VCE Chemistry

Units 3&4 Revision Lecture

Presented by:
Stephen Zhang
 PLAN FOR TODAY

Session 1
• Electrochemistry revision galvanic & electrolytic cells
• Chemical equilibrium revision (part 1)
Session 2
• Chemical equilibrium revision (part 2)
• Organic chemistry and spectroscopy revision
Session 3
• Exam preparation approach and exam tactics
 ELECTROCHEMISTRY

• Electrochemistry is all about electron exchange ⇒ redox!

•

Oxidation ⇔ loss of electrons M ⇌ M+ + e-

Reduction ⇔ gain of electrons M+ + e- ⇌ M

• N.B. there are other (synonymous) definitions of oxidation and reduction that are
used in other areas of chemistry!
• Electrons move from reductant to oxidant if the process is thermodynamically
favourable.
 ELECTROCHEMISTRY
Example:
Zn(s) + Cu2+(aq) ⇌ Zn2+(aq) + Cu(s)
• Classic example of redox reaction basis of Daniell cell.
• Equilibrium is heavily weighted towards the right (Ecell = +1.10V)
• Zn2+ (aq)/Cu(s) is thermodynamically more stable than Zn(s)/Cu2+(aq), hence the
reaction is a spontaneous process.

energy reactants
(enthalpy)

released energy
products

Reaction progress
 ELECTROCHEMISTRY

In a redox reaction, one species is the oxidant, and the other is the reductant.

• The oxidant causes oxidation (of the reductant) and is itself reduced
• The reductant causes reduction (of the oxidant) and is itself oxidised

How do we know when oxidation (or reduction) has occurred? We use oxidation
states
• Hypothetical charges assigned to atoms in a compound
• Equal to the charge an atom would have all bonds were purely ionic
CO2 SO42- MnO4- O2 NaH
 ELECTROCHEMISTRY

Assigning oxidation states - revision

• Neutral element ⇒ zero (e.g. Fe, Zn)
• Simple or polyatomic ions ⇒ sum of oxidation states = overall charge (e.g. NO3-,
Fe2+)
• Hydrogen ⇒ +1 (except in hydrides, LiH, NaH)
• Oxygen ⇒ -2 (except in H2O2)
• Fluorine ⇒ -1
 ELECTROCHEMISTRY

VCAA 2013
 ELECTROCHEMISTRY

Combustion reactions are redox reactions.

C3H8 + 5O2 → 3CO2 + 4H2O
• What is the oxidant? What is the reductant?

Remember the rules for balancing half-equations?

 ELECTROCHEMISTRY

1. Balance the (k)ey atoms all except for hydrogen and oxygen
2. Balance the (o)xygen atoms with H2O
3. Balance the (h)ydrogen atoms with H+
4. Balance (c)harge with electrons (e-)
5. Chuck on our (s)tates

- to
both sides to eliminate H+
 ELECTROCHEMISTRY

How do we predict a given pair of (oxidant, reductant) will react? We use the
electrochemical series.
• Experimentally-derived series of chemical species in order of reactivity
 ELECTROCHEMISTRY

Always remember
• Upper left ⇒ strongest oxidant
• Upper right ⇒ weakest reductant

• Lower right ⇒ strongest reductant

• Lower left ⇒ weakest reductant
 ELECTROCHEMISTRY

Galvanic cells
• Galvanic cells are an example of
primary cells.
• Anode compartment and
cathode compartment.
• Internal circuit (salt bridge) and
external circuit

A voltage difference between

anode and cathode drives the
reaction.
 ELECTROCHEMISTRY

Electrolytic cells
• Electrolytic cells are the reverse of
galvanic cells.
• Examples of secondary cells
• Non-spontaneous redox reactions are
driven forwards by input of energy
(electrical current)
• Electrodes are inserted directly into
electrolyte and current passed through
 ELECTROCHEMISTRY

products
energy
(enthalpy)

reactants

Reaction progress
 ELECTROCHEMISTRY
Electrolyte will contain several redox-active
species.
• Strongest oxidant is reduced at the
cathode
• Strongest reductant is oxidised at the
anode
• Molten electrolytes: quite simple to
determine the oxidant/reductant.
• Remember to consider H2O in the case
of an aqueous electrolyte!
• Alkali + alkali earth (groups 1&2) metals

aqueous solution!
 ELECTROCHEMISTRY

VCAA 2010
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 MOLE AND CHARGE CALCULATIONS

