acid/base
18.3.9 Prediction of the relative pH of aqueous salt solutions formed by the different combinations of strong and weak acid and
base

Acid-Base Titration
 Titration is a technique used in analytical chemistry to determine the concentration of an
unknown acid or base
 Titration involves the slow addition of one solution where the concentration is known to a
known volume of another solution where the concentration is unknown until the reaction
reaches the desired level. For acid/base titrations, a color change from a pH indicator is
reached or by using a pH meter
 A titration curve is a graph of the pH (vertical axis) versus the amount of reagent progressively
added to the original sample. All acid titration curves follow the same basic shapes
 At the beginning the solution has a low pH. This pH will increase as a strong base is added

Strong Acid and Strong Base Titration Curve

 The first curve shows a strong acid being titrated by a strong base
 There is the initial slow rise in pH until the reaction nears the point where just enough
base is added to neutralize all the initial acid. This is where the volume of acid is equal
to the volume of the base and has the maximum gradient
 This point is called the equivalence point (also called, point of inflection or end point)
 For a strong acid-base reaction, this occurs at pH=7
 As the solution passes the equivalence point, the pH slows its increase where the
solution approaches the pH of the titration solution

Weak Acid and Strong Base Titration Curve

 A weak acid only partially dissociates from its salt
 The pH will rise normally at first, but as it reaches a zone where the solution seems to
be buffered, the slope levels out. This is called the buffer region. This happens because
the weak acid will only partially dissociate
 After this zone the pH will rise sharply through its equivalence point and levels out
again like the strong acid/strong base reaction
 The equivalent point is more than 7 because the strong base will neutralize the weak
acid more compared to neutralizing a strong acid
 The half-equivalent point is when just enough base is added for half of the acid to be
converted to the conjugate base
 When this happens, the concentration of H+ ions equals the K 𝑎 value of the acid, where pH = pK 𝑎
 The half-equivalent point occurs halfway through a buffered region where the pH barely changes for a lot of base added
Strong Acid and Weak Base or Weak Acid and Weak Base Titration Curves
 For a strong acid and a weak base the equivalence point will be below 7, because the strong acid will take longer to
neutralize with a weak base

Indicators
 An indicator is a weak acid (or base) in where 𝐻𝐼𝑛 and 𝐼𝑛− are different colors:
𝐻𝐼𝑛 ⇌ 𝐻 + + 𝐼𝑛−
[In− ]
K 𝑖𝑛 = [H+ ] ×
[HIn]
 In basic solution equilibrium moves to the right. In acid equilibrium moves to the left
 Indicator should change color at equivalence point. The color will change at equivalent point when [In− ] = [HIn],
therefore K 𝑖𝑛 = [H+ ]
 Thus pK 𝑖𝑛 = pH
 Different indicators have different K 𝑖𝑛 values and so change color within different pH ranges

Indicator 𝐩𝐊 𝒊𝒏 pH Range Use

Methyl Orange 3.7 3.1-4.4 Titration with strong acids

Phenolphthalein 9.3 8.2-10.0 Titration with strong

bases

Bromophenol Blue 9.3 3.0-4.6

 To find which indicator to use, the pH at the equivalent point must be in the appropriate pH range

Salts Hydrolysis
 Salt Hydrolysis: The process in which a salt reacts with water to give back the acids and the base
𝑆𝑎𝑙𝑡 + 𝑊𝑎𝑡𝑒𝑟 → 𝐴𝑐𝑖𝑑 + 𝐵𝑎𝑠𝑒
 To predict whether a salt will form an acidic, basic or neutral solution when dissolved in water, split the salt into
individual ions, and find out if those ions are acidic or basic
o If the salt is composed of a strong acid and weak base it will produce an acidic solution
o If the salt is composed of a weak acid and a strong base it will produce a basic solution
o The salt of a strong acid and a strong base is always neutral
 Or, split to salt into individual atoms, then pair the individual ions with either a hydrogen ion or the OH group.
o If the charge on the individual atom is positive (cation), it is a base
o If the charge on the individual atom is negative (anion), it is an acid
 Then compare whether it’s a strong acid or a strong base
 Example: NaCl gives Na+ and Cl-. Therefore Na+ is a cation so has an OH group which gives NaOH while Cl- is an anion so is
paired with a hydrogen ion to give HCl

Buffers
 Buffer: Solutions that can resist pH change upon the addition of an acidic or basic components
 Buffer solutions can be prepared by mixing a weak acid with a solution of salt containing its conjugate base
 Buffer solutions can also be prepared by partial neutralization of a weak acid with a strong base
Topic 9: Redox processes
9.1 Oxidation and reduction
9.1.1 Oxidation and reduction can be considered in terms of oxygen gain/hydrogen loss, electron transfer or change in oxidation
number
9.1.2 An oxidizing agent is reduced and a reducing agent is oxidized

9.1.3 Variable oxidation numbers exist for transition metals and for most main-group non-metals

9.1.4 The activity series rank metals according to the ease with which they undergo oxidation

9.1.5 The Winkler Method can be used to measure biochemical oxygen demand (BOD), used as a measure of the degree of
pollution in a water sample
9.1.6 Deduction of the oxidation states of an atom in an ion or a compound

9.1.7 Deduction of the name of a transition metal compound from a given formula, applying oxidation numbers represented by
Roman numerals
9.1.8 Identification of the species oxidized and reduced and the oxidizing and reducing agents, in redox reactions

9.1.9 Deduction of redox reactions using half-equations in acidic or neutral solutions

9.1.10 Deduction of the feasibility of a redox reaction from the activity series or reaction data

9.1.11 Solution of a range of redox titration problems

9.1.12 Application of the Winkler Method to calculate BOD

Oxidation and Reduction

 In oxidation and reduction reactions (also called redox Oxidation Reduction
reactions), electrons move between atoms
 Oxidation involves the loss of electrons. The more a Loss of electrons Gain of electrons
substance is oxidized, the more positive it gets
Loss of hydrogen Gain of hydrogen
 Reduction involves the gain of electrons. The more a
substance is reduced the more negative it gets
Gain of hydrogen Loss of oxygen
 Remember: OIL RIG (Oxidation is loss, reduction is gain)

Oxidant and reductant

Definitions

Oxidant – A substance that readily oxidizes other substances

Reductant – A substance that readily reduces other substances

 An oxidizing agent makes oxidation happen. In order to

Oxidizing agent Reducing agent
make oxidation happen, the agent must take the
electron from the substance
Gains electrons Loses electrons
 So, oxidizing agents are reduced
 Common oxidizing agents include halogens, ozone, Oxidizes another reactant Reduces another reactant
maganate (VII) ions and hydrogen peroxide
 A reducing agent makes reduction happen. In order to Is reduced during the Is oxidized during the
make reduction happen, the agent must give an reaction reaction
electron to the substance
 So, reducing agents are oxidized
 Common reducing agents include hydrogen, carbon, carbon monoxide and sulfur dioxide
Oxidation state
 The oxidation state (also known as oxidation number) is the total number of electrons that an atom either gains or loses to
form a chemical bond with another atom
 Oxidation numbers are represented by a roman number. Example: Cu2O: Copper (I) oxide, FeCl2: Iron (II) chloride
 Oxidation states can be used to identify which species have been oxidized and which have been reduced
o An increase in oxidation number means oxidation (so reducing agent) (Loss of electrons, becomes more positive)
o A decrease in oxidation number means reduction (so oxidizing agent) (Gain of electrons, becomes more negative)
 Oxidation states are written as NUMBER and then SIGN
 To assign oxidation states to atoms in a molecule or compound we follow some very specific rules:

Sum of oxidation state for a neutral compound: 0 Sum of oxidation state for a polyatomic ion: Ion charge

Element by itself: 0 Group 1/2/3: Always +1/+2/+3

Monatomic ion: Ion charge D-Block elements have variable oxidation states

Halogens: Usually -1 (+1 with oxygen) Hydrogen: +1 (-1 with metals)

Oxygen: -2 (-1 in peroxide) Florine: Always -1

Question: Deduce the oxidation state of Cr in K2Cr2O7

𝐾: +1 (2 × +1) = +2 𝑂: −2 (7 × −2) = −14

No charge on compound so equals 0: +2 − 14 + 2𝑥 = 0 = +6
Therefore 𝐶𝑟: +6

Redox Half Equations

 In a redox reaction, one substance always becomes reduced while the other one oxidized
 To balance redox equations, we write out the half-equations for the oxidation and reduction reactions
 Redox reactions can take place in neutral, acidic or basic solutions
o In acidic solutions, follow the steps below
o In neutral solution, balance the reaction as if it were in acidic solution
o In basic solution, instead of adding H+ ions add OH- ions
 In order to write a balanced redox reaction we must: write the two half equations first and then add them together to get an
overall equation (OHe)
1. Write the unbalanced redox equation
2. Separate the reaction into its two half equations (Identify species that is reduced and that is being oxidized)
3. Balance all atoms other than O and H
4. Balance the O atoms by adding water (on the opposite side)
5. Balance the H atoms by adding H+ ions
6. Balance the charges on both sides of the equation by adding electrons to the more positive sides

Question: Write the redox half equations for the following reaction

𝑀𝑛𝑂4 − + 𝐹𝑒 2+ → 𝑀𝑛2+ + 𝐹𝑒 3+
1. Equation 1: 𝑀𝑛𝑂4 − → 𝑀𝑛2+ Equation 2: 𝐹𝑒 2+ → 𝐹𝑒 3+
2. Balanced; Equation 1: 𝑀𝑛𝑂4 − → 𝑀𝑛2+ Equation 2: 𝐹𝑒 2+ → 𝐹𝑒 3+
3. O; Equation 1: 𝑀𝑛𝑂4 − → 𝑀𝑛2+ + 4𝐻2 𝑂 Equation 2: 𝐹𝑒 2+ → 𝐹𝑒 3+
4. H; Equation 1: 𝑀𝑛𝑂4 − + 8𝐻 + → 𝑀𝑛2+ + 4𝐻2𝑂 Equation 2: 𝐹𝑒 2+ → 𝐹𝑒 3+
5. e-: Equation 1: 5𝑒 − + 𝑀𝑛𝑂4 − + 8𝐻 + → 𝑀𝑛2+ + 4𝐻2𝑂 Equation 2: (𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒 − ) × 5
6. 𝑀𝑛𝑂4 − + 5𝐹𝑒 2+ + 2𝐻+ → 𝑀𝑛2+ + 5𝐹𝑒 3+ + 𝐻2 𝑂
The activity series
 The activities series is a chart of metals listed in order of declining relative reactivity and their
strength as reducing agents
o Metals at the top of the activity series are more reactive and stronger reducing agents
(more readily oxidized)
o Metals at the bottom of the activity series are less reactive and weaker reducing agents
(less readily oxidized)
 It is used to determine the products of single displacement reactions. The greater the difference in
reactivity of two metals, the more rapidly the reaction would occur. However, the metal acting as the
reducing agent must occur higher in the reactivity series that the one being reduced.
 A metal can only displace another in a compound if it is higher in the activity series (more reactive)
 Almost always the most reactive non-metal ends up as an ion. For instance, since Fe is higher in the activity series it ends up
as 𝐹𝑒 2+
𝐹𝑒 + 𝑃𝑏 2+ → 𝐹𝑒 2+ + 𝑃𝑏
 The activity series can also be used to determine whether a reaction will occur or not as more reactive elements will replace
less reactive elements in a compound.

Redox titration
 Redox titration: Titration of a reducing agent by an oxidizing agent or titration of an oxidizing agent by a reducing agent
 Redox titration is used to determine the concentration of an analyte containing either an oxidizing or a reducing agent
 This analytical technique can be used to find the amount of iron in a sample
 In redox titration Fe2+ is oxidized to Fe3+ by an oxidizing agent:
𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒 −
The oxidizing agent is usually acidified potassium manganate (VII) or potassium dichromate (VI)
 Steps of redox titration:
1. Calculate the amount, in moles, of MnO4- (or other oxidizing agents) required to react with the Fe2+, using 𝑛 = 𝐶𝑉
2. Use the molar ratio to determine the amount (in mol) of Fe2+ ions in the solution
3. Calculate the mass of iron in the tablet using the equation 𝑚 = 𝑛𝑀
4. Calculate the percentage by mass of iron in the tablet

The Winkler Method

 Biochemical oxygen demand: The amount of oxygen used by the aerobic microorganisms in water to decompose the organic
matter in water over a fixed period of time
 This is because high levels of oxygen can mean low levels of pollution as there will be more aerobic microorganisms respiring
 The Winkler method is used to measure the concentration of dissolved oxygen in a sample of water
 The equations involved are:

 Just remember ratio of O2 to S2O32- is 1:4 as one mole of O2 reacts with 4 mols of S2O32-
9.2 Electrochemical cells
9.2.1 Voltaic cells convert energy from spontaneous, exothermic chemical processes to electrical energy

9.2.2 Oxidation occurs at the anode (negative electrode) and reduction occurs at the cathode (positive electrode) in a voltaic cell

9.2.3 Electrolytic cells convert electrical energy to chemical energy, by bringing about non-spontaneous processes

9.2.4 Oxidation occurs at the anode (positive electrode) and reduction occurs at the cathode (negative electrode) in an
electrolytic cell
9.2.5 Construction and annotation of both types of electrochemical cells

9.2.6 Explanation of how a redox reaction is used to produce electricity in a voltaic cell and how current is conducted in an
electrolytic cell
9.2.7 Distinction between electron and ion flow in both electrochemical cells

9.2.8 Performance of laboratory experiments involving a typical voltaic cell using two metal-ion half-cells

9.2.9 Deduction of the products of the electrolysis of a molten salt

Voltaic cells
 Voltaic cells convert energy from spontaneous, exothermic chemical processes to electrical energy
o i.e. voltaic cells create electricity using a chemical reaction
o Note these reactions should happen on their own as they are spontaneous
 Voltaic cells consist of two half cells. In a half-cell, a metal electrode is placed in an aqueous solution of its ions
 Two half cells are connected to form a voltaic cell, allowing electrons to flow during the redox reaction and produce
electrical energy. The half-cells are joined by a wire to transfer electrons and a salt bridge
to transfer ions.
 The Daniel’s cell contains a copper electrode in a copper solution and a zinc electrode in a
zinc solution. The reaction can be written as:
𝐶𝑢2+ + 𝑍𝑛 → 𝐶𝑢 + 𝑍𝑛2+
 The metal higher in the activity series is oxidized and the metal lower in the activity series
is reduced. Therefore:
o Oxidation occurs at the anode (negative electrode) in a voltaic cell (negative
because Zn has a weak pull for electrons, so it loses electrons which makes the solution negative)
o Reduction occurs at the cathode (positive electrode) in a voltaic cell (positive because Cu has a stronger pull for
electrons, so it gains electrons which makes the solution positive)
 Remember: An Ox, Red Cat (Anode Oxidation, Reduction Cathode)
 Current is conducted by electron flow in wires and movement of ions in salt bridge
 Electricity is produced because electrons flow from the oxidized substance, where electrons are being lost, to the reduced
substance, where electrons are being gained (as electrons are electricity)
 The salt bridge completes the circuit and neutralizes any buildup of charge by the following ion movement:
o Anions in the salt bridge move from the anode to the cathode
o Cations move in the salt bridge move from the cathode to the anode

