HSC Chemistry Notes

• Module 5 – Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
• Module 6 – Acid and Base Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
• Module 7 – Organic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
◦ Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
◦ Alcohols, Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
◦ Organic Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
◦ Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
• Module 8 – Applying Chemical Ideas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
◦ Analysis of Inorganic Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .58
◦ Analysis of Organic Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
◦ Chemical Synthesis and Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
• Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
◦ Organic Chemistry Reaction Flowchart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
◦ Distinguishing Individual and Multiple Cations in Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . .84
◦ Distinguishing Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
◦ Naming Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
◦ Infrared Absorption Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
◦ UV-Vis Absorption Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
13
◦ C NMR Chemical Shift Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
◦ Solving Spectroscopy Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

Patrick Nah (納君誠)

Baulkham Hills High School

12/11/2019

———— Made using LATEX ————

Oc 2019, Patrick Nah

–1–
Copyright
Except as permitted by the Australian Copyright Act 1968, no part of this document may be reproduced, stored in a
retrieval system, communicated or transmitted in any form or by any means without prior permission of the copyright
owner.

This document is permitted to be used by students and teaching staff of Baulkham Hills High School for educational
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owner directly, but use of this document in this circumstance is restricted to private study by said entities. It is not
to be re-sold for profit or shared without prior permission of the copyright owner.

Disclaimer/s
This document aims to cover the course requirements of the Chemistry Syllabus produced by NE SA for the 2019
and future cohorts. Some sections of this document do exceed the scope of the course, while there may be potential
deficiencies in addressing other sections of the syllabus. Hence, the author does not guarantee that this document will
meet your requirements in preparation for HSC Chemistry, or is free from inaccuracies in information. The author
does not assume responsibility for any viruses or other harmful components possibly occurred from downloading this
document from any third-party websites.

Acknowledgements
I would like to acknowledge the following individuals, publications and institutions:
• Baulkham Hills High School’s Chemistry faculty
• James Bang, for reviewing draft versions of this document
• Peak HSC, with particular thanks to Sir Edward Trang and Sir Roy Fu
• Chan, D. et. al. (2019) Pearson Chemistry 12. Melbourne, Victoria. Pearson Australia.
• Davis, A. et. al. (2018) Chemistry in Focus Year 12. Melbourne, Victoria. Cengage Learning Australia.
◦ Diagrams have occasionally been utilised from this document

Abbreviations
Some symbols or abbreviations that may not have been explicitly defined in their required context are included below:

Term Definition Term Definition

∆H Enthalpy change VSEPR Valence Shell Electron Pair Repulsion (Theory)
∆S Entropy change K Kelvin (not to be confused with equilibrium constant)
∆G Gibbs Free Energy kPa, MPa Kilopascal and Megapascal, units of pressure
EA Activation energy atm Atmosphere, a unit of pressure
LCP Le Châtelier’s Principle Q Heat energy
c Concentration C Specific heat capacity (not to be confused with c)
◦ ◦ ◦
n (Number of) Moles 1 , 2 , 3 Primary, Secondary and Tertiary (organic compounds)
V Volume ∆ Heat (when used in isolation)
MM Molar mass e− Electron
ρ Density [O] Oxidation (not to be confused with oxygen, O)
P Pressure H-bond Hydrogen bonding
KE Kinetic energy M Molarity (mol L−1 )
δ− Negative dipole UV Ultraviolet (light)
+
δ Positive dipole λ Wavelength
MP Melting point δ Chemical shift (not to be confused with δ − or δ + )
n n n!


BP Boiling point Cr or r Combination, i.e. (n−r)!r!

–2–
 HSC Chemistry Notes
Module 5
Equilibrium

Non-Equilibrium Systems
• Enthalpy is the total energy possessed by a substance at constant pressure
• Entropy refers to the total “disorder” of a system
◦ Formal definition: The total number of possible arrangements of components in a system
◦ Increasing entropy occurs due to state transitions from solid → liquid → aqueous → gaseous
◦ Increasing volume increases the number of ways in which particles (and hence energy) can be distributed
throughout a system, increasing entropy
• Reactions favour a movement towards increased randomness (+∆S) and release of heat energy (–∆H)
• The formula for Gibbs Free Energy is ∆G = ∆H − T ∆S
◦ If ∆G < 0, the reaction is spontaneous; if ∆G ≥ 0 the reaction is non-spontaneous
◦ refers to a “standardised value” (e.g. ∆H is standardised enthalpy)
◦ As a general rule, the following table outlines the conditions for spontaneity

Table 1: Enthalpy and Entropy Changes

. +∆H −∆H

+∆S Spontaneous at high temperature Always spontaneous

−∆S Never spontaneous Spontaneous at low temperature

Static Equilibrium
• Definition: A state of equilibrium where reactants and products are not interacting with each other
• Reaction occurs in one direction and stops when one or more reactants are completely consumed, or there is an
extremely high EA barrier for the reverse reaction
• Rates of both forward and reverse reactions are zero after the reaction finishes, or they are extremely slow
◦ E.g. graphite → diamond (due to extremely high EA of reverse reaction)
• Some reactions are non-equilibrium reactions and irreversible (e.g. combustion of octane, photosynthesis)
◦ Photosynthesis is non-spontaneous (∆G > 0), and is driven by spontaneous reactions
• All physical reactions are reversible, such as a change of state or shape (e.g. dissolving a crystal lattice)
• A steady state involves macroscopic constancy, but does not require equilibrium or a closed system
◦ A blue Bunsen flame involves combustion of gas, but gas is continuously supplied to maintain the flame

–3–
Dynamic Equilibrium
• Requires a reversible reaction (
) in a closed system
◦ EA of forward and reverse reactions should be low enough for sufficient particles to collide successfully, and
they should be similar. There should be minimal entropy change between products and reactants
∗ EA is the difference in enthalpy between reactants and the activation complex (an unstable state of
high enthalpy where bonds between reactants are broken and new bonds in products are yet to form)
• Given sufficient time, the rate of the forward reaction equals the rate of the reverse reaction
◦ Change in concentration of products over time equals change in concentration of reactants over time
• Examples of dynamic equilibrium include:
◦ Haber Process: 3 H2(g) + N2(g)
2 NH3(g)
◦ Soft drink in a sealed bottle: CO2(g)
CO2(aq)

Features of Dynamic Equilibrium

• Equilibrium is dynamic
◦ Continuous interchange between reactants and products occurring at the same rate, hence constant con-
centrations of reactants and products
• Macroscopic constancy
◦ All observable properties (e.g. colour, concentration, pressure and density) are constant
• Can be reached from either direction

Equilibrium Position
• The extent of the forward or reverse reaction at equilibrium
◦ If reactants are favoured, equilibrium lies to the left
◦ If products are favoured, equilibrium lies to the right
• E.g. ionisation of CH3 COOH lies to the left, ionisation of HCl lies very far to the right

Factors Affecting Equilibrium

Le Châtelier’s Principle (LCP)
If a system at dynamic equilibrium is subject to a change in conditions, the system will shift as to partially counteract
the imposed change, until a new equilibrium is established.

Concentration
• Consider N2 O4(g)
2 NO2(g)
◦ An increase in [NO2 ] will cause equilibrium to shift in the direction opposing the change as per LCP. By
shifting towards the left, [NO2 ] will decrease partially, and so [N2 O4 ] will increase
• Addition of a pure solid or liquid does not affect equilibrium position, but addition of a gas does
◦ Pure solids and liquids have constant concentrations, which are set to 1
n m ρ
◦ c= V = M M ×V = MM = constant
• Addition of water may indirectly affect equilibrium position
◦ Consider AgCl(s)
Ag+ –
(aq) + Cl(aq)
∗ Addition of water increases the volume that aqueous species are dissolved in (lowering the concentra-
tion), and thus equilibrium shifts to the right to increase the concentration of Ag+ and Cl – partially

–4–
Pressure/Volume
• Applies to equilibria with at least one gaseous substance
1
◦ P∝ V as per Boyle’s Law
◦ Pressure is a measure of force per unit area (or the average kinetic energy per particle), proportional to
the frequency of collisions with container walls
• Increased pressure or decreased volume favours the reaction producing fewer moles of gas, and vice versa
◦ Fewer moles of gas reduces number of collisions with container walls, reducing pressure as per LCP
• For reactions with same number of moles on both sides, neither side is favoured (e.g. H2(g) + I2(g)
2 HI(g) )
• Addition of inert or noble gases at constant volume does not affect equilibrium
◦ Total pressure increases, but partial pressures of individual gases remain constant
∗ Gas concentrations (due to same partial pressures) remain constant if volume is constant
∗ Collisions with noble gas molecules do not cause side reactions

Temperature
• By LCP, an increase in system temperature will favour the net endothermic reaction to absorb heat, which
partially reduces system temperature, and vice versa

Catalysts
• No effect on equilibrium position
◦ Lowers the EA for both forward and reverse reactions by providing an alternative reaction pathway
◦ Rates of both forward and reverse reactions at equilibrium increase equally (relative concentrations of
products and reactants remain constant)
• Reduces time taken to reach equilibrium

Collision Theory
• Rate of reaction depends on frequency of successful collisions between reactant particles
◦ Must collide with sufficient KE to overcome EA
◦ Must collide with correct orientation (this isn’t an important consideration for this section)

Concentration
• An increase in concentration leads to a faster rate of reaction for which the added species is a reactant
◦ An increase in the number of molecules of a certain species increases the likelihood of collisions
• Adding water favours the reaction less dependent on collisions (i.e. with fewer reactants)

Pressure/Volume
• Decreasing pressure reduces collision frequency as molecules are less packed, so reaction less dependent on
collisions (with fewer particles reacting) favoured, shifting equilibrium towards the side with more molecules
• Increasing pressure increases collision frequency as molecules are more packed, so reaction more dependent on
collisions (with more particles reacting) favoured, shifting equilibrium towards the side with fewer molecules
• If there is an equal number of moles on both sides, neither reaction is favoured

Temperature
• Increasing temperature increases the rate of both forward and reverse reactions (higher average KE)
◦ Higher EA of endothermic reaction means a greater proportion of molecules have sufficient KE to overcome
EA barrier, and so the endothermic reaction rate increases more than the exothermic reaction rate
• Decreasing temperature reduces rate of both forward and reverse reactions
◦ Lower EA of exothermic reaction means a relatively greater proportion of molecules have sufficient KE to
overcome EA barrier, so the exothermic reaction rate decreases less than the endothermic reaction rate

–5–
Equilibrium Graphs
• The following diagrams refer to the Haber Process: N2(g) + 3 H2(g)
2 NH3(g) ∆H = −92.4 kJ mol−1

Reaching Equilibrium

• At equilibrium, the concentrations of all species (reac-

tants and products) remain constant
Concentration (mol L−1 )

3x • Note the stoichiometric change in the concentrations of

H2 reactants and products prior to reaching equilibrium, in
x
the ratio 1:3:2. This ratio corresponds with the molar
N2 coefficients of the reaction

NH3 2x

Time

Addition of a Species

• Addition of H2 causes equilibrium to shift to the right to

partially oppose this change (as per Le Châtelier’s Prin-
3x
Concentration (mol L−1 )

ciple)
y ◦ This causes a partial reduction in [H2 ] and [N2 ], and
H2 a partial increase in [NH3 ]
x • Again, note the stoichiometric change in concentrations
N2 prior to reaching equilibrium
2x
• The final [H2 ] is greater than the initial [H2 ], since equi-
NH3
librium only partially counteracts the increase in [H2 ] –
in the diagram y > 0
Time

Change in Pressure

• An increase in pressure (or an equivalent decrease in vol-

ume) causes the reaction involving more moles of gas to
increase to a greater extent than the reaction involving
3x
−1
)

fewer moles of gas

Concentration (mol L

• This shifts equilibrium to favour the reaction that pro-

H2 duces fewer moles of gas, favouring the formation of NH3 ,
x
and offsetting the increase in [H2 ] and [N2 ]
2x
N2 • The “spike” in concentration is proportional to the con-
centration of a species prior to the change in pressure –
NH3
in this case, the sudden increase in concentration is equal
to half the original concentration
Time • Again, note the stoichiometric change in concentrations
prior to reaching equilibrium

–6–
Change in Temperature

• An increase in temperature causes equilibrium to shift to

favour the heat-absorbing endothermic reaction to reduce
Concentration (mol L−1 )

temperature as per Le Châtelier’s Principle

3x
• Equilibrium shifts to the left, culminating in a decrease
H2 in [NH3 ] and an increase in [H2 ] and [N2 ]
x
N2 • The absence of a “spike” in concentration of any species
indicates a change in temperature
NH3
2x • Again, note the stoichiometric change in concentrations
prior to reaching equilibrium

Time

Rates of Reaction Curve

• This general curve demonstrates that as reactants form

products, the reaction rate of the forward reaction slows
Reactants (due to a lower reactant concentration leading to fewer
collisions between reactant molecules), while the rate of
Rate of Reaction

the reverse reaction increases (due to higher concentra-

tion of products)
• Eventually, the rate of both forward and reverse reactions
Equilibrium become equal, at which point equilibrium is reached
Products Reached

Time

Equilibrium Constant
[C]c [D]d
• For aA + bB
cC + dD, Keq = [A]a [B]b
when the reaction is at equilibrium

• Do not simplify equations, as this will alter the value of K

1
√
◦ Reversing reaction causes K , doubling coefficients causes K 2 , halving coefficients causes K, adding equi-
libria multiplies their respective K values together
• For heterogeneous reactions (reactants and products are not in the same phase), exclude pure solids and liquids
as these have constant concentration (assumed to be 1)
• Magnitude of K reflects equilibrium position
◦ K > 103 : Equilibrium lies well to the right
◦ K ≈ 1 (0.1 − 10) : Significant concentrations of both products and reactants at equilibrium
◦ K < 10−3 : Equilibrium lies well to the left
• No units are required for K or Q, but concentrations are in mol L−1 , and temperature should be specified
• When measuring concentrations, use non-destructive techniques which do not alter concentration (e.g. using
colourimetry or a pH meter)

Reaction Quotient
• Used when a system is not known to be at equilibrium
[C]c [D]d
• Q= [A]a [B]b

• If Q = K, the reaction is at equilibrium at the given temperature

–7–
 • If Q < K, the net forward reaction proceeds from L to R (towards products) until Q = K
• If Q > K, the net reverse reaction proceeds from R to L (towards reactants) until Q = K

Effect of Temperature on Equilibrium Constant

• Only temperature can affect K, since ∆G = −RT lnK
• As temperature increases, K increases for endothermic reactions, and decreases for exothermic reactions
◦ As temperature increases, the system shifts to favour the endothermic reaction. If the endothermic reaction
is the forward reaction, K increases; if the endothermic reaction is the reverse reaction, K decreases

Gases
• Mole fraction is the number of moles of a certain species of gas out of the total moles of gas (XA for a gas A)
• Partial pressure is the molar fraction of a certain species times total pressure, often in atm (PA = XA × P )
(PC )c (PD )d
• For aA(g) + bB(g)
cC(g) + dD(g) , Kp = (PA )a (PB )b

• Only include gaseous species in the expression

• Kp is only affected by temperature

Solubility
• Solvent is the medium that the solute dissolves in
• Solute is the compound that becomes dissolved
• A substance is soluble if the solvent-solute > solute-solute bond strength
◦ A substance is largely insoluble if the solvent-solute < solute-solute bond strength
• To dissolve a substance, solvent molecules break up solute structures and surround solute molecules
• Ionic compounds are soluble when attractions between water and ions overcome the attractions between ions

Ionic Compounds
Most ionic compounds are soluble in water. The dissociation process is:

1. Ionic bonds break and the salt dissociates into ions.

2. Some hydrogen bonds between water molecules break.

3. Ion-dipole bonds form hydration spheres (water only) or solvation shells (general term for all solvents).

(a) δ + of water is attracted to the anion, and δ − of water is attracted to the cation by ion-dipole bonds
(b) For NaCl, 6 water molecules surround each ion

δ−
δ+ δ+ O
H H δ+ δ+
H
δ+
δ− H
δ+
H
δ+ H δ+
O δ− H H δ−
O O
δ− δ−
δ+ O O δ+
H H H
δ+
H
δ+

Na +
δ+ Cl− δ+

H
δ+
δ− δ− H
δ+ H H
O O
δ− δ−
δ− O δ+ δ+ O
δ+ O δ+ H H
H H H
δ+
H
δ+
δ+ δ+
H H δ−
O

Figure 1: Hydration Spheres

–8–
Enthalpy Considerations
H O
• Consider NaCl(s) −−2−→ Na+ –
(aq) + Cl(aq)

• Steps 1 and 2 from above require energy, and when ions are hydrated in step 3, energy is released
◦ To be soluble, the energy required to separate ions has to be less than the energy released when ions are
hydrated (lattice enthalpy < enthalpy of hydration)
◦ The more energy released compared to energy required, the more soluble (∆Hsol < 0)
◦ Smaller ions and higher charges reduce solubility (due to higher lattice enthalpy)

Water of Crystallisation and Complex Ions

• Water attaches to salts or ions in a fixed ratio H2 O
• Molecules that form dipole bonds with metal ions are ligands, with
H2 O OH2
water forming a dative (coordinate covalent) bond with the central
CoCl2
compound, following VSEPR theory
H2 O OH2
• Water is removed by heating to form an anhydrous compound
H2 O
• E.g. CoCl2 · 6 H2 O(s)
CoCl2(s) + 6 H2 O(`)
Figure 2: Cobalt(II) Chloride Hexahydrate
Measuring Solubility
• A saturated solution contains the maximum amount of solute that can be dissolved in a given quantity of solvent
at a given temperature
◦ Displays macroscopic constancy, with the rate of dissolution equal to the rate of precipitation/crystalisation
• Solubility is the maximum amount of solute that can dissolve in a given quantity of solvent at a given temperature
◦ Equal to the concentration of the saturated solution at that temperature
• If the electrostatic attraction between ions exceeds the strength of ion-dipole interactions, a precipitate forms
◦ The supernate is the clear solution above the precipitate
• Generally, solubility increases with temperature, since the dissolution of most salts is endothermic
• There are 3 classes of solubility
◦ Soluble: Compound dissolves more than 10 g L−1
◦ Sparingly soluble: Compound dissolves 1–10 g L−1
◦ Insoluble: Compound dissolves less than 1 g L−1 , or no dissociation (e.g. covalent network structures)
• When there is a possibility for two salts to precipitate, the less soluble one will precipitate first (don’t just check
the Ksp value – the molar solubility must be calculated)

Solubility Rules

Table 2: Solubility Rules

Soluble Exceptions Insoluble Exceptions

Group 1, NH+4 , Ba
2+
, Sr2+ soluble;
NO−
3 None OH− 2+
Ca slightly soluble
CH3 COO− Ag+ insoluble O2− Group 1, NH+
4 , Ba
2+
, Sr2+ , Ca2+ soluble
Ag+ insoluble;
Cl− 2+ S2− Groups 1 and 2, NH+
4 soluble
Pb slightly soluble
Ag+ insoluble;
Br− 2+ CO2−
3 Group 1, NH+
4 soluble
Pb slightly soluble
I− Ag+ , Pb2+ insoluble SO2−
3 Group 1, NH+
4 soluble
Ba , Pb2+ , Sr2+ insoluble;
2+
SO2− PO3− Group 1, NH+
4 soluble
4
Ag+ , Ca2+ slightly soluble 4

–9–
Solubility Product
−
• For Aa Bb(s)
aA+
(aq) + bB(aq) Ksp =[A+ ]a [B – ]b

• When the rate of dissolution equals the rate of precipitation, dynamic equilibrium is reached
• For salts that produce the same number of ions when dissociated, Ksp can be used to compare solubility
◦ For salts without the same number of ions, molar solubility must be compared
• As solubility varies with temperature, specify the temperature with Ksp

Ionic Product
• Used to predict if a precipitate will form
• For non-equilibrium systems
• Qsp =[A+ ]a [B – ]b
• If Qsp < Ksp , the reaction proceeds from left to right (towards products) until Qsp = Ksp
◦ No precipitate will form, with an unsaturated solution produced
• If Qsp > Ksp , the reaction proceeds from right to left (towards reactants) until Qsp = Ksp
◦ A precipitate forms, with a supersaturated solution produced
• If Qsp = Ksp , equilibrium has been reached (a saturated solution exists)

Common Ion Effect

• An ionic compound is dissolved in a solution with an ion in common (e.g. AgI salt dissolved in a KI solution)
• By LCP, an increase in concentration of soluble ions shifts equilibrium left, favouring the reverse reaction
• A salt is less soluble in a solution with a common ion

Detoxifying Foods – Aborigines

• Cycads contain cycasin, so seeds must be detoxified for consumption
• Seeds are crushed to increase surface area, then soaked in water to leach out soluble toxins
◦ Cycasin has a high solubility of 56.6 g L−1 in water, due to the presence of multiple polar O – H functional
groups capable of forming hydrogen bonds with water
◦ Placing baskets in flowing creeks meant the toxin was carried away – no equilibrium was reached due to
the open system (if a container was filled with water, water was discarded when dynamic equilibrium was
reached, and the process repeated to progressively remove the toxin)
∗ If seeds were placed in a bowl of water, dissolution of the toxin would stop when the solution is saturated
• Fermentation to decompose toxins
• Cycad powder was baked into bread to thermally decompose toxins before consumption

O O N
HO N⊕

O
HO OH

OH

Figure 3: Cycasin – C8 H16 N2 O7

– 10 –
 HSC Chemistry Notes
Module 6
Acid and Base Reactions

Naming Inorganic Compounds

• Inorganic acids have H written first, whereas non-acidic compounds have H written after (e.g. LiH)
• Oxyacids contain H, O and another element. They dissolve to produce an oxyanion
◦ If the anion ends with -ite, the acid ends with -ous
◦ If the anion ends with -ate, the acid ends with -ic
◦ Hypo- and per- are used if the oxyanion can form multiple oxyacids
∗ HClO, HClO2 , HClO3 , HClO4 (hypochlorous, chlorous, chloric and perchloric acids respectively)
• Binary compounds have a different name if dissolved in water
◦ HCl is hydrogen chloride, but HCl(aq) is hydrochloric acid

Properties of Inorganic Acids and Bases

Table 3: Properties of Acids and Bases

Acids
Sour taste, corrosive
+
Conducts electricity in solution (H3 O )
Turns blue litmus red
Bases
Bitter taste, caustic, slippery
Conducts electricity in solution (OH – )
Turns red litmus blue

Common Acids

Table 4: Common Acids

Acid Use Strength Proticity

HCl In stomach, brick cleaner Strong Monoprotic
H2 SO4 Fertilisers, car batteries Strong Diprotic
HNO3 Explosives and fertilisers Strong Monoprotic
CH3 COOH Vinegar Weak Monoprotic carboxylic group (acidic proton)*
H2 CO3 Carbonated drinks Weak Diprotic
H3 PO4 Fertilisers Weak Triprotic
C6 H8 O7 In citrus Weak Triprotic carboxylic groups (acidic protons)*

* Generally, hydrogen atoms are acidic if they are attached to an electronegative atom, most often oxygen.

