CHEMISTRY

MODULE 7
Organic Chemistry

CHEMISTRY MODULE 7 – ORGANIC

CHEMISTRY

NOMENCLATURE

Inquiry question: ​How do we systematically name organic chemical

compounds?

● investigate the nomenclature of organic chemicals, up to C8, using IUPAC

conventions, including simple methyl and ethyl branched chains, including: (ACSCH127) – alkanes –
alkenes – alkynes – alcohols (primary, secondary and tertiary) – aldehydes and ketones – carboxylic
acids – amines and amides – halogenated organic compounds
● explore and distinguish the different types of structural isomers, including
saturated and unsaturated hydrocarbons, including: (ACSCH035) – chain isomers – position
isomers – functional group isomers

HYDROCARBONS

Inquiry question: ​How can hydrocarbons be classified based on their structure and
reactivity?
 ● construct models, identify the functional group, and write structural and molecular
formulae for homologous series of organic chemical compounds, up to C8 (ACSCH035) : – alkanes –
alkenes – alkynes
● conduct an investigation to compare the properties of organic chemical
compounds within a homologous series, and explain these differences in terms of bonding
(ACSCH035)
● analyse the shape of molecules formed between carbon atoms when a single, double or
triple bond is formed between them
● explain the properties within and between the homologous series of alkanes with
reference to the intermolecular and intramolecular bonding present
● describe the procedures required to safely handle and dispose of organic substances
(ACSCH075)
● examine the environmental, economic and sociocultural implications of obtaining
and using hydrocarbons from the Earth

PRODUCTS OF REACTIONS INVOLVING

HYDROCARBONS

Inquiry question: ​What are the products of reactions of hydrocarbons and how do they
react?

● investigate, write equations and construct models to represent the reactions of

unsaturated hydrocarbons when added to a range of chemicals, including but not limited to:

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 1 OF 65

– hydrogen (H​2​) – halogens
(X​2​) – hydrogen halides (HX)
– water (H​2​O) (ACSCH136)
● investigate, write equations and construct models to represent the reactions of
saturated hydrocarbons when substituted with halogens

ALCOHOLS

Inquiry question: ​How can alcohols be produced and what are their
properties?

● investigate the structural formulae, properties and functional group

including: – primary – secondary – tertiary alcohols
 ● explain the properties within and between the homologous series of alcohols with
reference to the intermolecular and intramolecular bonding present
● conduct a practical investigation to measure and reliably compare the enthalpy of
combustion for a range of alcohols
● write equations, state conditions and predict products to represent the reactions of
alcohols, including but not limited to (ACSCH128, ACSCH136): – combustion – dehydration –
substitution with HX – oxidation
● investigate the production of alcohols,
including: – substitution reactions of halogenated organic
compounds – fermentation
● investigate the products of the oxidation of primary and secondary alcohols
● compare and contrast fuels from organic sources to biofuels, including ethanol

REACTIONS OF ORGANIC ACIDS AND

BASES

Inquiry question: ​What are the properties of organic acids and

bases?

● investigate the structural formulae, properties and functional group

including: – primary, secondary and tertiary alcohols – aldehydes and ketones
(ACSCH127) – amines and amides – carboxylic acids
● explain the properties within and between the homologous series of carboxylic acids
amines and amides with reference to the intermolecular and intramolecular bonding present
● investigate the production, in a school laboratory, of simple esters
● investigate the differences between an organic acid and organic base
● investigate the structure and action of soaps and detergents
● draft and construct flow charts to show reaction pathways for chemical synthesis,
including those that involve more than one step

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 2 OF 65

POLYMERS

Inquiry question: ​What are the properties and uses of

polymers?

● model and compare the structure, properties and uses of addition polymers of ethylene
and related monomers, for example: – polyethylene (PE) – polyvinyl chloride (PVC) – polystyrene (PS) –
 polytetrafluoroethylene (PTFE) (ACSCH136)
● model and compare the structure, properties and uses of condensation polymers, for
example: – nylon – polyesters

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 3 OF 65

IUPAC
 NOMENCLATURE
OUTCOMES
● investigate the nomenclature of organic chemicals, up to C8, using IUPAC
conventions, including simple methyl and ethyl branched chains, including: (ACSCH127) – alkanes –
alkenes – alkynes – alcohols (primary, secondary and tertiary) – aldehydes and ketones – carboxylic
acids – amines and amides – halogenated organic compounds
● analyse the shape of molecules formed between carbon atoms when a single, double or
triple bond is formed between them

HYDROCARBONS

Hydrocarbons are compounds that contain ​only carbon ​and ​hydrogen​. They are the main constituents of
natural gas and crude oil.

Hydrocarbons can be ​saturated ​(in hydrogen) or ​unsaturated​, depending on whether they contain just
single bonds or double/triple bonds, respectively.

ALKANES

- Contain only C-C ​single ​bonds in backbone - Saturated hydrocarbon

- General formula for straight chained and branched alkanes = C​n​H​2n+2

Alkanes are called ​saturated hydrocarbons ​because no more hydrogen atoms can be added to the
carbon atoms.

Alkanes are a ​homologous series​: family of compounds that can be represented by one general molecular
formula.

Name Molecular Formula MP BP

methane -182 -164

ethane -183 -89

propane -190 -42

butane -138 0

pentane -130 36
 hexane -95 69

heptane -91 98

octane -57 126

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MOLECULAR STRUCTURE OF
ALKANES

BRANCHED ALKANES

Branched alkanes are alkane compounds containing ​alkyl side

groups.

Alkyl Groups Molecular Formula

Methyl

Ethyl

Propyl

Butyl

Pentyl

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STEM NOMENCLATURE

Longest Carbon Chain Prefix Number of identical groups Prefix

1 Meth- 5 Pent-

2 Eth- 6 Hex-

3 Prop- 7 Hept-

4 But- 8 Oct-

NAMING BRANCHED CHAIN ALKANES

1) Find the ​longest continuous chain of carbon atoms​. Assign a parent name based on this
number. 2) Find whatever groups that are not part of the longest continuous chain. Name these as
prefixes ​and put
them in ​alphabetical order​. 3) Assign numbers to groups by counting from one end of the
chain. A chain has two ends, and the end we
start from is the one that gives the ​lowest set of numbers ​to the
groups.
eg: 3-methylhexane

NAMING ALKANES WITH MULTIPLE ALKYL

GROUPS

Number of identical groups Prefix Number of identical groups Prefix

2 Di 5 Penta

3 Tri 6 Hexa

4 Tetra 7 Hepta

LOWEST SET OF NUMBERS

To determine the lowest set of numbers:

1) Work out the numbers for the ​two possible names (​ going along the longest carbon chain in both
directions) 2) List the numbers in each name in ​increasing order ​3) Compare the first number of each
name
a. If there is a difference, the name with the ​lower number is correct ​b. If the numbers are the
same, move onto the second number and so on until there’s a difference

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ALKENES

- Contains at least one C=C double bond in backbone

- Unsaturated hydrocarbons - General formula =
C​n​H​2n
 Carbon atoms with double and triple bonds can accept more hydrogen therefore alkenes and
alkynes are ​unsaturated hydrocarbons​.