Cell diagram
 A cell diagram is a shorthand notation to represent the redox reactions of an electrical cell
 For the cell above, the cell diagram is as follows:
𝑍𝑛|𝑍𝑛2+ ‖𝐶𝑢2+ |𝐶𝑢
 A single vertical line is used to separate different states of matter on the same side
 A double vertical line represents a salt bridge between the half-cells
 The anode (where oxidation occurs) is placed on the left side of the ||
 The cathode (where reduction occurs) is placed on the right side of the ||
Electrolytic cells
 Electrolytic cells convert electrical energy to chemical energy, by bringing about non-spontaneous processes. The
electrical energy from a battery can force a non-spontaneous reaction to happen
o The power source should be a battery or a DC power source
o The electrodes are placed in the electrolyte, connected to the power source by electrical wires
o The electrodes cannot touch each other.
 The electrical energy supplied by the power source induces a flow of electrons from the anode to the cathode
 However, unlike in voltaic cells, the power source causes the polarity of the electrodes to change
o The positive pole of the external power source makes the anode of the electrolytic cell positive
o Now the anode is the positive electrode and the cathode is the negative electrode
 When the current reaches the electrolyte, the electrical energy is carried by ions, which migrate to the electrodes. The redox
reactions taking place at the electrodes take the ions of out solution and allow it to continue

 Unlike voltaic cells, the electrodes must be made from an inert, heat resistant material like graphite or platnium
 The flow of energy in an electrolytic cell has two forms. From the anode to the cathode, the electrons pass along a
conductive wire in the form of electrical energy. Therefore, the current is conducted by the movement of electrons in the
external part of the circuit
 However, electrical energy cannot move through the electrolyte, so the current moves in a different form. At the cathode,
electrons are accepted by the positive ions. The flow of current in the electrolyte is facilitated by ions, or chemical energy-
the positive ions flow towards the cathode and the negative ions flow towards the anode
 In the electrolysis of molten sodium chloride, sodium metal and chlorine gas are formed
 In order to find the products of the electrolysis of a molten salt:
1. Write down what chemicals are being used
2. Create two half equations of each chemical
3. Determine towards which electrode the different ions will flow. The cations are attracted to the cathode and the
anions are attracted to the anode
4. Combine the two half reactions and check that the complete reaction is balanced

Voltaic Cell vs Electrolytic Cell

Voltaic cell Electrolytic cell

Chemical energy is converted to electrical energy Electrical energy is converted to chemical energy

Reaction is exothermic Reaction is endothermic

A spontaneous reaction produces an electric current An electric current drives a non-spontaneous reaction

Current is conducted by electron flow in wires and Current is conducted by electron flow in wires and
movement of ions in salt bridge movement of ions in electrolyte

Anode is negative Anode is positive

Cathode is positive Cathode is negative
19.1 Electrochemical cells
9.1.1 A voltaic cell generates an electromotive force (EMF) resulting in the movement of electrons from the anode (negative
electrode) to the cathode (positive electrode) via the external circuit. The EMF is termed the cell potential (𝐸°)
-3
9.1.2 The standard hydrogen electrode (SHE) consists of an inert platinum electrode in contact with 1 mol dm hydrogen ion
and hydrogen gas at 100kPa and 298K. The standard electrode potential (𝐸°) is the potential (voltage) of the reduction
-3
half-equation under standard conditions measured relative to the SHE. Solute concentration is 1 mol dm or 100 kPa for
gases. 𝐸° of the SHE is 0V
9.1.3 When aqueous solutions are electrolyzed, water can be oxidized to oxygen at the anode and reduced to hydrogen at the
cathode
9.1.4 ∆𝐺° = −𝑛𝐹𝐸°. When 𝐸° is positive, ∆𝐺° is negative indicative of a spontaneous process. When 𝐸° is negative, ∆𝐺° is
positive indicative of a non-spontaneous process. When 𝐸° is 0, then ∆𝐺° is 0
9.1.5 Current, duration of electrolysis and charge on the ion affect the amount of product formed at the electrodes during
electrolysis
9.1.6 Electroplating involves the electrolytic coating of an object with a metallic thin layer

9.1.7 Calculation of cell potentials using standard electrode potentials

9.1.8 Prediction of whether a reaction is spontaneous or not using 𝐸° values

9.1.9 Determination of standard free-energy changes (∆𝐺°) using standard electrode potentials

9.1.10 Explanation of the products formed during the electrolysis of aqueous solutions

9.1.11 Perform lab experiments that could include single replacement reactions in aqueous solutions

9.1.12 Determination of the relative amounts of product formed during electrolytic processes

9.1.13 Explanation of the process of electroplating

Standard electrode potential

 The direction electrons move between the anode and cathode are determined by the difference in potential energy.
Electrons will more from areas of higher potential energy to areas of lower potential energy
 In a voltaic cell the potential difference is called the cell potential (also sometimes called EMF: electromotive force)
 This is denoted as: 𝐸𝑐𝑒𝑙𝑙
 The cell potential is different for each voltaic cell, as its value depends on the concentration of the reactants and products
along with the temperature and pressure
 For standard cell potential, the temperature of the reaction is assumed to be 25°C, the concentration of the reactants and
products is 1M, and reaction occurs at 1atm pressure
 The standard cell potential is denoted 𝐸 𝜃 𝑐𝑒𝑙𝑙 and can be written as oxidation potential + reduction potential. For voltaic cell:

𝐸 𝜃 𝑐𝑒𝑙𝑙 = 𝐸 𝜃 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 ± 𝐸 𝜃 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛

 The 𝐸 𝜃 values are intensive quantities, therefore they are not multiplied by the coefficients of the equation
 If 𝐸𝑐𝑒𝑙𝑙 is negative then reaction is non-spontaneous and will not happen in a voltaic cell

Question: Calculate E°cell for the following redox reaction under standard conditions

2𝐴𝑙 + 3𝑆𝑛2+ → 2𝐴𝑙 3+ + 3𝑆𝑛

First, calculate 𝐸 𝜃 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 and 𝐸 𝜃 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 (remember to take out common coefficients)
Oxidation: 2(𝐴𝑙 → 𝐴𝑙 3+ ) − 𝐸 𝜃 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 = 𝐸 𝜃 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = +1.66𝑉

Reduction: 3(𝑆𝑛2+ → 𝑆𝑛) 𝐸 𝜃 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 = −0.137𝑉

Therefore, 𝐸 𝜃 𝑐𝑒𝑙𝑙 = 𝐸 𝜃 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 − 𝐸 𝜃 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 = −0.137𝑉 + (+1.66𝑉)
Cell potential and Gibbs free energy
 For a spontaneous reaction, 𝐸 𝜃 𝑐𝑒𝑙𝑙 must be positive and ∆𝐺 𝜃 must be negative
 However, when 𝐸 𝜃 𝑐𝑒𝑙𝑙 is negative and ∆𝐺 𝜃 is positive the reaction will be non-spontaneous, and the reverse reaction is
spontaneous
 If the reaction is non-spontaneous then a voltaic cell will not work with those metals

𝑬𝜽 ∆𝑮𝜽 Spontaneity

positive negative spontaneous reaction

negative positive non-spontaneous reaction

zero zero reaction is at equilibrium

 Merging electrochemistry with thermodynamics gives this formula:

∆𝐺 𝜃 𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸 𝜃 𝑐𝑒𝑙𝑙

n=moles of electrons transferred in the reaction
F= Faraday constant (96500 C mol-1)

Standard hydrogen electrode (SHE)

 The SHE is a hydrogen half-cell comprising a solution of 1 mol dm–3 H+ ions at 298 K, hydrogen gas at 100 kPa and 298 K and
a platinum electrode. It is linked to a second half-cell through an external circuit. The reaction occurring is:
o The standard hydrogen electrode is used as a reference to measure the electrode potential of other half-cells
 The value of the standard electrode potential (𝐸 𝜃 ) is zero, which forms the bases one needs to calculate cell potentials using
different electrodes or different concentrations
 The standard hydrogen electrode is set up as:
o A wire attached to a piece of platinum (or covered in platinum)
o The wire is immersed in a 1.0M strong acid solution (Generally HCL)
o A glass tube around the wire (electrode)
o H2 gas is bubbled in at a pressure of one atmosphere and a
temperature of 25°C through the glass tube into the solution
o This gives 0.0V
o However, when the SHE is attached to another half-cell this will give
the 𝐸 𝜃 𝑐𝑒𝑙𝑙 of the other half cell

Electroplating
 Electroplating involves the electrolytic coating of an object with a thin
metallic layer
 The purpose of electroplating includes:
o Appearance
o Protection
 The electroplating process:
o Both an anode and a cathode (the metal to be coated) are
immersed in an electrolytic bath that is composed of a solution of salts, including the metal to be plated
o A direct current of electricity is passed through the solution, effecting the transfer of metal ions onto the cathodic
surface, plating the metal onto the item
Electrolysis of Water
 Pure water is a very poor conductor of electricity and cannot undergo significant electrolysis without adding an electrolyte
o NaOH is added to increase its conductivity
 Factors that affect the amount of product formed at the electrodes during electrolysis are:
o Time of electrolysis: The longer the electrolysis is performed, the greater the quantity of products formed. This is a
directly proportional relationship
o Current: The higher the current, the greater the quantity of product formed. This is a directly proportional
relationship
o Charge of the ions: The smaller the charge on the ion, the greater the number of moles of product formed. Thi sis an
inversely proportional relationship

Products of Electrolysis
 To deduce the products of electrolysis:
1. Write down what chemicals you have in your set up. Normally inert electrodes are used, so the chemicals in
question are the cations and anions of the molten salt itself
2. Determine towards which electrode the different ions will flow. The cations are attracted to the negative electrode
and will migrate towards it. Likewise, the anions will migrate to the positive electrode (the anode)
3. At the surface of the negative cathode, the positive ions are reduced as they gain electrons from it. Likewise, at the
positive anode the anions are oxidized as they lose electrons to the positive surface
4. If it is not directly obvious, use section 24 of the IB data booklet to find the most powerful half reactions that can
take place.
5. Combine the two half reactions and check that the complete reaction is balanced. Note that there must be an equal
number of electrons in both half equations.
Topic 10: Organic Chemistry
10.1 Fundamentals of organic chemistry
10.1.1 A homologous series is a series of compounds of the same general formula, which differ from each other by a common
structural unit
10.1.2 Structural formulas can be represented in full and condensed format

10.1.3 Structural isomers are compounds with the same molecular formula but different arrangements of atoms

10.1.4 Functional groups are the reactive parts of molecules

10.1.5 Saturated compounds contain single bonds only and unsaturated compounds contain double or triple bonds

10.1.6 Benzene is an aromatic, unsaturated hydrocarbon

10.1.7 Explanation of the trends in boiling points of members of a homologous series

10.1.8 Distinction between empirical, molecular and structural formulas

10.1.9 Identification of different classes: alkanes, alkenes, alkynes, halogenoalkanes, alcohols, ethers, aldehydes, ketones, esters,
carboxylic acids, amines, amides, nitriles and arenes

10.1.10 Identification of typical functional groups in molecules eg phenyl, hydroxyl, carbonyl, carboxyl, carboxamide, aldehyde,
ester, ether, amine, nitrile, alkyl, alkenyl and alkynyl
10.1.11 Construction of 3D models (real or virtual) or organic molecules

10.1.12 Application of IUPAC rules in the nomenclature of straight-chain and branched chain isomers

10.1.13 Identification of primary, secondary and tertiary carbon atoms I halogenoalkanes and alcohols and primary, secondary and
tertiary nitrogen atoms in amines
10.1.14 Discussion of the structure of benzene using physical and chemical evidence

Homologous series # C atoms Prefix

 Homologous series: A series of compounds of the same family, with the same general
1 meth-
formula, which differ from each other by a common structural unit
 The main features of a homologous series are: 2 eth-
o Members of a homologous series show a gradation in their physical properties due
to the gradual increase of sizes and weight (example: boiling points increase) 3 prop-
o Members of a homologous series show similar chemical properties as all
compounds in the series have the same functional group (functional groups are the 4 but-
reactive part)
5 pent-
o Successive members of a homologous series differ by a –CH2— group
 Members of a homologous series are represented by same formula. They are named by:
6 hex-
o Prefix: # Of carbon atoms in the longest chain
o Suffix: Homologous series to which the compound belongs

Homologous Series Description Formula Suffix

Alkanes Saturated hydrocarbons containing carbon-carbon single bonds 𝐶𝑛 𝐻2𝑛+2 -ane

Alkenes Unsaturated hydrocarbons containing carbon-carbon double bonds 𝐶𝑛 𝐻2𝑛 -ene

Alkynes Unsaturated hydrocarbons containing carbon-carbon triple bonds 𝐶𝑛 𝐻2𝑛−2 -yne

Organic compound classes
 Each class name contains a specific functional group which is a chemical group (small molecule) that determines the specific
chemical properties of a compound, which in turn determines the type of chemical reactions it undergoes
 This means that different compounds/classes in organic chemistry undergo characteristic reactions depending on the
functional groups they contain
o Functional groups are specific groups of atoms or bonds within molecules that are responsible for the characteristic
chemical reaction of those molecules
o A functional group is either named as a prefix or a suffix
 Example classes and functional groups include:

Class: Alkane Alkenes Alkynes

Functional Group: −𝐶 − 𝐶 − −𝐶 = 𝐶 − −𝐶 ≡ 𝐶 −

Suffix - ane - ene - yne

Class: Alcohols Aldehyde

Functional Group: −𝑂𝐻

Name/Suffix Hydroxyl - ol Aldehyde - al

Class: Amine Amide

Functional Group:

Name Amines Carboxyamide

Class: Ether Ester Nitrile

−𝐶 ≡ 𝑁
Functional Group: −𝑂 − 𝐶

Name Ether Ester Nitrile

Class Ketones Carboxylic Acid Arenes

Functional Group:

Name/Suffix Carbonyl - one Carboxyl Phenyl

Class Halogenoalkanes

Functional Group: −𝐹 −𝐶𝑙 −𝐵𝑟

Prefix Fluoro- Chloro- Bromo-

Structural Formulas of Organic Compounds
 Structural formulas can be represented in full and condensed format
o Full structural formula shows the molecular geometry of the molecule. All bonds must be shown
o Condense structural formula (aka semi-structural) omits all bonds and groups together
 Skeletal formula (stereochemical formula) shows carbon-to-carbon backbone without any hydrogen atoms, however will
show functional groups like Br2

Structural Isomers
 Structural Isomers: Compounds with the same molecular formula
but different arrangement of atoms
 Each isomer is a distinct compound having unique physical and
chemical properties

Primary, Secondary and tertiary carbon atoms

 A primary carbon atom is bonded to zero or one other carbon atom
 A secondary carbon atom is bonded to two other carbon atoms
 A tertiary carbon is bonded to three other carbon atoms