– 11 –
Common Bases
• Alkalis are a subset of bases which are soluble in water
• Bases are useful cleaners as they react with fats and oils to form water-soluble salts

Table 5: Common Bases

Base Use Strength

NaOH Cleaning agent Strong
NH3 Cleaning agent, fertilisers Weak
Na2 CO3 Washing powder, neutralising spills Weak
NaHCO3 Baking soda Weak
Mg(OH)2 Antacids Strong
Ca(OH)2 Limewater, cement Strong

Common Reactions
• Acid + Metal Hydroxide → Salt + Water

• Acid + Metal Oxide → Salt + Water

◦ Net ionic equation is: H+ – + –

(aq) + OH(aq) → H2 O(`) or H3 O(aq) + OH(aq) → 2 H2 O(`)

• Acid + Metal Carbonate → Salt + Water + Carbon Dioxide

• Acid + Active Metal → Salt + Hydrogen

Neutralisation
• Acid + Base → Salt + Water
• Neutralisation reactions are simply proton transfers
◦ E.g. HCl(aq) + NaOH(aq) → NaCl(aq) + H2 O(`) [Neutral salt]
◦ 2 CH3 COOH(aq) + Na2 CO3(aq) → 2 CH3 COONa(aq) + H2 O(`) + CO2(g) [Basic salt]
◦ HCl(g) + NH3(g) → NH4 Cl(s) [Acidic salt]
• Due to the different pH of different salts, use an appropriate indicator during titrations

Applications of Neutralisation
• Antacids contain a base (e.g. CaCO3 or Mg(OH)2 ), relieving symptoms of reflux by neutralising excess stomach
HCl
• Tartaric acid acts as a leavening agent, reacting with NaHCO3 to help cakes rise by forming CO2 gas
• Fertilisers containing (NH4 )2 SO4 or NH4 NO3 are made by neutralising sulfuric or nitric acid with NH3
• Neutralising industrial wastewater
◦ Acidic water is passed through limestone (CaCO3 ), or Na2 CO3 is applied
◦ Alkaline water is neutralised with H2 SO4 , HCl or HNO3
• Neutralising corrosive acid or base spills
◦ Isolate area, dilute with large amounts of water (to reduce concentration), don’t use concentrated acids or
bases (which are very exothermic)
◦ Solid NaHCO3 is amphiprotic – it can neutralise both acids and bases
∗ Stable (safe to store and handle), weak (relatively safe if used in excess), cheap, easy to clean up
compared to liquids

– 12 –
Enthalpy of Neutralisation
• Enthalpy change when an acid and alkali react to produce one mole of water, at 298 K and 1 atm
◦ Exothermic, since formation of covalent bonds between hydrogen and hydroxide ions releases energy
◦ H3 O + –
(aq) + OH(aq) → 2 H2 O(`) is the net ionic equation, hence the same enthalpy of neutralisation value
exists for reactions involving a strong acid and strong base
−Q
• Q = mC∆T , and ∆Hneut = n(H2 O) formed

• To convert from J g−1 to J mol−1 , multiply by M M

• Assumptions include:
◦ Salt solution has the same specific heat capacity as water (salts have a different specific heat capacity)
◦ No thermal energy is lost to the surroundings (assuming an isolated system exists)
• A weak acid or base reduces the enthalpy of neutralisation as the ionisation of non-dissociated molecules is
endothermic
• Improvements include:
◦ Using an electronic thermometer for accuracy
◦ A more insulated calorimeter (e.g. using a lid, or covering with aluminium foil)
◦ Repetition to increase potential for reliability

Acid Theories
Lavoisier
• Observed non-metal oxides produced acids when dissolved in water
◦ CO2(aq) + H2 O(`)
H2 CO3(aq)
• Proposed acids contained oxygen
• However, some metal oxides were basic, and some acidic substances (e.g. HCl) did not contain oxygen

Davy
• Observed H2 gas was produced when electrolysing acid solutions
◦ Proposed acids contained hydrogen
• Did not account for hydrogen in other substances (e.g. methane), relative strengths of acids and bases, or
neutralisation
• Von Liebig proposed acids contained “replaceable hydrogen” (metal displaces hydrogen of an acid in a reaction)

Arrhenius
• Proposed that acids dissociate to produce H+ ions in aqueous solutions
◦ Concentration of H+ ions could be used to compare strengths of acids
• Bases dissociate to produce OH – ions in aqueous solutions
• This helped define strong and weak acids and led to neutralisation theory (synthesis of water), and pH
• Did not consider bases such as metallic carbonates or metallic oxides (e.g. MgO) that could neutralise acids
• Could not explain the basicity of ammonia which does not contain OH –
• Only considered aqueous solutions (did not consider other solvents such as toluene, or different states, e.g.
NH3(g) + HCl(g)
NH4 Cl(s) )
◦ H+ ions do not exist by themselves in aqueous solutions

– 13 –
Brønsted-Lowry Theory
• Acids donate protons (H+ ), while bases accept protons
• Acidity occurs due to an acid’s interaction with the solvent (treat solvent as a reactant)
• Solves case of NH3(g) + HCl(g)
NH4 Cl(s) as HCl donates a proton
• An acid gives up a proton to form its conjugate base
◦ Acid + Water
Conjugate Base + H3 O+
◦ Protons do not exist in isolation in aqueous solutions – they are hydrated to form H3 O+
• A base accepts a proton to form its conjugate acid
◦ Base + Water
Conjugate Acid + OH –
◦ E.g. NH3(aq) + H2 O(`)
NH+ –
4(aq) + OH(aq)
• Conjugate acids and bases differ by one H+ from the original species
◦ Acid is the protonated form, base is the deprotonated form
• The stronger an acid is, the weaker its conjugate base (as the reverse reaction is reduced), and vice versa
• General form is BL Acid + BL Base
Conjugate Base + Conjugate Acid
• Generalisation of Arrhenius’ Theory
◦ Most acid-base reactions occur in water, so Arrhenius’ Theory is often sufficient, and used for convenience
• Cannot explain some reactions involving non-metal oxides and metal oxides which occur without solvents
◦ E.g. CaO(s) + SO3(g) → CaSO4(s)
• Cannot account for the acidic nature of BF3 or AlCl3 which act as acids, but lack hydrogen (not proton donor)

Lewis
• Allows acids and bases to be identified even if H
H H
no solvent is present
• Acid is e− pair acceptor, base is e− pair donor N N⊕
F
• A coordinate covalent/dative bond involves both H + F B
H H
F B
e− donated from a ligand to the central complex
(in Figure 4, the e− pair is donated from N to an F F
F
unoccupied orbital on the B to form a full octet)
Figure 4: Lewis Adduct Formation
• In the case of HCl, there is no empty orbital,
but the high electronegativity difference between Cl and H forms a permanent dipole. As such, it can accept a
lone pair of electrons, but this breaks the molecule up (e.g. NH3(aq) + HCl(aq) → NH+ –
4(aq) + Cl(aq) )

pH Scale
• Brønsted-Lowry definition of acids as proton donators led to the pH scale (measure of [H3 O+ ])
• At 298 K and 1 atm, acidity occurs when pH < 7, neutrality when pH = 7, basicity when pH > 7
• pH = −log10 [H+ ] = −log10 [H3 O+ ] and so [H3 O+ ] = 10−pH

• pOH = −log10 [OH− ] and so [OH – ] = 10−pOH

• Note: number of significant figures should equal number of decimal points for pH, and vice versa

Measuring pH
• Non-destructive (pH meter)
◦ Calibrate beforehand with buffer solutions of pH 4.0, 7.0, 10.0
◦ Accurate, but expensive
• Destructive (indicators)
◦ Cheap, but only gives a pH range (less accurate)
◦ Universal indicator follows ROYGBIV going from acidic to basic

– 14 –
Indicators
• Chemicals that change colour depending on pH
• Complex molecules that exist in at least 2 intensely coloured forms
• HIn(aq) + H2 O(`)
H3 O+ –
(aq) + In(aq)

◦ Indicator is a weak acid or base

◦ Addition of an acid causes equilibrium to shift to the left as per LCP
◦ Addition of a base causes a reduction in [H3 O+ ] due to neutralisation, so equilibrium shifts right

Uses of Indicators
• Testing acidity or alkalinity of soil to ensure optimum conditions for plants
◦ Use indicator from soil testing kit and BaSO4 for a white background
• Testing swimming pool water with a phenol red indicator (ideal pH is ≈ 7.4)
• Chemical analysis
◦ Determining if solutions are acidic, neutral or basic
◦ Estimating equivalence points in acid-base titrations (do not use universal indicator for titrations)

Strength and Concentration

• Strength is the degree of ionisation or dissociation
◦ The ability to donate protons (for acids) or accept protons (for bases) under Brønsted-Lowry theory
• Strong acids almost completely dissociate to release H+ ions in aqueous solutions: HA(aq) → H+ –
(aq) + A(aq)

• Weak acids only partially dissociate: HA(aq)

H+ –
(aq) + A(aq)

• The same applies for dissociation of alkalis to produce OH – ions under Arrhenius’ Theory
• Concentration is the number of moles of acid/base molecules in a given volume of solvent
• Assuming the same concentration, a strong acid has a higher [H3 O+ ] and hence lower pH than a weak acid, as
does a strong polyprotic acid compared to a strong monoprotic acid

− + − + +
++ −
− − −
+ + + −
+ − +
− −
+ − − −+ −
− − −
− + + − + + −
+ +
+ − + − − + + +
− + − +

Concentrated strong acid Dilute strong acid Concentrated weak acid Dilute weak acid
Unionised + Positive Ion − Negative Ion

Figure 5: Modelling Strength and Concentration

Monoprotic and Polyprotic Acids

• Monoprotic acids ionise to produce one H+ ion per acid molecule
◦ E.g. CH3 COOH(aq)
H+ –
(aq) + CH3 COO(aq)

• Polyprotic acids ionise in a stepwise manner, whereby subsequent ionisations are weak
–
◦ H2 SO4(aq) → HSO4(aq) + H+
(aq)
–
◦ HSO4(aq)
SO24(aq)
–
+ H+
(aq)

– 15 –
 ◦ Subsequent ionisations require a H+ to be removed from a negatively charged ion rather than from a neutral
molecule – stronger attractive forces must be overcome, leading to weaker ionisation
• Alternatively, the above reactions can have water as a reactant, forming hydronium ions

Self-Ionisation of Water

• Water undergoes limited self-ionisation, H2 O(`) + H2 O(`)

H3 O+ –
(aq) + OH(aq)

◦ Water acts as a very weak acid and a very weak base, hence it is amphiprotic
• At 298 K, KW = [H3 O+ ][OH− ] = 1 × 10−14

• By taking the logarithm of both sides, pH + pOH = 14 at 298 K

• Neutral: [H3 O+ ] = [OH− ] = 1 × 10−7 mol L−1 at 298 K
• Acidic: [H3 O+ ] > [OH− ]
• Basic: [H3 O+ ] < [OH− ]

Temperature
• Self-ionisation of water is endothermic, hence the forward reaction is favoured at higher temperatures
◦ Higher [H3 O+ ] and [OH – ] values occur at higher temperatures, but both are equal (KW increases as
temperature increases)
∗ pH and pOH both decrease, but remain equal
◦ Water is still neutral regardless of temperature, as [H3 O+ ] = [OH− ], even if pH 6= 7

Amphiprotic Substances
• Substances which can behave as both proton donors and acceptors
◦ E.g. self-ionisation of water
∗ One H2 O molecule acts as a Brønsted-Lowry acid, the other as a Brønsted-Lowry base
◦ For other reactions, if the solute is a stronger acid than water, water acts as a base. If the solute is a
stronger base than water, water acts as an acid
• Can write successive ionisations of acids in chains, writing the basic substance from the left
◦ CO23 – /HCO3– /H2 CO3
◦ PO34 – /HPO24 – /H2 PO4– /H3 PO4
◦ Substances in the middle (shown in blue) are amphiprotic
• To show a substance is amphiprotic, write two equations. There are 2 ways:
◦ HCO3– + H2 O
CO23 – + H3 O+ and HCO3– + H2 O
H2 CO3 + OH –
– – 2–
◦ HCO3 + OH
CO3 + H2 O and HCO3– + H3 O+
H2 CO3 + H2 O
◦ Either case is fine, but some markers may prefer the second set of equations
• Don’t confuse with amphoteric substances, which act as an acid or base but do not transfer hydrogen (e.g. ZnO)
◦ Acid: ZnO(s) + H2 SO4(aq)
ZnSO4(aq) + H2 O(`)
◦ Base: ZnO(s) + H2 O(`) + 2 KOH(aq)
K2 Zn(OH)4(aq)
• However, one of the equilibria will predominate: If Ka > Kb , the acidic reaction will predominate; if Ka < Kb ,
the basic reaction will predominate

KA and KB
• pKa + pKb = 14 at 298 K

• Ka × Kb = KW = 1 × 10−14 at 298 K. The proof is shown below (states are excluded for simplicity):
[H3 O+ ][A− ]
◦ HA + H2 O
H3 O+ + A− and so Ka = [HA]
[OH− ][HA]
◦ A− + H2 O
HA + OH− and so Kb = [A− ]
◦ Ka × Kb = [H3 O+ ][OH− ] = 1 × 10−14

– 16 –
Acidity Constant
• pH can be used as a direct measure of H3 O+ for strong acids, but not weak acids
[H3 O+ ][A− ] [H3 O+ ]2
• Ka = [HA] = [HA] , for monoprotic acids

• Also called acid dissociation constant or acid ionisation constant

• At equilibrium, the [HA] of a weak acid can be assumed to be its original concentration, due to limited dissoci-
ation
◦ Also, H3 O+ produced by self-ionisation of water is very small, and can be ignored
• Strong acids have a higher Ka value than weak acids due to a higher degree of ionisation (theoretically, absolute
complete ionisation will result in a Ka of ∞, but this isn’t true, even for strong acids such as HCl)
◦ For polyprotic acids, consider stepwise ionisation, denoted as Ka1 and pKa1 , etc.
∗ Subsequent ionisations have a lower Ka , and hence a higher pKa
• pKa = −log10 (Ka )
◦ pKa is smaller in strong acids and higher in weak acids

Percentage Ionisation
[A− ] [H3 O+ ]
• Note that [A− ] = [H3 O+ ], so Percentage Ionisation = [HA] × 100% = [HA] × 100%

Basicity Constant
[HB+ ][OH− ] [OH− ]2
• For B(aq) + H2 O(`)
HB+ –
(aq) + OH(aq) , Kb = [B] = [B]

◦ pKb = −log10 (Kb )

• At equilibrium, the [B] of a weak base is assumed to be the original concentration of the weak base solution, as
the dissociation of a weak base is very limited
◦ Also, OH – produced by self-ionisation of water is very small, and can be ignored
• Strong bases have a higher Kb than weak bases due to complete ionisation
• pKb is smaller in strong bases and higher in weak bases

pH of Salts
• Generally, a strong acid and strong base neutralisation forms a neutral salt
◦ Strong acid and weak base neutralisation forms an acidic salt
◦ Weak acid and strong base neutralisation forms a basic salt
◦ For weak acid and weak base reactions, if Ka > Kb the salt is acidic; if Ka < Kb the salt is basic
• Method for showing the acidity/basicity/neutrality of a salt:

1. Write the dissociation reaction of the salt in water.

(a) Write hydrolysis reactions between ions and water (if they occur).
(b) Reactions can be assumed to not occur if ions are extremely weak conjugate bases (e.g. Cl – for HCl),
or group I or II cations. You should still mention their presence, but state they do not react with H2 O.
2. Conclude whether the salt is acidic, basic or neutral based off hydronium and/or hydroxide ions formed:
“The hydrolysis of ion (...) will lead to formation of H3 O+ or OH – , and hence a decrease/increase in pH
(acidic/basic salt).”

• Amphiprotic salts generally arise from an amphiprotic anion such as HCO3– or H2 PO4–

– 17 –
Standard Solutions
Primary Standards
• Used to directly make solutions of accurately known concentration. Properties include:
◦ Available in very pure form
◦ Accurately known chemical formula (in most cases, no water of hydration)
◦ Stable (no mass changes or reactions with air or water)
◦ Highly soluble in distilled water (no precipitates are formed)
◦ High molar mass (loss of mass has less effect on number of moles lost, minimising errors in calculations)
• Basic standard: Anhydrous sodium carbonate (Na2 CO3 ) is the reagent’s pure form
• Acid standard: Oxalic acid dihydrate (H2 C2 O4 · 2 H2 O) is the reagent’s stable form, despite water of hydration

Secondary Standards
• Prepared by titrating against a primary standard of known concentration
• Reasons why the following substances are not primary standards:
◦ HCl is volatile, releasing fumes (losing mass and lowering concentration)
◦ H2 SO4 and NaOH are hygroscopic (absorbing water, leading to an overestimation of moles in a given mass)
◦ NaOH may react with CO2 in the air (overestimation of number of moles in a given mass)
◦ Na2 CO3 · 10 H2 O is deliquescent and spontaneously loses water to the atmosphere (use anhydrous form)
• Secondary standards must be used relatively soon after standardisation to maintain accuracy

Titrations
Equipment
• Volumetric flasks hold an accurately known volume, and are used to make standard solutions
• Pipettes deliver an accurately known volume (aliquot) of analyte into the conical flask
• Burettes deliver variable volumes of titrant (titre) into the conical flask
◦ The titre is the minimum volume of solution required to reach the equivalence point
• Rinse glassware with distilled water (for validity)
◦ Pipettes and burettes must then be rinsed 3 times with the solution to be delivered, to prevent solution
being diluted by residual water
◦ Distilled water may be left undried in the conical flask, since the number of moles of aliquot is not affected

Equivalence and End Points

• Equivalence point has stoichiometric equivalence between the number of H+ and OH – ions
◦ Reactions with strong acids and bases go to completion (only one reagent is required to be strong, but if
both are weak, then equilibrium is attained)
• The end point is when the indicator changes colour
◦ The titration is stopped when the end point is reached, and this is used to estimate the equivalence point
(end point should lie on steep part of titration pH curve)

Errors in Titrations
• Mistakes are avoidable errors (e.g. spilling aliquot, incorrectly rinsing a pipette, burette or volumetric flask)
◦ Discard these results as they are inaccurate
• Systematic errors produce a consistent bias (e.g. uncalibrated balance or using an unsuitable indicator)
• Random errors (e.g. difficulty in judging where meniscus lies)
◦ Minimised by taking average of three concordant titres

– 18 –
Specific Indicators

Table 6: Indicators

Indicator Colour Change Range Colour

Phenolphthalein 8.3–10.0 Colourless → Slightly pink → Pink-red
Bromothymol Blue 6.0–7.6 Yellow → Green → Blue
Litmus 5.0–8.0 Red → Purple → Blue
Methyl Orange 3.1–4.4 Red → Orange → Yellow

Titration Method
1. Prepare burette, rinse with distilled water and with titrant (3×), and clamp vertically.

2. Fill burette with titrant to 0.00 mL mark (or below) using funnel, and ensure there are no air bubbles. Record
the initial burette reading to 2dp.

3. Rinse pipette with distilled water and then analyte (3×).

4. Fill pipette with aliquot, and transfer to a pre-cleaned conical flask (rinsed with distilled water only).

(a) Beware of parallax error when using a pipette (base of meniscus should be on the mark), and put pipette
tip in contact with wall of conical flask to prevent the formation of bubbles.
(b) Pipette is calibrated to have a drop remaining in the tip – do not try to extract this drop.

5. Add 2 drops of a suitable indicator. Place a sheet of white paper under the conical flask to make colour changes
easier to see by increasing contrast.

6. Position burette tip over conical flask and transfer titrant until endpoint is reached (when close to endpoint,
add titrant drop by drop, stirring continuously).

(a) At end point, colour change persists for > 10 seconds (since temporary colour change results from uneven
stirring, where a localised portion of the solution has a higher or lower pH).

7. Record final burette reading to 2dp, and calculate the titre volume.

8. Repeat for 3 concordant titres within 0.10 mL of each other (the first “rough” titre is often ignored).

Back Titration
• Involves comparing the number of moles of excess reactant to the original substance being analysed
• Used when:
◦ There is difficulty in determining the end point due to a slow reaction
◦ The sample is insoluble but reacts with an acid or base
◦ The sample is toxic, volatile, unreactive or gaseous

Redox Titration
• Self-indicating salts include KMnO4 and K2 Cr2 O7 , which change colour after the equivalence point is reached.
The equivalence point can also be estimated with indicators such as starch, pH meters or potentiometers
–
• E.g. MnO4(aq) + 8 H+ – 2+
(aq) + 5 e → Mn(aq) + 4 H2 O(`)

◦ After the equivalence point, excess KMnO4 will produce a permanent purple tinge
– –
◦ However, brown MnO2 can be formed: 4 MnO4(aq) + 2 H2 O(`) → 4 MnO2(s) + 3 O2(g) + 4 OH(aq)
• E.g. Cr2 O27(aq)
–
+ 14 H+ – 3+
(aq) + 6 e → 2 Cr(aq) + 7 H2 O(`) , which transitions from an orange to a green colour

• An acid is required to supply the H+ (usually H3 PO4 )

• Uses include determining ascorbic acid content of foods (since acid-base titrations react with other acids present),
and determining ethanol content of wine by oxidising the ethanol to ethanoic acid

– 19 –
Titration Curves
• The following titration curves involve an acidic titrant being added to a basic analyte
• If a base is added instead of an acid, the pH curve increases rather than decreases as shown here

Strong Acid and Strong Base

14 • E.g. HCl(aq) + NaOH(aq) → NaCl(aq) + H2 O(`)

12
• Equivalence point is at pH = 7 (neutral salt formed)
10
• Higher starting pH due to strong base
8
pH = 7
• Steep part of curve from pH 3–10 suits many indicators, although
pH

6
bromothymol blue is the best choice (6.0–7.6)
4

Titre (mL)

Strong Acid and Weak Base

14 • E.g. HCl(aq) + NH3(aq) → NH4 Cl(aq)

12
• Equivalence point is at pH < 7 (acidic salt formed)
10
• Lower starting pH due to weak base, assuming that the comparison is
8
being made between strong and weak bases of similar concentrations
pH

6 pH < 7
• Buffer resists addition of HCl initially (see inflection), as
4
NH3(aq) + H2 O(`)
NH+ –
4(aq) + OH(aq)
2
• Steep part of curve from pH ≈ 4–8 suits bromothymol blue (6.0–7.6)
Titre (mL) and bromocresol green (4.0–5.6)

Weak Acid and Strong Base

14 • E.g. CH3 COOH(aq) + NaOH(aq) → CH3 COONa(aq) + H2 O(`)

12
• Equivalence point is at pH > 7 (basic salt formed)
10
pH > 7 • Higher starting pH due to strong base
8
• No buffer as NaOH is reacted with a weak acid
pH

6
◦ If the base was the titrant, then a buffer would exist
4

2 • Steep part of curve from pH ≈ 6–10 suits phenolphthalein (8.3–10.0)

Titre (mL)

Weak Acid and Weak Base

14 • E.g. CH3 COOH(aq) + NH3(aq)

CH3 COONH4(aq)
12
• No steep part of curve to estimate equivalence point, hence rarely used
10

8
pH ≈ 7
pH

Titre (mL)

– 20 –
Conductometric Curves
• For consistency, the base is the titrant and the acid is the analyte
• Useful for very dilute solutions, or dark and turbid solutions where a colour change is hard to perceive
• Charge carriers are mobile ions, and smaller ions are more conductive (since they move easier)

Strong Acid and Strong Base

• E.g. HCl(aq) + NaOH(aq) → NaCl(aq) + H2 O(`)

• High initial conductivity from H+ , Cl –
• Reduced conductivity as neutralisation occurs: H3 O+ –
(aq) + OH(aq) → 2 H2 O(`)
Conductance

• Lower conductivity at equivalence point due to Na+ , Cl – ions only

• Conductivity increases after equivalence point due to addition of excess Na+
and OH –

Strong Base Titre (mL)

Strong Acid and Weak Base

• E.g. HCl(aq) + NH3(aq) → NH4 Cl(aq)