The double bond carbon atoms are called ​functional groups ​because they are sites of chemical
activity.

- A ​functional group ​is an atom, or group of atoms, which give a compound some ​characteristic
physical ​and
chemical properties​.

It is necessary to assign a number to describe the location of the double bond. The bonds are numbered
much like carbons. The lowest number is assigned to the bond.

ALKYNES

- Contain at least one C≡C triple bond in backbone

- Unsaturated hydrocarbons - General formula =
C​n​H​2n−2

SHAPE
aroun
Bonds around Carbon Angle between Bonds Number of VSEPR groups Shape

Four Single Bonds 109.5 4 Tetrahedral

Two single bonds and one

double bond Two Double bonds or one
Trigonal planar riple bond and one single
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 7 OF 65
EXTENSION: CYCLIC
HYDROCARBONS

Hydrocarbon compounds in which the carbon atoms have joined to form ​closed ring structures ​are called
cyclic ​(or alicyclic) hydrocarbons. They may also be saturated or unsaturated:

- Those that contain only ​C-C ​bonds are called c

​ ycloalkanes​. - Those that contain ​C=C ​bonds or
C≡C ​bonds are called ​cycloalkenes ​and c ​ ycloalkynes ​respectively.

Due to the extra C-C bond that closes the ring structure, there are ​always two less hydrogen atoms

than the respective straight chain. ​Cyclohexane 3-methylcycloheptene EXTENSION:

​ AROMATIC
HYDROCARBONS

A unique type of cyclic structure is the ​aromatic hydrocarbons​. These structures contain a ​ring of carbon
atoms ​linked together such that they have ​delocalised electrons​. Delocalised electrons are not held within
bonds but are free to move around a structure.

Benzene

- The electrons of the double bond are free to move around the entire ring, forming a “cloud” of
delocalised
electrons above and below the plane of the ring. - The delocalisation is shown by drawing a
circle around the inside of the ring. This depiction represents the
equivalent nature of the six carbon-carbon
bonds.
The delocalisation of the electrons in aromatic compounds gives them significantly different properties to
alkenes. They have much greater stability and are often unreactive.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 8 OF 65

PHYSICAL
PROPERTIES
OUTCOMES
● conduct an investigation to compare the properties of organic chemical
compounds within a homologous series, and explain these differences in terms of bonding
(ACSCH035)
● explain the properties within and between the homologous series of alkanes with
reference to the intermolecular and intramolecular bonding present

PROPERTIES OF
HYDROCARBONS

Members of the same homologous series

have:

- A ​similar structure ​and the same general formula and functional group (each member of a
homologous
series differs by a −CH​2 ​− unit from the previous
member) - A pattern to their physical properties - Similar
chemical properties

MELTING AND BOILING POINTS

The ​melting ​and ​boiling points ​are measures of the thermal energy ​required to overcome
intermolecular forces​.

- As ↑ intermolecular forces → ↑ E​heat ​→ ↑ MP and ↑ BP

The ​packing ​of molecules also affects the boiling and melting
point.

- Packing depends on molecular shape. Molecules that are ​small, symmetrical ​or ​unbranched ​tend to
be able
to pack more closely together. This results in ​stronger intermolecular forces​. - The effect of
packing on intermolecular forces strength is more significant for molecules in ​solid states
(melting point).

MELTING AND BOILING POINTS OF ALKANES

Alkane molecules are ​nonpolar, ​the only intermolecular force is ​dispersion forces​. As the length of the
carbon chain increases, the overall force of attraction between molecules also increase. (Dispersion forces is
proportional to molar mass). Because boiling and point is determined by the strength of intermolecular forces,
boiling point increases as alkane chain length increases.

Molecular shapes ​also influence the strength of dispersion forces. ​Straight-chained ​alkanes are able to fit
together more closely and tend to have higher boiling points than their corresponding chain isomers.

Melting point is affected by the strength of the dispersion forces, size and shape of the
molecule.

Melting points of hydrocarbons follow the same general patterns as boiling points, with a few exceptions.
The melting points of straight-chain hydrocarbons increase as the number of carbon increases.
However, there are ​deviations ​in this trend, relating to whether the molecules have an ​even or odd
number of ​carbon atoms​.

Chains with ​even numbers ​of carbon atoms pack ​slightly more efficiently ​in the solid state than chains
with ​odd numbers​. The more efficient packing requires more energy to melt the compound resulting in a
higher melting point.

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Name Molecular Formula Molecular Mass (​g/mol​) MP (​°C​) BP (​°C​)

methane 16.04 -182 -164

ethane 30.07 -183 -89

propane 44.09 -190 -42

butane 58.12 -138 0

 pentane 72.15 -130 36

hexane 86.17 -95 69

heptane 100.2 -91 98

octane 114.2 -57 126

- BP (C​1 −
​ C​4​) < 25°C ∴ Gaseous at RTP - BP (C​4 −
​ C​8​) > 25°C ∴ Liquids at RTP - Generally, as ↑
molecular mass → ↑MP, however methane and ethane’s BP > propane. This is because
ethane and methane’s shapes allow them to pack tighter relative to propane, increasing IMF and
hence MP.

BOILING POINTS OF ALKENES AND

ALKYNES

Alkenes and alkynes, like alkanes, are ​nonpolar hydrocarbons. ​Their molecules are also nonpolar so the
forces of attraction between them are only weak dispersion forces. Members of these homologous series
have relatively low boiling points similar to those observed for alkanes with the same number of carbon
atoms.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 10 OF 65

As with alkanes, the boiling points of alkenes and alkynes increase with molecular size as the strength of
dispersion forces between molecules increase.

- The boiling points of alkenes are slightly lower than alkanes with the same number of carbon atoms.
- Alkynes have higher boiling points than both alkenes and alkanes that have the same number of
carbon
atoms. This is due to the increase packing because of its linear
shape.

Since alkenes have lower molecular mass compared to alkanes with the same number of carbon atoms, the
strength of the dispersion forces is weaker. Hence the boiling points are lower.

MELTING POINTS OF ALKENES AND

ALKYNES

Alkenes, alkynes and haloalkanes follow the similar pattern to alkanes. As the length of the carbon chain
increases, the melting point increases. The alkenes ​ethene, propene ​and ​butene a​ re all gases at room
temperature, alkenes with 5-14 carbons are liquid, and longer-chained molecules are solid.