Primary Secondary Tertiary

 A
l
-
c
o
h
o
l
s

also follow the primary/secondary/tertiary nomenclature except instead of a hydroxyl group there will be a halogen
 Amines are named according to the number of carbons attached to nitrogen
o Primary secondary, and tertiary amines are nitrogen bound to one, two and three carbons, respectively
Nomenclature for organic compounds: IUPAC system
 Organic compounds are named according to the nomenclature of IUPAC
1. Find the longest continuous chain of carbon atoms to find the stem of the name:
o 1C: Meth
o 2C: Eth
o 3C: Prop
o 4C: But
o 5C: Pent
o 6C: Hex
2. Check for single, double, or triple bonds in the chain
o Single bonds: an
o Double bonds: en
o Triple bonds: yn
3. Check for function groups and add their prefix or suffix to the name
o Alkenes: ene/Alkyne: yne/Alcohol: ol/Ether: oxyalkane/Aldehyde: al/Ketone: one
o Carboxylic acid: oic acid/ Ester: oate/Amide: amide/Amine: amine/Nitrile: enetrile/Arene: Benzene
4. Add a number in fron tof the suffix or predix to indicate the position of the functional group
5. If more than one of the SAME functional group is present, use:
o Di for 2
o Tri for 3
o Tetra for 4

Benzene
 Benzene is an aromatic, unsaturated hydrocarbon with the molecular formula C6H6
o As it only contains carbon and hydrogen atoms, benzene is classed as a hydrocarbon
 The six carbon atoms are joined in a ring with one hydrogen atom attached to each
 Benzene derived products are known to be pleasantly fragrant
 So organic compounds containing benzene rings were classified as being “aromatic” and are called arenes
 The benzene functional group is described as a phenyl group and has the formula C6H5
 The 1:1 ratio of hydrogen to carbon in benzene indicates a high degree of unsaturation, greater than alkenes or alkynes
 Benzene has no isomers and is reluctant to undergo addition reactions
10.2 Functional group chemistry
10.2.1 Alkanes have low reactivity and undergo free-radical substitution reactions

10.2.2 Alkenes are more reactive than alkanes and undergo addition reactions

10.2.3 Bromine water can be used to distinguish between alkenes and alkanes

10.2.4 Alcohols undergo nucleophilic substitution reactions with acids (also called esterification or condensation) and undergo
oxidation reactions
10.2.5 Halogenoalkanes are more reactive than alkanes. They can undergo (nucleophilic) substitution reactions. A nucleophils is
an electron- rich species containing a lone pair that it donates to a electron –deficient carbon
10.2.6 Addition polymers consist of a wide range of monomers and form the basis of the plastics industry

10.2.7 Benzene does not readily undergo addition reactions but does undergo electrophilic substitution reactions

10.2.8 Writing equations for the complete and incomplete combustion of hydrocarbons

10.2.9 Explanation of the reaction of methane and ethane with halogens in terms of a free-radical substitution mechanism
involving photochemical hemolytic fission
10.2.10 Writing equations for the reactions of alkenes with hydrogen and halogens and of symmetrical alkenes with hydrogen
halides and water
10.2.11 Outline of the addition polymerization of alkenes

10.2.12 Relationship between the structure of the monomer to the polymer and repeating unit

10.2.13 Writing equations for the complete combustion of alcohols

10.2.14 Writing equations for the oxidation reactions of primary and secondary alcohols (using acidified potassium dichromate (VI)
or potassium manganite (VII) as oxidizing agents). Explanation of distillation and in the isolation of the aldehyde and
carboxylic acid products
10.2.15 Writing the equation for the condensation reaction of an alcohol with a carboxylic acid, in the presence of a catalyst (eg
concentrated sulfuric acid) to form an ester
10.2.16 Writing the equation for the substitution reactions of halogenoalkanes with aqueous sodium hydroxide

Homolytic and Heterolytic bond fission

 In homolytic bond fission, a covalent bond between two atoms in a molecule breaks with each atom taking one electron
from the bond
 Homolytic bond fission results in the formation of free radicals which are highly reactive species with unpaired electrons
 In heterolytic bond fission, a covalent bond between two atoms in a molecule breaks with one atom taking both bonding
electrons
 Heterolytic bond fission results in the formation of ions (cation and anion). The more electronegative atom usually takes
both bonding electrons

Benzene reactions
 The Kekulé structure of benzene consists of alternating carbon to carbon single and double bonds
 The actual structure of benzene is a resonance hybrid structure with equal bonds that are
intermediate in length and strength between a single and a double bond
 Benezene undergoes electrophilic substitution reactions in which a hydrogen atom is replaced by another group
o An electrophile is a species which is electron deficient (either a positive ion or has a positive charge)
 For instance benzene reacts with chlorine to form chlorobenzene (to the right)

Alkanes Reactions
 Alkanes undergo very few reactions as they are relatively unreactive
 This is because the C-H bond is a non-polar bond and the C-C and C-H are relatively strong
 The two types of reactions that alkanes undergo are combustion reactions and free radical substitution reactions

Combustion
 Complete combustion (in excess oxygen) of any hydrocarbon produces carbon dioxide and water
 Provided the combustion is complete, all hydrocarbons will burn with a blue flame
 However, the bigger the hydrocarbon, the more likely it will burn with a yellow, smoky flame (as it is more difficult to
completely combust)
 An incomplete combustion (lack of oxygen) can lead to the formation of carbon or carbon monoxide. I.e. the hydrogen in the
hydrocarbon reacts with the oxygen first, then the carbon gets to react with the rest
 Incomplete combustion produces carbon monoxide and water
o Carbon monoxide is produced as a colorless poisonous gas
o Carbon monoxide binds irreversibly (or very strongly) making a particular molecule of hemoglobin useless for
carrying oxygen
o If you breath in enough carbon monoxide you will die from a sort of internal suffocation
 The chemical equation for the complete combustion of alkanes is:
𝐶𝑥 𝐻𝑦 + 𝑂2 → 𝐶𝑂2 + 𝐻2 𝑂

 The chemical equation for incomplete combustion of alkanes is:

𝐶𝑥 𝐻𝑦 + 𝑂2 → 𝐶𝑂 + 𝐻2 𝑂

 A good technique to balancing these types of equations are to use CHOD (Carbon, Hydrogen, Oxygen, Double)

Example: Propane Combustion

With propane (C3H8), you can balance the carbons and hydrogens as you write the equation down. Balance alkanes,
carbon dioxide and water first. Then balance the oxygens:
𝐶3 𝐻3 + 5𝑂2 → 3𝐶𝑂2 + 4𝐻2 𝑂

 Hydrocarbons become harder to ignite as the molecules get bigger. This is because bigger molecules don’t vaporize so easily.
Furthermore, bigger molecules have greater Van der Waals attractions which makes it more difficult for them to break away
from their neighbors and turn to gas

Free radical substitution

 Alkanes undergo free radical substitution reactions
 In a substitution reaction, an atom or group of atoms is replaced by another atom or group
 The most common type of substitution reactions of alkanes involve halogenation
 Substitution reactions happen in which hydrogen atoms are replaced one by one by a halogen
 Unlike the complex transformations of combustion, the halogenation of an alkane appears to be a simple substitution
reaction in which a C-H bond is broken and a new C-X bond is formed
 Replacing hydrogen atoms in an alkane molecule with chlorine or bromine is called chlorination or bromination
 This type of reaction requires a catalyst to active the reaction usually in the form of UV light
 Free radicals are species with unpaired electrons which are represented by a dot
 We describe the substitution of a halogen by a sequence of steps known as a reaction mechanism. The three stages of the
mechanism are called initiation (known as photochemical homolytic fusion), propagation and termination
Initiation:
 Initiation occurs in the presence of UV light
 Photochemical homolytic fission then occurs where the
bond between the halogen (in this case Bromine) is broken
by UV light which produces two halogen radicals (two
bromine radicals)
 In initiation steps the number of free radicals increases
Propagation:
 In propagation these reactions keep the chain reaction going
o First the bromine free radical will then react with methane to produce a methyl radical and hydrogen bromide (the
hydrogen will bond with the bromine radical)
o Then the methyl radical (produced in the first propagation step) will react with a bromine molecule to produce
bromomethane and a bromine radical
o CH3Br can continue to react through similar propagation steps to form CH2Br2, CHBr3 and eventually CBr4
 In propagation the number of free radicals stays the same

Termination:
 Free radicals react with each other to form molecules. Since the radicals are
much more reactive than the molecules, the reaction stops when there are no
more radicals
 In termination steps the number of free radicals decreases

Tests for unsaturation

 Bromine water can be used to distinguish between an alkane and an alkene
o Bromine water has a distinctive brown color
 Alkenes are more reactive than alkanes due to their double carbon bond
 Alkenes react spontaneously with bromine water due to their unsaturated nature
o When alkenes come into contact with bromine water, they cause it to decolorize
o An addition reaction will take place and results with an alkane with two bromine functional groups
 Alkanes do not react with spontaneously bromine water due to their saturated nature
o When alkanes come into contact with bromine water, there is no color change

Alkene reactions
 Alkenes undergo electrophilic addition reactions in which two molecules combine to produce a larger molecule (which also
breaks the double bond). The types of reactions include:

Hydrogenation
 An alkene reacts with hydrogen to form an alkane
 The double C=C bond is broken and converted to a C-C single bond. The H2 then breaks open and attaches itself as two
individual H atoms to the carbon in the question
 Catalyst used in this reaction: Finely divided nickel
Hydration
 An alkene reacts with steam to form an alcohol
 The double C=C bond is broken and is converted into a C-C single bond
 H2O then breaks open and attaches itself as H and OH to the carbon atoms that are now open

 Catalyst used in this reaction: H2SO4

Halogenation
 Alkenes react with halogens to produce dihalogen compounds

Addition Polymerization:
 Addition polymers are formed when smaller unsaturated molecules (monomers) react together
o PVC or poly (vinyl chloride) is a polymer made from the monomer unit chloromethane (vinyl chloride)
o Poly (propene) is an additional polymers made from the monomer unit propene
o The polymerization of 2-methylpropene forms the polymer poly (2-methylpropene) or butyl rubber
 In addition polymerization, small monomers that contain a C=C double bond link together to form a longer polymer
 During the process the double bonds in the monomers are converted into single bonds in the polymer

Alcohol Reactions
 Alcohols are molecules containing the hydroxyl functional
group (-OH) that is bonded to the carbon
 The hydroxyl functional group strongly contributes to the
physical properties of alcohols. The hydroxyl group is polar so
increases the solubility of alcohol in water
 Chemical reactions in alcohols occur mainly at the functional
group, but some involve hydrogen atoms attached to the OH-
 Alcohols undergo three major kinds of alcohol reactions:

Oxidation
 Because a variety of oxidizing agents can bring about oxidation, the symbol [𝑂] above the arrow indicates an oxidizing agent
without specifying a particular one
 Oxidation reactions with alcohols are used to make aldehydes, ketones and carboxylic acids
 They can also be a way to distinguish between primary, secondary and tertiary alcohols
o Primary alcohols are oxidized to form aldehydes and can be oxidized again to form carboxylic acid
 o Secondary alcohols are oxidized to form ketones
o Tertiary alcohols are not readily oxidized
 The oxidizing agent used in these creations are normally a solution of potassium (VI) dichromate (K2Cr2O7)
Primary Alcohols:
 The oxidation of any primary alcohol is a two-step process that first produces an aldehyde which is then further oxidized to a
carboxylic acid
 The alcohol is heated under reflux with an excess of the oxidizing (put heat under arrow in equation) and using K2Cr2O7
 When the reaction is complete, the carboxylic acid is distilled off
 The full equation for the oxidation of a primary alcohols is (put heat under arrow in equation):
[𝑂]
𝑃𝑟𝑖𝑚𝑎𝑟𝑦 𝑎𝑙𝑐𝑜ℎ𝑜𝑙 → 𝐴𝑙𝑒ℎ𝑦𝑑𝑒
[𝑂]
→ 𝐶𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑖𝑐 𝐴𝑐𝑖𝑑

Secondary Alcohols:
 The oxidation of any secondary alcohol is a one-step process that produces a ketone. After ketone is produced, no further
oxidation is possible as the carbon atom of the ketone has no more hydrogen attached to it
 The equation for the oxidation of secondary alcohols is:
[𝑂]
𝑆𝑒𝑐𝑜𝑛𝑑𝑎𝑟𝑦 𝑎𝑙𝑐𝑜ℎ𝑜𝑙 → 𝐾𝑒𝑡𝑜𝑛𝑒
 During the second stage of the primary alcohol reaction, the oxygen was “slotted in” between the carbon and the hydrogen
in the aldehyde group to produce the carboxylic acid. In this case, there is no such hydrogen so the reaction has nowhere
further to go:

Tertiary Alcohols:
 Tertiary alcohols can't be oxidized since the carbon atom that holds the alcohol group has zero hydrogens attached to it

Example: Write the equation for the formation of ethanoic acid from ethanol

𝐻+/𝐶𝑟2𝑂7 2− 𝐻+/𝐶𝑟2 𝑂7 2−
𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3𝐶𝑂𝑂𝐻
ℎ𝑒𝑎𝑡 𝑟𝑒𝑓𝑙𝑢𝑥
Combustion
 Alcohols are flammable. They burn in air because of the presence of a hydrocarbon chain
 They burn to produce carbon dioxide and water. This property allows alcohols to be used as a fuel
 The chemical equation for combustion of alcohols is:
𝐶𝑥 𝐻𝑦 𝑂𝐻 + 𝑂2 → 𝐶𝑂2 + 𝐻2 𝑂

 A good technique to balancing these types of equations are to use CHOD (Carbon, Hydrogen, Oxygen, Double)

Example: Write an equation for the combustion of ethanol

𝐶2 𝐻5 𝑂𝐻 + 𝟑𝑂2 → 𝟐𝐶𝑂2 + 𝟑𝐻2 𝑂

Esterfication
 Esters are formed when carboxylic acids react with alcohols in the presence of sulfuric acid as a catalyst
 The name of esters is key to finding which specific alcohol and acid it has been made from:
o The alcohol is always named as an alkyl group
o The acid is always named as an alkanoate group
 For instance ethyl propanoate is made from an ethanol group and propaoic acid

Halogenalkane Reactions
 Halogenoalkanes contain an atom of fluorine, chlorine, bromine or iodine
 Halogenoalkanes are more reactive than alkanes and can undergo nucleophilic substitution reactions
 Halogenoalkanes undergo either substitution or elimination reactions depending on the type of halogenoalkane:
o Primary: Mainly substitution reactions
o Secondary: Both substitution and elimination
o Tertiary: Mainly elimination

Substitution nucleophilic reactions

Definitions

Substitution – Swapping a halogen atom for another atom or group of atoms

Nucleophile: An electron rich species that can donate a pair of electrons to form a covalent bond

 In a substitution reaction, the halogen atom is replaced by an –OH group to give an alcohol
 The halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide
o Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile
substances from the mixture
 Halogenoalkanes undergo substitution nucleophilic reactions (the replacement of one atom by another atom or group)
o The halogen is more electronegative than the carbon atoms forming a polar bond
o The halogen has a partial negative charge and the carbon has a partial negative charge and the carbon has a partial
positive charge (electron deficient)
 Nucleophiles are electron rich species that contain a lone pair of electrons that is donates to an electron deficient carbon
 Halogenoalkanes react with alkalis such as NaOH to form alcohols
 The hydroxide ion behaves as a nucleophile
 Elimination reactions
 Halogenoalkanes also undergo elimination reactions in the presence of sodium or potassium hydroxide
o Elimination: removal of small molecule (often water) from the organic molecule