• High initial conductivity from H+ and Cl –
• Reduced conductivity due to neutralisation, as ammonium ions are less mo-
Conductance

bile: H+ +
(aq) + NH3(aq) → NH4(aq)

◦ In most cases neutralisation is: H3 O+ –

(aq) + OH(aq) → 2 H2 O(`)

• No visible increase in conductivity after equivalence point due to NH3 being

a weak base with limited ionisation
Weak Base Titre (mL)

Weak Acid and Strong Base

• E.g. CH3 COOH(aq) + NaOH(aq) → CH3 COONa(aq) + H2 O(`)

• Lower initial conductivity due to weak acid with limited ionisation
• Decrease in conductivity due to neutralisation: H3 O+ –
(aq) + OH(aq) → 2 H2 O(`)
Conductance

• Equivalence point is not at the vertex

Not at Vertex ◦ CH3 COO – initiates common ion effect, shifting equilibrium left
◦ Formation of CH3 COONa increases conductivity before equivalence
point
Strong Base Titre (mL)

There is another possibility (suggested by NE SA sample answers) – refer to the same equation above:
• Low initial conductivity due to weak acid with limited ionisation
• Increased conductivity as CH3 COO – ions are formed when NaOH is
added
Conductance

• Equivalence point occurs when all CH3 COOH has been neutralised
• Steeper gradient after equivalence point as NaOH is a strong base, and
Na+ and OH – are better charge carriers than CH3 COO –

Strong Base Titre (mL)

– 21 –
Weak Acid and Weak Base

• E.g. CH3 COOH(aq) + NH3(aq)

CH3 COONH4(aq)
• Low initial conductivity due to a weak acid with limited dissociation
• Conductivity declines slightly due to the limited degree of neutralisation
Conductance

• Increased conductivity then occurs as added NH3 pushes equilibrium right,

with formation of more CH3 COONH4 . CH3 COONH4 dissociates into
CH3 COO – and NH+ 4 , which are better charge carriers

• The equivalence point occurs when no more CH3 COONH4 is formed

Weak Base Titre (mL)
• Excess NH3 added after equivalence point does not visibly increase conduc-
tivity (ammonia is a weak base with little dissociation)

Buffers
• Solutions which resist changes in pH if small amounts of acids or bases are added
◦ Requires similar molar concentrations of a weak conjugate acid-base pair
◦ E.g. CH3 COOH and CH3 COO – (From CH3 COONa); or NH3 and NH+
4 (from NH4 Cl)
◦ Cannot contain a strong acid/base as it will have an extremely weak conjugate, and hence no equilibrium
is attained (no shift in equilibrium can occur to resist pH changes)
–
• HA(aq) + H2 O(`)
A(aq) + H3 O+
(aq)

◦ Addition of acid increases [H3 O+ ], leading to equilibrium shifting to the left to minimise the increase in
[H3 O+ ] as per LCP, hence minimising decrease in pH
◦ Addition of base leads to additional OH – reacting with H3 O+ , reducing [H3 O+ ] – hence, equilibrium shifts
right to minimise this decrease in [H3 O+ ], minimising the increase in pH
∗ Or, OH – reacts with the acid itself, minimising the increase in [OH – ]: HA + OH –
A – + H2 O
• Buffer capacity is maximised if the weak conjugate acid-base pair have high and equimolar concentrations as it
can counteract addition of both acids and bases
◦ Definition: Number of moles of H3 O+ required to decrease the buffer’s pH by 1, per litre of buffer solution
−
• pH = pKa + log10 [A ]
[HA] (i.e. Henderson-Hasselbalch Equation)
[A− ]
◦ A buffer’s effective range is pH = pKa ± 2, i.e. 10−2 ≤ [HA] ≤ 102
◦ Note that for evaluating Ka , [A− ] 6= [H3 O+ ] in a buffer system

Natural Buffers
• Sea water: H2 CO3 + H2 O
HCO3– + H3 O+
◦ H2 CO3 comes from two equilibria, with CO2 dissolving in water, then reacting with water to form H2 CO3
◦ Addition of an acid is counteracted by equilibrium shifting to the left, minimising the increase in [H3 O+ ]
and the associated decrease in pH
◦ Addition of a base reacts with H3 O+ through neutralisation, so the forward reaction is favoured, preventing
an increase in pH
• Minerals and organic matter in soils act as buffers maintaining pH between 6.0–7.0
• HCO3– /H2 CO3 and Hb/HHb+ buffers in blood maintain a pH of 7.35–7.45
◦ H2 CO3 + H2 O
HCO3– + H3 O+
◦ Hb + H3 O+
HHb+ + H2 O, where HHb+ is protonated haemoglobin
◦ These ensure the function of enzymes which catalyse biochemical reactions
∗ A wrong pH can cause enzymes to denature, causing death

– 22 –
Industrial Titrations
• Determining acid and alcohol contents of wines
◦ Suitable techniques include back titrations, titrations with NaOH or redox titrations
• Determining acid content in fruit juices and soft drinks (mainly C6 H8 O7 – citric acid)
• Determining amount of acids/bases in medications such as aspirin (often back titrations due to low solubility)
• Determining acidity/basicity of wastewater by titrating against NaOH or HCl
• Purity of metals with potentiometric titration
◦ The metal is dissolved in a strong acid, precipitated, and conductivity measured by electrodes, with the
lowest conductivity at the equivalence point
◦ E.g. A pre-weighed mass of Ag is dissolved in HNO3 , and KCl is added to precipitate out AgCl
• Automatic titrators have an automated burette, and use a pH or conductivity probe to determine equivalence
point via a computer
◦ Useful for carrying out repeated titrations with higher accuracy and efficiency

Aboriginal Applications
• Leaves of the soap tree contain basic saponins, with a similar structure to soap molecules
◦ When crushed, leaves act as an antiseptic and skin cleanser
• The peanut tree contains basic alkaloids which treat stings caused by insects and marine creatures (e.g. methanoic
acid from ant bites)
• Alkaline nature of clay neutralises stomach acid, relieving indigestion

– 23 –
 HSC Chemistry Notes
Module 7
Organic Chemistry

• Hydrocarbons
• Alcohols, Aldehydes and Ketones
• Organic Acids and Bases
• Polymers

– 24 –
 ——— Hydrocarbons———
• Carbon is a group 14 element with 4 valence electrons, and can form 4 covalent bonds with other atoms
• Organic compounds are carbon-based compounds, excluding carbon oxides, HCO3– , CO23 – , CN – , etc.

Representing Molecules
• Structural formulae (expanded or condensed) show arrangements of bonds in an organic compound
◦ Unless drawn with wedges (see Figure 6), lines don’t always correspond to bond geometry
• Space-filling models show a molecule’s physical appearance, but do not show bonds properly
• Ball-and-stick models show 3D bonds, but the “sticks” have no physical reality, as bonds involve electron orbitals
overlapping
• Molecular formulae show the number of atoms of each element, but not bonding pattern or arrangement

Types
• Aromatic hydrocarbons contain benzene rings
• Aliphatic hydrocarbons are any other hydrocarbon
◦ Saturated compounds have only C – C bonds between carbons and cannot form any more bonds
◦ Unsaturated compounds have at least one multiple bond between carbons, and can bond with more atoms
• Cyclic hydrocarbons involve a closed carbon ring structure (e.g. cyclopentane or benzene)

Functional Groups
• A group of atoms defining the reactivity of a molecule
• Functional groups may be substituents, but not all substituents are functional groups
• A homologous series is a family of compounds with the same functional group or general formula (e.g. Cn H2n )

Alkanes, Alkenes and Alkynes

• Alkanes are a homologous series with the general formula Cn H2n+2 , where n ≥ 1
• In Figure 6, the solid wedge represents a bond coming out of the page, whereas the dashed wedge represents a
bond going into the page

H H H
120° 180°
109.5° 108.7pm
C C C H C C H
H
H
H H
H

Figure 6: Hydrocarbon Bonding Geometry

Table 7: Hydrocarbon Bonding Geometry

Bonding Around C Atom Bond Geometry Bond Angle*

4 single bonds Tetrahedral 109.5◦
1 double and 2 single bonds Planar 120◦
2 double bonds Linear 180◦
1 triple and 1 single bond Linear 180◦

* These are approximate values. For example, the planar bond in ethene is 121.3◦ due to VSEPR theory. Other
slight deviations from the listed bond angles may occur

– 25 –
Properties of Alkanes
• Non-polar (C – H bond is slightly polar, but geometry usually cancels this out)
• Relatively low MP/BP, as dispersion forces are the only intermolecular force
◦ As molecular size increases, there are more atoms, and more locations for instantaneous dipoles (unequal
electron sharing), hence more dispersion forces ⇒ higher MP and density
◦ At room temperature, C1 – C4 are gases, C5 – C18 are liquids and C>20 are waxy solids
• Unbranched alkanes pack closer than branched alkanes, resulting in stronger dispersion forces and higher MP’s
• Does not conduct electricity – no permanent dipoles or ions
• Insoluble in water – dispersion forces between water and the hydrocarbon are insufficient to overcome hydrogen
bonding between water molecules (simply speaking, alkanes are insoluble due to lack of polarity)
◦ Soluble in non-polar solvents, with solubility increasing with increasing chain length
• Addition of – CH2 to each alkane leads to a constant increase in dispersion forces, so MP increases linearly

Alkenes and Alkynes

• Functional groups of double and triple bonds, respectively
• Homologous series with formulae Cn H2n and Cn H2n – 2 respectively, where n ≥ 1

Properties of Alkenes and Alkynes

• Similar physical properties to alkanes (low MP, low density compared to water, insoluble in water, poor conduc-
tors of electricity)
• Alkanes have slightly lower BP’s than alkynes, and slightly higher BP’s than alkenes
◦ Alkanes have 2 and 4 more hydrogen atoms than alkenes and alkynes respectively, so there are more
instantaneous dipoles, and hence more dispersion forces
◦ HOWEVER, the linear geometry of alkynes allow them to pack closer than tetrahedral alkanes (which pack
closer than planar alkenes). This is more important than the slight difference in dispersion forces
• Different chemical properties – Alkenes/alkynes are unsaturated, and more reactive due to their π bonds

SPDF Hybridisation
• σ bonds are formed from the following overlaps: s − s, pz − pz, s − pz (an example is the C – H bond)
• π bonds are formed from the following overlaps: px − px or py − py
◦ Weaker as electrons are not equidistant from the nucleus, although they are equidistant in σ bonds
◦ Alkenes have a π and a σ bond, while alkynes have 2 π bonds and a σ bond
• A carbon atom has the spdf arrangement 1s2 2s2 2p2 : 1s: ↑ ↓ 2s: ↑ ↓ 2p: ↑ ↑ ↑
◦ Evidently, only 2 covalent bonds can be formed
◦ Due to the relatively small difference in energy between the 2s and 2p orbitals, a hybridised sp3 orbital is
formed. The carbon is in an excited state due the energy required to promote an electron to the 2p orbital
◦ Consequently, the electron arrangement is as follows: 1s: ↑ ↓ sp3 : ↑ ↑ ↑ ↑
◦ This allows carbon to form 4 covalent bonds

Bonding
• The orbitals are arranged in a tetrahedral
Hydrogen atom Hydrogen nucleus
manner due to VSEPR, and attract hydro- embedded in new
molecular orbital
gen atoms, which embed themselves in the
molecular orbital to form a σ bond

Methane

Figure 7: σ Bonding in Methane

– 26 –
 • Similarly, the C – C bond is a σ bond, as demonstrated by
the bonding in ethane (Figure 8). The remaining sp3 orbitals
merge to produce a σ covalent bond
◦ The same case applies for larger alkanes
• For alkenes and alkynes, the extra p orbitals will merge to
form a π bond, which will determine the shape of the molecule
◦ Considering the remaining unpaired electron orbitals, a
double bond creates a planar molecule whereas a triple
bond creates a linear molecule
Figure 8: σ Bonding in Ethane
Alkane Reactions
Combustion
25
• Complete combustion involves sufficient oxygen (e.g. C8 H18(`) + 2 O2(g) → 8 CO2(g) + 9 H2 O(`) )
13
• Incomplete combustion involves insufficient oxygen (e.g. C8 H18(`) + 2 O2(g) → 4 CO(g) + 4 C(s) + 9 H2 O(`) )
◦ Incomplete combustion has a lower enthalpy of combustion as less bonds are broken and then formed
◦ CO impacts health above 10 ppm by replacing O2 in haemoglobin, so cells cannot undergo respiration
◦ Crystalline soot can enter airways, and also bonds to form toxic substances (carcinogens)

Substitution with Halogens

• Requires energy in the form of UV light, since alkanes are less reactive
◦ Stepwise process, with one hydrogen being replaced by a halogen each time
◦ Different stepwise products have different BP’s, so fractional distillation can separate them

H H H H
UV Light
H C C H + .Br2 . .Br C C H + H .Br

H H H H

Figure 9: Substitution of Alkanes with Halogens

• This is, however, a simplified process

• In reality, the halogen (in this case, Br2 ) forms
free radicals under UV light, and reacts through a
three-stage mechanism (see Figure 10)
◦ Note that the Br• free radical formed in
Step 3 will be re-used in a chain reaction as a
reactant in Step 2. If any two radicals,
including the alkane radicals, combine, the
reaction terminates
• Note that the reaction in Figure 9 is the net
reaction of the multistep reaction in Figure 10

Figure 10: Free Radical Substitution

Properties of Halogenated Compounds
• Haloalkanes are used as refrigerants and flame retardants (including CFC’s)
• Polar bond (C – X) allows formation of dipole-dipole interactions between molecules, with stronger intermolecular
forces and higher MP’s than corresponding pure hydrocarbons
• Slightly soluble in water due to polar C – X bond, but influence of the polar group decreases as chain length
increases (since greater dispersion forces overpower dipole-dipole interactions)

– 27 –
Unsaturated Hydrocarbon Reactions
Combustion
• Complete or incomplete
• For incomplete combustion, products include a combination of CO2(g) , CO(g) or C(s) , plus H2 O(`)

Addition Reactions
• A π bond is broken, forming two new bonding sites (one on either carbon), increasing capacity for atoms
• Atoms then add across the bond being considered
• Degree of the bond is reduced by one

Hydrogenation (H2 )
• Converts alkenes into alkanes
• Metal catalyst (Pt, Ni, Pd) used
◦ Hydrogen adsorbs onto catalyst, breaking H – H bond, and forming two weak metal-hydrogen bonds
◦ Alkene adsorbs onto catalyst, breaking double bond, forming weak carbon-metal bonds
◦ Hydrogen bonds with carbon, forming the alkane, which then leaves the surface of the catalyst
• Used to convert unsaturated fats to saturated fats (e.g. in margarine)
◦ More single C – C bonds are formed, but some double bonds may remain
• For alkynes, a poisoned Pd catalyst (Lindlar’s Catalyst) prevents the alkene from reacting to form an alkane
◦ Bonding sites are blocked off on the catalyst

H H
H H
Pt Catalyst
C C + .H2 . .H C C H.
H H
H H

Figure 11: Hydrogenation

Halogenation (X2 )
• Due to reactivity of halogens and the π bond, no catalyst is required
• Decolourisation of bromine water indicates a double/triple bond, as alkanes only react with Br2 under UV light
◦ Note: The bromine water test is generally used for liquid alkenes/alkynes only
• One halogen atom is added to each carbon atom in the multiple bond
• 1,2-dibromoethane (see below in Figure 12) is used as a petrol additive to enhance performance

H H
H H
C C + Br2 . H C C H
H H
.Br. .Br.

Figure 12: Halogenation

Hydrohalogenation (HX)
• Hydrogen atom is added to one carbon atom in double/triple bond, and halogen atom is added to the other
• No UV light is required for this reaction
• Bromoethane and other haloalkanes are used as solvents and refrigerants

– 28 –
 H H
H H
C C + HCl .H. C C Cl
H H
H H

Figure 13: Hydrohalogenation of Alkene

H H
H C C H + HCl C C
.H. .Cl.

Figure 14: Hydrohalogenation of Alkyne

Hydration (H2 O)
• Hydration of an alkene forms an alcohol, using a dilute H2 SO4 or H3 PO4 catalyst
• Hydration of alkynes forms a ketone with a H2 SO4 and HgSO4 catalyst (except for ethyne, which forms ethanal)
◦ C – O bond is stronger than C – C bond, so a carbonyl compound is more stable
• Note that water is in the gaseous state (steam), using temperatures of approximately 300◦ C
• Reflux should also be used for hydration

H H
H H
Dilute H2 SO4
C C + H2 O. .H C C OH
∆ = 300◦ C
H H
H H

Figure 15: Hydration of Alkene

H H .O. .H.
H2 SO4
H C C C H + H2 O. H C C C H
HgSO4
H H .H.

Figure 16: Hydration of Alkyne

Markovnikov’s Rule

H H H H H H H H H

H C C C H C C C .H. + H C C C H
+ HBr
H H H .Br. H H .H. .Br.
Asymmetrical Alkene Major Product Minor Product

Figure 17: Markovnikov’s Rule

• If a symmetrical reagent (e.g. Cl2 ) is added across a multiple bond, the same group is added to each carbon
• If an asymmetrical reagent (e.g. H2 O or HBr) is added to an asymmetrical alkene, Markovnikov’s Rule states
that H will favour bonding to the carbon with the most H already attached, producing a major product
◦ The minor product involves the H bonding to the carbon with fewer H already attached

– 29 –
 ∗ The minor product does still form, and must be drawn unless stated otherwise
◦ Sometimes, two “major” products are possible – they are said to be in a 50:50 ratio (e.g. pent-2-ene and
HBr will form 2-bromopentane and 3-bromopentane)

Naming and Drawing

Naming
1. Name the longest carbon chain – this name comes last.

2. Identify any substituents, arranging in alphabetical order.

3. If identical substituents exist, apply prefixes (“di-”, “tri-”, “tetra-”, etc.).

4. Add numbers to identify the position of substituents, so that the locant series has the lowest number possible
(i.e. 2, 7, 8 is lower than 3, 4, 5, even though the sum of the latter is smaller).

(a) If there is the possibility for the same locant number, assign the lowest number to the substituent that is first
alphabetically, and assign the numbers so that the lowest list of numbers occurs (e.g. 2,2,7-trimethyloctane,
not 2,7,7-trimethyloctane).
(b) Allocate the lowest number to the major functional group (e.g. C – C takes priority over alkyl substituents).
(c) For cyclic hydrocarbons, no number is required if only one functional group is present. Otherwise, start
with the number 1 and work clockwise/anticlockwise to attain the lowest locant numbers.

5. Separate numbers and letters with dashes. Separate numbers and numbers with commas.

Table 8: Common Substituent Prefixes

Substituent Name Substituent Name

– CH3 Methyl – Cl Chloro
– CH2 – CH3 Ethyl – Br Bromo
–F Fluoro –I Iodo

Drawing
1. Draw parent chain and multiple bond (if any).

2. Add substituents in required positions, noting that the multiple bond has the lowest locant number.

3. Add hydrogen atoms so each carbon has 4 bonds.

Isomerism
• Structural isomers are compounds with the same molecular formulae but different structural formulae
◦ Chain isomers involve the re-arrangement of the carbon chain (often with a carbon from the parent chain
turned into an alkyl substituent, or vice versa)
◦ Position isomers involve a functional group or substituent changing position on the parent carbon chain
◦ Functional group isomers have the same molecular formula, but different functional groups (e.g. carboxylic
acids and esters, or aldehydes and ketones)
• Isomers can have different BP’s, depending on how sterically hindered the functional groups or substituents are
• Stereo (geometric) isomers can only occur if there is a re- H H H CH3
striction of rotation (e.g. C – C bond or ring structure)
C C C C
◦ There are cis and trans isomers
H3 C CH3 H3 C H
◦ The names (Z)-but-2-ene and (E)-but-2-ene are also
valid respectively Cis-but-2-ene Trans-but-2-ene

Figure 18: Stereoisomers

– 30 –
Organic Substance Safety
• MSDS sheets list IUPAC name, concentration, hazards, precautions for handling and first-aid procedures
◦ IUPAC naming reduces confusion as many substances have non-standard names

Risks – Physical Properties

• Many organic substances are volatile (due to weak intermolecular forces) and evaporate at room temperature
◦ They have invisible vapours, but many have pungent odours
• Highly flammable if vaporised
◦ Flashpoint is lowest temperature a liquid can form an ignitable mixture with air on the surface of the liquid
◦ A compound is highly flammable if its flashpoint is below 23◦ C, such as in methanol and ethanol

Exposure
• Inhalation: Vapours dissolve in bloodstream and accumulate in organs
• Absorption/ingestion: Dissolves through skin or intestine lining, and enters bloodstream
• Acute poisoning: Short-term exposure, often from vapours (e.g. dizziness, headaches)
• Chronic poisoning: Long-term exposure (e.g. organ damage, chronic fatigue, central nervous system damage)

Prevention
• Eliminate harmful chemicals (e.g. benzene substituted for cyclohexane for use in electroplating)
• Isolation (e.g. lab coat, safety glasses, fume cabinet, extraction fan)
• Avoid using a naked flame – use a hot plate or heating mantle instead

Disposal
• No organic waste should be washed down the sink, as it can poison plants and animals (use waste container)
• Collect wastes differently (e.g. halogenated compounds should be separated from alcohols due to different risks)

Implications of using Hydrocarbons

• Organic matter retains some chemical energy from photosynthesis
• 3 main hydrocarbons are coal, crude oil/petroleum and natural gas

Benefits and Uses

• Positive economic growth and development through industrialisation
• Hydrocarbons are energy-dense fuels used in cooking, automobiles, factories etc.
• Feedstocks for production of plastics, paints, medicines etc.