Alkynes follow the same general trend for melting points seen in alkanes and alkenes. The ​position of
the triple bond ​can greatly affect the melting points as the shape of the molecule changes.

SOLUBILITY (LIKE DISSOLVE

LIKE)

The solubility of a substance depends on the ​strength ​of the ​IMF within the solute ​and ​within the solvent
(cohesive forces), in comparison to the ​IMF ​between the solute and solvent (adhesive forces).

The generalisation is that ​polar compounds ​tend to only dissolve well in ​polar compounds ​and
non-polar ​compounds only dissolve in ​non-polar compounds​.

Hydrocarbons are soluble in each other as well as in non-polar organic compounds such as benzene, diethyl
ether and carbon tetrachloride (tetrachloromethane). This is because the ​cohesive forces ​within the solvent
are also ​weak dispersion forces ​that are ​similar in strength to the dispersion forces within
hydrocarbons​.

DENSITY
The density of a substance is a measure of its ​mas per unit volume. ​(g/mL or
g/cm​3​)

Alkane Formula Density ​(g/cm​3 ​at 20°C) ​Molecular Mass ​(g/mol)

Pentane C​5​H​12 ​0.626 72.15

Decane C​10​H​22 0.730

​ 142.3

Pentadecane C​15​H​32 ​0.768 212.4

Isosane C​20​H​42 ​0.789 282.6

Alkanes are immiscible with water (cannot mix). When mixed, two layers form and the alkane will float on
water. This occurs as the ​density of all alkanes < water​.

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VOLATILITY

Volatility is the ​ability of a liquid ​(or solid) ​to escape and form a vapour​. ↑ BP → ↑ IMF Strength → ↑
Volatility

Volatility is measured by ​vapour pressure​, which is a measure of concentration in the gas phase above the
liquid. It is ​constant ​at a ​constant temperature​.

Hydrocarbons are ​non-polar ​and hence have ​dispersion forces ​as their only ​intermolecular force​.
Since the intermolecular forces are ​relatively weak​, their ​bonds are easily overcome ​and hence the
BP is relatively low​. Therefore, hydrocarbons will be volatile.

↑ Molecular Mass → ↑ Strength of dispersion forces → ↑ E​heat →

​ ↓ Volatility at a constant temperature.

VISCOSITY

Viscosity refers to a substance’s ​resistance to fluid flow. ​Liquids with a relatively high resistance to flow
have high viscosity. For a substance to flow, particles must flow over each other. Viscosity depends on:

- Strength of intermolecular forces. ↑ IMF → ↑ Viscosity -

Size of molecules. ↑ Size → ↑ Viscosity - Temperature. ↑
Temperature → ↓ Viscosity

Viscosity decreases with ​increasing temperature​. At higher temperatures, molecules have ​greater kinetic
energy​. Thus, the molecules move around more which increases the space between molecules. This
causes the ​intermolecular forces ​to be ​weaker ​and ​hence viscosity decreases​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 12 OF 65

FUNCTIONAL
GROUPS
OUTCOMES
 ● investigate the nomenclature of organic chemicals, up to C8, using IUPAC
conventions, including simple methyl and ethyl branched chains, including: (ACSCH127) – alcohols
(primary, secondary and tertiary) – aldehydes and ketones – carboxylic acids – amines and amides –
halogenated organic compounds

FUNCTIONAL GROUPS

A functional group is an ​atom or group of atoms ​which give a compound ​some characteristic physical
and ​chemical property​.

A homologous ​series ​is a family of organic compounds with the ​same general formula ​or ​functional
groups ​with ​similar chemical properties​.

ALCOHOLS (ALKANOLS)

Alcohols are formed when a H atom on a hydrocarbon has been replaced with an -OH
group.

For naming:

1) Find ​longest continuous chain ​of carbon atoms that contain the functional group. Assign a stem
name and
use the suffix “​-ol​”. 2) Name the substituents as prefixes in alphabetical order. ​3) Number the
chain ​so that the functional group at the end of the name gets the lowest possible number.

eg: 2-ethylbutan-1-ol
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 13 OF 65
Alcohols can also be classified according to the number of carbon atoms attached to the carbon bearing
the -OH group.

- A ​primary ​(1°) alcohol is one in which the carbon bearing the -OH group is bonded to ​one ​other
carbon
atom. - A ​secondary ​(2°) alcohol is one in which the carbon bearing the -OH group is bonded to
two ​other carbon
atoms. - A ​tertiary ​(3°) alcohol is one in which the carbon bearing the -OH group is bonded to
three ​other carbon
atoms.

These three types of alcohols have ​different physical ​and ​chemical

properties​.

Butan-1-ol Hexan-3-ol 2-methylpentan-2ol Primary Alcohol Secondary Alcohol Tertiary

Alcohol

ALDEHYDES AND KETONES

(CARBONYLS)

A ​carbonyl ​functional group consists of carbon attached to an ​oxygen atom ​by a ​double
bond​.
The difference between ​aldehydes ​(​alkanals​) and ​ketones ​(​alkanone​) is the ​position ​of the carbonyl group
along the carbon chain:

- If the carbonyl group is on a ​terminal ​carbon (at the end of a chain), it is called an ​aldehyde​, which is
given
the suffix “​-al​”. - If the carbonyl group is in the ​middle ​of the carbon chain, it is called a ​ketone​,
which is given the suffix “​-
one”​.

Aldehyde: Ketone:

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 14 OF 65

- When the ​aldehyde ​is the ​suffix​, the aldehyde carbon is assigned the number 1. Since it is always
carbon 1,
“1” (terminal carbon) is omitted from the name. (“-al”) Eg.
2-methylbutanal

- When the ​ketone ​is the ​suffix​, the carbon chain is numbered so that the ketone is assigned the
lowest
number​. (“-one”) eg. Pentan-3-one.
CARBOXYLIC ACIDS (ALKANOIC
ACIDS)

Carboxylic acids contain the carbonyl group, C=O, connected to a ​hydroxyl ​group. The carboxyl group is
abbreviated as -COOH, and is given by the ​suffix ​“​-oic acid​”.

- Since the carboxylic acid ​uses up 3 bonds ​on the carbon atom, it must be situated at the ​end of the
chain
(terminal carbon).