Key knowledge for mole and charge calculation:

• Charge is measured in Coulombs (C)
• -

𝐹 = 96500 C mol−1

𝑄 = 𝑛𝐹

• Current is the rate of transfer of charge: measured in Amperes (1 A = 1 C s-1)

1 A is a lot of current (more than enough to kill) so we typically quote values in mA

(10-3 A)
 ELECTROCHEMISTRY

Secondary cells
• Secondary cells are rechargeable can
be driven forwards (like galvanic cells)
but also backwards (like electrolytic cells)
• Requirements for being a secondary cell:
• Discharge reaction must be reversible
• Products of discharge must remain in
contact with electrodes

• Polarity of electrodes will never change

(+ or -)
• Anode and cathode will swap between
recharge and discharge.
 ELECTROCHEMISTRY

Example: Nickel-metal hydride (NiMH) cells -- DISCHARGE

MH(s) + OH-(aq) → H2O(l) + M(s) + e- [anode]

NiO(OH)(s) + H2O(l) + e- → Ni(OH)2(s) + OH-(aq) [cathode]
 ELECTROCHEMISTRY

Example: Nickel-metal hydride (NiMH) cells -- RECHARGE

MH(s) + OH-(aq) → H2O(l) + M(s) + e- [anode]

NiO(OH)(s) + H2O(l) + e- → Ni(OH)2(s) + OH-(aq) [cathode]
 ELECTROCHEMISTRY
VCAA 2009
 ELECTROCHEMISTRY

VCAA 2013
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 ELECTROCHEMISTRY

VCAA 2014
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 CHEMICAL EQUILIBRIUM

Consider the following reaction:

aA + bB ⇌ cC + dD

Remember that we define the reaction quotient at each point in the reaction
Cc Dd
Q=
Aa Bb

Important: we can only use the concentration for aqueous (aq) and gaseous (g)
species! For liquids and solids, we always take concentration = 1.
 CHEMICAL EQUILIBRIUM

As the reaction progresses, 𝑄 → 𝐾

c d
C eqm D eqm
K = Q at equilibrium = a b
A eqm B eqm
Important: the equilibrium constant K only depends on the temperature of reaction!

At constant temperature, K will have the same value regardless of starting

concentration.
 CHEMICAL EQUILIBRIUM

Le Principle

If a system in equilibrium is subject to a change, the system will respond to partially

oppose that change.

• This is just a rule

 CHEMICAL EQUILIBRIUM

Consider the reaction

2SO2(g) + O2(g) ⇌ 2SO3(g), ΔH < 0

• What is the effect of adding more SO2?

• What is the effect of adding more SO3?

• What is the effect of raising the temperature?

• What is the effect of increasing the reaction volume?

 CHEMICAL EQUILIBRIUM

Consider the reaction

2SO2(g) + O2(g) ⇌ 2SO3(g), ΔH < 0

• What is the effect of adding more SO2?

Reaction will shift right
• What is the effect of adding more SO3?
Reaction will shift left
• What is the effect of raising the temperature?
Reaction will shift left
• What is the effect of increasing the reaction volume?
Reaction will shift left
 CHEMICAL EQUILIBRIUM

The equilibrium constant 𝐾

(reaction volume, concentration of reactants, etc.).

However, 𝐾 does depend on the reaction temperature.

Example:
2NO2(g) ⇌ N2O4(g), ΔH = -57.1 kJ mol-1
What is the effect of ↑ temperature on the equilibrium constant?
 CHEMICAL EQUILIBRIUM

In general..

Exothermic reactions:
↑ temperature ⇒ ↓ 𝐊
↓ temperature ⇒ ↑ 𝐊

Endothermic reactions:
↑ temperature ⇒ ↑ 𝐊
↓ temperature ⇒ ↓ 𝐊
 CHEMICAL EQUILIBRIUM

Exactly how does it work?