Crude Oil and Processing

• Crude oil is a complex mixture of hydrocarbons formed from decayed marine organisms
• Oil accumulates under domes of impermeable rock, which prevents migration to the surface
◦ A layer of natural gas may form between the crude oil and the impermeable rock
• Crude oil is heated to 400◦ C, with fractions separated according to BP (decreasing BP going up the column)
• Cracking involves decomposition of heavier fractions (e.g. kerosene) into lighter fractions (e.g. octane)
◦ Demand for lighter fractions such as octane is not met simply by fractional distillation
◦ Catalytic cracking uses a zeolyte catalyst, temperatures of 500◦ C and pressure 5–20 atm
◦ Thermal cracking uses higher temperatures of 800◦ C and pressure 70 atm
◦ E.g. C15 H32(`) → 2 C2 H4(g) + C3 H6(g) + C8 H18(`)

– 31 –
CO2
• Combustion produces CO2 , which absorbs infrared radiation, contributing to the enhanced greenhouse effect
◦ Leads to rise in average global temperatures, climate change, species extinction and rising sea levels
◦ Lower pH of oceans
∗ CO2(g)
CO2(aq) , then
∗ CO2(aq) + H2 O(`)
H2 CO3(aq) , then
–
∗ H2 CO3(aq) + H2 O(`)
HCO3(aq) + H 3 O+(aq)
∗ All of these equations are shifted to the right by an increase in [CO2(g) ], with an overall increase in
[H3 O+ ]
∗ Damages coral reefs and shells of shellfish/crustaceans
• CO2 emissions can be minimised by reducing reliance on fossil fuels
• Post-combustion capturing reduces net emissions
◦ CO2 is passed into an absorber liquid (e.g. amine)
and captured
◦ CO2 is removed, cooled and compressed into a liquid,
and geologically stored (carbon sequestration)
◦ Removes up to 90% of emissions

SO2 and NOx Figure 19: Carbon Capturing

• SO2 is produced from combusting fuels with sulfur impurities

• Oxides of nitrogen are produced from high-temperature combustion in car engines
• At low levels, SO2 (1 ppm) and NO2 (3–5 ppm) act as respiratory irritants
◦ NO2 can react with sunlight to produce photochemical smog
• Can form acid rain
◦ S(g) + O2(g) → SO2(g) , then 2 SO2(g) + O2(g) → 2 SO3(g) , then SO3(g) + H2 O(`) → H2 SO4(aq)
◦ N2(g) + O2(g) → 2 NO(g) , then 2 NO(g) + O2(g) → 2 NO2(g) , then 2 NO2(g) + H2 O(`) → HNO3(aq) + HNO2(aq)
• Consequences of acid rain:
◦ Increased water acidity disrupts reproductive cycles (e.g. fish eggs due to higher CaCO3 solubility)
◦ Leaching of heavy metal ions from soil into water (e.g. Pb2+ , Cd2+ )
◦ Damage to crops and forests
∗ Defoliation of forests prevents photosynthesis
∗ Reduced crop productivity
∗ Acidic soils lead to Al3+ leaching by reacting with otherwise insoluble Al(OH)3
◦ Erosion of marble structures: H2 SO4(aq) + CaCO3(s) → CaSO4(aq) + CO2(g) + H2 O(`)
◦ Erosion of metal structures: H2 SO4(aq) + Fe(s) → FeSO4(aq) + H2(g)
• NO2 can react with oxygen in the presence of UV light to form ozone, which has adverse health effects
• SO2 emissions can be minimised with low-sulfur coals, and collecting SO2 emissions for H2 SO4 production
• NOx emissions minimised by using catalytic converters in cars: 2 NO(g) + 2 CO(g) → 2 CO2(g) + N2(g)

CO and C(s)
• Produced by incomplete combustion
• CO is toxic at low concentrations as it binds preferentially to Hb 200 times better than O2
◦ Starves cells of oxygen by reducing the amount of O2 transported to cells
• C(s) is soot, which is carcinogenic
• Petrol engines have a low air-to-fuel ratio, so air injectors reduce CO emission and improve energy efficiency
• Catalytic converters reduce NO and CO emissions

– 32 –
Polymer Pollution
• Over 300 million tonnes of plastic are produced annually worldwide, but only 10% is recycled
• Plastic codes 1 (PET), 2 (HDPE), 3 (PVC) and 4 (LDPE) are usually recyclable
• Recycling uses 30% of the energy required to make a new product, whilst reducing raw materials required
• Decomposition of plastics is an environmental risk (e.g. ingestion by wildlife)

Benzene
• Not an alkene H
• 3 of the 4 valence electrons have normal covalent bonding, while the
H C H
fourth electron is delocalised and free to move around the structure C C
◦ Different physical and chemical properties to other hydrocarbons
C C
without delocalised electrons H C H
• Molecular formula of C6 H6 , with all bonds being planar and at 120◦
H
• Originally assumed to have alternating single and double bonds, so
Figure 20: Benzene Structure
that all carbon atoms have 4 bonds
◦ But all carbon-carbon bonds are the same length (average between the length of a single and double bond)
◦ This drawing in Figure 20 is the “average” structure as there is only one π bond
◦ Clouds of delocalised electrons form above and below carbon ring
• Cyclic delocalisation ensures molecular stability, and reactions that break the ring require high temperatures
and pressures

– 33 –
 ——— Alcohols, Aldehydes and Ketones ———
• Alcohols have the hydroxyl ( – OH) functional group
◦ General formula for alkanols is Cn H2n+1 OH, where n ≥ 1
◦ Primary alcohols have one carbon atom bonded to the carbon atom attached to the – OH group (or zero
in the case of methanol), secondary alcohols have 2, tertiary alcohols have 3

H H H H H H H CH3 H

H C C C OH. H C C C H H C C C H

H H H H .OH. H H .OH. H
Primary (propan-1-ol) Secondary (propan-2-ol) Tertiary (2-methylpropan-2-ol)

Figure 21: Primary, Secondary and Tertiary Alcohols

Naming Alkanols
1. Identify the longest carbon chain, and add the suffix “-ol ”.

2. Identify the position of the – OH group, assigning the lowest locant number possible.

3. Add substituents as usual.

4. If there is more than one – OH group, use the suffixes “-diol ”, “-triol ”, and so on.

Properties of Alcohols
• – OH group contains a highly electronegative oxygen with 2 pairs of non-bonding electrons

BP
• Higher BP than alkanes of similar molecular mass, which only have weak dispersion forces
• Polar – OH group forms strong hydrogen bonds between alcohol molecules
• Primary alcohols have the highest BP, followed by secondary, then tertiary
◦ – OH group is sterically hindered by neighbouring atoms in secondary and tertiary structures (harder to
form hydrogen bond)
◦ Molecules cannot pack as closely in secondary and tertiary structures, reducing dispersion force strength

H H δ+ H H
H
δ− δ−
H C C O O C C H

δ+
H H H H H

Figure 22: H-Bonding Between Alcohols

Solubility
• Much higher water solubility than alkanes
• Polar – OH group forms H-bonds with water, so short-chain alcohols such as ethanol are infinitely soluble
◦ Longer-chain alcohols have greater dispersion forces between alcohol molecules which outweigh the hydrogen
bonding with water, reducing water solubility (octan-1-ol and higher are insoluble)
• Primary alcohols are generally more soluble as the – OH group is not sterically hindered

– 34 –
 • Solubility in organic solvents increases with chain length, due to stronger dispersion forces between the alcohol
and solvent. Smaller alcohols are immiscible in polar solvents as alcohol-alcohol dispersion forces are weaker
than solvent-solvent dispersion forces

H H

δ− δ+
H C C O H
H
δ+ δ−
H O
H H

Figure 23: H-Bonding Between Alcohols and Water

Amphipathic Nature of Alcohols

• Alcohols contain a hydrophilic, polar end ( – OH) .H. .H.
◦ Can form ion-dipole bonds (e.g. with Na+ ), hydrogen bonds
.H. C C OH
(e.g. with H2 O) and dipole-dipole interactions (e.g. with HBr)
• Contains a hydrophobic, non-polar end (hydrocarbon chain) .H. .H.
◦ Can form dispersion forces (e.g. with I2 , or other hydrocarbons) Non-polar End Polar End

• Can dissolve polar and non-polar substances Figure 24: Amphipathic Nature
◦ Methylated spirits can dissolve non-polar oils and grease

Production of Alcohols
From Alkenes
• Hydration of alkenes involves a dilute H2 SO4 or H3 PO4 catalyst attacking the double bond, allowing water to
attach. Refer to Figure 15

Substitution of Haloalkanes
• Halogen atom replaced by hydroxyl group if reacted with water
• However, a reaction with water is very slow, so OH – is often used
• Haloalkanes are more likely to undergo substitution as the C – X bond is weaker than C – C or C – H bonds
◦ Except C – F, which is stronger than C – C and C – H. C – I is the most reactive
• Tertiary haloalkanes are the most reactive, followed by secondary and then primary alcohols

H H H H
H2 SO4
H C C X + H2 O. H C C OH + HX
∆
H H H H

Figure 25: Substitution with Water

H H H H

H C C X + OH− . H C C OH + X− .

H H H H

Figure 26: Substitution with Hydroxide Ions

– 35 –
Fermentation
Yeast Enzymes/Zymase
• C6 H12 O6(aq) 2C2 H5 OH(aq) + 2CO2(g) + Heat
∆ ≈ 37◦ C
• Requires renewable sources of starch and sugars (e.g. sugar cane, corn, grapes)
• Anaerobic yeast convert glucose to ethanol by metabolic pathways (glucose being an energy source for yeast),
with ethanol being excreted

Enzymes
• Yeast can only ferment monosaccharides (simple sugars with one ring and 4–6 carbons) such as glucose or
fructose
• Enzymes break down dissacharides (e.g. sucrose) to monosaccharides
Yeast Enzyme
◦ C12 H22 O11(aq) + H2 O(`) −−−−−−−−−→ 2 C6 H12 O6(aq)
• Polysaccharide chains (e.g. cellulose or starch) are decomposed by hydration
Yeast Enzyme
◦ (C6 H10 O5 )n(aq) + n H2 O(`) −−−−−−−−−→ n C6 H12 O6(aq)

Conditions for Fermentation

• Suitable fruit or grain mashed up in water (to produce an aqueous solution of glucose)
• Temperature of ≈ 37◦ C, or yeast will denature
• Low pH of 4–6 to kill bacteria
• Alcohol-tolerant yeast
• Anaerobic conditions, as oxygen would otherwise oxidise ethanol to ethanal and then ethanoic acid
◦ Difficult to achieve a pure sample, so fractional distillation should be used
◦ An air lock can be used with a water-filled S-bend, with waste CO2 gas escaping as bubbles
• Dilute ethanol concentration (12–15% v/v) or yeast will die (must continuously distill, with ethanol being the
distillate as it has a lower BP than water)
◦ Through distillation, a yield of ≈ 95% can be obtained
• To test for successful fermentation, use the limewater test for CO2

Enthalpy of Combustion
Combustion
• Complete combustion: CO2 and H2 O are products
• Incomplete combustion: A mixture of CO2 , CO, C(s) and H2 O are products

Enthalpy of Combustion (Calorimetry)

• Molar heat of combustion – energy released by complete combustion of one mole of a substance
• All combustion reactions are exothermic (∆Hc < 0), releasing heat into the environment

• Use Q = mC∆T and ∆Hc = − Q

n

• Water is written in the liquid state, since a gaseous state alters the enthalpy value
• Energy efficiency is assumed to be 100% (Law of Conservation of Energy)

Analysing Enthalpy of Combustion

• Generally, experimental results have poor accuracy, straying from theoretical values
◦ Assumes that all heat was transferred to water, but some goes to the air, glass beaker, tripod, gauze etc.
◦ Incomplete combustion produces less energy than complete combustion (look for soot or orange flame)
◦ Loss of heat from water or container to atmosphere (use aluminium insulation, lid, or bomb calorimeter)

– 36 –
 ◦ Evaporation of alcohol from wick of spirit burner means more mass of alcohol is lost (∆H is underestimated)
◦ Use an electronic thermometer that has a more precise temperature reading than an analogue thermometer
∆Hc
• Heat released per gram = MM

∆Hc
• Heat released per litre = MM × density of fuel (in g L−1 )
◦ Note that density is often given in g mL−1 , so multiply the required value by 1000

Reactions of Alcohols
Dehydration of Alcohols
• Alcohols form alkenes when heated with concentrated H2 SO4 or H3 PO4 , with water being a by-product
◦ Concentrated H2 SO4 is a dehydrating agent and absorbs water (opposite of hydration with dilute H2 SO4 )
• Occurs at room temperature for 3◦ alcohols, but higher temperatures are required for 1◦ and 2◦ alcohols
◦ Tertiary alcohols have the most stable carbocation, leading to greater reactivity
• Alternatively, a Al2 O3 catalyst can be used for “cracking” at high temperatures and pressures

H H
H H
Conc. H2 SO4
.H. C C OH C C + .H2 O.
∆ (180◦ C)
H H
H H

Figure 27: Dehydration of Alcohols

Zaitsev’s Rule
• If dehydration of an alcohol results in multiple products, the major product is the more substituted alkene
◦ The major product will have more alkyl groups attached to the carbon atoms in the double bond, and
fewer hydrogen atoms attached to these two carbons (kind of the opposite of Markovnikov’s Rule)
◦ Sometimes, there are two major products possible – they are said to be in a 50:50 ratio

Substitution with Hydrogen Halides

• Produces a haloalkane and water, with the – OH group replaced by – X
• 3◦ alcohols are the most reactive, followed by 2◦ then 1◦ . Methanol is relatively unreactive with HX
• Hydrogen halide reactivity increases going down the halogen group, with HF being the least reactive and HI
being the most reactive

H H H H
H2 SO4
H C C OH + HI H C C I + HOH
∆
H H H H

Figure 28: Substitution with Hydrogen Halides

Reactivity Order
• Dehydration: Tertiary > Secondary > Primary
• Substitution: Tertiary > Secondary > Primary
• The stability of the carbocation determines reactivity

– 37 –
Oxidation of Alcohols
• Alcohols are oxidised by strong oxidising agents (e.g. MnO4– or Cr2 O27 – , which are acidified with H+ )
–
◦ MnO4(aq) + 8 H+ – 2+
(aq) + 5 e → Mn(aq) + 4 H2 O(`)
◦ Cr2 O27(aq)
–
+ 14 H+ – 3+
(aq) + 6 e → 2 Cr(aq) + 7 H2 O(`)

• In organic chemistry, oxidation is the loss of H or gain of O

◦ Oxidation involves an increase in the oxidation state, reduction involves a decrease in the oxidation state

Redox Reaction Procedure

Consider the oxidation of CH3 CH2 OH to CH3 COOH (states have been excluded for simplicity):

1. Balance O using H2 O: CH3 CH2 OH + H2 O → CH3 COOH

2. Balance H using H+ : CH3 CH2 OH + H2 O → CH3 COOH + 4 H+

3. Balance charge: CH3 CH2 OH + H2 O → CH3 COOH + 4 H+ + 4 e – (This is the oxidation half-equation)

4. Write the reduction half-equation for the oxidising agent: Cr2 O27 – + 14 H+ + 6 e – → 2 Cr3+ + 7 H2 O

5. Cancel the electrons in the two half-equations (in this case, multiply the oxidation half-equation by 3 and the
reduction half-equation by 2)

(a) 3[CH3 CH2 OH + H2 O → CH3 COOH + 4 H+ + 4 e – ] + 2[Cr2 O27 – + 14 H+ + 6 e – → 2 Cr3+ + 7 H2 O]

(b) The net equation would then be: 3 CH3 CH2 OH + 2 Cr2 O27 – + 16 H+ → 3 CH3 COOH + 4 Cr3+ + 11 H2 O

Primary Alcohols
• Oxidise to form an aldehyde, which subsequently oxidises
to form a carboxylic acid
• Acidified dichromate is added drop-by-drop to oxidise
ethanol to ethanal, with heat from a heating mantle
• To isolate the aldehyde, distill it from the reaction mixture
to prevent further oxidation, since both the alcohol and
carboxylic acid have a higher BP than the aldehyde
◦ Weak oxidising agents will not oxidise all the way to
the carboxylic acid, stopping at the aldehyde
◦ Alternatively, adding an excess of alcohol will render Figure 29: Oxidation/Distillation Setup
the oxidant a limiting reagent

O O
[O] [O]
R C OH C R C

R H OH

Figure 30: Primary Alcohol Oxidation

H H H H
O O
H C C OH Cr2 O27 – /H+ H C C Cr2 O27 – /H+ H C C
Heat H Heat OH
H H H H
Ethanol Ethanal Ethanoic Acid

Figure 31: Primary Alcohol Oxidation: Ethanol

– 38 –
Secondary Alcohols
• Oxidise to form ketones, which cannot be further oxidised

OH O
[O]
R C R0 C

H R R0

Figure 32: Secondary Alcohol Oxidation

H OH H H O H

H C C C H MnO4– /H+ H C C C H
Heat
H H H H H
Propan-2-ol Propanone

Figure 33: Secondary Alcohol Oxidation: Propan-2-ol

Tertiary Alcohols
• Cannot be oxidised without drastic conditions as oxidation requires OH
removal of H from the C atom attached to the – OH group (must [O]
break C – H bond, which doesn’t exist in tertiary alcohols) R C R00 No Reaction
◦ Must break the stronger C – C bond, requiring more energy
R0

Figure 34: 3◦ Alcohol Oxidation

Distinguishing Alcohols
• Cr2 O27 – is orange, which turns green when reduced to 2 Cr3+ (chromium(III))
• MnO4– is purple, which turns colourless when reduced to Mn2+ , but can form brown MnO2 (less reliable)
• Alcohols are colourless, so any colour change is from the oxidising agent
• Tertiary alcohols have no observable colour change (since no reaction occurs)

Biofuels
• Biofuels are a subset of sustainable fuels, which have the following general properties:
◦ Must be produced as quickly as it is consumed
◦ The environment must be able to absorb and process any waste products without major damage

Ethanol Uses

• Solvent due to its amphipathic nature • Antiseptics

• Alcoholic beverages • Supplement in motor fuel

Bioethanol (Fuel)
• Produced from fermentation of sugars and starches/cellulose (polymers of glucose)
• Takes up arable land to grow crops, with land degradation (erosion, salinity, runoff) and competition with food
production (which can worsen food shortages) being issues
• Ethanol is theoretically “greenhouse neutral ” as combustion releases the same amount of CO2 as used in pro-
duction

– 39 –
 ◦ 6 CO2(g) + 6 H2 O(`) → C6 H12 O6(aq) + 6 O2(g)
◦ C6 H12 O6(aq) → 2 C2 H5 OH(aq) + 2 CO2(g)
◦ 2 C2 H5 OH(`) + 6 O2(g) → 4 CO2(g) + 6 H2 O(`)
◦ Note that the third equation is multiplied by 2 to demonstrate the conservation of moles
◦ Other energy inputs are required (e.g. energy for distillation and harvesting), so not actually carbon-neutral
∗ Still emits 20–50% less net CO2 than other fossil fuels per unit of energy
• Ethanol burns more cleanly than petrol/octane, with a lower oxygen-to-fuel ratio of 3:1 vs. 12.5:1 for petrol
◦ Ethanol already has oxygen in it, so it is more likely to undergo complete combustion
◦ Less incomplete combustion, hence higher energy efficiency and less CO and C(s) pollutants
• Lower fuel economy and energy released compared to petrol
◦ Ethanol: 1370 kJ mol−1 , or 29.7 kJ g−1
◦ Petrol: 5470 kJ mol−1 , or 49.7 kJ g−1
• If added to petrol, ethanol boosts the octane rating, limiting premature combustion (knocking)
• Can be used at up to 15% without modification of engines, and E10 is widely available
◦ Higher blends are not commercially available in Australia and require engine modification (different air-to-
fuel ratios, and ethanol is corrosive to engines at high concentrations)
◦ E10 has minimal difference in fuel economy compared to standard petrol
• Harder to start cars in cold weather as ethanol has a higher flash point than octane
• Cost of producing ethanol is higher than petrol, but government uses subsidies and tax concessions

Biogas
• Produced by breakdown of organic waste (e.g. sewage) by anaerobic bacteria in a digester tank
◦ Decomposes complex carbohydrates into CO2 and CH4 , which are collected separately
• Organic wastes can then be used as fertilisers

Biodiesel
• A combustible ester is produced from fatty acids (e.g. corn or coconut oils)
◦ Uses waste vegetable oils or animal fats from the food industry
• Triglycerides undergo a transesterification reaction with methanol and a KOH or NaOH catalyst, to produce an
ester and glycerol
◦ Components are then gravity-separated as glycerol is denser than biodiesel
• Biodiesel can be used at up to 20% without engine modification
• Little difference in fuel economy compared to diesel
• Only contributes small net amount of CO2 to the atmosphere due to production processes
• Safer than diesel since it has a higher flash point and is less likely to spontaneously ignite

O
H2 C OH O
H2 C O C R
O
OH –
HC OH + 3 H3 C O C R
HC O C R + 3 CH3 OH
O
H2 C OH
H2 C O C R

Figure 35: Biodiesel Formation by Transesterification

– 40 –
Aldehydes and Ketones
• Contain the carbonyl functional group (C – O) O O
• Aldehydes (RCHO) have the carbonyl group on the terminal carbon
C C
• Ketones (RCOR’) have the carbonyl group on a non-terminal carbon R .H. R .R0 .
• They are functional group isomers of each other
Aldehyde Ketone

Figure 36: Aldehydes/Ketones

Naming Aldehydes
1. Identify longest carbon chain with – CHO group, replacing “-e” with “-al ”.

2. No locant number is required for – CHO as it is on the terminal carbon.

3. Name any substituents as usual, noting that the carbonyl group has a locant number 1.

Naming Ketones
1. Identify the longest carbon chain with the C – O group, replacing “-e” with “-one”.

2. The C – O group must have the lowest locant number possible (only required for n ≥ 5).

Properties
• Oxygen is more electronegative than carbon, so C – O bond is polar, forming dipole-dipole interactions
• Higher BP than hydrocarbons of similar molecular mass (to exclude differences in dispersion forces, as these
should be similar for molecules of similar molecular mass)
◦ Increasing chain length increases BP linearly due to stronger dispersion forces
◦ Lower BP than corresponding alcohols as hydrogen bonds are stronger than dipole-dipole interactions
• Carbonyl group forms H-bonds with water, but aldehydes/ketones are less soluble than alcohols
◦ Small aldehydes and ketones are soluble, but increasing chain length increases dispersion forces between
aldehyde/ketone molecules which outweigh H-bonds with water, hence reducing solubility
◦ Increasing solubility in organic, non-polar substances with increasing chain length due to stronger solvent-
solute dispersion forces
• Aldehydes are generally more reactive than ketones
◦ C – O group in ketones is more sterically hindered by alkyl groups compared to aldehydes (it is harder to
form H-bonds in ketones)

R
δ− δ+
C O H O

R0
H

Figure 37: H-Bonding Between Aldehydes/Ketones and Water

R
δ+ δ−
C O
R
R0
δ− δ+
O C

R0

Figure 38: Dipole-Dipole Interactions Between Aldehydes/Ketones

– 41 –
 ——— Organic Acids and Bases ———
Carboxylic Acids
• Contain a carboxyl ( – COOH) functional group
• General formula for an alkanoic acid is Cn H2n+1 COOH, where n ≥ 0

Naming
1. Identify longest carbon chain containing – COOH group, and add “-oic acid ” (don’t forget carbon on – COOH).

2. No locant number is required for the – COOH group since it is at the end of the chain (number 1).

3. Name any substituents as usual.

Properties
• – OH and C – O groups make the carboxyl group polar (due to electronegativity differences)
• Much stronger intermolecular forces than molecules of similar molecular mass, hence higher BP
◦ Hydrocarbon chain forms dispersion forces, – OH forms H-bonds, C – O forms dipole-dipole interactions
• Dimers can be formed: Two carboxylic acid molecules form H-bonds with each other, increasing BP
◦ This effectively doubles the dispersion force strength compared to single carboxylic acids
• Small carboxylic acids (e.g. HCOOH) are very soluble in water since they form strong H-bonds and dipole-dipole
interactions with water (more soluble than alcohols due to both C – O and – OH groups)
• Larger carboxylic acids are soluble in non-polar solvents due to stronger dispersion forces between the carboxylic
acid and the solvent overcoming polar H-bonds between dimers
• Carboxylic acids function as surfactants, with the polar, hydrophilic head lining up on the water surface

δ+
H δ−
H
O
δ+ δ− δ+
H C C O H
δ− δ+
O H
H

Figure 39: H-Bonding Between Carboxylic Acids and Water

R H
δ+

δ−
C O O
O O
δ−
C
δ+
H R

Figure 40: Carboxylic Acid Dimer

Monoproticity
• The only hydrogen atom which can react with a base is on the – COOH (acidic proton)
◦ The hydrogens on the hydrocarbon chain have non-polar bonds, so H cannot be drawn away and leave its
electron behind
• Acid strength is increased by substituting highly electronegative atoms onto the hydrocarbon chain
◦ Electronegative substituent attracts electron, weakening – OH bond, making it easier to form H+ ion
◦ Dichloroethanoic acid is 3000 times stronger than ethanoic acid

– 42 –
Amines and Amides
• Amides are stable in aqueous solutions with limited acid-base behaviour, but amines can act as weak bases
◦ N in amines draws in electron density, stabilising the positive charge gained from a H+
◦ For amides, the electronegative O draws electron density from N, making it more difficult to accept a proton
• Simple amines may ionise in water (e.g. CH3 CH2 NH2(g) + H2 O(`)
CH3 CH2 NH+ –
3(aq) + OH(aq) )

Amines
• Functional group – NH2
• Primary amines have 1 alkyl group attached to the nitrogen atom, 2◦ amines have 2, 3◦ amines have 3

Naming Amines
1. Identify longest carbon chain attached to N, and add suffix “-amine”. Assign N the lowest locant number.