Eg: 2,2,3-trimethylbutanoic acid

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 15 OF 65

IUPAC Name Common Name
 Methanoic acid (HCOOH) Formic acid

Ethanoic acid (CH​3​COOH) Acetic acid

Propanoic acid (CH​3​CH​2​COOH) Propionic acid

Butanoic acid (CH​3​CH​2​CH​2​COOH) Butyric acid

Pentanoic acid (CH​3​CH​2​CH​2​CH​2​COOH) Valeric acid

2-Hydroxypropanoic acid (HC​3​H​5​O​6​) Lactic acid

2-Hydroxypropane-1,2,3-tricarboxylic acid (H​3​C​6​H​5​O​7​) Citric acid ​AMINES AND

AMIDES

Amines and amides both contain ​nitrogen​. Amides contain the group. They use the ​suffix ​“​-amine​” or
the prefix “​amino-​”.

Amides ​are ​carboxylic acids ​where the OH group has been replaced with an ​amine. ​They use the ​suffix
“​amide​”. When they quoted as the prefix, the carbonyl and the amine are named separately (using the
prefixes “oxo” and “amino” respectively).

Eg. 3-methylpentan-2-amine

Eg. 5-amino-3-methyl-oxopentanoic acid

 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 16 OF 65
HALOGENATED ORGANIC COMPOUNDS

Halogenated organic compounds have hydrogen atoms ​replaced ​with a ​halogen ​(Group 17
element).

The ​halogen functional groups ​are named using ​prefixes ​placed in front of their name of the
alkane:

• Br: bromo
• Cl: chloro
• F: fluoro
• I: iodo

Eg. 1,2-dibromo-3,4-difluoropentan-3-one

DIFFERENT FUNCTIONAL GROUPS

The highest priority functional group takes the suffix, and the other functional groups are placed earlier in the
name.

Aldehyde > Ketone > Alcohol > Alkyne =

Alkene

Name Structure Suffix Prefix

Carboxylic Acid (Alkaonic acid) -oic acid

Amide -amide oxo- & amino-

(The carbonyl & amine
groups are named as if
they were separate)

Aldehyde (Alkanal) -al oxo-

Ketone (Alkanone) -one oxo-

Alcohol (Alkanol) -ol hydroxy-

Amine -amine -amino

Alkene -ene -en-

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 17 OF 65

STRUCTURE
ISOMERS
OUTCOMES
● explore and distinguish the different types of structural isomers, including
 saturated and unsaturated hydrocarbons, including: (ACSCH035) – chain isomers – position
isomers – functional group isomers

ISOMERS

Structural isomers are molecules that have the ​same molecular formula, ​but their atoms are arranged in
different ways, giving rise to ​different structural formulae​.

Although isomers have the same molecular formula, they are different compounds with ​different
chemical ​and ​physical properties​, as well as different names.

CHAIN ISOMERS

Chain isomers involve ​rearrangement ​of the carbons in the ​backbone, ​resulting in a different number of
carbons in the longest chain or different branching in the carbon chain.

EXAMPLE – HEXANE

An alkane with the molecular formula C​6​H​14 has

​ 5 chain isomers. Each isomer has the same molecular
formula but has a different arrangement and a different name.

Hexane

2-methylpentane 3-methylpentane

2,2-dimethylbutane 2,3-dimethylbutane
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 18 OF 65
POSITION ISOMERS

Position isomers result when molecules have the same ​carbon chain ​but the ​functional group ​is at a
different location​.

Position isomers only exist for molecules that ​contain functional groups​, where the chain is long
enough for the functional group to occupy different positions. (Eg. Not possible for ethene or ethane).

EXAMPLE – BUTENE

But-1-ene But-2-ene

FUNCTIONAL GROUP ISOMERS

Functional group isomers result when the atoms in the molecules are ​arrange in different ways ​that
lead to the isomers having ​different functional groups​.

EXAMPLE

Propanoic acid and 1-hydroxypropan-2-one are functional group isomers as both molecules have the
formula C​3​H​6​O​2​, but propanoic acid contains a carboxyl functional group while 1-hydroxypropan-2-one
contains carbonyl and hydroxyl functional groups.
 Propanoic acid 1-hydroxypropan-2-one

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GEOMETRIC ISOMERS

Two atoms joined by a single bond can rotate freely around the single bond. Geometric isomers can
occur when there is restricted rotation somewhere in the molecule. Restricted rotation can occur about a
C=C or a ring.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 20 OF 65
 HYDROCARBON
REACTIONS
OUTCOMES
● investigate, write equations and construct models to represent the reactions of
unsaturated hydrocarbons when added to a range of chemicals, including but not limited to: –
hydrogen (H​2​) – halogens (X​2​) – hydrogen halides (HX) – water (H​2​O) (ACSCH136) ​COMBUSTION
REACTIONS

All combustion reactions are ​exothermic​. It may be ​complete ​or

incomplete.

For complete combustion to occur, ​excess oxygen m

​ ust be readily available, and the products are always
carbon dioxide ​and ​water.

25​ O​ → 8CO​ + 9H​ O​

C​8​H​18(l) ​+ ​ 2 ​ 2(g) ​ 2(g) ​ 2​ (l)

Incomplete combustion occurs when there is ​insufficient oxygen​. The products are ​water ​and ​three
different oxidations of carbon, ​soot, carbon monoxide and carbon dioxide​.

Incomplete combustion results in ​less energy ​being produce per mole of fuel combustion, making it ​less
efficient​. This is due to the reduction of C=O bonds being formed. The formation of C=O releases a large
amount of energy.

Alkenes and alkynes tend to burn with a more ​sooty flame ​compared to alkanes due to the ​higher
percentage of carbon atoms​. Some of the carbon may not combine with oxygen.

- Standard molar heat of combustion is the energy ​released​. Therefore, it is ​positive​. - Standard
enthalpy of combustion is ​always negative ​as combustion is exothermic. It is the ​change in
enthalpy​.

REACTIONS OF UNSATURATED
HYDROCARBONS

STABILITY OF CARBON BONDS

The bond energies dictate the overall reactivity of hydrocarbon compounds. ​Subsequent carbon-carbon
bonds ​in a multiple bond are less stable and ​weaker ​than the original single covalent bond.
 - This means that ​double ​and ​triple bonds ​are ​highly reactive ​and can break open more easily and
allow
atoms to join (saturate). - This makes the ​alkenes ​and ​alkynes highly reactive ​compared
to alkanes. - Alkenes and alkynes are able to react with a number of chemical reactions called
addition reactions​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 21 OF 65

ADDITION REACTIONS OF ALKENES

HYDROGENATION

Alkenes react with hydrogen gas in the presence of a metal catalyst to form a ​saturated
alkane​.

Saturated Alkane

Alkene + H​2(g)

HALOGENATION (BROMINATION AND CHLORINATION)

Bromine adds to almost all alkenes very rapidly at RTP to give a compound that has two bromines on
adjacent carbons. The reaction occurs spontaneously at RTP.
This is used as in indicator for alkenes and
alkynes.