2SO2(g) + O2(g) ⇌ 2SO3(g)

SO3 2
Q=
SO2 2 O2 2

Initially, suppose Q = K. What would be the effect on 𝑄

• ↑ SO2
• ↑ reaction volume
 CHEMICAL EQUILIBRIUM

VCAA 2008
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 CHEMICAL EQUILIBRIUM
VCAA 2010
 CHEMICAL EQUILIBRIUM
VCAA 2010
 CHEMICAL EQUILIBRIUM

Numerical equilibrium problems..

• Example: calculate the final equilibrium concentrations
• Initial concentrations of all species
• Value of the equilibrium constant 𝐾
• Equilibrium concentration of one species
 CHEMICAL EQUILIBRIUM

VCAA 2009
 CHEMICAL EQUILIBRIUM

ICE (initial, change, equilibrium) tables are a very useful tool for solving equilibrium
problems.

2NOCl(g) ⇌ 2NO(g) + Cl2(g)

2NOCl ⇌ 2NO Cl2

−2𝑥 +2𝑥 +𝑥
 CHEMICAL EQUILIBRIUM

Consider the reaction

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g), K = 0.67
Initially, 0.1 mol CO(g), 0.2 mol H2(g), 0.1 mol CH4(g) and 0.3 mol H2O(g) were added to a sealed
1.0L reaction vessel. At equilibrium, 0.032 mol CH4 was detected.

What were the equilibrium concentrations of the other species?

 CHEMICAL EQUILIBRIUM

Carbon monoxide poisoning

• Haemoglobin (Hb4) binds 4×O2 molecules, in order to transport O2 to tissues
Hb4 + 4O2 ⇌ Hb4(O2)4

• Carbon monoxide (C≡O) competes with O2 to bind to Hb.

Hb4 + 4CO ⇌ Hb4(CO)4,

However CO has a much higher affinity for active site than O2

≫
 CHEMICAL EQUILIBRIUM

What is an expression for the equilibrium constant of the displacement reaction?

Hb4(O2)4 + 4CO ⇌ Hb4(CO)4 + 4O2

ORGANIC CHEMISTRY
 ORGANIC CHEMISTRY

Alkanes
• General formula: CnH2n+2
• Fairly unreactive undergoes combustion and substitution reactions.

Alkenes
• General formula CnH2n
• More reactive than alkanes able to undergo addition reactions.

Alkynes
• General formula CnH2n-2
• Even more reactive than alkenes also undergo addition reactions
 ORGANIC CHEMISTRY

Haloalkanes
• General formula: R X (X = F, Cl, Br, I)
• Pretty damn reactive (polar C X bond)

Can be produced by reaction of alkanes with X2 or alkenes with X2 or HX. Need to

use heat + UV radiation to catalyse the reaction.

CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g) (alkanes)

C2H4(g) + Cl2(g) ⇌ CH2Cl CH2Cl(g) (alkene, with X2)
C2H4(g) + HCl(g) ⇌ CH3CH2Cl(g) (alkene, with HX)
 ORGANIC CHEMISTRY

Alkanols
• General formula: R OH (primary alkanols)
• Commonly undergo oxidation reactions (plus heaps more)
• Remember the distinction between primary, secondary and tertiary alkanols!
 ORGANIC CHEMISTRY

Alkanols can be synthesised by reaction of an haloalkane with OH-

CH3CH2Cl + OH- → CH3CH2OH + Cl-

 ORGANIC CHEMISTRY

We can produce ethanol by hydration of ethene

C2H4(g) + H2O(g) → CH3CH2OH(g)

Note that this cannot be extended to other alkenes (these will form the secondary

Example: what would be the H2O addition (hydration) product of propene?

 ORGANIC CHEMISTRY

Alkanols can undergo oxidation reactions to form a variety of compounds,

including alkanols, ketones and carboxylic acids.