2. Name and number any alkyl substituents not attached to the N.

3. Any other alkyl groups attached to the N should be labelled as “N-alkyl ”.

4. For multiple amine groups, use “-diamine”, “-triamine”, etc.

5. A similar system is used for naming amides (see Figure 45).

Drawing Amines
1. Draw main carbon chain and position N as required.

2. Draw other substituents, including alkyl substituents attached to the N.

3. Nitrogen atom should have 3 bonds, not 4 (fill remaining bonds with hydrogen atoms).

Properties of Amines
• Nitrogen is the 4th most electronegative element, so – NH2 is very polar
• Primary and secondary amines can form H-bonds due to the N – H bond
◦ Higher BP’s than alkanes of similar molecular mass, but lower BP’s than alcohols
◦ N is less electronegative than O, so hydrogen bonds are weaker than those in alcohols (N – H is less polar)
◦ Small amines are water soluble through forming hydrogen bonds with water, but increased chain length
increases dispersion forces between amines – larger amines are less soluble but have higher BP’s
• Tertiary amines cannot form hydrogen bonds as they have a saturated nitrogen atom without any N – H bonds
(lower BP than primary and secondary amines, and usually insoluble)
• Amines are weak bases, as the nitrogen has a lone pair of electrons, and its δ − charge attracts protons
◦ Can accept a H+ ion from an acid to form a protonated amine
∗ CH3 NH2(aq) + H2 O(`)
CH3 NH+ –
3(aq) + OH(aq) , forming protonated methanamine
∗ CH3 NH2(aq) + HCl(aq) → CH3 NH3 Cl(aq) , forming methylammonium chloride

δ+ δ+
H H H H

δ− δ−
H C N N C H

δ+ δ+
H H H H

Figure 41: H-Bonding Between Amines

– 43 –
Amides
• Amides have the CONR functional group, with the general for- δ−
O δ+
mula RCONR’ H
• Carboxylic acids react with ammonia to form a primary amide H C
δ+
N
δ−

• Carboxylic acids react with a primary amine to form a secondary amide δ+

H
• Note the condensation reaction similar to esterification
Figure 42: Amide Dipoles
H .H. H O
O
H C C + N H H C C N H + HOH
O H.
H H H H

Figure 43: Formation of Primary Amides

H .H. H O
O
H C C + N H H C C N H + HOH
O H.
H CH3 H CH3

Figure 44: Formation of Secondary Amides

Naming Amides
1. Replace “-oic acid ” with “-amide” for the alkyl group from the carboxylic acid.

2. Name any alkyl groups bonded to the nitrogen atom as “N-alkyl ” (see Figure 45).

3. Note that nitrogen forms 3 bonds, not 4.

O H H O

H C N CH2 CH3 H C C C N CH3

CH3 H H CH3
N-ethyl-N-methylmethanamide N,N-dimethylpropanamide

Figure 45: Naming Amides

Properties of Amides
• Primary and secondary amides have 2 polar groups (N – H and C – O) and are capable of more extensive hydrogen
bonding than related amines
• Tertiary amides have the C – O bond only, and cannot form H-bonds as they have a saturated N atom
◦ Primary and secondary amides can
form H-bonded networks and dimers,
and have very high MP’s/BP’s. Pri-
mary amides have higher BP’s than
carboxylic acids as there are 2 H
atoms on the N, and hence 2 loca-
tions for H-bonding, compared to one
on the carboxylic acid
• Smaller amides are soluble as they form Figure 46: Amide Dimers
strong H-bonds with water molecules

– 44 –
 ◦ As amides becomes larger, there are stronger dispersion forces between amide molecules, outweighing the
polar end and reducing water solubility
◦ More soluble than alcohols of similar molecular mass, as H-bonds form with both C – O and – NH2
• Amides do not act as bases under standard conditions
◦ The δ + carbon repels H+ , so amides cannot accept H+ easily
◦ When an amide does react with a strong acid (e.g. HCl) in the presence of H2 O, an alkanoic acid is formed
∗ CH3 (CH2 )n CONH2(aq) + HCl(aq) + H2 O(`) → CH3 (CH2 )n COOH(aq) + NH4 Cl(aq)

Esters
• Formed from the esterification reaction of a carboxylic acid and alcohol
• The OH from the carboxylic acid and H from the alcohol form water in an acid-catalysed condensation reaction
• Structural formula RCOOR’, with the functional group – COOC –
• Carboxylic acids and esters are functional group isomers

Naming
• Name in the form “alkyl alkanoate”
• First name is based off the alcohol, second name is based off the carboxylic acid
• To name the molecule, split the molecule in two along one of the C – O single bonds and inspect the alkanoic
acid and alkanol from the two fragments

H H H O H
O
H C C + HO C H Conc. H2 SO4 H C C O C H + H2 O
...OH. ∆, Reflux
H H H H
Ethanoic Acid Methanol Methyl Ethanoate Water

Figure 47: Esterification Reaction

Properties of Esters
• Esters do not have the capacity for hydrogen bonding as they lack the – OH bond
• Lower MP/BP than carboxylic acids or alcohols of similar mass (as esters only have dispersion forces and
dipole-dipole interactions), so esters are usually liquids at room temperature
◦ Increase in chain length increases dispersion forces, resulting in higher BP
• Most esters are insoluble in water due to large hydrophobic alkyl groups (smaller esters are slightly soluble)
◦ But are good organic solvents due to strong dispersion forces
◦ Can only form hydrogen bonds with water

R
δ+
δ−
C O H O

O
H
0
R

Figure 48: H-Bonding Between Ester and Water

– 45 –
Preparing Esters
1. Mix 10 mL pure ethanol and 20 mL glacial acetic acid in a distillation flask. Add 10 drops of 18 M H2 SO4 .

2. Clamp the flask and immerse in a 500 mL beaker of water.

3. Add ceramic boiling chips.

4. Attach reflux condenser and heat with heating mantle for 20–30 minutes.

5. Use a separating funnel, distillation or “salting out” to purify the ester.

Conditions
• Esterification is very slow in nature, so concentrated H2 SO4 is added as a catalyst,
and heat is provided to increase reaction rate
◦ Concentrated H2 SO4 (18–37 M) is a dehydrating agent, so it absorbs water,
increasing ester yield as equilibrium shifts right as per LCP
◦ Bunsen burner is not used as volatile reactants will evaporate, reducing yield
∗ Heating mantle reduces ignition risk for volatile substances
• Reflux setup – volatile components evaporate and are cooled by a condenser, then
return back to the reaction mixture in liquid state to maximise yield
◦ The open system allows higher temperatures to be used whilst avoiding Figure 49: Reflux
dangerous gas pressure buildup associated with closed systems
• Can add one reactant in excess, so equilibrium shifts right, maximising yield as per LCP
• Boiling chips allow air bubbles to congregate on their surface, forming larger bubbles which rise to the surface
◦ Without boiling chips, rapid boiling releases gas bubbles, increasing pressure (which presents an explosion
risk), or leads to dangerous vibrations during reflux
◦ Provide nucleation sites to prevent superheating (heating above BP) or bumping (vigorous, uneven boiling)
• The level of heat can be controlled with a heating mantle. A water bath provides even heating, unlike a Bunsen

Purifying
• Esterification is an equilibrium reaction with both products and reactants
• Ester is not very soluble, carboxylic acids and alcohols are soluble if small, H2 SO4 is soluble
• Use a separating funnel to separate immiscible substances
◦ Organic layer is usually less dense, so it is on top (to test, drop 1 drop of water – it should pass through
the organic layer)
• Can also distill ester as it has a lower BP than alcohols and carboxylic acids
• Alternatively, “salting out” can be used
◦ Wash solution with water to remove water-soluble substances, saturate the mixture with a base (Na2 CO3
or NaHCO3 ), then use a separating funnel
◦ Any ester remaining in the non-organic layer is displaced by the salt formed by the reaction between the
carboxylic acid and the base, as water will form ion-dipole bonds with the more soluble carboxylate salt,
and in doing so, breaks hydrogen bonds with the ester
◦ The Na2 CO3 or NaHCO3 will react with the H2 SO4 catalyst, stopping the reaction

Uses of Esters
• Natural esters are found in flavours of fruits or natural perfumes of flowers
• Artificial esters can mimic natural odours in perfumes, and are used as artificial flavours in food
◦ Ethyl butanoate (CH3 CH2 CH2 COOCH2 CH3 ) is pineapple flavouring
◦ Octyl ethanoate is orange flavouring
• Polyesters are ester chains used for fabrics and plastic bottles

– 46 –
Soaps and Detergents
Saponification
• The esters that make up natural vegetable oils and animal fats are called triglycerides
◦ They have 3 fatty acids attached to a glycerol molecule
◦ Fats are solid at room temperature, while oils are liquid at room temperature

O
H2 C OH
O H2 C O C R
O
Condensation
HC OH + 3R C OH
Hydrolysis HC O C R + 3 H2 O
O
H2 C OH
H2 C O C R

Figure 50: Formation of Triglyceride by Esterification

• Saponification is essentially the reverse of an esterification reaction

◦ Ester is hydrolysed under basic conditions and converted to glycerol and the salt of a carboxylic acid (soap)
◦ This process makes soaps from natural fats and oils

Glycerol
• 1,2,3-propanetriol forms the backbone of fats and oils H H H
• Important by-product of soap-making, with uses including
H C C C H
pharmaceuticals, confectionary and cosmetics
OH OH OH

Figure 51: Glycerol

Fatty Acids
• Long, unbranched carboxylic acids O
• Natural fats/oils have ≥ 8 C atoms
◦ Can be saturated or unsaturated OH

Figure 52: Stearic (Octadecanoic) Acid

Process
• The fatty acid is reacted with a base

1. Triglyceride + 3 H2 O
3 Fatty Acids + Glycerol (Hydrolysis)
2. 3 Fatty Acids + 3 NaOH/KOH → 3 Salts of Fatty Acids + 3 H2 O

• Overall, the net reaction is Triglyceride + 3 NaOH/KOH

Glycerol + 3 Salts of Fatty Acids

O
H2 C OH
H2 C O C R O
O
HC OH + 3 Na+ O− C R
HC O C R + 3 NaOH
O
H2 C OH
H2 C O C R

Figure 53: Saponification

– 47 –
Structure of Soap
• Soaps are salts of fatty acids (long carbon chain with a carboxylate head and K+ or Na+ ion)
◦ Hydrocarbon tail is non-polar and hydrophobic, forming dispersion forces with non-polar substances
◦ Ionic head is polar and hydrophilic, forming ion-dipole and hydrogen bonds with water
∗ Ion-dipole bonds are much stronger than H-bonds, and required for dissolution of soap in water

O− Na+

Figure 54: Sodium Stearate

Soap as a Cleaning Agent

• Soaps act as surfactants (surface active agents) which de-
Water Water with Surfactant
crease the surface tension of water
◦ Hydrophilic ends bond with water and disrupt the
hydrogen bonding network of water molecules
◦ Water then can “wet” dirt particles easier Surface
• Hydrophobic tail of soap bonds with dirt, oil, fats or other
non-polar molecules with dispersion forces Figure 55: Surfactant Action

• Soap tails surround dirt, forming a micelle (spherical cluster of surfactant molecules) when agitated
• Micelles are surrounded by negatively charged soap heads, so micelles repel each other and do not accumulate
• At low concentrations, soap forms a monolayer, with hydrophilic heads lining up on the water surface
◦ At higher concentrations, micelles are formed

Grease particle made

soluble by soap

Micelle

Grease on Surface

Figure 56: Cleaning Action of Soap

Emulsions
• Stable dispersion of small droplets of one liquid throughout another liquid
◦ Requires an emulsifier to stabilise them (e.g. proteins in milk)
• Oil and water are immiscible due to different polarities
◦ Soap acts as an emulsifier between oil and water as it forms an “indirect” solvent-solute bond by bonding
to both water and oil, hence dispersing oil throughout water

– 48 –
Problems with Soap
• Hard water contains high concentrations of Ca2+ and Mg2+ ions
◦ These ions react with soap to form “scum”, reducing its cleaning efficiency
–
◦ 2 CH3 (CH2 )16 COO(aq) + Ca2+
(aq) → Ca[CH3 (CH2 )16 COO]2(s)
◦ Detergents do not form precipitates with Ca2+ and Mg2+ as any complexes formed are soluble

Detergents
• Synthetic surfactants (detergents) have largely replaced soaps as major cleaning agents
• Detergents are derived from fossil fuels
• Detergents are more effective cleaning agents in hard water as they do not form precipitates with Ca2+ or Mg2+
• Anionic detergents (Figure 57)
◦ Contains a negatively charged head, so it is very strong
◦ Forms complexes with Ca2+ and Mg2+ , so it can still act as a cleaning agent (e.g. EDTA)
◦ Used in dishwashing powders, laundry, car cleaners (cheap)
◦ Very highly foaming
• Cationic detergents (Figure 58)
◦ Does not form complexes with Ca2+ and Mg2+ due to positively charged head
◦ Weaker than anionic detergents
◦ Used in hair conditioners and antiseptics (biocidal properties), but it is expensive
◦ Not highly foaming
• Non-ionic detergents (Figure 59)
◦ Used in reducing foam created by anionic detergents
◦ Generally have a polar functional group head (e.g. – OH or – COOH)
◦ Weaker, or comparable to cationic detergents
◦ Used in glass cleaners or other uses where bubbling needs to be minimised (expensive)
◦ Note: The carbons on the main chain can periodically be replaced by oxygen, forming ethoxy groups

O S O− Na+
H3 C
O

Figure 57: Anionic Detergent (Sulfonate Head)

CH3

N+ CH3 Cl−
H3 C
CH3

Figure 58: Cationic Detergent (Quaternary Ammonium Head)

O O O OH
H3 C

Figure 59: Non-Ionic Detergent

– 49 –
 ——— Polymers ———
• Polymers are macromolecules – monomers joined by covalent bonds

Thermosetting and Thermoplastic Polymers

• Thermoplastics soften if heated, by overcoming rather weak intermolecular forces (mainly dispersion forces, but
also sometimes dipole-dipole and hydrogen bonds)
◦ Can be melted, remoulded or recycled (e.g. polyethylene, polyethylene terephthalate, polyvinyl chloride)
• Thermosetting polymers do not change shape or soften if heated, due to covalent cross-links
◦ Mostly non-recyclable (e.g. melamine, polyurethane)

General Properties of Polymers

• Lightweight • Durable • Acid and base-resistant

• Non-conductive of electricity • Flammable • Impermeable to water

Addition Polymers
• No loss of atoms as by-products (polymer has same empirical formula as monomer)
• Monomer must have a double bond between two carbon atoms, which is broken to give each carbon an electron
to form a covalent bond with adjacent monomers
• The general process of addition polymerisation is shown in Figure 60, where X represents any functional group

CH2 CH ... CH2 CH CH2 CH CH2 CH ...

n
X X X X

Figure 60: General Addition Polymer Structure

Naming Polymers
• Use the prefix “poly-”, e.g. polyethylene
• Use brackets if the monomer name has more than one word or has a number; e.g. poly(vinyl chloride) or
poly(1-chloroethene)

Polyethylene
• Chain of ethene (ethylene) monomers
• One bond in C – C is broken by an initiator with high temperatures and pressures, allowing formation of a
covalent bond between carbon atoms of adjacent monomers as there is one free electron per carbon atom
• Basically an extremely long alkane, with very strong dispersion forces (so it is solid at room temperature)

H H H H H H
 
H H
H H  
 
n C C ... . C C C C C C . ... .OR.  C

C 

 
H H
H H H H H H H H n

Figure 61: Polyethylene

– 50 –
HDPE and LDPE
• LDPE is produced in a gas phase with high temperatures (300◦ C) and pressures
(1000–3000 atm), with an initiator (organic peroxide)
◦ Formed too rapidly to be linear, with significant alkyl branching (amorphous)
◦ Prevents close packing of polymer chains, weakening dispersion forces
◦ Low density, low MP, high flexibility, low tensile strength, transparent (due to
gaps between molecules), impermeable to water
◦ Used in plastic bags, wire insulation and milk bottles Figure 62: LDPE
• HDPE is produced by the Ziegler-Natta process using low temperatures (60◦ C)
and pressures (20 atm) with a titanium(II) chloride catalyst
◦ Unbranched polyethylene chains pack closer (crystalline structure), with
stronger dispersion forces and higher density
◦ Chains are generally longer than LDPE, increasing dispersion force strength
◦ Stronger dispersion forces, hence higher MP and lower flexibility, higher tensile
Figure 63: HDPE
strength, opaque, impermeable to water
◦ Used in rubbish bins, buckets and food containers

Polytetrafluoroethylene/PTFE/Teflon
• Monomer is tetrafluoroethene or tetrafluoroethylene
◦ Note: Not a direct substitution of hydrogen with fluorine on the ethene monomer
◦ Very polar C – F bonds form strong dipole-dipole interactions between polymer chains, increasing durability
◦ The fluorine atoms are electronegative and are resistant to forming dispersion forces with non-polar sub-
stances (e.g. dirt and oil)
◦ Very strong, high MP, low coefficient of friction, non-stick properties
• Used in non-stick coatings for pans, artificial body parts and insulating aerospace wiring

δ− δ− δ− δ− δ− δ−  
F F F F F F F F
F F  
 
n C C ... . C C C C C C . ... .OR.  C

C 

 
F F δ− δ− δ− δ− δ− δ−
F F F F F F F F n

Figure 64: Polytetrafluoroethylene

Poly(Vinyl Chloride)/PVC/Poly(1-Chloroethene)
• Monomer is chloroethene or vinyl chloride
• Amorphous due to large Cl atoms branching out
◦ Unlike most amorphous substances, PVC is rigid and hard
• Cl is highly electronegative, attracting the electron in the C – Cl bond, creating a permanent dipole. Hence,
there are dipole-dipole interactions and dispersion forces
• Low electrical conductivity and flammability
• Pure, unplasticised polymer is rigid and hard
◦ Plasticisers can act as “spacers” to weaken intermolecular forces by spreading polymer chains apart (in-
creasing flexibility)
∗ However, this makes the material non-recyclable
• Uses of plasticised PVC include water hoses, credit cards, electrical insulation and drainage pipes
◦ Outdoor applications require stabilisers such as TiO2 to prevent decomposition in UV light

– 51 –
 H H H H H H
 
H H
H H  
 
n C C ... . C C C C C C . ... .OR.  C

C 

 
Cl H
Cl H Cl H Cl H Cl H n

Figure 65: Polyvinyl Chloride

Polystyrene/PS/Polyethenylbenzene
• Monomer is ethenylbenzene/phenylethene/styrene (with the – C6 H5 functional group)
• Amorphous, as benzene (phenyl) rings are oriented randomly along chain, and stick out due to their large size
◦ Symmetrical phenyl rings have no polarity, so only dispersion forces hold chains together
◦ Phenyl rings interlock and restrict chain movement, so crystalline PS is hard and transparent, but brittle
◦ Expanded PS is formed from a gas blown into liquid PS (often pentane gas). It is lightweight, a heat
insulator, has a lower MP and is shock-absorbant
• Crystal PS is used in CD cases and screwdriver handles, and expanded PS is used in refrigerator parts and foam
food containers
• Styrene can be copolymerised with < 10% butadiene to improve impact resistance

H H H H H H
 
H H
H H  
 
n C C ... . C C C C C C . ... .OR.  C

C 

 
H H H H H n

Figure 66: Polystyrene

Polypropylene
• 3 variations which depend on the orientation of the – CH3 group
◦ Atactic: Weak dispersion forces as chains are further apart (soft, low MP)
∗ Used for sealants
◦ Syndiotactic: Chains pack closer, with moderate dispersion forces (tough and clear, but somewhat soft)
∗ Used in packaging and medicine (such as in tubing, since it is stable to gamma radiation)
◦ Isotactic: Chains pack close together, with stronger dispersion force strength (clear and hard)
∗ Used for ropes and crates
• Isotactic and syndiotactic structures are stereoregular (semi-crystalline)

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

C C C C C C C C C C C C C C C C C C C C C C C C

CH3 CH3 CH3 CH3

Atactic Syndiotactic Isotactic

Figure 67: Types of Polypropylene

Relating Properties and Structure

Crystallinity
• Crystalline: Rigid, higher MP, greater density, translucent/opaque, non-permeable to air, water or chemicals

– 52 –
 • Amorphous: Flexible, lower MP, lower density, transparent, may be permeable to air, water or chemicals

Chain Branching
• Chains with little branching pack more closely, forming crystalline structures
◦ Stronger dispersion forces, higher MP, rigid, more dense
• Branched structures result in less orderly packing and require more reaction energy input, as the C – H bond is
broken to insert a branch
◦ Lower MP, more flexible, less dense

Chain Length
• Chains have different lengths in polymers, so the average molecular mass is considered
• The larger the chain length and lesser the difference in chain lengths, the higher the MP and hardness (due to
stronger dispersion forces)
• Long chains can withstand moulding, whereas shorter chains are more flexible
• HDPE has a longer average chain length than LDPE, so it is harder and has a higher MP

Side Groups and Substituents

• Larger side groups restrict the movement of polymer molecules, reducing flexibility (e.g. Cl in PVC)
◦ The benzene rings in PS can interlock like “teeth”, limiting flexibility
• Lower MP due to weaker dispersion forces, as molecules cannot pack as closely
• Polar groups such as – OH and – NH2 cause hydrogen bonding, with stronger intermolecular forces

Cross-Linking
• Linear chains can be linked by cross-chains, which form covalent or ionic bonds with polymer chains
• Cross-links increase MP, hardness and elasticity (ability to return to original shape), but reduce flexibility
• Cross-linked polymers are thermosetting and often non-recyclable

Additives
• Pigments/dyes for colour (e.g. perspex)
• Plasticisers soften the polymer and increase flexibility
◦ Phthalates (a carboxylate) disrupt the dispersion forces in PVC (e.g. for use in garden hoses)
• Stabilisers such as TiO2 prevent UV or heat decomposition, especially for PVC (e.g. in outdoor piping)
• Blowing gases through liquid polystyrene (most often pentane) to form expanded polystyrene (“styrofoam”)
• Strong C – C and C – H bonds mean most synthetic polymers are non-biodegradable
◦ Copolymerisation with natural polymer sections allow the polymer to biodegrade into smaller sections

Condensation Polymers
• Formed when monomers chemically combine by eliminating a small molecule as a by-product (usually H2 O)
◦ If x monomers are condensed to form a condensation polymer, then (x − 1) H2 O molecules are eliminated
(consider 1 H2 O molecule per covalent bond formed)
• An organic molecule with a functional group at the end of the chain undergoes condensation with a functional
group on the end of another molecule, often forming a copolymer
◦ Functional groups include – NH2 , – OH and – COOH
• Natural condensation polymers include cellulose, starch, wool, silk and hair
• Synthetic condensation polymers include polyesters (e.g. PET) and polyamides (e.g. nylons)

– 53 –
Polyesters
• Monomers are joined by an ester link, requiring either – COOH or – OH at the ends of monomers
• There are 2 ways of producing polyesters
◦ A monomer with a hydroxyl group on one end and a carboxyl group on the other [See Figure 68]
◦ A diol monomer reacting with a dicarboxylic acid monomer [See Figure 69]