ADDITION OF HX (HYDROHALOGENATION)

Any of the hydrogen halides (HF, HCl, HBr and HI) can add to the double bond of an alkane to give the
corresponding alkyl halide. The double bond is converted into a single bond.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 22 OF 65

PREDICTING A MAJOR PRODUCT

When an asymmetric reagent, such as HBr is added to an asymmetric alkene, more of one isomer is
produced than the other.

- The predominant isomer is called the ​major product a​ nd the other isomer(s) is called the ​minor
product(s)​. - In some reactions, only the major product will be formed.

The major product obtained from an addition reaction can be predicted using ​Markovnikov’s
rule​.
In addition reactions involving unsymmetrical alkenes, the hydrogen atom will predominantly bond to the
carbon atom bearing the greater number of hydrogen atoms​.

ADDITION OF WATER (HYDRATION)

Water alone does not react with alkenes, but if an aqueous acid catalyst (eg. Dilute H​2​SO​4​) is added and the
mixture is heated, water adds to the C=C double bond to give an alkanol.

ADDITION REACTIONS OF ALKYNES

Alkynes undergo addition reactions in a similar fashion to

alkenes.

- One of the three bonds in the triple bond is broken, and two new bonds form. The original triple bond
is
converted into a double bond. - The second addition reaction can be stopped by controlling
equivalents of reagent used or by using a
specialised reagent.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 23 OF 65
HYDRATION OF ALKYNES

The addition of water to alkynes is different.

- Alkynes do not react with water with only an acid catalyst. A mercury(II) catalyst, such as ​mercury(II)
sulfate​,
must also be present. - A ​carbonyl ​(ketone or aldehyde) is produced instead of an alcohol.
The alcohol forms as an intermediate
which quickly rearranges to form the carbonyl.

SUBSTITUTION REACTIONS OF
ALKANES

A substitution reaction occurs when an ​atom ​or ​functional group ​in a molecule is ​replaced or substituted
by another atom or group.

Alkanes are far less reactive than alkanes and alkynes as C-C single bonds are ​relatively strong​.
However, their ​hydrogen atoms ​can be ​substituted by halogens​. These reactions do not occur
spontaneously at RTP.

Substitution of alkanes can only be carried out with ​chlorine ​and ​bromine ​(fluorine reacts too explosively, and
iodine does not react) and required energy in the form of ​ultraviolet (UV) radiation​.

Chloromethane is called the ​substitution product ​of this

reaction.

OUTCOME
● describe the procedures required to safely handle and dispose of organic substances
(ACSCH075)

All organic waste should be discarded into appropriately ​labelled waste

containers​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 24 OF 65

PHYSICAL PROPERTIES OF
ALCOHOLS
OUTCOMES
 ● investigate the structural formulae, properties and functional group
including: – primary – secondary – tertiary alcohols
● explain the properties within and between the homologous series of alcohols with
reference to the intermolecular and intramolecular bonding present

INTERMOLECULAR AND INTRAMOLECULAR BONDING IN

ALCOHOLS

Alcohols contain a ​highly electronegative oxygen ​atom. This creates a polar bond in the
molecule.

- The ​hydrocarbon chain ​of the alcohol is ​non-polar ​(alkyl chain) and can form ​dispersion
forces​. It is
hydrophobic (repelled from water). - The ​-OH functional group ​is ​polar ​and can form h
​ ydrogen
bonds, dipole-dipole ​and ​ion-dipole ​bonds. It is
hydrophilic (attracted to water).

As the chain length of an alcohol increases, the ​strength of the dispersion force increases​. However, the
extent of ​hydrogen bonding ​does ​not change​.

- The strength of the ​hydrogen bonding ​depends primarily on the molecule’s ​shape ​and the
number of
hydrogen bond donors ​and a
​ cceptors
available.

Thus the ​length ​of the hydrocarbon chain ​influences ​the ​properties ​within the homologous series of
alcohols, and the hydroxyl group influences the differences in properties between alcohols and other
homologous series.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 25 OF 65
MELTING AND BOILING POINT OF ALCOHOLS

Alkanol Molecular Mass (g/mol) Melting Point ​(°C) ​Boiling Point ​(°C)

Methanol 32.04 -98 65

Ethanol 46.07 -114 78

Propan-1-ol 60.09 -126 97

Butan-1-ol 74.12 -90 118

Pentan-1-ol 88.15 -79 138

Hexan-1-ol 102.17 -52 157

Heptan-1-ol 116.20 -34 176

Octan-1-ol 130.22 -16 195

 - ↑ Chain length → ↑Molecular mass → ↑ Strength of dispersion forces → ↑BP and ↑ MP - However, the
shape of ethanol and methanol allow them to pack more closely together than propan-1-ol,
thus resulting in stronger intermolecular forces and a higher
MP.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 26 OF 65

The ​position of the hydroxyl group ​within the molecule can also affect the melting and boiling points of
alcohols.

For example, three alcohols with the same molecular formula:

C​4​H​9​OH
 Alcohol
P ​(°C)
Type of

Primary Butan-1-ol 118

Secondary Butan-2-ol 100

Tertiary 2-methylpropan-2-ol 82

Secondary ​and ​tertiary ​alcohols have ​lower boiling points ​than primary alcohols with the same number
of carbon atoms.

- Since the three alcohols are ​isomers​, their ​dispersion forces ​will be the same. - However, the
hydrogen bonding ​is weaker in ​secondary a ​ nd ​tertiary ​alcohols. The alkyl group adjacent to
the OH group hinders the OH groups from getting closer together, ​restricting ​their ability to form
strong hydrogen bonds. ​- Hence the ​lower boiling points ​arise from ​weaker hydrogen bonding ​in
secondary and tertiary alcohols.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 27 OF 65
ALKANES VS ALKANOLS

- Hydrogen bonding allows the alkanols to have a higher boiling point than similar molecular mass
alkanes.

SOLUBILITY IN WATER ​Alkanol Solubility in Water at RTP (g/100mL)

Methanol Miscible

Ethanol Miscible

Propan-1-ol Miscible

Butan-1-ol 7.9
 Pentan-1-ol 2.3

Hexan-1-ol 0.59

Small alcohols dissolve well in water. However, ​solubility in water decreases ​with ​increasing carbon
chain length​.

The solubility of alcohols in water is ​dictated b

​ y ​size ​because the opposing effects of the polar and
non-polar portions of the molecule.

- The polar hydroxyl group is ​hydrophilic ​(“water loving”) and the non-polar hydrocarbon chain
is
hydrophobic ​(“water-hating”)

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 28 OF 65

Water molecules ​cannot solvate ​the ​large non-polar ​carbon chains in long
alcohols.