20.1 Types of organic reactions

Nucleophilic Substitution Reactions:

20.1.1 SN1 represents a nucleophilic unimolecular substitution reaction and S N2 represents a nucleophilic bimolecular
substitution reaction
20.1.2 For tertiary halogenoalkanes the predominant mechanism is SN1 and for primary halogenoalkanes it is SN2. Both
mechanisms occur for secondary halogenoalkanes
20.1.3 The rate determining step (slow step) in an SN1 reaction depends only on the concentration of the halogenoalkane,
𝑟𝑎𝑡𝑒 = 𝑘[ℎ𝑎𝑙𝑜𝑔𝑒𝑛𝑜𝑎𝑙𝑘𝑎𝑛𝑒] For SN2, 𝑟𝑎𝑡𝑒 = 𝑘[ℎ𝑎𝑙𝑜𝑔𝑒𝑛𝑜𝑎𝑙𝑘𝑎𝑛𝑒][𝑛𝑢𝑐𝑙𝑒𝑜𝑝ℎ𝑖𝑙𝑒]. SN2 is stereospecific with an inversion
of configuration at the carbon
20.1.4 SN2 reactions are best conducted using aprotic, non-polar solvents and 2N1 reactions are best conducted using protic,
polar solvents
Electrophilic Addition Reactions:

20.1.5 An electrophile is an electron-deficient species that can accept electron pairs from a nucleophile. Electrophiles are Lewis
acids
20.1.6 Markovnikov’s rule can be applied to predict the major product in electrophilic addition reactions of unsymmetrical
alkenes with hydrogen halides and interhalogens. The formation of major product can be explained in terms of the relative
stability of possible carbon cations in the reaction mechanism
Electrophilic Substitution Reactions:

20.1.7 Benzene is the simplest aromatic hydrocarbon compound (or arene) and has a delocalized structure of 𝜋 bonds around its
ring. Each carbon to carbon bond has a bond order of 1.5. Benzene is susceptible to attack by electrophiles
Reduction Reactions:

20.1.8 Carboxylic acids can be reduced to primary alcohols (via the aldehyde). Ketones can be reduced to secondary alcohols.
Typical reducing agents are lithium aluminum hydride (used to reduce carboxylic acids) and sodium borohydride
Nucleophilic Substitution Reactions

20.1.9 Explanation of why hydroxide is a better nucleophile than water

20.1.10 Deduction of the mechanism of the nucleophile substitution reactions of halogenoalkanes with aqueous sodium hydroxide
in terms of SN1 and SN2 mechanisms. Explanation of how the rate depends on the identity of the halogen (ie the leaving
group), whether the halogenoalkane is primary, secondary or tertiary and the choice of solvent
20.1.11 Outline the difference between protic and aprotic solvents

Electrophilic Addition Reactions

20.1.12 Deduction of the mechanism of the electrophilic addition reactions of alkenes with halogens/interhalogens and hydrogen
halides
Electrophilic Substitution Reactions:

20.1.13 Deduction of the mechanism of the nitration (electrophilic substitution) reaction of benzene (using a mixture of
concentrated nitric acid and sulfuric acid)
Reduction Reactions:

20.1.14 Writing reduction reactions of carbonyl containing compounds: aldehydes and ketones to primary and secondary alcohols
and carboxylic acids to aldehydes, using suitable reducing agents.
20.1.15 Conversion of nitrobenzene to phenylamine via a two-stage reaction.
 Definitions

Nucleophile: An electron rich species that can donate a pair of electrons to form a covalent bond (Acts like a Lewis
base). i.e. they are strongly attracted to a region of positive charge. OH- is a better nucleophile than H2O because it
has a negative charge whilst the water molecular only has a dipole. Therefore it is more attracted
Leaving group – A substituent which easily withdraws its bonding electrons to form a separate, stable species

Nucleophilic Substitution Reactions

 There are two major classes of nucleophilic substitution reactions: SN1 and SN2

 This can be thought of like cats. Cat #1 finds Cat #2 on his comfy chair and wants to sit. He has two option:
o He can wait for Cat #2 to leave, and then sit in the comfy chair
o Or he can be a bitch and kick Cat #2 out of the comfy chair
 Situation 1 resembles SN1 reactions, and Situation 2 represents SN2 reactions. The chair is the solvent, Cat #1 is nucleophile
 In the substitution reaction where the halogen is substituted, the halogen is referred to as the leaving group (Cat #2)
 Halogenoalkanes undergo nucleophilic substitution reactions as the bond between the carbon atoms and the halogen is
polar as the halogen is highly electronegative giving the carbon atoms a partial positive charge

SN1: Nucleophilic unimolecular substitution reaction

 SN1 is a two step reaction that involves the formation of a carbocation intermediate
 As SN1 reaction initiates, the leaving group will depart from the substrate, and in doing so creates a stable intermediate
 However, soon after the nucleophile will attack and bond to the intermediate which results in the final product
 Note there is a complete loss of stereochemistry as the nucleophile can bond anywhere
 The reaction is unimolecular. The rate determining step depends on the concentration of the leaving group only
 Tertiary halogenoalkanes undergo SN1 reactions (so replace leaving group with the halogen name when explaining)
 Some factors favoring SN1 reactions include:
o Weak nucleophiles
o More substitute substrates
o Better leading groups
o Solvent charge

SN2: Nucleophilic biomolecular substitution reaction

 SN2 is a one step reaction that involves the formation of an unstable transition state
 The nucleophile will first attack the opposite side of the leaving group, despite the leaving group haven’t not departed yet
 An unstable transition state is then formed in which the carbon is weakly bonded to the leaving group and the nucleophile
 The carbon to the leaving group breaks heterolytically and the leaving group departs
 The backside attack causes an inversion of stereochemistry
  The rate is bimolecular. The rate determining step (slow step) depends on both the concentration of the leaving group and
the nucleophile
 Primary halogenoalkanes undergo SN2 reactions (so replace leaving group with the halogen name when explaining)
 Some factors favoring SN2 reactions:
o Good nucleophiles
o Less substituted substrates
o Poor leaving groups

SN1 SN2

Mechanism Two step mechanism Single connected step

First order kinetics Second order kinetics:

Kinetics
𝑟𝑎𝑡𝑒 = 𝑘[𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝑔𝑟𝑜𝑢𝑝] 𝑟𝑎𝑡𝑒 = 𝑘[𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝑔𝑟𝑜𝑢𝑝][𝑛𝑢𝑐𝑙𝑒𝑜𝑝ℎ𝑖𝑙𝑒]

Stereochemistry Loss of stereochemistry Sterochemical inversion

Nucleophile* Weak Strong

Substrate* Highly substituted Less substituted

Leaving group* Good Poor

*Favorable conditions

Choice of solvent
 A protic solvent is one in which there is a hydrogen atom attached to an oxygen or nitrogen atom and that is capable of
being donated
 Polar, protic solvents are preferred for SN1 reactions
 Examples of commonly used protic solvents include: water, methanol, ethanol, methanoic acid and ethanoic acid
 An aprotic solvent is one which does not possess a hydrogen atom that is capable of being donated. Aprotic solvents can be
polar or non-polar. Common examples include: propanone and ethyl ethanoate (both polar) as well as hexane and benzene
(non-polar) Polar, protic solvents are preferred for SN1 reactions
 Non-polar, aprotic solvents are preferred for SN2 reactions

Electrophilic addition reactions

Definitions

Electrophile: An electron deficient species that can accept an electron pair to form a new covalent bond (Acts like a
Lewis Acid)

 An addition reaction is a reaction in which two molecules join together to make a bigger one
 Nothing is lost in the process and all the atoms in the original molecules are found in the bigger one
 An electrophilic addition reaction is an addition reaction where a molecule with a region of high electron density is attacked
by something carrying some degree of positive charge
 Electrophilic addition reactions involves any alkane with molecules such as
halogens or hydrogen halides
 The δ+ hydrogen atom of H-Br is attracted towards the C=C in ethene. The two electrons from the π -bond in the C=C attack
the hydrogen atom and, at the same time, the H−Br bond breaks to form a bromide ion
 A lone pair of electrons on the bromide ion attacks the positively-charged carbon atom on the carbocation intermediate
forming a coordinate bond
 The correct drawing for the mechanism includes curly arrows and lone pairs of electrons

Markovnikov’s Rule
 Markovnikov’s rule helps to determine which atoms in an electrophile join to which of the two carbon atoms in a C=C

 As you can see the hydrogen and bromine can be bonded to two different spots (as shown by major and minor)
 To decide which one bonds where remember “the hydrogen rich get richer”
 In other words the carbon with the more hydrogen will gain more hydrogen
 Major is used to describe the more likely structure
 Markovnikov’s rule only applies to asymmetrical alkenes where two products are possible (does not apply to ethene)

Nitration of benzene
 Benzene reacts with a mixture of concentrated nitric acid (HNO3) and concentrated sulfuric acid (H2SO4) to form
nitrobenzene (C6H5NO2) and water
𝐶6 𝐻6 + 𝐻𝑁𝑂3 → 𝐶6 𝐻5 𝑁𝑂2 + 𝐻2 𝑂
 This reaction requires a H2SO4 catalyst, and roughly 55°C
 The nitration of benzene involves the electrophilic substitution mechanism:
o A pair of electrons from the π -system attacks the NO2+ electrophile forming a coordinate bond and destroying the
delocalization
o The HSO4− ion acts as a base, pulling off a hydrogen atom and reforming sulfuric acid
o The C−H bond breaks and the two electrons reform the delocalized π -system

o The C−H bond breaks and the two electrons reform the delocalized π -system.

Reduction of carbonyl compounds

 The carbon to oxygen bond is a polar bond because of the difference in electronegativity between carbon and oxygen
 Primary and secondary alcohols can be oxidized to aldehydes, ketones, or carboxylic acids depending on the conditions
 These oxidation reactions can be reversed by using a suitable reducing agent
o Sodium borohydride (NaBH4) in aqueous or alcoholic solution (protic solvents)
o Lithium aluminum hydride (LiAlH4) in anhydrous conditions such as dry ether (aprotic solvent). The reaction is then
acidified to obtain the product
o Both these reagents produce the hydride ion (H-) which acts as a reducing agent undergoing a nucleophilic addition
reaction with the electron deficient carbon atom of the carbonyl group
 Reduction reactions
 Nitrobenzene can be reduced to phenylamine in a two stage reaction
o Nitrobenzene is reacted with Sn and concentrated HCl (heat under reflux in a boiling water bath). The product is the
phenylammonium ion
o The C6H5NH3+ is reacted with NaOH to remove the hydrogen ion (H+) and produce phenylamine

20.2 Synthetic routes

20.2.1 The synthesis of an organic compound stems from a readily available starting material via a series of discrete steps.
Functional group interconversions are the basis of such synthetic routes
20.2.2 Retro-synthesis of organic compounds

20.2.3 Deduction of multi=step synthetic routes given starting reagents and the products (s)

Reaction pathways
 Read up: https://prezi.com/gxhp4xojcjci/ib-chemistry-organic-reaction-pathways/

Retro-Synthesis
 Retro-synthesis involves planning a synthesis backwards, by starting at the product, and taking it back one step at a time to
simple, available starting materials

20.3 Stereoisomerism
10.2.1 Stereoisomers are subdivided into two classes – conformational isomers, which interconvert by rotation about a 𝜎 bond
and configurational isomers that interconvert only by breaking and reforming a bond
Configurational isomers are further subdivided into cis=trans and E/Z isomers and optical isomers
10.2.2 Cis-trans isomers can occur in alkenes or cycloalkanes (or heteroanalogues) and differ in the position of atoms (or groups)
relative to a reference plane. According to IUPAC, E/Z isomers refer to alkenes of the form 𝑅1𝑅2𝐶 = 𝐶𝑅3𝑅4 (𝑅1 ≠
𝑅3, 𝑅3 ≠ 𝑅4 where neither R1 nor R2 need be different from R3 or R4
10.2.3 A chiral carbon is a carbon joined to four different atoms or groups

10.2.4 An optically active compound can rotate the plane of polarized light as it passes through a solution of the compound.
Optical isomers are enantiomers. Enantiomers are non-superimposeable mirror images of each other. Diastereomers are
not mirror images of each other.
10.2.5 A racemic mixture (or racemate) is a mixture of two enantiomers in equal amounts and is optically inactive
10.2.6 Construction of 3-D models of a wide range of stereoisomers
10.2.7 Explanation of stereoisomerism in non-cyclic alkenes and C3 and C4 cycloalkanes
10.2.8 Comparison between the physical and chemical properties of enantiomers
10.2.9 Description and chemical properties of enantiomers
10.2.10 Distinction between optical isomers using a polarimeter

Isomerism
 An isomer of a molecular is a molecule with the same molecular formula but a different structural or spatial arrangement of
atoms. This variation can lead to difference in physical or chemical properties
 Isomers can be split into two broad groups: structural isomers, and stereoisomers

Structural Isomerism
 Structural isomers have their atoms and functional groups attached in different ways
 Structural isomers can be split again into three main subgroups:

Chain isomers
 Chain isomers are molecules with the same molecular formula, but different arrangements of the carbon “skeleton”
 Organic molecules are based on chains or carbon atoms, and for many molecules this chain can be arranged differently:
either as one continuous chain, or a chain with multiple side groups of carbons branching off
 The name of the molecules can be changed to reflect this

Position isomers
 Position isomers are based on the movement of a “functional group” in the molecule
 Remember a functional group is the part of a molecule that gives it its reactivity
 Nothing else about the molecule changes, simply where the functional group in it is, and the name

Functional Isomers
 Also referred to as functional group isomers, these are isomers where the molecular formula remains the same, but the type
of functional group in the atom is changed. This is possible by rearranging the atoms within the molecule so that they’re
bonded together in different ways

Stereoisomerism
 Stereoisomerism have different spatial arrangement of atoms
 There are two types of stereoisomerism: Geometric isomerism, and optical isomerism
Geometric isomerism

Conformational isomerism: Interconvert by rotation around the sigma bond

 This type of isomerism most frequently involves carbon double bonds
 This means that the rotation of these bonds is restricted, compared to single bonds, which can rotate freely
 In other words if there are two different atoms, or groups of atoms, they can be arranged in different ways to give different
molecules