• Primary alkanols are oxidised first to aldehyde intermediates (R COH) and

then to carboxylic acids (R CO2H)

• Secondary alkanols are oxidised directly to ketones

 ORGANIC CHEMISTRY

Oxidation and reduction in organic chemistry

• Oxidation and reduction are defined slightly differently in organic chemistry
(compared to electrochemistry)
• Oxidation is defined as the loss of H or gain of O
• Reduction is defined as the loss of O or gain of H

The organic chemistry definition of oxidation/reduction is the same as that for

compounds.
 ORGANIC CHEMISTRY

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 ORGANIC CHEMISTRY

Products of primary alkanol oxidation

Aldehydes
• General formula: R COH
• Fairly reactive (easily oxidised to afford the carboxylic acid)

Carboxylic acids
• General formula: R CO2H
• Carboxylic acids are weakly acidic. In solution, they exist in equilibrium with
carboxylate anions.
R CO2H ⇌ R CO2- + H+
 ORGANIC CHEMISTRY

Products of secondary alkanol oxidation

Ketones
• Presence of a secondary carbonyl (C=O)
• Ketone chemistry is quite complex but also useful able to form C-C bonds!

• Slow oxidation can be caused by O2 (e.g. wine souring)

• Laboratory use of dichromate (Cr2O72-) or permanganate (MnO4-) solutions
(harsh oxidants)
• These strong oxidants (when used in excess) typically push the reaction to the
carboxylic acid (difficult to stop at the aldehyde)
 ORGANIC CHEMISTRY

Esterification reactions
• Condensation reaction between primary alcohol and carboxylic acid
• remember that the required catalyst is
H2SO4(l) or conc. H2SO4
In general, avoid writing H2SO4(aq)

+
 ORGANIC CHEMISTRY

VCAA 2005
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 ORGANIC CHEMISTRY

Combustion analysis
• Combustion analysis is used to determine molecular formula
• The key is to calculate the mass of C and H in the original compound, and then
subtract this from the mass of compound ⇒ mass of O
• Then look at the ratio

n(C):n(H):n(O)

• This will provide the empirical formula. Need molar mass (e.g. from mass spec)
to determine molecular formula!
 ORGANIC CHEMISTRY

Example:
15.25g sample of an organic compound was combusted in excess O2 to produce
34.71g CO2 and 14.20g H2O.
What is the empirical formula of the compound?
 ISOMERISM

Two main types of isomerism

You are expected to be familiar with structural, geometric and optical isomerism

Structural isomerism same molecular formula but different connectivity

between atoms in the structure.

Geometric isomerism (for disubstituted C=C) same molecular formula and

connectivity, but different orientation of groups across a double bond.

Optical isomerism same molecular and structural formula, but orientation of

groups is different about a chiral carbon. Chiral carbon has 4 different groups
attached to it.
 ISOMERISM

Geometric isomerism

cis-1,2-dichloroethene trans-1,2-dichloroethene

Optical isomerism

(S)-lactic acid (R)-lactic acid

 SPECTROSCOPY

Mass spectra
•
• Can be asked to identify simple fragmentation patterns, e.g.
m/z = 15 ⇒ CH3+ m/z = 29 ⇒ CH2CH3+
• Always remember that fragmentation produces one cation fragment and one
free radical

CH3CH2CH2Cl + e- → [CH3CH2]+ + ⋅CH2Cl + 2e-

 SPECTROSCOPY

• isotopic effects
35Cl:37Cl = 3:1
12C:13C = 99:1

79Br:81Br = 1:1

• These will result in split peaks (e.g. commonly observed in the parent molecular
ion)
SPECTROSCOPY
 SPECTROSCOPY

Infrared (IR) spectroscopy

• Just need to remember the band wavenumber and shape!
 SPECTROSCOPY

Infrared (IR) spectroscopy

• Just need to remember the band wavenumber and shape!
 SPECTROSCOPY

Summary of peaks to know and love

• O H (alkanols): big, smooth, intense peak at ~3300cm-1
• O H (acids): big, dirty peak at ~3000cm-1
• C H: group of very thin, sharp peaks at ~3000cm-1 (not very useful)
• N H: intense peak at ~3400cm-1
• C=O: smooth, thin, very intense peak at ~1750cm-1
 SPECTROSCOPY

NMR Spectrometry
• chemical shifts, peak splitting, and the number of carbon/proton
environments
• Number of peaks = number of 13C/1H environments
• 𝑛 + 1 rule for multiplicity of peaks
• Relative positioning of peaks (upfield/downfield) more important than absolute
chemical shift (𝛿)
 SPECTROSCOPY