- The -OH group can form hydrogen bonds with water, allowing solvation of this portion of the
molecule. - However, to solvate the large non-polar carbon chain, many strong hydrogen bonds
between water
molecules need to be broken. Since the alkyl chain has no strong attraction to water, these
cohesive hydrogen bonds cannot be broken​. - Thus, the alkyl end remains unsolvated, and
solubility in water is drastically decreased.

A very general rule for solubility in water, if it has less than a 4:1 carbon : oxygen ratio, it is
soluble.

Small alcohols ​are ​good solvents ​for dissolving both polar and non-polar substances due to the
presence of both polar and non-polar areas in the molecule.

- The polar hydroxyl group can form polar interactions such as ​ion-dipole, hydrogen bonding and
dipole-
dipole ​forces with other polar and ionic substances - The non-polar hydrocarbon
chain can form ​dispersion forces ​with other non-polar substances.

SOLUBILITY IN ORGANIC SOLVENTS

Alcohols become more ​soluble ​in ​non-polar organic solvents ​such as hexane, benzene and toluene, as
the ​length of the carbon chain increases​.

- The large alkyl chain can form strong dispersion forces with other non-polar substances. These are
strong
enough to disrupt hydrogen bonds holding the alcohol together. -
Therefore, the alcohol molecules separate and disperse throughout the solvent.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 29 OF 65

REACTIONS OF
ALCOHOLS

OUTCOMES ​● write equations, state conditions and predict products to represent the reactions of
alcohols,
including but not limited to (ACSCH128,
ACSCH136): – combustion – dehydration –
substitution with HX – oxidation
● investigate the products of oxidation of primary and secondary alcohols

DEHYDRATION

When alcohols are heated with concentrated ​sulfuric ​or ​phosphoric acid ​as a catalyst, an OH and a H
atom on the adjacent carbon will be eliminated from the alcohol to give an ​alkene ​and ​water.

The reactivity and rate of reaction varies depending on the type of

alcohol.

- ​Tertiary ​alcohols are the ​most reactive ​and always react the fastest. Dehydration occurs readily at
room
temperature. - ​Primary ​and ​secondary ​alcohols require higher temperatures. Primary alcohols
are ​less reactive ​and react
slower than secondary alcohols.

SUBSTITUTION REACTION OF
HALOALKANES

Alcohols undergo substitution in the presence of a ​hydrogen halide ​(HCl, HBr, HI) to give the
corresponding ​alkyl halide ​and ​water​.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 30 OF 65
The trend in reactivity is the same as for dehydration. For primary alcohols, the rate of reaction is also
dependent on the hydrogen halide used. HCL is the slowest whilst HI is the fastest.

OXIDATION

Alcohols can be oxidised with strong oxidising agents, such as acidified solutions of permanganate (MnO​4-​​ )
or dichromate (Cr​2​O​72-​
​ ) to give carbonyl compounds. A ​change in oxidation states ​can be seen for the

carbon atoms​.

OXIDATION OF PRIMARY ALCOHOLS

Primary alcohols are oxidised into ​carboxylic

acids​.

- The oxidation of alcohols is driven by a simultaneous reduction reaction, usually of ​inorganic

reagents​.
Either ​acidified permanganate ​(MnO​4-​ ​purple in colour) or ​dichromate ​(Cr​2​O​72- ​
​ orange in colour) can be

used as the oxidant. - The oxidation occurs stepwise: the alcohol is first oxidised to the ​aldehyde​, which is
then oxidised into the
carboxylic acid​.
Aldehydes are ​very reactive ​and the second oxidation generally occurs too rapidly for it to be separated
practically.

MnO​4-​ ​: Purple → colourless

​
Cr​2​O​72-
​ : Orange → green

OXIDATION OF SECONDARY
ALCOHOLS

Secondary alcohols can be oxidised to produce

ketones​.

- Either ​acidified permanganate ​(MnO​4-​ ​purple in colour) or ​dichromate ​(Cr​2​O7​ 2- ​

​ orange in colour) can be

used
as the oxidant. - Since there are no hydrogen atoms attached to the ketone carbon, no further
oxidation can occur. - Secondary alcohols are ​generally less reactive ​than ​primary alcohols​, thus
require ​higher temperatures ​and
longer reaction times ​to be
oxidised.

Slower decolourisation of the acidified

oxidants.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 31 OF 65

OXIDATION OF TERTIARY ALCOHOLS

Tertiary alcohols cannot be oxidised to give any carbonyl compound. The carbon bearing the hydroxyl group
has no hydrogen atoms, thus it cannot be oxidised.

COMBUSTION

Alcohols can readily combust in the same manner as hydrocarbons. They can undergo complete and
incomplete combustion.

Alcohols are ​good fuels ​as the combustion of alcohol is ​highly exothermic ​and since they are already
oxygenated, ​they are more prone to complete combustion.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 32 OF 65

PRODUCTION OF
ALCOHOLS
OUTCOMES
● investigate the production of alcohols,
including: – substitution reactions of halogenated organic
compounds – fermentation

PRODUCTION BY ADDITION (HYDRATION)

Water alone does not react with alkenes, but if an aqueous acid catalyst (eg. Dilute H​2​SO​4​) is added and the
mixture is heated, water adds to the C=C double bond to give an alkanol.

PRODUCTION BY SUBSTITUTION

Alcohols can also be prepared from substitution reactions of

haloalkanes​.

This reaction occurs by heating the haloalkane with a solution of ​sodium hydroxide ​or ​potassium
hydroxide​. The hydroxide ion from the aqueous base replaces the halogen atom to generate an alcohol
and halide salt.

X: Cl, Br, I. Fluoroalkanes will not react as the C-F bond requires too much energy to
break.

This reaction occurs due to the ​highly polarised carbon-halogen ​bond, which produces a partial positive
charge on the carbon atom.

- The partially positive carbon atom can be easily “attacked” by a negatively charged hydroxide ion.
- This results in the formation of a covalent carbon-oxygen bond. In the process, the negative
 charge is
donated to the electronegative halogen atom, which leaves as a halide
ion.

The ​rate ​of this reaction is dependent on the ​type of haloalkane ​and the ​halogen ​atom that leaves the
molecule.

- Haloalkanes can be categorised as primary, secondary and tertiary. The reactivity is highest for
primary,
followed by secondary and then tertiary. - This is because the ​presence ​of ​alkyl groups ​greatly
hinders ​the ​ability of the hydroxide ion ​to approach the
partially positive carbon and thus slows the
reaction.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 33 OF 65

The type of halogen atom leaving the molecule also has an effect on the rate. The reaction occurs the fastest
with iodide, followed by bromide and then chloride. This is because the carbon-halogen bonds are of different
strengths.