Configurational isomerism: Interconvert only by breaking a bond

 Optical isomers are so named due to their effect on plane-polarized light and come in pairs
 They usually (although not always) contain a chiral center, which is a carbon atom, with four different atoms attached to it
 These atoms or groups can be arranged differently around the central carbon in such as a way that the molecule can’t be
rotated to make the two arrangements align. This is referred to as “non-superimposable mirror images” where one of the
isomers is the mirror image of the other
Cis-trans isomerism:
 Cis-trans isomerism occurs when there is restricted rotation around a bond either because of a double bond or as a result of
the ring structure in a cyclic molecule
 Cycloalkanes contain a ring structure that restricts rotation. When the molecule contains two or more different groups
attached to the ring, two different isomers are formed
o Cis isomers have the same groups on the same side of the double bond/ring
o Trans isomers have the same groups on opposite sides of the double bonds/ring
E/Z/ Isomerism
 A chiral carbon is a carbon atom bonded to four different atoms or groups
Optical isomerism
 A chiral carbon is a carbon atom bonded to four different atoms or groups
 Mirror images are non-superimposable and are known as enantiomers
 Diastereomers are stereoisomers that are non-superimposable but not mirror images
 Ordinary light consists of waves that vibrate in all planes perpendicular to its direction of travel
 Plane-polarized light consists of waves vibrating in one plane only
Topic 11: Measurement and data processing
11.1 Uncertainties and errors in measurements and results
10.1.1 Qualitative data includes all non-numerical information obtained from observations not from measurements

10.1.2 Qualitative data are obtained from measurements, and are always associated with random errors/uncertainties,
determined by the apparatus, and by human limitations such as reaction times
10.1.3 Propagation of random errors in data processing shows the impact of the uncertainties on the final result

10.1.4 Experimental design and procedure usually lead to systematic errors in measurement, which cause a deviation in a
particular direction
10.1.5 Repeat trials and measurements will reduce random errors but not systematic errors

10.1.6 Distinction between random errors and systematic errors

10.1.7 Record uncertainties in all measurements as a range (±) to an appropriate precision

10.1.8 Discussion of ways to reduce uncertainties in an experiment

10.1.9 Propagation of uncertainties in processed data, including the use of percentage uncertainties

10.1.10 Discussion of systematic errors in all experimental work, their impact on the results and how they can be reduced

10.1.11 Estimation of whether a particular source of error is likely to have a major or minor effect on the final result

10.1.12 Calculations of percentage error when the experimental result can be compared with a theoretical or accepted results

10.1.13 Distinction between accuracy and precision in evaluating results

Quantitative and Qualitative Data

 Quantitative data is data taken from measurements made in the laboratory and is associated with random errors
 Qualitative data includes non-numerical data obtained from observations, not from measurements
 A results table should include quantitative data with units and uncertainties
 Quantitative data should be recorded to the appropriate precision
 Qualitative data should also be recorded

Absolute and Percentage uncertainties

 The absolute uncertainty of digital apparatus is ± the smallest scale division
𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑈𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 = × 100%
𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑚𝑒𝑛𝑡
 Absolute uncertainty of mass balance is ±0.01g
 Absolute uncertainty of analog apparatus is ± half the smallest scale division
o Absolute uncertainty of measuring cylinder is ±0.5cm3
 Absolute uncertainty of burette is ±0.05cm3

Random Errors
 Random errors are caused by unpredictable changes in the experiment (in the conditions or apparatus)
 With random errors, there is an equal probability of the measured value being too high or too low
 Examples of random error:
o Changes in the environment during the experiment (such as a change in the room temperature)
o Observer misinterpreting the reading
o Insufficient data (not conducting repeat trials)
 Random errors cannot be eliminated but can be reduced by conducting repeat trials
 They can also be reduced by using precise apparatus (such as a volumetric pipette rather than a beaker to measure volume)
 Systematic Errors
 Systematic errors occur as a result of a flaw in the experimental design of apparatus
 Systematic errors cause the measured value to be consistently higher or lower than the actual value
 They cannot be reduced by conducting repeat trials
 Examples of systematic error:
o Heat loss in an experiment to measure enthal py change
o Losing a product (such as a gas) in a reaction
o Overshooting the endpoint in a titration
o Reading from the top of the meniscus when measuring volume
o Forgetting to zero a mass balance

Percentage error
 Percentage error is a measure of how close the experimental value is to the theoretical or accepted value
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 − 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝐸𝑟𝑟𝑜𝑟 = × 100%
𝑇ℎ𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒
 If the experimental value is less than the theoretical value, the percentage error will be negative

11.3 Spectroscopic identification of organic compounds

10.1.1 The degree of unsaturation or index hydrogen deficiency (IHD) can be used to determine from a molecular formula the
number of rings or multiple bonds in a molecule
1
10.1.2 Mass spectrometry (MS), proton nuclear magnetic resonance spectroscopy ( H NMR) and infrared spectroscopy (IR) are
techniques that can be used to help identify compounds and to determine their structure
10.1.3 Determination of the IHD from a molecular formula
1
10.1.4 Deduction of information about the structural features of a compound from percentage composition data, MS, H NMR or
IR

Index of Hydrogen Deficiency (IHD)

 The index of hydrogen deficiency (IHD) is a count of how many molecules of H2 need to be added to convert the molecule to
the corresponding, saturated, non-cyclic molecule. In other words a degree of unsaturation
 The IHD for a hydrocarbon with 𝑥 carbon atoms and 𝑦 hydrogen atoms:
(2𝑥 + 2 − 𝑦)
𝐼𝐻𝐷 = × 100%
2
 Note:
o Sulfur and oxygen do not affect IHD
o Halogens (F, Cl, Br and I) are treated like H atoms
o For each nitrogen atom, add one to the number of carbon and hydrogen atoms
 By calculating the IHD, we can tell from the molecular formula how many multiple bonds and rings are present in the
molecule. For compounds that contain other atoms other than hydrogen:

IHD Multiple bonds/rings present in molecule

0 Single bonds

1 Double bond/Ring structure

2 Triple bond
Infrared Spectroscopy
 When molecules absorb energy in the IR region of the electromagnetic spectrum, it causes the bonds between the atoms to
vibrate (the bonds stretch and bend)
 The frequency of IR radiation that is absorbed is measured as the number of waves per centimeter
 The fingerprint region can be used to identity an unknown
compound by comparing with the IR spectra of known compounds
 However a bond will only interact with IR radiation if it is a polar
covalent bond (non-polar bonds do not absorb IR radiation)
 The intensity depends on the dipole moment of the bond:
o Strongly polar bonds produce strong bands
o Bonds with medium polarity produce medium bands
 Note IR is not generally used to determine the whole structure of an
unknown molecule
 In order to analyze IR graph we need to look for:
o Tongue: A broad, rounded peak in the region
o Swords: These peaks are almost always the strongest peaks in the entire spectrum and are relatively narrow, giving
them a somewhat “sword-like” appearance
 Once we have identified our “tongue” and our “swords” compare the wavelength value to the value in Table 26
 Note that the graph can be divided up into a functional group region, and the fingerprint region. The fingerprint region is
located on the right while the functional group region is located on the left and involves the tongue

Mass Spectrometry
 While mass spectrometry is used to determine the relative atomic mass (Ar) of an
element it can also be used to determine the structure of a compound
 Inside the mass spectrometer, some of the molecular ions break down to produce
fragments
 A fragmentation pattern is produced which gives useful information about the structure
of the compound
 When determining the structure of a compound don’t use the mass/charge (m/z) value
 Instead take the largest value and subtract every other value from it

1
H NMR: Proton nuclear magnetic resonance spectroscopy
 NMR or nuclear magnetic resonance spectroscopy is a technique used to determine a compound’s unique structure
 The position of the NMR signal is measured relative to the signal produced by TMS tetramethylsilane
 The chemical shift is measured relative to the point 0
 If there are two of the same group (two CH3 groups), look at the groups of atoms that those groups are bonded to, if they
are the same then the protons are in the same chemical environment, if not they are in different chemical environments
 First look at:
o Number of hydrogen types
o Peaks
o Neighbors
o Cause of shift
Option B: Biochemistry
B.1 Introduction to biochemistry
B.1.1 The diverse functions of biological molecules depend on their structures and shapes
B.1.2 Metabolic reactions take place in highly controlled aqueous environments

B.1.3 Reactions of breakdown are called catabolism and reactions of synthesis are called anabolism

B.1.4 Biopolymers form by condensation reactions and are broken down by hydrolysis reactions
B.1.5 Photosynthesis is the synthesis of energy-rich molecules from carbon dioxide and water using light energy
B.1.6 Respiration is a complex set of metabolic processes providing energy for cells
B.1.7 Explanation of the difference between condensation and hydrolysis reactions
B.1.8 The use of summary equations of photosynthesis and respiration to explain the potential balancing of oxygen and carbon
dioxide in the atmosphere

Biochemistry
 Biochemistry: The study of chemical process in living matter
 Biochemical processes are known as metabolism
 Metabolism: The sum of the chemical reactions occurring in an organism
 Metabolic reactions take place in highly controlled aqueous environments
 Metabolic reactions can classified be anabolic or catabolic

Definitions

Anabolism – The synthesis of complex molecules from simpler units, it requires energy (endothermic)
Catabolism – The breakdown of complex molecules into simpler units, it releases energy (exothermic)

Formation of polymers
 The functions of biological molecules depend on their shapes and structures.
 Biopolymers are commonly made of smaller, recurring sub units called monomers
 Biological polymers form by condensation reactions in which monomers react to form a polymer. This releases water
 Biological polymers are broken down by hydrolysis reactions in which a polymer breaks up into separate monomers. This
requires water

Photosynthesis and Respiration

 Photosynthesis: The synthesis of energy rich molecules (like glucose) from carbon dioxide and water using light energy
 Photosynthesis Equation: 6CO2 + 6H2O → C6H12O6 + 6O2
 Photosynthesis is an anabolic process as photosynthesis takes CO2 and H2O (somewhat low energy molecules), and then
assembles them into glucose. During photosynthesis oxygen is released
 Cell respiration: The controlled release of energy from organic compounds to produce ATP
 Respiration is a catabolic process because it breakdown small molecules. Respiration takes place in all living cells all the time.
o Anaerobic respiration need oxygen molecules as reactants
o Aerobic respiration does not need oxygen molecules as reactants
 Respiration Equation: C6H12O6 + 6O2 → 6CO2 + 6H2O
 Respiration Half Equation: C6H12O6 + 6H2O → 6CO2 + 24H+ + 24e-
6O2 + 24H+ + 24e- → 12H2O
 Anaerobic respiration:
o In yeast: C6H12O6 → 2C2H5OH + 2CO2 (Glucose → Ethanol + CO2)
o In animals: C6H12O6 → 2C3H6O3 (Glucose → Lactic Acid)
B.2 Proteins and enzymes
B.2.1 Proteins are polymers of 2-amino acids, joined by amide links (also known as peptide bonds)
B.2.2 Amino acids are amphoteric and can exist as zwitterions, cations and anions
B.2.3 Protein structures are diverse and are described at the primary, secondary, tertiary and quaternary levels
B.2.4 A protein’s three-dimensional shape determines its role in structural components or in metabolic processes
B.2.5 Most enzymes are proteins that act as catalysts by binding specifically to a substrate at the active site
B.2.6 As enzyme activity depends on the conformation, it is sensitive to changes in temperature and pH and the presence of
heavy metal ions
B.2.7 Chromatography separation is based on different physical and chemical principles
B.2.8 Deduction of the structural formulas of reactants and products in condensation reactions of amino acids, and hydrolysis
reactions of peptides
B.2.9 Explanation of the solubility’s and melting points of amino acids in terms of zwitterions
B.2.10 Application of the relationships between charge, pH and isoelectric point for amino acids and proteins
B.2.11 Description of the four levels of protein structure, including the origin and types of bonds and interactions involved
B.2.12 Deduction and interpretation of graphs of enzyme activity involving changes in substrate concentration, pH and
temperature
B.2.13 Explanation of the processes of paper chromatography and gel electrophoresis in amino acid and protein separation and
identification

Proteins
 Proteins are found in every cell and are fundamental to cell structure and operation
 Proteins are polymers built up from small monomer molecules called amino acids
 All amino acids have the alpha carbon bonded to a hydrogen atom (H), carboxyl
group (COOH), and amino group (NH2)
 The "R" group varies among amino acids
 2-amino acids are proteins that specifically have a NH2 and COOH bonded to the
same carbon atoms
 Formula of 2-amino acids: RCH(NH2)COOH

Functions of proteins in the body

1. Structural: collagen
2. Transportation: hemoglobin
3. Enzymes: biological catalysts
4. Protection: antibodies

Amino Acids Characteristics

 Amino acids are also amphoteric (so amphiprotic). They can act as a Brønsted –
Lowery acid or base by donating a proton or accepting a proton
 This also means that an ion can be formed that has both a negative and positive
charge. This is called a zwitterion
 Zwitterion: A molecule having separate positively and negatively charged groups
 Since zwitterions contains both positive and negative charges they will cancel each
other out and the overall charge will be neutral
 The isoelectric point of an amino acid is the pH that the amino acid will exist as a zwitterion
 A low pH has an acidic environment so there will be many H+ so the NH2 becomes N+H3. It becomes protonated
 A high pH has a basic environment so there will be many OH- so the COOH becomes COO-. It becomes deprotonated
 Amino acids at a lower pH than its isoelectric point can be described as a cation
 Amino acids at a higher pH than its isoelectric point can also be described as an anion
Peptide bonds/Amide Link
 Amino acids are linked together in proteins by a special kind of covalent bond known as a
peptide bond or amide link
 Peptide bonds are formed by condensation reactions. H2O is also released
 This bond occurs between a carboxyl group (COOH) on one molecule, and an amino
group (NH2) on another molecule
 Polypeptide chains can be broken down via hydrolysis reactions, which requires water to
reverse the process

Peptides
 Molecules made from amino acids are called peptides
o A dipeptide is formed when 2 amino acids join together to form a peptide chain
o An oligopeptide is formed when 3-10 amino acids join together
o A polypeptide is formed by many amino acids (>10)
 Polypeptides built with more than 50 amino acids are called proteins
 Polypeptides differ from one another by their length, number of amino acids and order of amino acids
 The amino acid sequence is what gives each polypeptide its unique properties

Protein Structure
 There are 4 levels of protein structure. These structures determine the function and shape of a protein

Primary Structure
 The primary structure refers to the sequence of amino acids in the polypeptide chain
 The primary structure is held together by peptide bonds (amide links)
 The sequence of a protein is unique to that protein, and defines the structure and function of the protein

Secondary structure
 The secondary structure of a protein refers to the folding of the polypeptide as a result of hydrogen bonding
 The folding can be either:
o α-helix in which the protein twists in a spiraling manner rather like a coiled spring
o β-pleated to give a sheet-like structure.
 Hydrogen bonds form between one of the lone oxygen atom and the hydrogen attached to a nitrogen atom (between
amine and carboxylic groups)
Tertiary Structure
 The tertiary structure of a protein refers to the overall twisting and folding of the
secondary structure to form a specific 3D shape
 The tertiary structure of a protein is held together by interactions between the
side chains (The R groups)
 These interactions are:
o Hydrogen bonds
o Ionic interactions
o Dispersion forces
o Disulfide links (sulfur bridges)
 Some side groups present on the amino acid chain are capable of forming bonds
with side groups elsewhere on the protein chain. As a result, sections of the chains
may be folded back on each other in intricate and unique shapes

Quaternary Structure
 The quaternary structure of proteins refers to the interactions between polypeptide chains
 The bonding is the same as tertiary bonding
 An example is hemoglobin that has a quaternary structure composed of four polypeptide chains

Fibrous and Globular Proteins

 Fibrous proteins are elongated molecules with a well-defined secondary structure
o Fibrous proteins have cross-linking at intervals to form long fibers or sheets
 Globular proteins are spherical molecules and have a well-defined tertiary structure
o Globular proteins are usually soluble to some extent in water as the hydrophobic side tends to be in the center