O CH3 O CH3 O CH3 O CH3

n HO C C OH + n HO C C OH ... O C C O C C ... + (2n − 1) HOH

H H H H

Figure 68: Polyester Produced from Single Monomer: Poly(2-hydroxypropanoic acid)

O O O O O O

n HO C R C OH + n HO R0 OH ... O C R C O R0 O C R C O ... + (2n − 1) H2 O

Figure 69: Polyester Formed From Diol and Dicarboxylic Acid Monomers

Polyethylene Terephthalate (PET)

• Monomers are terephthalic acid (benzene-1,4-dicarboxylic acid) and ethylene glycol (ethane-1,2-diol)
• Properties and uses:
◦ Impermeable to water
◦ A thermoplastic that is easily meltable and recyclable
◦ Contains repeating polar ester groups
∗ Moderately strong dipole-dipole interactions between polymer chains (high MP and tensile strength)
∗ Strong, stiff and impact-resistant
∗ However, PET is easily damaged by acids and alkalis, which break the ester link
∗ Uses include plastic drink bottles, food packaging and textile fibres

H H
O O
n C C + n HO C C OH

OH OH
H H

 O O 
H H
 C C  + (2n − 1) H2 O
 
 
O O C C
 
 
 
 
H H n

Figure 70: Polyethylene Terephthalate

Polyamides
• Repeated units held together by amide links ( – CONH – ), such as peptide links in proteins
• Can be produced from:
◦ A single monomer which is an amino acid [See Figure 71]
◦ Two different monomers (a diamine and a dicarboxylic acid) [See Figure 72]

– 54 –
 O O O O

n HO C R N H + n HO C R N H ... C R N C R N ... + (2n − 1) H2 O

H H H H

Figure 71: Polyamide Formed From Amino Acid

O O O O O

n HO C R C OH + n H N R0
N H ... N C R C N R 0
N C ... + (2n − 1) H2 O

H H H H H

Figure 72: Polyamide Formed From Diamine and Dicarboxylic Acid

Naming Nylons
• Naming is based off the number of carbon atoms in monomers
◦ Nylon-6 is formed from a 6-carbon monomer with a carboxyl and amine group (an amino acid)
◦ Nylon-6,6 is formed from hexane-1,6-diamine and hexanedioic (adipic) acid, so it is a copolymer
∗ Number for diamine comes first (remember that the carboxylic acid name also comes last in esters)

Nylon Properties and Uses

• Contains repeating polar amide groups
◦ There are strong H-bonds between polymer chains
◦ Can be drawn into strong and stiff fibres
◦ The largely crystalline nature of fibres cause very strong hydrogen bonding, although this effect is weakened
in the presence of water, which forms hydrogen bonds within any amorphous regions
◦ Nylons decompose in the presence of acids or alkalis, which break amide linkages
• Uses include:
◦ High-tensile-strength fibres (e.g. ropes, fishing lines, clothing fibres)
◦ Rigid plastics (pipes and machinery)
• Thermoplastic, so it is recyclable

Natural Polymers
Proteins
• Proteins are natural polyamides formed from condensation reactions of amino acid monomers
• Can form primary structures (sequence of amino acids), secondary structures (e.g. alpha helix), tertiary struc-
tures (3-dimensional), or quaternary structures (e.g. haemoglobin)

Amino Acids
• Contain an amine and carboxyl functional group, hence R
displaying acidic and basic properties H O
• Proteins only form from alpha-amino acids, which have the
N C C
amino and carboxyl functional groups joined to the same
carbon atom (α carbon) H OH
H

Types of R-Groups Amino Group Carboxyl Group

• Non-polar groups (i.e. alkyl substituents)
• Polar groups that form ions (e.g. – NH2 or – COOH) Figure 73: α-Amino Acid Structure
• Polar groups that don’t form ions (e.g. – OH or – SH)

– 55 –
Bonding
• Amino acids undergo condensation polymerisation in the same manner as nylons
• The link joining amino acids is called a peptide link, forming a polypeptide
• Proteins can be decomposed with HCl, but breakages are non-specific

Starch and Cellulose

• Cellulose consists of unbranched β-glucose chains, forming strong intermolecular hydrogen bonds between poly-
mer chains
◦ Due to its crystallinity, it is strong and rigid, but insoluble in water
• Starch consists of α-glucose chains
◦ Amylose is a straight-chain polymer which forms spirals due to inter-chain bonding
◦ Amylopectin is highly branched and does not spiral
• Glycogen is highly branched, with an amorphous structure of α-glucose monomers

Glucose
• Glucose is a monosaccharide that can form disaccharides OH OH
and polysaccharides
O O OH
• Polymers have the glycosidic link ( – C – O – C – )
OH OH
• Two isomers of glucose exist: α and β
HO OH HO
• During polymerisation, a water molecule is released as
OH OH
a by-product
Alpha Glucose Beta Glucose

Figure 74: α and β Glucose

– 56 –
 HSC Chemistry Notes
Module 8
Applying Chemical Ideas

• Analysis of Inorganic Substances

• Analysis of Organic Compounds
• Chemical Synthesis and Design

– 57 –
 ——— Analysis of Inorganic Substances ———
Monitoring for Ions
• Substances are considered pollutants if introduction into the environment leads to undesired effects
• Many environmental pollutants and impurities in manufactured products are ions
• Need to maintain high water quality for domestic and commercial use, and for health of ecosystems
◦ Clean water for drinking, preparing food and washing
◦ Agriculture and industry
◦ Habitat for aquatic organisms
• Mining uses water to process ores, releasing heavy metal ions (such as Pb2+ , Hg+ and Cd2+ )
• Sewage is treated to remove contaminants, but it still contains ions, namely NO3– and PO34 –
• Combustion of fuels can release trace heavy metals, which then contaminate rain or soils
• Most common cations are Na+ , Ca2+ , Mg2+ and K+
◦ Trace metals include Cu2+ , Fe2+ , Mn2+ , Zn2+ ; toxic heavy metals include Cd2+ , Pb2+ , Hg+
• Most common anions are Cl – , SO24 – , PO34 – , HCO3– , CO23 –
◦ NO3– and PO34 – cause eutrophication (excessive nutrient enrichment of water) and algal blooms

Lead – A Toxic Heavy Metal

• Exposure pathways include lead-based paints, old leaded petrol contaminating water and soil, and smelting of
lead ores/lead tailings, with bioaccumulation of lead over time
• Safe blood concentration of < 0.1 mg L−1 , and < 0.01 mg L−1 in drinking water
• Acute poisoning: Muscle weakness, loss of appetite, abdominal pain, nausea, constipation, diarrhea
• Chronic poisoning: Anaemia, kidney disease, impaired memory and concentration, peripheral neuropathy
• Need to monitor water and environmental quality to prevent these detrimental impacts

Water Hardness
• Hard water has high concentrations of mineral ions, particularly Ca2+ and Mg2+
• Often due to acidic rainwater running through limestone rocks and soil
• Ca2+ and Mg2+ precipitate with soap molecules, forming scum
◦ Ca2+ –
(aq) + 2 CH3 (CH2 )16 COO(aq) → Ca[CH3 (CH2 )16 COO]2(s)
◦ Scum disrupts the cleaning action of soap by preventing lathering, and can accumulate and block pipes

O− Na+

Long hydrocarbon, hydrophobic, non-polar tail Carboxylate polar head

Figure 75: Soap Structure

Eutrophication
• Excessive nutrient enrichment of waterways that leads to rapid proliferation of algae/plant life (algal bloom).
This blocks sunlight (prevents photosynthesis) and prevents diffusion of O2
• Mostly due to high levels of nitrate and phosphate (growth-limiting nutrients)
• Common sources of NO3– and PO34 – include:

– 58 –
 ◦ Oxidation of N and P in raw sewage
◦ Phosphate in laundry detergents (detergent builders)
◦ Excessive fertiliser runoff and animal wastes from farms ((NH4 )2 SO4 , NH4 NO3 , (NH4 )3 PO4 )

Table 9: Effects of Eutrophication on O2 Levels

Less O2 dissolved More O2 consumed

Algae reduces UV penetration for photosynthesis More algae/plants consume more O2
O2 diffusion from the air is hindered Bacteria use O2 to decompose dead organisms*

*Anaerobic decomposition will form CH4 and H2 S (which are toxic to aquatic organisms)

Monitoring Strategies
Colour of Solutions
• Quickest way to make a reasonable guess of an ion
• Not very accurate as some solutions are colourless, some may have the same colour, or some may change colour
◦ E.g. Fe2+ is pale green and Fe3+ is yellow/brown; but Fe2+ oxidises to Fe3+ in the presence of O2
∗ Note: Ni2+ is also a similar pale green

Flame Tests
• Some metal ions produce distinctive colours when their salts are volatilised in a blue Bunsen flame
• This can help distinguish the presence of certain metal cations

Method
1. Clean a Pt wire with 6 M HCl and place in a Bunsen flame as a control.

(a) Repeat until no more colour comes from the wire.

(b) This removes contaminants such as Na+ , which has a bright yellow flame.

2. Dip Pt wire into the sample (solid or in solution), and place into Bunsen flame, observing the colour produced.

An alternative method is to use spray bottles, but don’t spray downwards as the ions can stay in the Bunsen and
affect the flame colour.

Function
• Electrons absorb a “quantum” (exact and discrete amount) of energy and are excited to higher energy levels
• The electron is unstable in this excited state
• Electrons release the quantum of energy that they absorbed as they return to their ground state; this energy is
light of a particular wavelength
• Each element has unique discrete energy levels, hence emitting light of different wavelengths, forming a unique
emission spectrum
hc 1
• E = hf = λ , i.e. E ∝ λ
◦ Red light has the longest λ and lowest f (and hence the least energy)

Colours of Ions in a Flame

• Ca2+ is brick red • K+ is pale purple or lilac

• Ba2+ is pale (apple) green • Mg2+ is bright white
• Cu2+ is blue-green • Fe2+ is gold when very hot (e.g. in a Bunsen)
• Na+ is yellow-orange • Fe3+ is orange-brown

– 59 –
Advantages
• Quick and cheap to do
• Can be used with precipitation tests to confirm the identity of cations

Issues
• Only gives qualitative information (does not determine concentration of ions)
• Only applies to certain cations, and not anions (which emit UV light)
• Cannot easily distinguish between ions of the same element (e.g. Fe2+ and Fe3+ )
• Potential for contamination, especially with Na+
• Difficult to use on samples containing multiple cations
• Similar colours can be confused (e.g. Cu2+ vs. Ba2+ )
• Safety issue of naked Bunsen flame
• Unsafe for toxic heavy metals (e.g. Pb2+ )

Precipitation Tests – Cations

• Based on the formation of distinct coloured precipitates or metal complexes

Table 10: Solubility of Certain Cations and Anions

Anion Soluble Slightly Soluble Insoluble

+ +
CO2−
3 Na , K , NH+
4 – Most
2+
−
Cl Most Pb Ag+
OH− Na+ , K+ , NH+
4 , Ba
2+
Ca2+ Most
+ +
PO3−
4 Na , K , NH+
4 – Most
2+ 2+ 2+
SO2−
4 Most Ca , Ag Ba , Pb2+

• Soluble: All nitrates, group 1 salts, ammonium salts, most chlorides, most sulfates
• Insoluble: Most carbonates, hydroxides and phosphates

• Below are the precipitates formed from Cl – , SO24 – and OH – . All precipitates are white unless otherwise stated

Table 11: Chloride, Sulfate and Hydroxide Precipitates

Cl− Pb2+ *, Ag+

SO2−
4 Pb2+ , Ba2+ , Ca2+ *, Ag+
OH− Pb2+ , Cu2+ (blue), Fe2+ (green), Fe3+ (brown), Ca2+ *, Mg2+

*Assuming sufficiently high concentration, say ≥ 0.05 mol L −1

Multiple Cations
• Need to prevent cross-reactions (e.g. Ba2+ and Pb2+ both give a white precipitate with H2 SO4 )
• Once an ion is precipitated, it must be precipitated to completion and filtered out (this is not shown on the
simplified procedure below in Figure 77)
◦ Ensures that the ion will not undertake any more cross-reactions and interfere with subsequent tests
◦ Further tests are performed on the filtrate, not on a new sample
• Should test all pathways as there may be more than one ion present

– 60 –
 Figure 76: Flowchart For Identifying Individual Cations

Sample Add HCl Precipitate formed? Yes Pb2+

Yes Decomposes in UV: Ag+

No
Fresh sample
Add H2SO4 No
Precipitate formed?

Yes
Fresh sample

Add NaF Yes

Precipitate formed? Ca2+
No Ba2+

Fresh sample

Blue
Add NaOH Precipitate formed? Cu2+

Brown
Fe3+
Green Fe2+
White Mg2+

Figure 77: Flowchart For Identifying Individual Cations from Multiple Cations

Pb2+, Ag+, Ca2+, Ba2+, Mg2+, Fe2+, Fe3+, Cu2+

Add Excess HCl

White ppt → Pb2+, Ag+ No ppt

UV decomposition Add excess H2SO4

OR add excess NH3

White ppt→ Ba2+, Ca2+ No ppt → Mg2+, Cu2+,

Fe2+, Fe3+
Add NaF to original sample

Ppt Ppt doesn’t Add NaOH

dissolves dissolve → Pb2+
→ Ag+ White ppt No ppt
→ Ca2+ → Ba2+

No ppt White ppt Blue ppt Green ppt Brown ppt

→ None → Mg2+ → Cu2+ → Fe2+ → Fe3+

Other Confirmatory Tests

• Pb2+ will form a canary yellow precipitate with NaI solution
◦ Pb2+ –
(aq) + 2 I(aq) → PbI2(s)

• To distinguish between Ba2+ and Ca2+ , use NaF, which gives a white precipitate with Ca2+ only
◦ Ca2+ –
(aq) + 2 F(aq) → CaF2(s)
◦ But excess F – will also precipitate out Ba2+

– 61 –
 • Cu(OH)2 precipitate dissolves in excess NH3 to form a deep blue complex ion
◦ Cu(OH)2(s) + 4 NH3(aq)
Cu(NH3 )2+ –
4(aq) + 2 OH(aq)
◦ Useful if there could be other ions that precipitate with OH – (such as Fe2+ , Fe3+ or Mg2+ ), which make
it hard to see the characteristic blue colour of Cu(OH)2
◦ As NH3 is selective, it confirms copper is present
2+
• Fe decolourises acidified potassium permanganate solution
◦ 5 Fe2+ – + 3+ 2+
(aq) + MnO4(aq) + 8 H(aq) → 5 Fe(aq) + Mn(aq) + 4 H2 O(`)

• Fe3+ forms a blood-red complex ion with potassium thiocyanate (KSCN)

◦ Fe3+ – 2+
(aq) + SCN(aq)
Fe(SCN)(aq)

Precipitation Tests – Anions

CO2− −
3 , OH , CH3 COO
−

1. Red litmus paper should turn blue as pH > 7 (CO23 – and CH3 COO – are conjugate bases of weak acids).

2. Then, add an acid, preferably HNO3 .

(a) CO23 – produces salt, water and carbon dioxide (confirm using limewater test, or from effervescence).

3. Then add a cation that is expected to precipitate with OH – (such as Cu2+ ), but NOT Ag+ .

(a) If a precipitate is formed, then OH – is present.

(b) CH3 COO – does not precipitate with cations except Ag+ . Note the possible vinegar smell.

Cl− , Br− , I−
• Test by adding AgNO3 , since all nitrates are soluble
◦ Also add HNO3 to prevent carbonate from undertaking cross-reactions
◦ Ag+ –
(aq) + Cl(aq) → AgCl(s) , which is white
◦ Ag+ –
(aq) + Br(aq) → AgBr(s) , which is cream-yellow
◦ Ag+ –
(aq) + I(aq) → AgI(s) , which is bright yellow

SO2− 3−
4 , PO4

• In an acidified solution (say, pH < 2), Ba2+ will not precipitate with PO34 – , and only precipitates with SO24 –
–
◦ HSO4(aq) + H2 O(`)
SO24(aq)
–
+ H 3 O+
(aq) Ka = 10−2
◦ HPO24(aq)
–
+ H2 O(`)
PO34(aq)
–
+ H3 O+
(aq) Ka = 4.8 × 10−13
• The equilibrium containing PO34 – lies much further to the left, and an acidified environment shifts both equilibria
to the left as per LCP, such that [PO34 – ] is negligible

Other Confirmatory Tests

• CH3 COO – mixes with FeCl3 to form a red-brown solution
◦ Addition of dilute HCl causes the red-brown solution to disappear, by forming more FeCl3
◦ Addition of water and heating causes a red-brown precipitate to form
∗ Fe3+ –
(aq) + 3 CH3 COO(aq) + 2 H2 O(`) → Fe(OH)2 (CH3 COO)(s) + 2 CH3 COOH(aq)

• AgCl dissolves in dilute NH3 to form a colourless complex ion diamminesilver(I)

◦ AgCl(s) + 2 NH3(aq) → Ag(NH3 )+ –
2(aq) + Cl(aq)

• AgBr dissolves in concentrated NH3 to form a colourless complex ion diamminesilver(I)

◦ AgBr(s) + 2 NH3(aq) → Ag(NH3 )+ –
2(aq) + Br(aq)

• AgI does not dissolve in NH3

• PO34 – forms a canary-yellow precipitate with ammonium molybdate
◦ 12 (NH4 )2 MoO4(aq) + PO34(aq)
–
+ 3 H+
(aq) → (NH4 )3 PO4 · 12 MoO3(s) + 21 NH3(g) + 12 H2 O(`)

– 62 –
 Figure 78: Flowchart For Identifying Anions

OH-, CO32-, CH3COO-, Cl-, Br-, I-, SO42-, PO43-

Use Litmus Paper

Red litmus → No OH-, Blue Litmus → OH-

CO32-, CH3COO-, PO43- Add HNO3

Bubbling/effervescence Vinegar smell, No bubbling or vinegar smell

→ CO32- litmus turns red → Cl-, Br-, I-, SO42-, PO43-
→ CH3COO-
Add Ba(NO3)2

No ppt → Cl-, Br-, I-, PO43- White ppt

→ SO42-
Add AgNO3

White ppt Cream-yellow ppt Yellow ppt No ppt

→ Cl- → Br- → I-
Add Ba(NO3)2 and NH3 to fresh sample

White ppt No ppt

→ PO43- → None

*Note: Ag+ will only precipitate with PO34 – in basic conditions, for the same reasons as Ba2+

Advantages and Disadvantages of Precipitation Tests

Advantages
• Can identify both anions and cations, and heavy metals safely
• More reliable than simple flame tests
◦ Can be used in conjunction with flame tests as a confirmation test
• Can identify multiple anions or cations (although separately)

Disadvantages
• Only gives qualitative information (does not determine concentration of ions)
• Time-consuming to test all reagents
• Possibility of contamination and mixing up reagents
• Need to have a wide range of reagents available

Complexation Reactions
• Complex ions involve a central metal ion surrounded by ligands
◦ Ligands are molecules or ions which donate a lone pair of electrons to the central ion to form a coordinate
covalent (dative) bond
• Many complex ions exist in vibrantly coloured states which can be easily identified

– 63 –
 Table 12: Types of General Complexation Structures

Coordination Number Geometry Example Name of Ion

 
6 Octahedral H2 O 2+
Hexaaquairon(II)
 
 H2 O OH2 
 
Fe
 
 
 
H O OH2 
 2 
H2 O
 
N
4 Square Planar  2− Tetracyanonickelate(II)

 C 

 
N C Ni C N
 
 
 

 C 

N
 
4 Tetrahedral Cl 2− Tetrachloronickelate(II)
 
 
 

 Ni 

 
 Cl Cl 
Cl

+
h i
2 Linear H3 N Ag NH3 Diamminesilver(I)

Copper Complexes
• Copper(II) salts produce a blue solution in the form hexaaquacopper(II), or [Cu(H2 O)6 ]2+
• Addition of NaOH will form a dark blue precipitate tetraaquadihydroxycopper(II)
◦ [Cu(H2 O)6 ]2+ –
(aq) + 2 OH(aq) → [Cu(H2 O)4 (OH)2 ](s) + 2 H2 O(`)
◦ Addition of ammonia will lead to the precipitate dissolving
∗ [Cu(H2 O)4 (OH)2 ](s) + 4 NH3(aq)
[Cu(H2 O)2 (NH3 )4 ]2+ –
(aq) + 2 H2 O(`) + 2 OH(aq)
• Addition of NH3 will form a deep blue complex ion tetraamminediaquacopper(II)
◦ [Cu(H2 O)6 ]2+ 2+
(aq) + 4 NH3(aq) → [Cu(H2 O)2 (NH3 )4 ](aq) + 4 H2 O(`)
• Note that these equations differ from those on Page 62 due to inclusion of water of hydration
   
OH
 
H2 O H2 O
 2+    2+
 H2 O

OH2 
  H2 O OH2   H3 N

NH3 

     
 

 Cu

 
 Cu 


 Cu


     

 H2 O
 H O OH2 
 
 OH2 
  2   H3 N
 NH3 

H2 O OH H2 O
Hexaaquacopper(II) Tetraaquadihydroxycopper(II) Tetraamminediaquacopper(II)

Figure 79: Copper Complexes

Gravimetric Analysis
• Involves the measurement of mass (percentage composition or amount of components in a mixture)
• The species being analysed must be separated from the rest of the mixture (e.g. by precipitation with excess
reagent and filtration), dried, weighed and analysed for percentage composition
• Less commonly used for soluble salts (although evaporation can be used)

– 64 –
Prac – Analysing Sulfate Content of Fertiliser
Aim:
To determine the sulfur content of fertiliser by gravimetric analysis.

Method:
1. Accurately weigh a known mass of fertiliser and dissolve in distilled water and HCl.

(a) HCl provides acidic environment to precipitate BaSO4 and not Ba3 (PO4 )2 , and also removes any CO23 – ,
which would otherwise have a cross-reaction with Ba2+ .

2. Filter off any insoluble material.

3. Heat the solution until almost boiling (> 80◦ C) using a heating plate, and add BaCl2 dropwise.

(a) Stir continuously and note any “cloud” formation as BaCl2 strikes the solution.
(b) Heating and stirring allows BaSO4 to “clump” together rather than forming a fine powder which can pass
through filter paper, hence preventing lost mass.

4. Gently “digest” the mixture for 30 minutes to coagulate the precipitate, then allow to cool (cooling will maximise
precipitation as solubility is lower at lower temperatures).

5. Weigh a dry filter paper and filter the precipitate off.

(a) Rinse beaker to ensure all precipitate is transferred.

6. Test the filtrate with more BaCl2 , then rinse precipitate 2–3 times with water and ethanol.

(a) Since C2 H5 OH is amphipathic, it will rinse off Cl – , H+ and Ba2+ , which adhere to BaSO4 .