Bond Average Energy (kJ/mol)

C-F 485

C-Cl 338

C-Br 276

C-I 238

- The lower the bond energy, the easier it is to break the bond.

It is also possible for haloalkanes to undergo substitution reactions with ​water ​to form alcohols. This reaction
occurs much more ​slowly​, and the reactivity is highest for ​tertiary​.
PRODUCTION BY FERMENTATION

Fermentation is a process that involves the conversion of ​carbohydrates ​into ​simple alcohols ​by the
action of enzymes. This is a natural process used by microorganisms to extract energy.

Carbohydrates have the molecular formula of: C​x​(H​2​O)​y​. Carbohydrates are abundant in plant material.
They are also called saccharides.

- The simplest carbohydrates are monosaccharides. They are the building blocks of more
complex
carbohydrates, such as disaccharides like sucrose and polysaccharides like
cellulose.

The ​fermentation ​of ​monosaccharides​, such as glucose and fructose is the simplest form of
fermentation which process ​ethanol ​and c
​ arbon dioxide​.

This process relies on the presence of ​zymase​, an enzyme found in

yeast.

CONDITIONS FOR FERMENTATION

1) Zymase is present – found in yeast 2) Warm temperatures (30 −

40°C but depends on the yeast strain) 3) Anaerobic environment
(oxygen limited environment) 4) Aqueous solution of sugar

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 34 OF 65

- Fermentation of monosaccharides must be ​catalysed ​by ​zymase. ​Since zymase is a biological
catalyst, it is
sensitive to temperature. ​- Yeast can produce ethanol to concentrations up to only about ​15%
v/v​. This is due to ethanol being toxic
and around 15% v/v, yeast will start to die. - To produce higher
alcohol contents, it is necessary to ​distil ​the liquid:
- If the aqueous mixture from a fermentation process is subjected to fractional distillation,
95%
ethanol can be obtained. - To obtain 100% ethanol, more elaborate procedures such as
molecular sieving are required.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 35 OF 65
 ENVIRONMENTAL IMPACTS OF
HYDROCARBONS
OUTCOMES
● examine the environmental, economic and sociocultural implications of obtaining
and using hydrocarbons from the Earth

SOURCES OF
HYDROCARBONS

The primary source of hydrocarbons is from ​petroleum​. Petroleum is a mixture of hundreds and
thousands of different alkanes, ranging from methane up to alkanes with 40 or more carbons.

- The mixture of gases found in petroleum is called ​natural gas ​and the mixture of liquid components is
called
crude oil​. - Petroleum is found within pores of rocks
deep in the ground.

The complex mixture is separated into fractions according to their boiling points using ​fractional
distillation​.

- The petroleum is heated to about 400°C to produce ​hot liquid/vapour ​mixture that enters the
fractioning
tower. - Inside the tower are horizontal trays, each which contains many ​bubble caps ​upon which
alkanes condense - Fractions which have lower boiling points will rise higher in the column before
condensing. Fraction which
have higher boiling points will not rise as high and will condense towards the bottom of the
column.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 36 OF 65
Differences in physical and chemical properties of each petroleum fraction mean that they are suitable for
different purposes. Generally, ​light fractions ​(LPG, petrol, naphtha) are ​more useful a
​ nd are ​in higher
demand ​than heavy fractions (heavy fuel oil, lubricating oil, wax and asphalt).

Some of the longer alkanes are further processed through ​cracking​, which involves heating alkanes to high
temperatures in the absence of oxygen. This causes them to split and form ​shorter​, more useful alkanes as
well as alkenes.

- A ​zeolite ​catalyst, which consists of Al, Si and O, may be employed to allow this reaction to be
carried at
lower temperatures.

USES OF HYDROCARBONS
The major use of petroleum is transport. Hydrocarbons are ​excellent fuels ​and the combustion of
hydrocarbons is the ​primary source ​of e
​ nergy production globally.

Unsaturated hydrocarbons are highly reactive and can undergo addition reactions. This makes them
extremely important as ​raw materials ​for the production of o
​ ther organic chemicals, ​such as
haloalkanes and alcohols, and ​commercially valuable goods ​such as plastic.

THE PROBLEMS WITH USING

PETROLEUM

Petroleum deposits in the ground are formed by the burial and decomposition of prehistoric living
organisms over ​millions of years​. Thus, petroleum is a ​finite ​and ​non-renewable ​resource.

As the world’s crude oil diminishes, there will be enormous negative ​economic and sociocultural
consequences​. Such as the instability of world markets and increase costs of goods.

Another huge problem that arises is that the combustion of petroleum releases huge amounts of ​carbon
dioxide ​into the atmosphere.

- Carbon dioxide is a ​greenhouse gas​, so it absorbs infrared radiation from the atmosphere and
keeps our
Earth warm. - The extra carbon dioxide produces through combustion is a major contributor to the
enhanced greenhouse
effect ​which causes ​global warming​. - The consequences for global warming include ​rising sea
levels ​which in the long term will result in land loss and flooding, more frequent and intense ​extreme
weather events​, ​warming ​of the ​oceans ​and ​disruptions ​to the ​feeding behaviour ​of wildlife.

The higher concentrations of carbon dioxide has also resulted in the ​acidifications of oceans ​which is
threatening the survival of aquatic life.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 37 OF 65

 BIOFUELS
OUTCOMES
● compare and contrast fuels from organic sources to biofuels, including ethanol
ALTERNATIVE FUEL SOURCES
A possible solution to the reliance on non-renewable crude oil is to use ​biofuels​. Biofuels are
fuels derived from ​biomass​, which is biological material from living or recently living organisms
such as wood, crops, wet waste and animal waste.
BIOETHANOL
Bioethanol is ethanol produced from the ​fermentation ​of ​monosaccharides ​such as ​glucose
and ​fructose​.
Monosaccharides are the ​building blocks ​of more ​complex carbohydrates ​which make up
plant material. Thus monosaccharides can be sourced from:
- ​Sucrose ​based feedstock (eg. Sugarcane and fruits) - ​Starch ​based feedstock (eg. Grains
like wheat and corn) - ​Cellulose ​based feedstock (eg. Wood residues)
Fermentation usually involves mashing up grains, sugarcanes or fruits with water to create an
aqueous solution of sugar to which yeast is added.
- ​Sucrose ​(C​11​H​22​O​11​) and ​starch ​are readily ​hydrolysed ​into monosaccharides during the
fermentation
process as yeast contains the necessary enzymes required to catalyse the breakdown. -

Hydrolysis: ​C​11​H​22​O​11(aq) ​+ H​2​O​(l) ​→ 2C​6​H​12​O​6(aq)

- ​Fermentation: ​C​6​H​12​O​6(aq)