Properties Fibrous Proteins Globular Proteins

Shape Long and narrow Rounded/Spherical

Role Structural (strength and support) Functional (Catalysts and transport)

Solubility in water Insoluble in water Soluble in water

Sequence of amino acids Repetitive amino acid sequence Irregular amino acid sequence

Less sensitive to changes in heat and More sensitive to changes in heat

Stability
pH and pH

Examples: Collagen, keratin Hemoglobin, insulin, catalase

Summary:
Gel Electrophoresis
 Gel electrophoresis is technique used to separate mixtures of DNA, RNA or proteins according to molecular size
 The steps are as follows:
1. A solution of the sample is placed in a well-cut block of special gel
2. Positive and negative electrodes are connected to opposite ends of the gel, causing the ions in the sample to migrate
towards the oppositely charged electrode
3. When connected to a circuit, the amino acids move according to their electrical charge
 As previously mentioned, gel electrophoresis involves an electrical field. This field is applied such that one end of the gel has
a positive charge and the other end has a negative charge. Because DNA and RNA are negatively charged molecules, they will
be pulled towards the positively charged end of the gel
 However, proteins are not negatively charged, thus they must be mixed in a
detergent called sodium dodecyl sulfate
 After the DNA, RNA or protein molecules have been separated using gel
electrophoresis, bands representing molecules of different sizes can be detected
 The separated components are made visible by using various methods including
o Adding a dye that binds to them and fluoresces (glows) in UV light
o Adding radioactive probes that bind to them; the radiation is then used
to expose a photographic plate
o Shining lasers onto fragments that have a fluorescent dye incorporated
into their structure

Paper Electrophoresis
 Paper electrophoresis is similar to gel electrophoresis, but instead the mixture is placed on the middle of a paper

 When the pH is equal to their isoelectric point, amino acids will not move as they carry no net charge
 An amino acid is negatively charged when it’s isoelectric point is below the pH, therefore the amino acids exist as anions and
move to the positive charged size (generally the anode)
 An amino acid is positively charged when it’s isoelectric point is above the pH, therefore the amino acids exist as cations and
move to the negative charged size (generally the cathode)

Paper chromatography
 Paper chromatography can also be used to separate a mixture of amino acids
 The amino acids all differ in their ability to dissolve in the solvent (the mobile phase) and also in their ability to bind to the
stationary phase. Therefore, they will move up at different rates and reach different heights. Ninhydrin is often used as
locating agent to make the spots visible
 The amino acids can now be identified by comparing the Rf values or to pure
samples run under the same conditions
 The Rf values can be determined with the formula:
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑚𝑜𝑣𝑒𝑑 𝑓𝑟𝑜𝑚 𝑜𝑟𝑖𝑔𝑖𝑛 𝑏𝑦 𝑎𝑚𝑖𝑛𝑜 𝑎𝑐𝑖𝑑
𝑅𝑓 =
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑚𝑜𝑣𝑒𝑑 𝑏𝑦 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑓𝑟𝑜𝑚 𝑜𝑟𝑖𝑔𝑖𝑛
 Rf is always less than or equal to 1 and has no units
Enzymes
 Enzymes are globular proteins that act as biological catalysts, increasing
reaction rates of biological processes without being used up in the process
 Enzymes control the manufacture of complex substances, such as skin and
blood as well as the breaking down of chemicals to provide energy
 Compared with inorganic catalysts enzymes:
o Produce much faster reaction rates
o Operate under much milder conditions
o More sensitive and selective
o Can become denatured at high temperatures
 The active site of an enzyme is usually a flexible hollow or cavity within the molecule
 The induced-fit model is a theory that says the active site will change shape to enfold a substrate molecule
 A reactant molecule, known as the substrate is maneuvered into the site and it is there at the surface of the enzyme that the
reaction takes place
1. The reactant (substrate) enters the active site
2. Bonds formed between the enzyme and substrate weaken
lowering the reaction’s activation energy
3. The substrate breaks or rearranges into new products and these
products are released
 The selectivity of enzymes is one of their most important features
 It happens because the shape and functional groups in the active site of the enzyme allow it to bind only with certain
substrates. This is known as the Key and Lock model (however it is outdated)
 4 types of active site and substrate interaction
o Hydrogen bonding
o Ionic interactions
o Ion-dipole
o Dispersion force
 Characteristics of enzymes: biological catalysts, made of proteins, very specific, affected by change in pH and temperature

Denaturation
 The catalytic activity of an enzyme depends on its tertiary structure. A slight change in its three-dimensional shape can
render an enzyme inoperative as if the structure is disrupted, the substrate can no longer bind to the active site
 Loss of tertiary structure is known as denaturation (irreversible). It can be caused by:

Temperature
 Increasing temperature also increases enzyme activity at around double for every 10°C
 This is because collisions between substrate and active site happen more frequently at higher
temperatures due to faster molecular motion
 However, at high temperature the enzymes will become denatured and stop working. This is
because the heat causes vibrations inside the enzymes which break bonds needed to maintain
the structure of the enzyme

pH levels
 Increasing pH increases enzyme activity to an optimum point. Increasing pH beyond this optimum
point will reduce enzyme activity as about a certain pH the alkalinity denatures the enzyme so it
can’t catalyze the reaction at all

Heavy metal ions

 Heavy metals can poison enzymes by reacting with -SH groups replacing the hydrogen atom with a heavy metal atom or ion
so that the tertiary structure is altered
 Concentration
 Increasing substrate concentration increases enzyme activity. This is because random collisions
between substrate and active site happens more frequently with higher substrate
concentrations
 However, at high substrate concentrations the active site of the enzyme is saturated therefore
raising the substrate concentration has little effect on enzyme activity

B.3 Lipids
B.3.1 Fats are more reduced than carbohydrates and so yield more energy when oxidized
B.3.2 Triglycerides are produced by condensation of glycerol with three fatty acids and contain ester links. Fatty acids can be
saturated, monounsaturated or polyunsaturated
B.3.3 Phospholipids are derivatives of triglycerides
B.3.4 Hydrolysis of triglycerides and phospholipids can occur using enzymes or in alkaline or acidic conditions
B.3.5 Steroids have a characteristic fused ring structure, known as a steroidal backbone
B.3.6 Lipids act as structural components of cell membranes, in energy storage, thermal and electrical insulation, as transporters
of lipid soluble vitamins and as hormones
B.3.7 Deduction of the structural formulas of reactants and products in condensation and hydrolysis reactions between glycerol
and fatty acids and/or phosphate
B.3.8 Prediction of the relative melting points of fats and oils from their structures
B.3.9 Comparison of the processes of hydrolytic and oxidative rancidity in fats with respect to the site of reactivity in the
molecules and the conditions that favor the reaction
B.3310 Application of the concept of iodine number to determine the unsaturation of a fat
B.3.11 Comparison of carbohydrates and lipids as energy storage molecules with respect to their solubility and energy density
B.3.12 Discussion of the impact of lipids on health, including the roles of dietary high density lipoprotein (HDL) and low-density
lipoprotein (LDL) cholesterol, saturated, unsaturated, and trans-fat and the use and abuse of steroids

Types of fatty acids

 Fatty acids are key components of lipids, in plants, animals and microorganisms
 Fatty acids consist of a straight chain of an even number of carbon atoms, with hydrogen atoms
 Fatty acids all have a methyl group (CH3) on one end and a carboxyl group (COOH) at the other end
 In the middle is a chain of anywhere between 11-23 CH2 groups
 Fatty acids can be classified as follows:

Saturated Fatty Acids

 Saturated fatty acids only have single bonds between carbon atoms therefore they
have a straight structure
 These fatty acids are saturated because the carbons are carrying as many
hydrogen atoms as they can
 Because there are no bends, saturated fatty acids can pack more tightly together,
therefore saturated fatty acids are solid at room temperature
 General formula: CnH2n+1COOH

Unsaturated Fatty Acids

 Monounsaturated fatty acids have one double bond somewhere in the chain therefore they have a bent structure
 Polyunsaturated fats have at least two double bonds in their chain therefore have many bends/kinks in the chain
 Because they can’t pack closely together they are liquid at room temperature
 General formula of monounsaturated fatty acid: CnH2n-1COOH
 General formula of polyunsaturated fatty acid: CbH2n-3COOH
Lipids
 Lipids are a diverse group of hydrophobic compounds that include molecules like fats, oils, phospholipids and steroids
 Most lipids are hydrocarbons: molecules that include many non-polar carbon-carbon or carbon-hydrogen bonds
 Lipids are carbon compounds made by living organisms that are mostly or entirely hydrophobic
 There are three main types of lipids:

Phospholipids
 Phospholipids have only two fatty acids condensed onto the glycerol molecule
 The third –OH position of the glycerol molecule is occupied with a phosphate group
 Phospholipids are characterized by having a polar or hydrophilic head and two non-polar
hydrophobic tails
 As a result- phospholipids form a phospholipid bilayer which maximizes the interactions
between the non-polar tails and water
 Phospholipids bilayers provide the basis of membrane structures

Triglycerides
 A triglyceride molecule is derived from two types of molecular components:
o Polar head: This is derived from a single glycerol molecule. Glycerol is composed of three carbons, five hydrogens
and three hydroxyl groups
o Non polar tail: The non polar fatty acid tail group consists of three hydrocarbons (a functional group composed of
C-H bonds) and also have a polar carboxyl functional group
 The number of carbons in the fatty acid may range from 4-36
 Fats contain saturated fatty acids, whereas oils contain unsaturated fatty acids.
 Oils and fats are triglycerides, while other lipids like phospholipids and steroids have different structures
 Fats and oils are formed by condensation reactions between a single
molecule of glycerol and three molecules of fatty acids
 Triglycerides are broken down by hydrolysis reactions to produce a single
molecule of glycerol and three molecules of fatty acids
 Triglycerides at standard room temperature:
o Liquid = Oil
o Solid = Fats

Steroids
 Steroids are a type of lipid
 The steroid backbone is formed by the four rings of carbon.
 Although they do not resemble other lipids they are classified as lipids because they
are largely composed of carbons and hydrogens
 Cholesterol is the most common steroid. It is used as a precursor of many
biomolecules, including other steroids and the sex hormones
 Uses of steroids:
o Used to build up depleted muscle due to lack of activity and to assist in recuperation from an illness
 Abuses of steroids:
o Anabolic steroids are sometimes used by athletes to increase muscle and strength for an unfair advantage in sport
 Effects on males:
o Infertility, breast development, shrinking of balls, male pattern baldness
 Effects on females:
o Decrease in breast size and body fat, deepening of the voice, excessive growth of body hair
Functions of lipids
 Functions of lipids include
o Hormones
o Insulation
o Cell Membranes
o Energy storage

Iodine Number

Definitions

Iodine Number – The iodine number of a fat or an oil is the mass of iodine that reacts with 100g of the lipids

 The addition of iodine to unsaturated fats can be used to break the carbon double bonds, since one mole of double bonds
reacts with one mole of I2

 The iodine will bond to the double bonds so the mass of iodine used will depend on the number of double bonds
o Stearic/Palmitic/Lauric acids: no double bonds
o Oleic acid: one double bond
o Linoleic acid: two double bonds
o Linolenic acid: three double bonds
 The more unsaturated an oil is, the higher its iodine number will be

Question: Linoleic acid has the formula C18H32O2. Determine the iodine number of linoleic acid

1 mol of linoleic acid has 2 moles of double bonds

Therefore, two moles of I2 react with two moles of double bonds = 2 x 254(mass of iodine) = 508g I2
Furthermore 281 grams of linoleic acid react with 508 grams of iodine.

100g
508 g I2 × = 181 g
281 g linoleic acid

Answer: the iodine number of linoleic acid is 181 (no units)

Rancidity of fats
 When fats used in the food industry are stored for long periods of time, they can undergo chemical change which causes
them to become rancid. The result is fats and oils that cause a disagreeable smell, texture or appearance
 The two main causes of this are hydrolytic and oxidative rancidity

Hydrolytic Rancidity Oxidative Rancidity

 Hydrolytic rancidity is the hydrolysis of  Oxidative rancidity is caused by the oxidation

triglycerides to produce glycerol and (smelly) fatty  This reaction is catalyzed by light, or enzymes and metal ions
acids  It occurs in fats and oils with a high proportion of carbon to
 Hydrolytic rancidity occurs more quickly in the carbon double bonds
presence of heat and moisture  It can be controlled with anti-oxidants
 It is catalyzed by the enzyme lipase
 The rancid smell is due to the release of fatty acids
 Hydrolytic rancidity can be reduced by
refrigeration
 Cholesterol: HDL and LDL
 Cholesterol is transported through the body inside of lipoproteins. Lipoproteins consists of both lipids and proteins
 There are two types of lipoproteins: high density lipoprotein (HDL) and low-density lipoprotein (LDL)
 HDL has more protein and less fat, LDL has less protein and more fat
o HDL is known as “good cholesterol” as it removes cholesterol from the arteries
o LDL is called “bad cholesterol” as it deposits cholesterol on the arteries
 Too much cholesterol in your arteries may lead to a buildup of plaque known as atherosclerosis
 A high ratio of LDL to HDL can lead to an increased risk of heart disease, obesity,
atherosclerosis and blocked arteries

B.4 Carbohydrates
B.4.1 Carbohydrates have the general formula CX(H2O)y
B.4.2 Haworth projects represent the cyclic structures of monosaccharides
B.4.3 Monosaccharides contain either and aldehyde group (aldose) or a ketone group (ketose) and several –OH groups
B.4.4 Straight chain forms of sugar cyclize in solution to form ring structures containing an ether linkage
B.4.5 Glyosidic bonds form between monosaccharides forming disaccharides and polysaccharides
B.4.6 Carbohydrates are used as energy sources and energy reserves
B.4.7 Deduction of the structural formulas of disaccharides and polysaccharides from given monosaccharides
B.4.8 Relationship of the properties and functions of monosaccharides and polysaccharides to their chemical structures

Carbohydrates
 Carbohydrates is another term for a sugar
 Carbohydrates have several carbon atoms that have a hydrogen and a hydroxyl group
 All carbohydrates have an aldose or ketose group:
o Aldose carbohydrates contains one aldehyde group per molecule
o Ketose carbohydrates contain one ketone group per molecule
 Carbohydrates can be written as a straight chain structure or Haworth projections
o Haworth projections represent the 3D (cyclic) structures of monosaccharides

Monosaccharides
 The building blocks of carbohydrates are simple sugars called monosaccharides
 All monosaccharides have the molecular formula C6H12O6 (Empirical formula: CH2O)
 All monosaccharides contain a carbonyl (C=O) group and have at least two hydroxyl (-OH) groups
 In solution, isomers of monosaccharides are in equilibrium – two with ring structures and a straight chain molecule

Disaccharide
 Disaccharides: A molecule formed by condensation reactions between two monosaccharides
 As a result, a glyosidic bond is formed
 Like monosaccharides, disaccharides dissolve in
water, taste sweet and are also called sugars