7. Dry the precipitate until constant mass is attained (no water residues remain), and weigh the filter paper.

8. Calculate the percentage composition of SO24 – .

Problems – Underestimation:
• BaSO4 can form very small particles that may pass through the filter paper
◦ Form the precipitate slowly using hot digestion, to increase particle size through coagulation
◦ Cool the solution before filtering to decrease solubility
• If too much BaCl2 solution is added, the higher volume can mean traces of BaSO4 remain dissolved
• Did not precipitate to excess, or did not check filtrate for excess SO24 – remaining

Problems – Overestimation:
• BaSO4 has impurities
◦ HCl added to prevent PO34 – and CO23 – precipitation, improving accuracy
◦ Precipitate rinsed with distilled water and ethanol to remove excess Cl – or other ions
• BaSO4 precipitate is not completely dried
◦ Dry to constant mass in drying oven, not by drying in air which can expose the sample to contaminants
◦ Forgetting to weigh the filter paper and deducting its mass from the final mass

Precipitation Titrations
Mohr’s Method
• To quantify the concentrations of halide ions
• CrO24 – ions are used as an indicator, and AgNO3 is used as the titrant
◦ At the end point, all the halide has precipitated, so any added Ag+ will react to form red-brown Ag2 CrO4
• However, excess titrant is required to achieve a colour change, reducing accuracy

– 65 –
 ◦ Perform a blank titration with AgNO3 and CrO24 –
◦ Subtract the volume of the blank titration from the titrant required to reach the end point
• Must use the same amount of indicator each time – if there is too little indicator, more Ag+ is required to
produce a colour change
• Maintain pH of 6–9
◦ A pH too high will lead to Ag+ reacting with OH –
◦ A pH too low will form H2 CrO4

Volhard’s Method
• Back titration of acidic solution to determine quantity of an anion
• A known amount of AgNO3 leads to precipitation of the anion. Excess AgNO3 is then titrated against stan-
dardised KSCN to produce AgSCN(s)
• Some Fe3+ is included in the titrant, so blood-red Fe(SCN)2+ is produced once all the Ag+ ions have reacted
with SCN –
• A problem occurs if the precipitate formed is more soluble than AgSCN, such as AgCl
◦ The AgCl will dissolve as SCN – is added: AgCl(s) + SCN(aq)
– –
→ AgSCN(s) + Cl(aq)
◦ Must filter off the AgCl precipitate

Fajan’s Method
• End point is determined using a direct titration with an adsorption indicator
◦ Indicator adsorbs onto surface of precipitate at the endpoint, changing colour
• Not suitable if:
◦ Species being analysed is of low concentration – not enough precipitate for indicator to change colour
◦ High concentrations of non-reacting ions, since indicator might coagulate and not adsorb to the precipitate

Atomic Absorption Spectroscopy

• Highly sensitive, and can detect traces of ions to the ppm or ppb level
• AAS is capable of detecting 68 elements
• Key principle: Each element only absorbs (and emits) specific wavelengths of light, based off their electron shell
energy levels, which are unique to each element
◦ Electrons will release the same energy they absorbed as they return to the ground state
◦ The frequency and wavelength of light released is the same as that absorbed
• Lamp emits specific wavelengths of light
absorbed by the tested element
◦ The element itself is used in the
cathode to produce a set of unique
emission spectra (can be expensive)
◦ This is selective as other elements
have different discrete energy levels,
and absorb different wavelengths
◦ A higher proportion of light will be Figure 80: AAS Instrumentation
absorbed (compared to normal light),
hence minimising percentage error
• Analyte is atomised in a flame, converting molecules/compounds into ground state atoms in the vapour phase
• Light intensity drops as the sample absorbs light with specific wavelengths emitted by the lamp
◦ If a monochromator is not used, the drop in intensity is much smaller as the whole spectrum is considered
• A filter/monochromator selects one wavelength to be analysed, and its intensity is measured with v.s. without
the sample
◦ This ratio is used to calculate absorbance
◦ Absorbance is proportional to the concentration of the metal ion in the sample (A ∝ c)

– 66 –
Analysis
• Construct a calibration curve of concentration against absorbance using standard solutions
• Even though a linear relationship is expected (A = kc), do not assume this
• Never assume that the line passes through (0, 0), as a systematic error (e.g. contamination) can shift the curve
above the origin
• Concentration of a solution must be found by interpolation. If the absorbance is too high to interpolate, use
more concentrated standard solutions to reliably extend LOBF. Never extrapolate
◦ A problem at high concentrations is that opacity causes absorbance to taper off, so it is better to dilute
concentrated samples and interpolate, then multiply the found concentration by the dilution factor

Benefits
• Very accurate and sensitive, and detects ions at ppm/ppb levels
• Selective testing, generally not affected by contaminants (hence valid)
• Can calculate trace concentrations of toxic heavy metals such as Pb2+ that are hard to detect by colourimetry
or precipitation

Limitations
• AAS machines are expensive and lack the portability required for field testing
• Different lamps are needed for each element, so cations of interest must be known
• Cannot directly test for anions: Must bind the anion to a cation, determine the cation concentration using AAS,
then use molar ratios to determine the anion concentration
• Cannot differentiate between ions of the same element (such as Fe2+ and Fe3+ ), as they are both atomised to
the same ground-state atom

Colourimetry
• Measures the absorbance of light at a certain wavelength passing
through a coloured solution
◦ The concentration of the analyte is determined relative to
standards
◦ A blank cuvette of distilled water is used to calibrate
absorbance to zero (technically, any solvent such as HNO3
can be used, as long as it is consistently used)
• Complementary colour of solution is used for absorbance (e.g. blue
CuSO4 uses yellow light)
◦ For ROYGBV, GBVROY are the complementary colours
• The filter produces the required wavelength of light to be absorbed
by the analyte, but a problem is that the filtered wavelength may Figure 81: Colourimetry Setup
not be precisely the wavelength of maximum absorbance
• Beer-Lambert Law: A = ε`c and A = log10 II0

◦ A = absorbance (dimensionless quantity) ◦ c = concentration (mol L−1 )

◦ ε = molar absorptivity constant (L mol−1 cm−1 ) ◦ I0 = intensity of light entering sample
◦ ` = length of sample cell (cm) ◦ I = intensity of light exiting sample

Limitations
• Cannot be used for colourless solutions, or excessively concentrated/opaque solutions
• At high concentrations, high opacity means calibration curve may taper off as absorbance can no longer increase
• Easily affected by other light inputs
• Not suitable for a mixture of colours (e.g. analysing total iron concentration, if there is both Fe2+ and Fe3+ )

– 67 –
UV-Visible Spectroscopy
• There are 2 functions:
◦ Can confirm the identity of a compound by comparing its
absorption spectrum to database standards
∗ A “scan” of the solution using light of various wavelengths
produces an absorption spectrum similar to Figure 82
◦ Can also determine concentrations of solutions
∗ Measure the absorbance of light by the analyte at one of the
peak absorbance wavelengths (λmax ), and compare this to
standards by constructing a calibration curve
∗ Other compounds may interfere with the sample if they have
similar peak wavelengths – sometimes, it is better not to
choose the wavelength of absolute highest absorbance
◦ This technique is more useful than colourimetry since many
organic compounds are colourless and absorb UV light Figure 82: Absorption Spectra
• Fe2+ does not absorb strongly in the UV or visible spectrum
◦ Fe2+ is oxidised to Fe3+ , then KSCN is added to produce the complex FeSCN2+ , which can be analysed
with UV-Vis or colourimetry
◦ [Fe2+ ] can then be determined from a calibration curve, taking into account molar ratios and dilutions

Process
• Suitable wavelengths of light are 200–400 nm (UV spectrum) and 400–800 nm (Visible spectrum)
• Electrons are excited to a higher energy state when molecules are exposed to a wavelength corresponding to an
electron transition, and absorb this light
• Most organic molecules are colourless as they absorb light in the UV region
• Atoms (or groups of atoms) responsible for UV-Vis absorption are called chromophores
• A light source (tungsten/halogen and deuterium lamp) provides the required light of wavelength ≈ 200–800 nm
◦ Light is focused through a monochromator or diffraction grating (a glass or quartz prism), splitting light
into different wavelengths. This more accurately selects an exact wavelength for analysis by the detector
and computer, as compared to the filter in colourimetry
◦ The light is shone through a reference cell (containing the solvent only) and the sample solution simulta-
neously, to discount any absorption from the solvent
◦ An optical spectrophotometer records wavelengths at which absorption occurs, and the amount of absorp-
tion at each wavelength
∗ This information is sent to the computer to produce the required spectrum or calibration curve

Advantages and Disadvantages

Advantages
• Useful for identifying organic compounds, many of which are colourless
◦ Can compare absorption spectra to that of database standards
◦ Many organic compounds absorb light in the UV region
• Relatively cheap
• Small sample size
• Quick sample preparation
• Can also help calculate concentration using a calibration curve

Disadvantages
• Not very sensitive
• Absorbance patterns may be interfered with by unsuitable solvents or contamination

– 68 –
 ——— Analysis of Organic Compounds ———
Chemical Tests
• Simple tests to determine the presence of functional groups in a molecule

Alkenes
• When an alkene is mixed with bromine water, the brown bromine water is decolourised through an addition
reaction involving formation of a colourless, transparent haloalkane
• This can differentiate alkanes and alkenes, since alkanes require UV light to react with halogens by substitution
◦ Must test in the absence of UV light to ensure validity (e.g. a dark room)
∗ Even if there is some UV light from the sun, the substitution reaction will still be much slower than
the addition reaction
• However, this test is unable to distinguish between isomers of alkenes, or between alkenes and alkynes
• This test is mainly suitable for liquid or solid alkenes (C>6 ) as it is difficult to transfer gas into bromine water

Carboxylic Acids
• The carboxyl group is weakly acidic – can test with acid-base indicators (e.g. blue litmus turns red)
• Addition of Na2 CO3 will lead to effervescence in the presence of a carboxylic acid
◦ E.g. 2 CH3 COOH(aq) + Na2 CO3(aq) → 2 CH3 COONa(aq) + CO2(g) + H2 O(`)
◦ Limewater test confirms the presence of CO2 by forming a milky precipitate CaCO3
• Can react with an alcohol to form an ester, and test for a fruity odour

Alcohols
• When Na(s) is added to an alcohol, the Na slowly dissolves and gentle effervescence of gas occurs
◦ 2 CH3 CH2 OH(`) + 2 Na(s) → 2 CH3 CH2 O – Na+ + H2(g)
∗ Note: There is no state on the sodium ethoxide as it is dissolved in ethanol, not water
◦ For safety, dry the alcohol with anhydrous MgSO4 or CaCl2 prior to testing, and filter off this salt
◦ Can further test for H2 through the pop test
• Can also be tested with oxidising agents Cr2 O27 – or MnO4– , which are themselves reduced
◦ Cr2 O27(aq)
–
+ 14 H+ – 3+
(aq) + 6 e → 2 Cr(aq) + 7 H2 O(`)
–
◦ MnO4(aq) + 8 H+ – 2+
(aq) + 5 e → Mn(aq) + 4 H2 O(`)
◦ Colour changes only occur for primary and secondary alcohols, so this test does not identify tertiary alcohols
• The type of alcohol can also be determined by reacting with a ZnCl2/ HCl mixture
◦ Forms an immiscible alkyl chloride layer at the bottom of the mixture
◦ Tertiary alcohols react instantly, secondary alcohols react slowly, and primary alcohols may not react at all

Structural Elucidation
• Involves analytical techniques that provide information on the structure of a molecule
• Techniques include:
◦ Mass spectrometry for molecular mass/chemical formula
◦ Infrared spectroscopy for functional groups
◦ Proton nuclear magnetic resonance spectroscopy ( 1H NMR) for hydrocarbon skeleton analysis
◦ Carbon-13 nuclear magnetic resonance spectroscopy ( 13C NMR) for hydrocarbon skeleton analysis

– 69 –
Mass Spectrometry
• Involves ionising a vapourised sample and measur-
ing the mass-to-charge ratio (m/z) and relative
intensities of the ions formed
• A vapourised sample enters an ionisation chamber
and is bombarded with high energy electrons from
a high-voltage, heated filament
• A radical cation (or molecular ion) is produced by
electron impact
◦ M(g) + e – → M•+(g) + 2 e
–

◦ A radical is a species with an unpaired

electron – here, an electron is knocked off by
the collision with the high-energy electron
• Firing of high-energy electrons at an organic
molecule causes it to fragment into a smaller ion
and a free radical Figure 83: Mass Spectrometry Setup
◦ Covalent bonding involves sharing of electrons,
which is disrupted when an electron is displaced
◦ The free radical is neutral and uncharged, and is not detected
◦ For example, the CH4 fragment can split in 2 ways: CH4 → CH3 + + H• or CH4 → CH3 • + H+
∗ Only CH3 + and H+ would be detected. The free radical is neutrally charged, and does not deflect
• The ions are collimated into a fine beam through narrow slits, and are accelerated through an electric field into
a magnetic field
• When the ions enter the magnetic field, they deflect into a circular path
◦ If a neutral particle entered the magnetic field, it would not deflect
◦ Similarly, anions will not be deflected towards the detector

Deflection and Separation

m B 2 r2
• For a fixed voltage (V ) and magnetic field strength (B), z = 2V
B2 m
◦ Radius of deflection depends on m/z, since 2V is constant ⇒ z ∝ r2
◦ Since the charge (z) is set to +1, it is the mass of the ion which determines the deflection radius
• Sometimes, the ion is too heavy or too light to reach the detector plate, and is removed by a vacuum pump
◦ The vacuum also removes air particles and other gases, reducing interferences → improves validity
• Hence, the magnetic field strength is varied to separate ions by their m/z ratio
◦ A weaker magnetic field strength reduces deflection, hence the detector will detect particles with a lower
m/z ratio (and vice versa)
◦ The ions are then analysed with a computer to determine their m/z ratio, forming a mass spectrum

Analysis of Spectrum
• Relative abundance of all cations is plotted against m/z
• Since z (charge) is +1, then m/z is equal to molar mass
• The most abundant ion is the base peak, with a relative
abundance of 100%
◦ Other peaks are plotted as a percentage of the base peak
• The parent molecular ion (e.g. CH3 COOH•+ for CH3 COOH)
has the highest molecular mass, but might not be the base peak
• Molecules have a unique fragmentation pattern, so their spectra
can be compared to a database to identify the compound. This is
useful for distinguishing isomers (e.g. 2-methylbutane and pentane)
Figure 84: Mass Spectrum

– 70 –
Isotopes
• Different isotopes of elements can lead to different peaks based off their molar masses
◦ For example, CH3 35 Cl+ and CH3 37 Cl+ will have two molecular ion peaks (the M+ and M+2 peaks respec-
tively) at m/z = 50 and m/z = 52, with an intensity ratio of ≈ 3:1
◦ The same case applies with 79 Br+ and 81 Br+ , with an intensity ratio of ≈ 1:1
◦ Hydrogen, oxygen and carbon also have isotopes, but their relative abundance is negligible for mass spectra
• If only one element is being analysed, mass spectrometry can determine the relative abundance of each isotope

Common Fragment Ions

Table 13: Common Fragment Ions and Their m/z Ratios

m/z Fragment
15 CH+
3
17 OH+
29 CH3 CH+
2 or CHO
+

35 and 37 35
Cl+ and 37
Cl+
45 COOH+
79 and 81 79
Br+ and 81
Br+

Advantages and Disadvantages

Advantages
• Very accurate and sensitive, and can detect traces of compounds in small samples (such as drugs in blood)
• The molecular mass and chemical formula of a substance can be identified
• Provides qualitative and quantitative data (the relative intensity of peaks can be used to determine isotopes)
• Molecules have a unique mass spectrum which can be cross-checked with a database to confirm its identity

Disadvantages
• Very expensive to purchase and operate
• Non-portable and unsuitable for fieldwork
• Doesn’t identify hydrocarbon skeleton
• Requires a pure sample (it is extremely difficult to determine if 2 distinct substances are present)

Infrared Spectroscopy
• Involves molecules absorbing light in the infrared region
• Determines bonds and functional groups
• All molecules are constantly vibrating in discrete vibrational energy levels
◦ Stretching involves bond length changing
◦ Bending and twisting involve bond angle changing
◦ Can be symmetrical or asymmetrical
◦ Quantised absorption of infrared radiation causes molecules to move to a higher vibrational energy level
∗ Molecules vibrate with greater amplitudes in an excited state
◦ For a molecule to absorb IR, the vibration must result in a change in the dipole moment of the molecule
∗ For this reason, molecules such as O2 and N2 cannot be detected by IR spectroscopy
◦ Heavier atoms require more energy to transition to an excited state, as do double/triple bonds
∗ These heavier atoms and multiple bonds absorb high-frequency, lower-wavelength radiation (i.e. higher
wavenumber, since wavenumber = λ1 )

– 71 –
 Table 14: Some Simple Infrared Vibrations

Symmetrical Asymmetrical
Scissoring Bending
Stretching Stretching

O O O O
H H H H H H H
H

Process
• Analyte sample is placed in a cell, and a beam of
infrared radiation is passed through the sample
• A detector detects the percentage transmittance
for each wavelength and this data is transferred to
a recorder/computer
• Reference cell of the solvent discounts the effects
of materials in the equipment and the solvent

Figure 85: IR Instrumentation Setup

Infrared Spectra
• X-axis reports wavenumber ( λ1 ) in cm−1
• Y-axis reports transmittance (%) of light through the sample
• Most functional groups have characteristic infrared absorption bands
◦ There are 6 main regions to consider:

Region 1: ' 3100 cm−1

• N – H and O – H absorption bands occur here
• N – H band is usually sharper and less intense than the O – H absorption band
• Useful for identifying amines and alcohols
• Can also identify amides and carboxylic acids in conjunction with a C – O absorption band at ≈ 1650–1750cm −1
◦ The O – H absorption band in carboxylic acids is extremely broad, often being from 2500–3500 cm−1
∗ The O – H (acids) absorption is more sharp at the base, whereas the O – H (alcohols) absorption is more
parabolic

Region 2: ≈ 2700 − 3100 cm−1

• C – H absorption bands occur here
• Not much information is obtained here, as almost all organic compounds have C – H bonds
• Can vary in intensity from weak to strong

Region 3: ≈ 2100 − 2400 cm−1

• C–
– N absorption bands occur here (nitrile compounds)
• Absorption is a narrow, weak to medium band between 2220–2260 cm−1
• Additionally, C –
– C absorption bands occur between 2100–2250 cm
−1

Region 4: ≈ 1650 − 1850 cm−1

• C – O absorption bands occur here
• Absorption is a narrow and strong peak
• Useful for identifying aldehydes, ketones, carboxylic acids, esters and amides

– 72 –
Region 5: ≈ 1500 − 1700 cm−1
• C – C absorption bands occur here
• Absorption bands are sharp and of varying intensity
• Useful for identifying alkenes and aromatic compounds

Region 6: / 1500 cm−1

• Fingerprint region, with absorption bands in this region being unique for each compound
◦ Spectra can be compared to a pure database standard to determine the identity of a compound
• Not useful for identifying compounds for HSC purposes
• C – C absorption bands are common here

Terminology
• Absorption troughs reach downwards from a base-
line, where the transmittance in 100%
• Note that intensities of troughs vary with
concentration of the compound
• The terminology on the data sheet is as follows in
Figure 86:

Advantages and Disadvantages

Figure 86: IR Absorption Terminology
Advantages
• Quick process that provides information regarding functional groups in a molecule
• Is non-destructive, so the same compound can be tested with other techniques (such as Mass Spectrometry)
afterwards to confirm the identity of the compound
• Requires small samples, so it is useful for blood and urine testing for illicit drugs
• Sensitive and accurate

Disadvantages
• Provides limited information about the hydrocarbon skeleton of a molecule (such as length of carbon chain)
• Expensive and non-portable for fieldwork applications

Nuclear Magnetic Resonance Spectroscopy

• 1H and 13
C nuclei give information about the hydrocarbon skeleton
E2
• When matter is placed in a magnetic field, charged nuclei spin and produce
Energy
a small magnetic field
◦ Only nuclei with an odd number of nucleons possess spin that creates
a magnetic field, as the “spins” will “cancel out” if there are an even
number of nucleons E0 ∆E
• Normally, these nuclear spins have random orientations
◦ But when placed in a magnetic field, the nuclei will align either:
∗ With the applied magnetic field (lower energy level, more stable)
∗ Against the applied magnetic field (higher energy level, less stable) E1
◦ When irradiated with radiofrequency radiation, some nuclei will be
excited from the lower energy state to the higher energy state Figure 87: Spin States

– 73 –
 ∗ Nuclei absorb a quantised amount of energy corresponding to their resonance frequency, and “flip”
◦ Over time, some nuclei will flip back to their lower energy spin state
∗ This releases radio waves, which are detected and displayed on an NMR spectrum
∗ The difference in energy (∆E) between the lower and higher energy spin states (and hence the resonance
frequency) depends on the chemical environment of the nucleus
• Note that ∆E depends on the magnetic field strength
◦ If we plotted the frequencies emitted, there are 2 issues:
∗ Frequency numbers are very large
∗ The frequency emitted depends on ∆E (since E ∝ f ), and hence the magnetic field strength, B0 . But
B0 can vary between different NMR machines, so a scale independent of B0 is required

Spectrometer Setup
• The device consists of a large magnet, sample (often aque-
ous), radiofrequency generator and radiofrequency detector
• The sample is placed in a magnetic field and irradiated with
a range of radio frequencies, some of which are absorbed as
a nuclear flip
• The detector records the frequency of re-emitted radio waves
as nuclei return to the parallel state, and this information
is plotted by a computer to produce an NMR spectrum

Figure 88: NMR Setup

Solvents
• A solvent with no net magnetic dipole is used, to prevent conflicting peaks on the NMR spectrum
• Number of protons and neutrons in the solvent should cancel out
• Common solvents include D2 O (10 protons, 10 neutrons) and CD2 Cl2 (42 protons, 42 neutrons)

Chemical Shift Scale

• The resonance frequencies of nuclei are measured relative to CH3
tetramethylsilane (TMS)
• TMS is calibrated to zero on the spectrum H3 C Si CH3
• The resonance frequencies are reported as chemical shifts (ppm)
CH3
◦ Note: ppm is not associated with concentration
◦ δ= f (signal)−f (reference)
× 106 Figure 89: TMS
f (reference)

◦ This scale is independent of the applied magnetic field strength, so comparisons between different instru-
ments can be made
◦ Nonetheless, a lower chemical shift does correspond with a lower frequency emitted (inspect formula)

TMS
• TMS is chemically inert and will not react with the sample
• Silicon is less electronegative than carbon, so electrons spend more time around hydrogen nuclei, shielding them
13
• TMS has 4 equivalent C and 1H environments each, hence will only produce 1 peak at the end of the spectrum
◦ This peak is unlikely to interfere with peaks from the sample, as protons are very highly shielded

– 74 –
Chemical Environments
• Not all hydrogen or carbon nuclei will produce a distinct peak on the spectra
• A signal is observed for every different type of nucleus in a different chemical environment
• Nuclei are in the same environment if they are bonded to the same group of atoms in the same way
• If protons are in an identical environment, they will absorb the same frequency of radio waves, producing 1 peak
• A test for the 1H chemical environment is to substitute a “dummy” Cl atom onto each hydrogen. If the compound
produced is the same, the protons are in the same chemical environment (they are homotopic protons)
• Symmetry will generally reduce the number of chemical environments
◦ Rotation around a multiple bond can also reduce the number of chemical environments: Trans-but-2-ene
has 2 chemical environments

.H. .H. .H. .H. .H. .H. O .H. .H.

.H. .C. .C. .H. .H. .C. .C. .C. .H. .H. .C. C .C. .C. .H.

.H. .H. .H. .H. .H. .H. .H. .H.