Example
(from VCAA 2015)
 SPECTROSCOPIC PROBLEM SOLVING

• Individual spectroscopic techniques can only provide limited information

• However, each comprises only part of the toolset available to an analytical
chemist
• Combination of MS, IR, 1H and 13C NMR techniques is key to elucidation of
chemical structures.
Technique Information provided
Mass spectroscopy Molecular weight, parts of structure
(limited)
Infrared spectroscopy Functional groups present
NMR (proton and 13C) Connectivity of atoms in
compound
 SPECTROSCOPIC PROBLEM SOLVING

1. Look at the mass spectrum note the molecular weight.

Fragments present in mass spectra can also hint of structure(e.g. m/z=27 ⇒
methyl, etc.)
2. Look at infrared spectrum + molecular formula try to identify the functional
groups present (e.g. alkanol? Carboxylic acid? Ketone/aldehyde?)
3. Look at NMR (proton+13C) spectra and try to assign peaks to structural
fragments
4. Try to piece together fragments to make a coherent molecule ⇒ confirm
consistency with all provided data.
 EXAM PREPARATION TIPS

15 mins

150 mins = 2 hr + 30 mins

Section A 30 multiple choice

Section B - 90 marks worth of extended response
On average, 1.25 mins/mark
 EXAM PREPARATION TIPS

Directed study
• Focus on points of weakness!
• Refer to the study design for assessable topics tick off all the points!

Textbooks and notes

• Can provide a different perspective on topics, and double check that you

•
but make sure you identify points of weakness and brush up!
 EXAM PREPARATION TIPS

• Questions are important, but concepts are even more important.

• but
understanding the concepts behind topics will allow you to figure questions out
on the fly!
• Doing chapter reviews, topic tests, etc. from textbook is a great way to assess
conceptual understanding of a topic!
 EXAM PREPARATION TIPS

how you study, not how much you study.

Sure, we need to work hard. But we need to work right too =)

• Which topics am I struggling the most with right now?

•
• What resources do I have that would help me understand this better?
 EXAM PREPARATION TIPS

Practice exams
•
• Commercial exams are often biased or otherwise unreflective of what the actual

• VCAA website lists 2002-2016 exams → quite a lot of the question are relevant
• VCAA also provides the 2017 Sample Exam save this till last =)
 EXAM PREPARATION TIPS

quality ≫ quantity

• Take time to do reading! (refer to rant later)

• real thing (i.e. #gethyped)
•
• Think like an examiner what would they want to see?
EXAM PREPARATION TIPS
 EXAM PREPARATION TIPS

how to use reading time?

• You have 15 minutes of reading time use this wisely!
• I skimmed quickly through the paper familiarise myself with the layout of the
paper which questions are easier? Which questions are harder?
•
•
• Read question through think about how to approach?
• What topic is it testing?
 EXAM PREPARATION TIPS

Managing writing time...

• Your decision
• First 30s of writing time
• Should finish with multiple choice by 9:45am
• Should be halfway through extend response by 10:45am
• Checking clock semi-regularly (e.g. once every 10 mins) and noting track of how
I progressed through paper
• Stay calm at all costs once you panic, the exam is already over.
 EXAM PREPARATION TIPS

This is Steve.

Steve is tired.

Steve decides to smile.

Be like Steve
 EXAM PREPARATION TIPS

Multiple choice section

• Actually write some stuff
calculator
 EXAM PREPARATION TIPS

Extended response tips

Calculations questions: show all steps!
•
• Show your units easy way of checking calculations!
EXAM PREPARATION TIPS
 EXAM PREPARATION TIPS

Written responses
• How much detail should one provide? Look at the number of lines and the
mark allocation
 EXAM PREPARATION TIPS

Avoiding silly mistakes

• I still suffer from this problem big time

minimise it
• Use a highlighter and pay special attention to key and bolded words
• Always read the question twice once before doing the question and once
after doing the question! This saved me several times!
 EXAM PREPARATION TIPS

Ask me anything ☺
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