Polysaccharides
 Polysaccharides are polymers of carbohydrates made by linking monosaccharides into a chain
 Polysaccharides are polymers of glucose molecules linked together in different ways by condensation reactions
 Digestion of polysaccharides involves the hydrolysis (adding water) of the bonds between the monosaccharide residues
 Enzymes catalyze these reactions in the digestive tract of animals, including humans
 Polysaccharides are insoluble in water as they are much larger molecules compared to monosaccharides/disaccharides
 One of the most important polysaccharides is starch. Starch exists in two forms:
 Amylose Amylopectin

Amylose is a straight chain polymer of D-glucose units Amylopectin consists of D-glucose units with both 1,4
with 1,4 glycosidic bonds and 1,6 glycosidic bonds

Soluble in water Insoluble in water

 Most plants use starch as a store of carbohydrates and thus energy

 Cellulose is a polymer of D-Glucose contains 1,4 linkages
 Cellulose, together with lignin, provides the structure to the cell walls of green plants
 Most animals, including all mammals do not have the enzyme cellulase so are unable to digest cellulose or other dietary fiber
polysaccharides

Functions of carbohydrates
 Functions of carbohydrates include
o To provide energy: Foods such as bread, biscuits, cakes, potatoes and cereals are all high in carbohydrates
o To store energy: Starch is stored in the liver of animals in the form of glycogen. Glycogen has almost the same
chemical structure as amylopectin
o As precursors for other important biological molecules

B.5 Vitamins
B.5.1 Vitamins are organic micronutrients which (mostly) cannot be synthesized by the body but must be obtained from suitable
food sources
B.5.2 The solubility (water of fat) of a vitamin can be predicted from its structure
B.5.3 Most vitamins are sensitive to heat
B.5.4 Vitamin deficiencies in the diet cause particular diseases and affect millions of people worldwide
B.5.5 Comparison of the structures of vitamins A, C and D
B.5.6 Discussion of the causes and effects of vitamin deficiencies in different countries and suggestion of solution

Vitamins
 Vitamins are organic micronutrients which cannot be synthesized by the body and must be obtained from suitable food
sources (except vitamin D)
 The ability of vitamins to be transported and stored in the essentially aqueous environment of the body is important, so
vitamins are classified as either fat-soluble or water-soluble
 Water solubility of any organic molecule depends on forming many hydrogen bonds (many –OH groups)
 Vitamins that consist almost entirely of carbon and hydrogen are fat-soluble
 All vitamins have two common functional groups: carbon-carbon double bone and hydroxyl group

Vitamin A (Retinol)
 Fat soluble as there are non-polar hydrocarbon chain and ring
 Vitamin A is important for low-light vision
 A lack of vitamin A causes night blindness
 Vitamin C (Ascorbic Acid)
 Water soluble as there is a large number of polar OH groups which are able to form hydrogen
bonds with water molecules
 Due to its solubility in water, it is not retained by the body for long periods
 Water soluble vitamins such as vitamin C are sensitive to heat and are destroyed by cooking
 Keeping food containing vitamin C in the refrigerator slows down this process
 A lack of vitamin C causes scurvy

Vitamin D (Calciferol)
 Fat soluble: non-polar hydrocarbon chain and ring
 Vitamin D stimulates the uptake of calcium ions, important for healthy bones and teeth
 Vitamin D is made in the body by the action of sunlight on the skin
 A lack of vitamin D can cause rickets

Vitamin deficiencies
 The absence of a regular, balanced supply of the diverse nutrients needed in the diet is known as malnutrition
 Malnutrition occurs when either too much food is consumed, which leads to obesity, or the diet is lacking in one or more
essential nutrients
 Causes of vitamin deficiencies:
o Lack of distribution of global resources
o Depletion of nutrients in the soil
o Lack of education about balanced diets
 Solutions to vitamin deficiencies:
o Taking nutritional supplements
o Genetically modifying foods to increase vitamin content
o Educating people about balanced diets

B.6 Biochemistry & the environment

B.6.1 Xenobiotics refer to chemicals that are found in an organism that are not normally present there

B.6.2 Biodegradable/compostable plastics can be consumed or broken down by bacteria or other living organism
B.6.3 Host-guest chemistry involves the creation of synthetic host molecules that mimic some of the actions performed by
enzymes in cells, by selectively binding to specific guest species, such as toxic materials in the environment
B.6.4 Enzymes have been developed to help in the breakdown of oil spills and other industrial wastes
B.6.5 Enzymes in biological detergents can improve energy efficiency by enabling effective cleaning at lower temperatures

B.6.6 Biomagnification is the increase in concentration of a substance in a food chain

B.6.7 Green chemistry, also called sustainable chemistry, is an approach to chemical research
B.6.8 Discussion of the increasing problem of xenobiotics such as antibiotics in sewage treatment plants
B.6.9 Description of the role of starch in biodegradable plastics
B.6.10 Application of host-guest chemistry to the removal of a specific pollutant in the environment
B.6.11 Description of an example of Biomagnification, including the chemical source of the substance,
B.6.12 Discussion of the challenge sand criteria in assessing the “greenness” of a substance used in biochemical research
Biodegradability
 Biodegradable plastics and compostable plastics can be broken down or consumed by bacteria or other living organisms
through natural processes.
 However, although some plastics are organic in origin they are petroleum based so cannot easily be broken down by natural
organisms and cause big pollution problems
o PLA (polylactide) is a biodegradable plastic derived from renewable resources such as corn starch
o The breakdown of starch based plastics (bioplastics) produces carbon dioxide and water
o Starch based polymers constitute over 50% of the biodegradable plastics as it is easily broken down by
microorganisms and being renewable it is good alternative to fossil fuel based plastics
o Starch grains in the plastic will swell when they come in contact with water (e.g. in a landfill). This breaks the plastic
up into many much smaller pieces, which increases the overall surface area and consequently the rate of the
breakdown reactions
 Specific enzymes have been developed to help in the dispersal and breakdown of oil spills and other industrial wastes
 Bioplastics can be broken down in hydrolysis reactions due to the presence of ester linkages or glyosidic links (requires heat
and moisture)/ When some biodegradable plastics decomposed in landfills, they produce methane gas which is a very
powerful greenhouse gas (anaerobic conditions)

Advantages Disadvantages

 Renewable resource  Require use of land

 Broken down by bacteria or other organism  Increases use of fertilizes and pesticides
 Reduces plastic waste  Might breakdown before end of use
 Reduce use of petrochemicals  Release of methane/greenhouse gas during
degradation

Host-Guest chemistry
 Host-guest complexes are composed of two or more molecules or ions that are held
together through non-covalent bonding
 Host–guest chemistry is very similar to enzymes as it uses host molecules (like enzymes)
that bond with specific guest molecules (like substrates) to form host-guest complexes
(like enzyme-substrate complexes)
 The difference between host-guest complexes and enzyme-substrate complexes is that in
host-guest chemistry the host is a synthetic molecule specially developed to bond to a
specific ‘target’ molecule (guest)
 Note that – as in enzyme-substrate complexes – the bonds that hold the host-guest complex together are all non-covalent
attractions, e.g. hydrogen bonds and dipole-dipole, ionic and hydrophobic attractions
 Host-guest chemistry can be applied to the removal of xenobiotics in the environment
 The binding between a xenobiotic and a host produces a supramolecule

Biomagnification and Bioaccumulation

 Biomagnification: A process that leads to increasing concentrations of (unwanted) substances in animals as you go higher up
the food chain
 Bioaccumulation: The accumulation (build up) of a substance within an organism over time
 An example includes DDT:
 DDT is an insecticide that was used to control mosquito populations that spread diseases such as malaria and typhus
 DDT is readily soluble in fat and does not break down therefore it accumulates in fatty tissue
 In the 1960s bird of prey such as ospreys suffered a decline in numbers which was due to the toxic effect of DDT
 The use of DDT as an insecticide was banned in many countries in the 1970s
 Xenobiotics
 Xenobiotics are chemical substances found within an organism that are not naturally produced by or expected to be present
within an organism
 Antibiotics are xenobiotics in animals as they are not produced by animals, nor are they part of a normal diet

Dioxins and PCBs

 Dioxins and polychlorinated biphenyls (PCBs) are toxic chemicals that persist in the environment
 Once dioxins enter the body, they accumulate due to their chemical stability and can be absorbed by fatty tissue
 Long term exposure to these substances causes a range of adverse effects on the nervous, immune, and endocrine systems
 They may also be carcinogenic (cancer causing)

Green Chemistry
 ‘Green chemistry’ is an approach to chemical research and engineering that seeks to minimize the production and release to
the environment of hazardous substances. The five principles that aim to achieve green chemistry include:
o Developing water based processes and products instead of solvent-based processes and products
o Efficient use of energy in processes such as developing new catalysts for lower production temperatures
o Efficient use of reactants in processes. i.e. developing a reaction with high atom economy
o Developing processes that can use renewable reactants
o Developing waste-free products

B.7 Proteins and enzymes

U1 Inhibitors play an important role in regulating the activities of enzymes

U2 Amino acids and proteins can act as buffers in solution

U3 Protein assays commonly use UV-vis spectroscopy and a calibration curve based on known standards

U4 Determination of the maximum rate of reaction (Vmax) and the value of the Michaelis constant (Km) for an enzyme by
graphical means, and explanation of its significance
U5 Comparison of competitive and non-competitive of enzymes with reference to protein structure, the active site and
allosteric site
U6 Explanation of the concept of product inhibition in metabolic pathways

U7 Calculations of the pH of buffer solutions, such as those used in protein analysis and in reactions involving amino acids in
solution
U8 Determination of the concentration of a protein in solution from a calibration curve using the Beer-Lambert Law

Induced-fit model
 A more recent model which improves on the lock and key model is the
induced fit model
 The induced-fit model: A theory that states the active site of an enzyme
will change shape to enfold a substrate molecule
 Since enzymes are rather flexible structures, the active site is continually
reshaped by interactions with the substrate
 This enables a more precise fit to be achieved between the enzyme and substrate
 When the product leaves the enzyme, the enzyme returns to its original form
Inhibitors
 The binding of an inhibitor can stop a substrate from entering the enzyme's active site
 Inhibition of enzymes occurs when a substance prevents the enzyme from doing its job
 These inhibitors work as either a competitive inhibitor or a non-competitive inhibitor

Competitive inhibitors
 Competitive inhibition: These inhibitors have a similar structure to the substrate therefore they compete for the enzyme’s
active site. These reduce the activity of the enzyme because they block the substrate entering the active site
 To reduce the impact of competitive inhibition we can increase the concentration of the substrate
 The enzyme can still reach maximum efficiency in the presence of a competitive inhibitor,
just at a decreased rate as the active site conformation is not changed

Non-Competitive inhibitors
 Non-competitive inhibition: Impede enzymatic reactions by binding to the allosteric site which
is away from the enzyme active site
 This changes the conformation of the active site, so the substrate can no longer bind with the enzyme
 A non-competitive inhibitor reduces the efficiency of an enzyme, as the substrate can no longer bind to the enzyme
because the active site conformation was changed

Competitive inhibition Non-competitive inhibition

Substrate and inhibitor are (chemically) the same shape Substrate and inhibitor are (chemically) not a similar shape

Inhibitor binds to the active site Inhibitor binds to the allosteric site

Inhibitor does not change the shape of the active site Inhibitor changes the shape of the active site

Increases in substrate concentration do not affect the

Increases in substrate concentration reduce the inhibition
inhibition

Both types of inhibitor reduce enzyme activity

Both types of inhibitor bind to the enzyme

Both types of inhibitor prevent the substrate from binding to the active site

Graphical analysis of enzyme activity

 The relationship between substrate concentration and enzyme activity can be shown by a graph where:
 Vmax occurs when all active sites are saturated with substrate
 When this happens increasing the substrate concentration does not increase the rate of an enzyme-catalyzed reaction
 Michaelis constant (Km): Km is the substrate concentration at one-half of its Vmax
 Km is inversely proportional to enzyme activity
o A higher Km the lower the activity of the enzyme
o A lower Km the higher the activity of the enzyme
 Vmax has units of rate (e.g. mol dm-3 s-1)
 Km has units of concentration (e.g. mol dm-3)
 Competitive inhibitor: Same Vmax different Km
 Non-competitive inhibitor: Different Vmax same Km
B.8 Nucleic acids
U1 Nucleotides are the condensation products of a pentose sugar, phosphoric acid and a nitrogenous base – adenine (A),
guanine (G), cytosine (C), thymine (T) or uracil (U)
U2 Polynucleotides form by condensation reactions

U3 DNA is a double helix of two polynucleotides strands held together by hydrogen bonds

U4 RNA is usually a single polynucleotide chain that contains uracil in place of thymine, and a sugar ribose in place of
deoxyribose
U5 The sequence of bases in DNA determines the primary structure of proteins synthesized by the cell using a triplet code,
known as the genetic code, which is universal
U6 Genetically modified organisms have genetic material that has been altered by genetic engineering techniques, involving
transferring DNA between species
A1 Explanation of the stability of DNA in terms of the interactions between its hydrophilic and hydrophobic components

A2 Explanation of the origin of then negative charge on DNA and its association with basic proteins (histones) in
chromosomes
A3 Deduction of the nucleotide sequence in a complementary strand of DNA or a molecule of RNA from a given
polynucleotide sequence

Structure of nucleotides
 DNA and RNA are two types of nucleic acid. They are both polymers of sub-units called nucleotides
 Each nucleotide consists of three parts:
1. A pentose group (A five-carbon sugar)
2. Phosphate Group (PO4-3)
3. A nitrogenous base
 There are two differences between DNA and RNA nucleotides
1. The type of pentose is ribose in RNA but deoxyribose in DNA
2. In both DNA and RNA there are four possible bases. There of these are the same.
However, the fourth base is thymine in DNA but uracil in RNA

DNA Structure
 Nucleotides are formed by condensation reactions between the components mentioned above
 The phosphate group of one nucleotide attaches to different sugar molecules at C3 and C5 forming
phosphodiester links between sugar molecules (+H2O)
 The negative charge in DNA is caused by the phosphate groups in the sugar-phosphate backbone.
The phosphate groups carry a 1– negative charge
 The negative charge of the phosphate groups causes DNA to bond closely with histones, which are
positively charged proteins found in chromosomes
 The backbone of the polynucleotide strand is an alternating sequence of sugar and phosphate groups
 The double helix of the DNA is stabilized by hydrogen bonds between complementary pairs of bases
o Adenine pairs with Thymine via two hydrogen bonds
o Guanine pairs with Cytosine via three hydrogen bonds
 In order for the bases to be facing each other and thus able to pair the strands must be running in
opposite directions. Therefore the two strands of DNA are described as being antiparallel.