1 1H environment 2 1H environments 3 1H environments

1 13C environment 2 13C environments 4 13C environments

Figure 90: Hydrogen and Carbon Environments

Other Features of Peaks

• The features under this heading are the only features shown by low-resolution 1H NMR. The features in subse-
quent sections are only present in high-resolution 1H NMR
• The number of peaks shows the number of unique chemical environments
◦ If there are less peaks than the corresponding number of carbon atoms, this suggests symmetry
• The location of peaks on the chemical shift scale can be compared to a table of standard values to determine
the chemical environment
◦ In ethanol, the electronegative oxygen atom forms a permanent dipole by attracting electron density away
from H, and deshields the proton, resulting in a larger chemical shift
◦ In ethanoic acid, the C – O group attracts electrons from the methyl group, so protons are less shielded.
Hence, less energy is required to flip the hydrogen nuclei compared to the methyl groups in ethane

Electron Shielding
• 1H nuclei are surrounded by electrons that also have a spin
◦ The electrons create a secondary magnetic field opposing
the applied magnetic field, meaning a stronger magnetic
field is required to change the spin state of the nucleus
◦ The nucleus is shielded from the applied field by electrons
• If there are electronegative groups (such as halogens, carbonyl
groups, oxygen or nitrogen) near a proton, electron density is
drawn away from the proton
◦ The proton becomes deshielded, resulting in a higher
chemical shift value
Figure 91: Electron Shielding

– 75 –
Integration
• The area under the peak is proportional to the number of hydrogen nuclei responsible for the signal
◦ Usually provided with the spectrum directly, or as an integration trace
◦ Peak heights can be used to estimate the area ratio if peaks have similar widths, but this is not always
reliable

Signal Splitting (Multiplicity)

• Splitting signal is due to spin-spin coupling with neighbouring, non-equivalent protons
• The intensity and chemical shift of a peak is the same as low-resolution NMR, but the signal may be split
• Protons attached to the neighbouring carbon atom can be aligned with the magnetic field or against it:
◦ Alignment with B0 increases Bnet , causing less shielding and shifting the peak downfield (larger δ)
◦ Alignment against B0 lowers Bnet , causing more shielding and shifting the peak upfield (lower δ)
◦ This slightly alters the resonance frequency of the 1H nuclei, resulting in several split peaks
• Alignments with B0 can be represented as ↑, and alignments against B0 can be represented as ↓
◦ If there is one neighbouring non-equivalent proton, there are 2 possibilities: ↑ or ↓
◦ If there are two neighbouring non-equivalent protons, there are 4 possibilities: ↑↑ , ↑↓ , ↓↑ and ↓↓
∗ The 2nd and 3rd possibilities have the same net result, leading to a triplet with relative intensity 1:2:1
◦ If there are three neighbouring non-equivalent protons, there are 8 possibilities: ↑↑↑ , ↑↑↓ , ↑↓↑ , ↓↑↑ , ↑↓↓ ,
↓↑↓ , ↓↓↑ , and ↓↓↓
∗ The red and blue possibilities have the same net results respectively, leading to a quartet (1:3:3:1)
◦ This trend follows Pascal’s Triangle to determine the intensity of peaks, that is, n Cr or nr

No Splitting
• Neighbouring environments that are identical do not cause splitting (such as in ethane)
• Protons in O – H or N – H groups do not display coupling, and are usually seen as broad singlets
◦ Some spectra may not show signals for these protons at all
∗ Possibly due to exchange of deuterium (D) from the solvent with H

Neighbouring 1 H
• The number of peaks within a signal is one more than the number of H attached to neighbouring carbon atoms
◦ Also known as the “(n + 1) rule” if there are n protons on neighbouring carbon atoms
• A H atom is considered “neighbouring” if it is at most three bonds away from the H atom being considered

Aromatic Compounds
• Integration can provide information about the number of substituents on COOH
an arene
• Multiplicity provides information about the splitting pattern .H. C .H.
◦ If a multiplet occurs (several close, but indistinguishable signals), this C C
indicates an aromatic ring
C C
• Para-substituted benzene rings have simpler spectra due to symmetry (see
.H. C .H.
Figure 92 for an example of the different 1H environments)
NO2
P-Nitrobenzoic Acid

Figure 92: Para-Substitution

13
C NMR
13 12
• Only C can be detected by NMR, since C has an equal number of protons and neutrons
13
• The C isotope has only 1.1% relative abundance, so NMR spectra take longer and are less detailed

– 76 –
 • Tests provide information about the number of different carbon environments in a molecule
13 13
◦ Signal splitting is not observed due to low abundance of C (low probability of 2 adjacent C nuclei)
◦ Integration is not obtained
• Number of signals indicates number of unique carbon environments
◦ If there are less signals then carbon atoms, this suggests symmetry
• The chemical shift values provide information about the chemical environment of each carbon, and can be
compared to the standard values on the data sheet
◦ Location of signal shows how shielded/deshielded the carbon nucleus is relative to TMS

Advantages and Disadvantages of NMR

Advantages
• Only requires small samples
• Provides a wealth of information about the hydrocarbon skeleton of a molecule
◦ 1H NMR is often enough to identify a molecule
• 1H NMR is relatively quick (a few minutes)
• Sample can be in solution

Disadvantages
• Very expensive, especially due to superconducting magnets
13
• C NMR is rather slow (a few hours) and is less detailed
• Non-portable for fieldwork analysis
• It is difficult to identify more than one organic compound at once, so NMR is generally unsuitable for analysing
a mixture of organic compounds

– 77 –
 ——— Chemical Synthesis and Design ———
• Synthesis reactions involve reacting reagents to produce a specific product with a useful industrial application
• Retrosynthetic analysis involves starting with the desired product, and removing carbons or simplifying the
structure until suitable reactants are found

Chemical Synthesis Processes

• Factors to consider include:
◦ Availability and cost of reagents
◦ Reaction conditions (including rate of reaction)
◦ Yield and purity
◦ Environmental, social and economic issues
◦ Safety (hazards to human health, pollution, disposal of waste etc.)
∗ For example, acetylsalicylic acid is used in aspirin, as salicylic acid is a stomach irritant

Availability and Cost of Reagents

• Reagents should be readily available and ideally cheap
• Metal processing is often located near mines to minimise transport costs, and ethanol fermentation plants are
located near farms for the same reason
• Hazardous facilities (e.g. nuclear power plants or lead smelting) are located away from population centres

Yield
• The theoretical yield refers to the quantity of product formed when a limiting reagent is completely consumed
• The actual yield is often less than the theoretical yield
◦ Most reactions are equilibrium reactions that do not go to completion ⇒ must make equilibrium lie as far
right as possible
∗ Removing products shifts equilibrium to the right as per LCP, increasing yield
∗ Reusing unused reactants reduces wastage, and causes a shift to the right
∗ Appropriate temperatures to favour forward reaction, but consider reaction rate and cost of heating
∗ Pressures should favour the forward reaction, but consider rate of reaction, cost and safety
∗ Catalysts do not increase yield, but increase reaction rate
◦ Impurities and contaminants reduce yield by creating side reactions
◦ Final product might be in a mixture, so it needs to be purified (part of it can then be lost)
Actual Yield
• Percentage Yield = Theoretical Yield × 100%
• In a multistep synthesis process (e.g. making plastics), yield can drop significantly at each step due to incomplete
and side reactions, with a compounding effect that reduces yield with each intermediate

Purity
• Purity refers to the quality of the final product
Mass of Useful Products
• Percentage Purity = Mass of All Products × 100%
• Particularly important for pharmaceuticals, food products, fuels and laboratory reagents (analytical-grade)
◦ Ethanol for fuel should be 95% purity, but ethanol for pharmaceuticals should be 99.99% purity

Atom Economy
• Percentage of atoms in a reaction present in the desired product
M M (Desired Product) m(Desired Product)
• Atom Economy = M M (All Reactants) × 100% = m(All Reactants) × 100%

• Addition reactions have 100% atom economy, but substitution or condensation reactions do not

– 78 –
Environmental, Social and Economic Issues
• Pollutants often result from chemical production due to fossil fuel combustion or unwanted by-products
• Environmental issues should be mitigated using the following hierarchy:

1. Prevent pollution by using alternative reactants.

2. Treat chemicals to make them safe prior to disposal.
3. Dispose of untreated chemicals safely.

• Costs should be minimised during production by considering reaction conditions (temperature, pressure, cata-
lysts, yield and purity)

Multistep, Linear and Convergent Pathways

• Multistep processes involve intermediates, which are reacted in subsequent steps
• Convergent pathways produce two or more intermediates separately, which are then reacted in the final reaction
◦ E.g. Ethyl ethanoate
∗ Starting with ethene, produce ethanol by hydration and then ethanoic acid by oxidation of ethanol.
Then react the ethanol and ethanoic acid intermediates under reflux
• Linear pathways involve a continuous set of reactions with intermediates at each stage
◦ E.g. Contact Process (Note: Some H2 SO4 from the final product is re-used in step 3)
1. S(s) + O2(g) → SO2(g)
2. 2 SO2(g) + O2(g) → 2 SO3(g)
3. SO3(g) + H2 SO4(`) → H2 S2 O7(`)
4. H2 S2 O7(`) + H2 O(`) → 2 H2 SO4(`)
• Convergent pathways are preferred as less intermediates are present in the final product

Haber Process
• Method to synthesis NH3 from component elements
• N2(g) + 3 H2(g)
2 NH3(g) ∆H = −92.4 kJ mol−1

Industrial Uses of Ammonia

• Fertilisers (as a source of N through NH4 )
◦ Ammonium nitrate, sulfate and phosphate are common fertilisers (n.b. not the N on NO3 )
• Used to make nitric acid
◦ Nitric acid is then used to make explosives (nitroglycerine)
◦ Synthetic dyes, fibres and plastics (e.g. nylon)
• Household cleaners and detergents
◦ Antiseptic agents and window cleaners
• Chemical analysis (e.g. to dissolve AgCl as a confirmatory test, or as a weak base in titrations)

Reaction Conditions
• Methods of optimising the Haber Process are summarised in Table 14:

Table 15: Haber Process Summary

Reduce: Maximise:
Costs Yield
Impurities Purity
Time Rate of Reaction

– 79 –
Greater Yield
• As predicted by LCP:
100
◦ Lower temperatures cause equilibrium to shift 90
right to favour the exothermic reaction
80
◦ Higher pressures favour the reaction producing

Yield of Ammonia
70
fewer moles of gas, shifting equilibrium right 350◦ C
60
◦ Higher reactant concentrations cause a shift to 400◦ C
50
the right
40 450◦ C
◦ Continuous removal of NH3 prevents dynamic
30 500◦ C
equilibrium from being attained, allowing
20 550◦ C
continuous formation of NH3
∗ Instead, a steady state is obtained 10

100 200 300 400

Pressure (atm)

Conditions Figure 93: Haber Process Yield Curve

• Higher temperature
◦ A greater proportion of reactant molecules have sufficient KE to overcome EA , and can undergo a successful
collision, increasing reaction rate
◦ Decreasing temperature increases yield (favours forward exothermic reaction)
◦ Compromise between reaction rate and yield, with temperatures of 400–500◦ C to give moderate yields
relatively quickly
◦ Excessively high temperatures can damage the catalyst
• Higher pressure
◦ A lower volume (higher pressure) increases the concentration of particles, so there are more successful
collisions between molecules, increasing reaction rate
◦ Increasing pressure shifts equilibrium right to partially reduce the pressure, increasing yield of NH3
◦ However, high pressures are expensive to maintain and there are risks of explosions, so pressures of 20–
25 MPa (200–250 atm) are used
• Powdered magnetite catalyst (Fe3 O4 )
◦ Provides alternative reaction pathway with a lower
EA , hence increasing number of particles with
Number of Particles

KE > EA , increasing the number of successful

collisions and hence reaction rate
200◦ C 300◦ C
◦ As per Figure 94, the number of molecules with
sufficient KE to react in an uncatalysed reaction is
the shaded area to the right of EA , whereas with a
catalyst, the number of molecules with sufficient
KE is the shaded region to the right of EA(catalyst)
◦ Allows high reaction rate despite lower temperatures EA(catalyst) EA
and pressures, reducing production costs

Figure 94: Maxwell-Boltzmann Curve

Economics
• Cost can be lowered by:
◦ Lower temperatures
◦ Lower pressures (also for safety)
◦ Stoichiometric ratio of reactants (reducing wastage compared to if one reactant was heavily in excess)
◦ Heat released by the exothermic reaction is recycled to heat the reaction
◦ No use of expensive catalysts
◦ Reducing wastage by recycling unused N2 and H2 gases in the reaction chamber

– 80 –
Compromises
• Moderate temperatures of 400–500◦ C to give moderate yields relatively quickly
• Relatively high pressures of 20–25 MPa
• Powdered Fe3 O4 catalyst (to increase surface area) allows lower temperatures to be used

However, these conditions only produce 30–40% yield.

• NH3 is liquefied upon formation, producing higher yield (main factor increasing yield)
◦ This prevents dynamic equilibrium being reached, which would otherwise reduce potential yield
• Unreacted gases and heat are recycled back to the reaction chamber
• Attempting to maintain stoichiometric ratio of 1:3 for N2 :H2 to prevent an excess of one reactant over another
• Produces up to 98% yield eventually

Availability of Reactants
• H2 is derived from purified natural gas (CH4 ): CH4(g) + H2 O(`)
CO(g) + 3 H2(g)
◦ Sulfur impurities are removed to prevent side reactions, and “poisoning” the catalyst by blocking off bonding
sites
◦ Sulfur is removed by heating impure natural gas with hydrogen gas to produce hydrogen sulfide, which is
then eliminated when reacted with zinc oxide to produce zinc sulfide and water
◦ Ammonia production in the Pilbara region occurs due to close proximity to large LNG producers, reducing
transport costs
• Air is introduced as an N2 source, but O2 is removed as it can combust with CH4 , especially with high temper-
atures and pressures
◦ Temperatures of −190◦ C are used, since at this temperature, N2 is a gas while O2 is a liquid
• Removal of CO and CO2 impurities, which can poison the catalyst
◦ CO is converted to CO2 with a Fe3 O4 catalyst
∗ CO(g) + H2 O(`)
CO2(g) + H2(g)
◦ CO2 is removed by reacting with a base, K2 CO3
∗ CO2(g) + K2 CO3(aq) + H2 O(`)
2 KHCO3(s) *

*Not a precipitate, but it is easier to dispose of this as a solid, so it is dehydrated

Reaction Setup
• N2 and H2 are injected at close to the stoichio-
metric ratio (1:3) to prevent wastage of reac-
tants
• Heat released by the exothermic reaction
generates steam to drive turbines and
compressors and to pre-heat gas mixtures,
reducing heating costs
• Pump/compressor increases pressure, hence
increasing yield
• NH3 is liquefied and removed from the reaction
chamber, preventing an equilibrium
• Unused N2 and H2 are returned to the reaction
chamber, reducing wastage Figure 95: Haber Process Setup

– 81 –
Environmental, Social and Economic Issues
• Environmental
◦ Fertilisers produced from ammonia can lead to nutrient runoff and eutrophication
◦ Ammonia is toxic and highly soluble in water, so contamination of water can occur
◦ High fossil fuel energy inputs are required to sustain high temperatures and pressures
• Social
◦ Ammonia production provides employment in both production and transportation
◦ Workers handling liquid ammonia require impermeable gloves, face shields, rubber boots and aprons
• Economic
◦ Maintaining high temperatures and pressures leads to high energy costs
◦ Strong pipes are required to maintain high pressures, which can be expensive
◦ Needs to be located near supplies of natural gas to minimise transport costs of inputs
◦ Needs to be located near rail/road/pipelines to minimise transport costs of the ammonia product

Issues With Chemical Synthesis

• For general impacts of chemical synthesis, refer to:
◦ “Implications of Using Hydrocarbons” (Pages 33–34)
◦ “Lead – A Toxic Heavy Metal” (Page 60)
◦ “Eutrophication” (Pages 60–61)

Green Chemistry
• Involves addressing impacts of chemical synthesis, such as:
◦ Legislation to minimise environmental impacts
∗ Liquid chemical waste such as sewage must be treated before being released
∗ Post-emission capture of gases before they are released into the atmosphere
◦ Eliminating use and production of hazardous substances
∗ Expanded polystyrene for food containers is being replaced with cardboard, and pentane is used to
expand the polystyrene rather than CFC’s

Green Polymers
• Ethanol is a source for ethene, a common feedstock, via dehydration
• Cellulose is a natural condensation polymer which is decomposed to glucose, which is then fermented to ethanol
◦ Difficult to decompose cellulose, due to long, linear chains with strong H-bonding and dispersion forces
◦ Concentrated H2 SO4 and heat is required
◦ Currently, decomposition of cellulose to produce ethene is less energy-efficient than simply cracking oils
• Algae farms can produce oils that can be converted to hydrocarbons
◦ Algae grows very fast compared to plants, meeting higher yield requirements

Biopolymers
• Made by living organisms, including those that are partially synthetic (e.g. starch-based polymers)
• Synthetic polymers are non-biodegradable by natural organisms (e.g. bacteria) or the environment (sun, wind
or water)
◦ One way of improving biodegradability is alternating biopolymer sections with synthetic sections
◦ A graft copolymer of starch and ethene is biodegradable
∗ Starch molecules absorb water and expand, breaking polymer apart
∗ Microbes can decompose the biopolymer sections

– 82 –
 Appendix

• Organic Chemistry Reaction Flowchart

• Distinguishing Individual and Multiple Cations in Solution
• Distinguishing Anions
• Naming Organic Compounds
• Infrared Absorption Data
• UV-Vis Absorption Data
13
• C NMR Chemical Shift Data
• Solving Spectroscopy Problems

– 83 –
——— Appendix 1 – Organic Reaction Flowchart ———
NaOH OR KOH
Oxidati Saponification
on
MnO - +
4 /H
OR
Cr O 2- + ROH/
2 7 /H Esterification
Conc. H2SO4

R-NHR’
Amide Formation

MnO4-/H+
MnO4-/H+
OR Oxidation
Oxidation OR Cr2O72-/H+
Cr2O72-/H+

Fermentation Dehydration Halogenation

Yeast Conc. H+ X2
Zymase H2O/Dilute H+
Hydration n
o Hy
ati dr H2 \P
+H2O X en og
H alo g en t
h ati
d ro on
H y
X2/UV
Substitution

——— Appendix 2 – Single Cation in Solution ———

Sample Add HCl Precipitate formed? Yes Pb2+

Yes Decomposes in UV: Ag+

No
Fresh sample
Add H2SO4 No
Precipitate formed?

Yes
Fresh sample

Add NaF Yes

Precipitate formed? Ca2+
No Ba2+

Fresh sample

Blue
Add NaOH Precipitate formed? Cu2+

Brown
Fe3+
Green Fe2+
White Mg2+

– 84 –
——— Appendix 3 – Multiple Cations in Solution ———
Pb2+, Ag+, Ca2+, Ba2+, Mg2+, Fe2+, Fe3+, Cu2+

Add Excess HCl

White ppt → Pb2+, Ag+ No ppt

UV decomposition Add excess H2SO4

OR add excess NH3

White ppt→ Ba2+, Ca2+ No ppt → Mg2+, Cu2+,

Fe2+, Fe3+
Add NaF to original sample

Ppt Ppt doesn’t Add NaOH

dissolves dissolve → Pb2+
→ Ag+ White ppt No ppt
→ Ca2+ → Ba2+

No ppt White ppt Blue ppt Green ppt Brown ppt

→ None → Mg2+ → Cu2+ → Fe2+ → Fe3+

——— Appendix 4 – Anions in Solution ———

OH-, CO32-, CH3COO-, Cl-, Br-, I-, SO42-, PO43-

Use Litmus Paper

Red litmus → No OH-, Blue Litmus → OH-

CO32-, CH3COO-, PO43- Add HNO3

Bubbling/effervescence Vinegar smell, No bubbling or vinegar smell

→ CO32- litmus turns red → Cl-, Br-, I-, SO42-, PO43-
→ CH3COO-
Add Ba(NO3)2

No ppt → Cl-, Br-, I-, PO43- White ppt

→ SO42-
Add AgNO3

White ppt Cream-yellow ppt Yellow ppt No ppt

→ Cl- → Br- → I-
Add Ba(NO3)2 and NH3 to fresh sample

White ppt No ppt

→ PO43- → None

– 85 –
 ——— Appendix 5 – Naming Organic Compounds ———
. Functional Group Suffix Alternative Name
Highest Priority Carboxyl -oic acid N/A
↓ Amide -amide Carbamoyl-
↓ Carbonyl (Aldehyde) -al Formyl-
↓ Carbonyl (Ketone) -one Oxo-
↓ Hydroxyl -ol Hydroxy-
↓ Amino -amine Amino-
↓ Alkene -ene N/A
↓ Alkyne -yne N/A
Lowest Priority Halo N/A N/A

• The functional group with the highest priority is assigned the lowest locant number possible, and this name is
used as the suffix (last part) of the organic compound’s name
• Lower-priority groups are indicated with a prefix or alternative name
• Any alkyl or halo substituents have equal priority, so they should be named alphabetically

——— Appendix 6 – Infrared Absorption Data ———

Bond Wavenumber (cm−1 ) Bond Wavenumber (cm−1 )
N H
3300–3500 C O 1680–1750
(amines)
O H
3230–3550 (broad) C C 1620–1680
(alcohols)
C H 2850–3300 C O 1000–1300
O H
2500–3500 (very broad) C N 1250–1340
(acids)
C N 2220–2260 C C 750–1100

——— Appendix 7 – UV Absorption Data ———

Chromophore λmax (nm) Chromophore λmax (nm)
C H 122 C C 173, 178, 196, 222
C C 135 C Cl 173
C C 162 C Br 208
C O 180, 290 O H 270
COOH 273 N H 280

– 86 –
——— Appendix 8 – Carbon NMR Data ———
13
C Environment Chemical Shift (ppm) Notes

C C 5–40 –

R C Cl or Br 10–70 –

O
20–50 –
R C C

R C N 25–60 –

C O 50–90 Alcohols and Esters

C C 90–150 –

R C N 110–125 –

110–160 –

O
160–185 Esters or Acids
R C

O
190–220 Aldehydes or Ketones
R C

– 87 –
 ——— Appendix 9 – Solving Spectroscopy Problems ———
1. Inspect the chemical formula to identify the elements present in the molecule.
• You may need to use the mass spectrum to obtain the molecular mass first, or, if given percentage compo-
sitions of each element, divide by the molar mass of each element to find the ratio.

2. Calculate the degree of unsaturation of the molecule.

• Modify the molecular formula as follows:
◦ Delete all oxygen atoms
◦ Replace halogens (F, Cl, Br, I) with H
◦ Subtract one H for each N
• Compare the modified molecular formula with that of the parent alkane (Cn H2n+2 )
◦ Every deficiency of 2 hydrogen atoms indicates 1 degree of unsaturation (a π bond or ring)

3. Inspect the infrared spectrum and focus on the following regions:

• > 3100 cm−1 : O – H and N – H bonds
• 2500–3300 cm−1 (very broad): O – H bond in carboxylic acids
• 2220–2260 cm−1 : C – N group
• 1650–1850 cm−1 : C – O group
• Also consider the lack of information – this means certain functional groups are not present

4. Inspect the 1H NMR spectrum and note the following features:

• Number of signals: Number of different 1H chemical environments
• Chemical shift: Type of chemical environment that the 1H nuclei are located in
• Integration (relative peak areas): Number of 1H nuclei in each chemical environment
• Multiplicity (splitting pattern): Number of 1H neighbours on adjacent carbon atoms
Tabulate the data with the following headings:
1
Multiplicity H Neighbours
δ (ppm) Integration Conclusion
(splitting pattern) (n + 1 rule)

13
5. Inspect the C spectrum and note the following features:
• Number of signals: Number of different carbon chemical environments
• Chemical shift: Type of chemical environment that the carbons are located in
Tabulate the data with the following headings:

δ (ppm) Conclusion

• If there are less peaks than the number of carbon atoms in the molecular formula, this suggests symmetry

6. Write down all fragments and combine them to draw a possible structure.
• Ensure that the structure drawn is consistent with the molecular formula, degrees of unsaturation and ALL
the spectra

– 88 –