Primary structure of DNA

 The primary structure consists of a linear sequence of nucleotides (the order of base pairs
covalently bonded to a sugar)
 Type of bonding: Covalent bonds
Secondary structure of DNA
 The secondary structure is the set of interactions between the bases (which parts of strands are bound to each other)
 In a DNA the two strands of DNA are held together by hydrogen bonds
 The greater degree of hydrogen bonding between G and C pairs makes these sections of the DNA chain harder to separate

DNA Charge
 The phosphate groups are negatively charged and give DNA molecules a negative charge
 This enables the molecules to interact with a group of proteins called histones
 The DNA molecules wrap around histones are become super coiled (called nucleotides)

RNA Structure
 RNA differs from DNA in that it has
o Ribose sugar instead of deoxyribose
o Uracil instead of thymine
o A single-stranded structure

DNA Replication
 Before DNA can be replicated the double stranded molecule must be “unzipped” into two single strands
 In order to unwind DNA the hydrogen bonds between the two DNA strands are broken
 This is done with an enzyme called helicase. DNA Helicase disrupts the hydrogen bonding between base pairs to separate the
strands into a Y shape (called replication fork)
 Now that the bases are exposed on the separated strands, they can act as a template where new
nucleotides attach by hydrogen bonds between complementary base pairs, C and G, A and T
 These bases then undergo a condensation polymerization reaction catalyzed by the enzyme DNA
polymerase to form two exact copies of the original DNA double helix

Transcription/Translation
 In transcription a segment of DNA is copied into mRNA by the enzyme RNA polymerase. The newly formed mRNA then
leaves the nucleus and heads to the ribosomes.
 Transcription uses an enzyme called RNA polymerase and a number of necessary proteins called transcription factors:
1. RNA polymerase separates the DNA strands and synthesizes a complementary RNA copy from one of the DNA strands
2. When the DNA strands are separated, ribonucleotide triphosphates align opposite their exposed complementary base
3. RNA polymerase removes the additional phosphate groups and uses the energy from this cleavage the covalently join
the nucleotide to the growing sequence
4. RNA sequence has now been synthesized, so RNA polymerase detaches from the DNA Molecule
 In translation mRNA is decoded by a ribosome to produce a polypeptide chain. In order to achieve this a triplet code
(codons) is used. Each codon consists of three nucleotides, corresponding to a single amino acid
 The triplet code allows up to 64 permutations. The 64 permutations represent the 20 naturally occurring amino acids
 Translation of an mRNA molecule by the ribosome occurs in the following stages:
1. mRNA binds to a ribosome
2. A tRNA molecule with an anticodon that is complementary to the codon on
mRNA binds to the mRNA
3. Another tRNA with an anticodon complementary to the second mRNA codon
attaches to the mRNA molecule at the ribosome
4. An enzyme joins the two amino acids on the tRNA molecules together via a
condensation reaction
5. The bond is broken between the tRNA molecule and the amino acid that was
just added to the polypeptide chain
6. The tRNA molecule is released and the ribosome moves down to the next mRNA codon
7. This process is repeated many times to form the amino acid chain
 DNA Transfer
 DNA can be transferred between species as the universal nature of the genetic code makes it possible for DNA from one
organism to be expressed into the DNA of a different species
 A genetically modified organism is one whose DNA has been altered, often by the insertion of DNA from a different species
 This is the bases of genetic engineering and gives rise to genetically modified organisms (GMO’s)

Benefits Concerns

 Longer shelf life  Long term effects unknown

 Improved flavor, texture and nutritional value  Linked to allergies (for people involved in their
 Increased resistance to disease processing)
 Increased yields

B.9 Biological pigments

B.9.1 Biological pigments are colored compounds produced by metabolism

B.9.2 The color of pigment is due to highly conjugated systems with delocalized electrons, which have intense absorption bands
in the visible region
B.9.3 Porphyrin compounds, such as hemoglobin, myoglobin, chlorophyll and many cytochromes are chelates of metals with
large nitrogen-containing macrocyclic ligands
B.9.4 Hemoglobin and myoglobin contain heme groups with the porphyrin group bound to an iron (II) ion

B.9.5 Cytochromes contain heme groups in which the iron ion interconverts between iron (II) and iron (III) during redox
reactions
B.9.6 Anthocynins are aromatic, water-soluble pigments widely distributed in plants. Their specific color depends on metal ions
and pH
B.9.7 Carotenoids are lipid-soluble pigments, and are involved in harvesting light in photosynthesis. They are susceptible to
oxidation, catalyzed by light
B.9.8 Explanation of the sigmoidal shape of hemoglobin’s oxygen dissociation curve in terms of the cooperative binding of
hemoglobin to oxygen
B.9.9 Discussion of the factors that influence oxygen saturation of hemoglobin, including temperature, pH and carbon dioxide

B.9.10 Description of the greater affinity of oxygen for fetal hemoglobin

B.9.11 Explanation of the action of carbon monoxide as a competitive inhibitor of oxygen binding

B.9.12 Outline of the factors that affect the stabilities of anthocyanins, carotenoids and chlorophyll in relation to their structures

B.9.13 Explanation of the ability of anthocyanins to act as indicators based on their sensitivity to pH

B.9.14 Description of the function of photosynthetic pigments in trapping light energy during photosynthesis

B.9.15 Investigation of pigments through paper and thin layer chromatography

Biological Pigments
 Biological pigments are colored compounds produced by living organisms (by metabolism)
 Pigment molecules absorb light in the visible region of the spectrum (400 – 700 nm). Pigment molecules absorb visible light
due to the nature of their chemical bonds
 The color that we see is the light that is not absorbed, but instead reflected
 The light that is reflected by the pigment is the complementary color of the light that is absorbed
Conjugated Systems
 Most simple organic compounds that have a few multiple bonds and functional groups do not absorb visible light. These
compounds appear colorless or white
 Pigment molecules absorb visible light because of the nature of their chemical bonds. In most cases they are highly
conjugated structures, meaning that the electrons in p-orbitals are delocalized through alternating single and double bonds
and through benzene ring structures.
 For multiple bonds to be conjugated they must be in an alternating double and single carbon-carbon bond
 As these electrons are not held tightly in one position they are able to become excited as they absorb certain wavelengths of
light energy. For molecules having conjugated systems, the ground
states and excited states of the electrons are closer in energy than
non-conjugated systems
 This means that:
o Larger conjugated systems absorb light of lower energy (longer wavelength)
o Smaller conjugated systems absorb light of higher energy (shorter wavelength)

Porphyrin ring compounds

 All porphyrin compounds are chelates of metals with large nitrogen-containing macrocyclic ligands
 Porphyrin compounds are planar ring structures with extensive conjugated systems
 It is made up of four heterocyclic rings, containing carbon and nitrogen, linked by bridging
carbon atoms
 The ring acts as a ligand, forming a chelate with a metal involving coordinate bonds
 Different porphyrin compounds contain different metals
 The whole structure formed is what known as a heme group

Hemoglobin and myoglobin

 The heme group, which is common to hemoglobin and myoglobin contains iron, usually in the +2 oxidation state
 Hemoglobin and myoglobin are only slightly related in primary structure and are both porphyrin compounds
 The secondary structures of myoglobin and the subunits of hemoglobin and myoglobin are also virtually identical
 Heme is a prosthetic group within protein molecules. Hemoglobin contains four heme groups, each bound within a
polypeptide chain. Therefore, hemoglobin has a quaternary structure, while myoglobin has a tertiary structure
 Hemoglobin is designed to carry oxygen in the blood, and myoglobin is designed to store oxygen in the blood
 Hemoglobin and myoglobin both bind reversibly with oxygen (O2) via the Fe (II) ion. The binding of oxygen is cooperative in
nature meaning it gets easier to bind oxygen after an initial heme group is bond to oxygen
 This is known as a conformational shift

Hemoglobin and oxygen

 From the graph, we can deduce the following about how this effects hemoglobin’s
ability to bind to oxygen
 At low concentrations of O2, hemoglobin has a low affinity for O2
 At high concentrations of O2, hemoglobin has a high affinity for O2
 Factors that affect the binding of oxygen to hemoglobin are
 Temperature: At higher temperatures hemoglobin can hold less O2
 pH and partial pressure of CO2: At a lower pH, hemoglobin can hold less O2

 Increasing the temperature, increasing the partial pressure of CO2 and decreasing the pH all reduce the affinity of
hemoglobin for O2
Adult hemoglobin
 Adult hemoglobin contains four polypeptide chains
 Two alpha chains and two beta chains
 Fetal hemoglobin contains two alpha chains and two gamma chains
 Fetal hemoglobin has greater affinity for oxygen than adult
hemoglobin:
 Adult hemoglobin has two alpha and beta chains while fetal hemoglobin has two alpha and two gamma chains
 This means the fetal hemoglobin can absorb O2 from the mother’s blood in the placenta.

Carbon monoxide
 Carbon monoxide (CO) commonly known as the silent killer has a strong affinity for hemoglobin
 CO is toxic to humans because it is a competitive inhibitor of oxygen and prevents the oxygen from bonding with the heme
group at the active site
 As a result:
o less oxygen is transported
o uptake of oxygen decreases
o it could cause hypoxia

Chlorophyll
 Chlorophyll, the main photosynthetic pigment, absorbs most strongly in the blue region of the light spectrum
 There are several forms of chlorophyll, but the pigment always contains magnesium. This is why magnesium deficiency in the
soil leads to loss of the green color in leaves

Cytochromes
 Cytochromes are proteins that also contain the heme group
 They are found embedded in membranes and are responsible for electron transport during the redox reactions of aerobic
respiration and photosynthesis. During these reactions they become successively reduced and then reoxidized as they in
turn accept and then pass on electrons

Pigments
 Pigments are colored biological compounds produced by metabolism (as opposed to synthetically produced).
o Anthocyanins are aromatic, water-soluble pigments widely distributed in plants. Their specific colour depends on pH
and the presence of certain metal ions.
o Carotenoids are lipid-soluble pigments, involved in harvesting light in photosynthesis. They are oxidized during light-
catalyzed reactions

Carotenoids
 Carotenoids are lipid-soluble pigments, involved in harvesting light in photosynthesis
 They are oxidized during light-catalyzed reactions
 Their molecules have extensive conjugated systems of alternative double carbon-to-carbon and single carbon-to-carbon
double bonds which gives them their color but also makes them susceptible to oxidation, including being catalyzed by light
 This is why they can act as antioxidants as oxidation can lead to a loss of vitamin A activity

Anthocyanins
 Anthocyanins are aromatic, water-soluble pigments widely distributed in plants
 Their specific colour depends on pH and the presence of certain metal ions
 Anthocyanins are water soluble as they have polar hydroxyl groups which allow them to form hydrogen bonds
 Anthocyanins are very sensitive to pH which also means they can be used as pH indicators. Although with different pH they
undergo different structures
  The color changes arise form transfer of H+ from OH groups, which alters the conjugation and so the absorbance at the
chromophore
B.10 Stereochemistry in biomolecules
U1 With one exception, amino acids are chiral, and only the L-configuration is found in proteins

U2 Naturally occurring unsaturated fat is mostly in the cis form, but food processing can convert it into the trans form

U3 D and L stereoisomers of sugars refer to the configuration of the chiral carbon atom furthest from the aldehyde or ketone
group, and D forms occur most frequently in nature
U4 Ring forms of sugars have isomers, known as alpha and beta, depending on whether the position of the hydroxyl group at
carbon 1 (glucose) or carbon 2 (fructose) lies below the plane of the ring (alpha) or above the plane of the ring (beta)
U5 Vision chemistry involves the light activated interconversion of cis- and trans- isomers of retinal

A1 Description of the hydrogenation and partial hydrogenation of unsaturated fats, including the production of trans-fats and
a discussion of the advantages and disadvantages of these processes
A2 Explanation of the structure and properties of cellulose, and comparison with starch

A3 Discussion of the importance of cellulose as a structural material and in the diet

A3 Outline of the role of vitamin A in vision, including the roles of opsin, rhodopsin and cis- and trans-retinal

A4 Explanation of how the complementary pairing between bases enables DNA to replicate itself exactly

A5 Discussion of the benefits and concerns of using genetically modified foods

U12 Deduction and interpretation of graphs of enzyme activity involving changes in substrate concentration, pH and
temperature
U13 Explanation of the processes of paper chromatography and gel electrophoresis in amino acid and protein separation and
identification

Stereochemistry
 Stereoisomers represent different spatial arrangements of the atoms in a molecule
 Many biopolymers can exist as stereoisomers, each with distinct characteristics generally meaning that only one form of the
isomer can be used
 A chiral molecule is non-superimposable on its mirror image so that the mirror
image is actually a different molecule
 An achiral molecule is a molecule that is superimposable on its mirror image

Enantiomers
 Enantiomers are pairs of stereoisomers that are chiral
 They have exactly the same connectivity but opposite three-dimensional shapes
 However, enantiomers are not the same as each other, one enantiomer cannot be
superimposed on the other but is a mirror image of the molecule
 Two enantiomers have identical physical properties, except for rotation

Proteins: Amino acids

 In amino acids, the carboxyl group, amino group, hydrogen atom and R group are all bonded to the same carbon
 Because there are four different groups all amino acids are chiral (except glycine) meaning that the amino acids are optically
active and can exist as two different stereoisomers (known as enantiomers)
 The different stereoisomers of amino acids are most commonly known as L and D forms
 The L and D forms of amino acids have identical physical properties and chemical reactivity’s
o L: Laevorieterity
o D: Dextroretarary
 All naturally occurring amino acids in proteins are in the L form
Lipids
 Unsaturated fatty acids can exist as cis or trans isomers, which arise due to the restriction on
rotation around the double bond
 The cis forms occurs when the same group has the same orientation relative to the double bond
 The trans from occurs when the same group has opposite orientation across the double bond
 Cis double bonds are naturally occurring fatty acids
 Trans double bonds are sometimes found in man-made fatty acids
 Molecules of the cis isomer cannot easily arrange themselves side by side to solidify so they tend to have lower melting
points than the corresponding trans isomer
 Partial hydrogenation of lipids occurs when only some of the carbon-to-carbon double bonds in the fat are broken
 Those that remain often get chemically modified from the cis-position to the trans-position
 The resulting fatty acids therefore are known as trans fats and can be found more readily in processed foods
 Consumption of a diet high in trans fats raises the level of Low Density Lipoprotein (LDL) cholesterol

Carbohydrates
 All simple sugars are chiral molecules as they contain at least on chiral carbon atom
 The stereoisomers are described as D and L again
 For sugars having two or more chiral carbon atoms the prefixes D and L refers to the configuration of the chiral carbon atom
furthest away from the carbonyl carbon
 D sugars are the most frequently occurring in nature
 The conversion of sugars in a straight chain into the Hayworth projects also creates an additional type of isomer, known as α
and β forms
 These are distinguished by the relative position of the OH group at C1
 Starch and glycogen are polymers of α–glucose, cellulose is a polymer of β-glucose

Vitamins
 Vitamin A also known as retinal is involved in the so-called visual cycle (the photochemical changes associated with our
ability to detect light)
 The retina of the eye contains two types of light-sensitive cells, known as rods and cones. The rod are stimulated by light of
lower intensity and do not provide color vision
 The major photoreceptor pigment in rods is a large conjugated protein molecule called rhodopsin. This consist of a protein,
rhodopsin, tightly bound to 11-cis-retinal, which is derived from vitamin A
 Rhodopsin is able to absorb light due to it’s highly congugated system
 When rhodopsin is exposed to light, a transformation of 11-cis retinal occurs, changing it to 11-trans retinal
 As a result 11-trans retinal no longer fits into the rhodopsin/protein. This leads to a conformational change in
rhodopsin/protein generating nerve signal