→ 2C​2H​
yeast ​ ​ 2CO​2(g) -​ ​Cellulose i​ s difficult to break down to its component sugars as
​ 5​OH​(aq) +
the enzyme cellulase is not readily available
for industrial use.
Bioethanol ​has been developed as a substitute for petroleum-based ethanol and as an
alternative to petrol. It has the potential to be used as standalone fuel to completely replace
petrol but is usually used as an additive to petrol.
- In Australia, most cars post-1986 can use up to ​10% ethanol (E10 fuel)​.
BIOGAS
Biogas consists of ​mixtures of gases​, such as ​methane​, ​carbon monoxide ​and ​hydrogen​,
released from the natural ​breakdown of organic matter b ​ y anaerobic bacteria.
- The organic matter is sourced from ​natural wastes ​from agriculture and households, such as
manure​,
human sewage, food processing wastes ​and ​crop wastes​. - To produce biogas, the waste
is placed in a ​large enclosed tank​, called the d ​ igester​, containing ​anaerobic
bacteria​. The gas released from the decay is collected by gas outlets.
The biogas collected can be combusted as a fuel to generate electricity or to heat boilers from
industrial processes and for cooking and heating water in homes.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 38 OF 65
The biofuel production represents a ​carbon cycle​, where plants absorb carbon dioxide during growth,
recycling ​the carbon dioxide released during combustion.

The use of biogas also helps reduce the enhanced greenhouse effect as ​methane ​is a greenhouse gas that
has a larger effect than carbon dioxide. By collecting it and using it to produce electricity, less is released into
the atmosphere. Another environmental benefit is that bioethanol and biodiesel are ​cleaner fuels ​than
petroleum fuels​.

- They are oxygenated, so complete combustion is more likely to occur and they do not contain
sulfur
impurities. - They are ​non-toxic ​and ​biodegradable​, thus do not pose as severe a threat to the
environment in the event
of a spill.

OBSTACLES IN THE PRODUCTION OF

BIOFUELS

In Australia, biomass sources currently being used are ​waste

residues​.

- Bioethanol is made from sugar cane molasses (waste) and waste from starch and red sorghum
production. - Biogas is generated from the treatment of waste water - Biodiesel is produced from waste
vegetable oil from restaurants and industrial food producers

However, this only produces a small percentage of Australia’s fuel needs. It is not possible to manufacture
enough biofuel from these sources to replace all petroleum fuels used today.

1) Large amounts of ​fertile land ​would be required to grow the

crops.
a. This requires clearing of forests and bushland which will contribute to an ​increase in carbon
dioxide
levels in the atmosphere and to ​habitat loss​. Fertile land is also limited thus it ​competes with food
crops​, resulting in increase in food prices. 2) Intensive farming can lead to ​land degradation ​and
erosion​. 3) A large amount of ​fertiliser ​would be required to replace the nutrients taken from the ground
4) A large amount of ​water ​would be required 5) There is also a ​large amount of energy ​required for
harvesting of crops and processing biofuels, energy that
is currently derived from fossil fuels. 6) Large scale commercial agriculture leads to the
reduction of biodiversity ​due to the loss of important
organic matter from that crop.

The potential of biofuels lies in making it ​financially viable ​compared to conventional petroleum-based
fuels.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 39 OF 65

ORGANIC ACIDS AND

BASES
OUTCOMES
● investigate the differences between an organic acid and organic base

CARBOXYLIC ACID

Organic acids ​are acids that have a carbon-based structure. The most common type of carboxylic acids are
alkanoic acids. They occur abundantly in nature.

- Propanoic acid is found in cheese -

Methanoic acid is produce in ant venom -
Lactic acid is in milk - Citric acid is in citric
fruits

All ​carboxylic acids ​are ​weak acids ​thus they will ​partially ​ionise in water to produce hydrogen or
hydronium ions.
 - Each carboxylic acid group is ​monoprotic ​- The covalent bond between oxygen and hydrogen is
highly polar​. The bonding electrons are strongly
attracted to oxygen so the hydrogen can be drawn easily by a ​base​, leaving behind a ​negative charge ​on
the ​oxygen​, - If more than one carboxylic acid group is present in the molecule, these acids will be
polyprotic​. For
example, citric acid is ​triprotic
(H​3​C​6​H​5​O​7​).

Different carboxylic acids will have different strengths, ionising to different extents. Their strengths can be
compared by comparing their ​acid dissociation constant ​K​a​.

Acid Formula K​a1 ​K​a2 ​K​a3

Methanoic HCOOH 1.8 × 10​−4

Ethanoic (acetate) CH​3​COOH 1.8 × 10​−5

Propanoic CH​3​CH​2​COOH 1.3 × 10​−5

Fluoroethanoic CH​2​FCOOH 2.2 × 10​−3

Citric H​3​C​6​H​5​O​7 ​7.4 × 10​−4 ​1.7 × 10​−5 ​4.1 × 10​−7

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 40 OF 65

The strength of a carboxylic acid is influenced by the ​length ​and ​substitution ​of the hydrocarbon
chain.

- As the ​chain length increases​, the ​strength of the acid decreases​. - This is because the alkyl groups
 are capable of ​donating electron density​. Carbon is more electronegative, so
it ​pulls electron density ​towards itself and ​away from hydrogen​. The additional electron density
allows carbon to ​“donate” ​additional negative charge to neighbouring carbon atoms. - This increases
​
the negative charge on the -COO​- group, making it more attracted to the H​+​.

- Substituting a ​highly electronegative atom​, such as a halogen, onto the hydrocarbon chain
increases the
strength of the acid​. The strong electron-withdrawing power of the substituent helps ​weaken ​the
oxygen- hydrogen ​bond. This makes it easier for the hydrogen to be dissociated.

- As the ​number of electronegative ​atoms i​ ncreases​, so does the ​strength of the

acid​. - ​Fluorine ​has the ​biggest electron-withdrawing effect​, then chlorine, bromine
and iodine.

AMIDES (WEAK B/L BASES)

Organic bases ​are organic compounds that are characterised by the presence of an atom ​with a
lone pair ​of ​electrons ​that can ​accept an H​+​.

- Nitrogen containing compounds such as ​amines ​are the most common organic
bases.
Many amine bases exist in nature. The most important being the ​four nitrogenous DNA bases: ​adenine,
cytosine, guanine and thymine, and the ​20 natural amino acids ​used to make ​proteins ​in living
organisms.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 41 OF 65

Amino acids ​are molecules that contain both a ​carboxylic acid ​and a ​basic
amine ​group.

Simpler amines are made by ​substitution ​reactions of ​haloalkanes ​with

ammonia.

Amines act as a ​base ​in an ​analogous ​manner to ammonia. The lone pair of electrons on the nitrogen can
accept a proton, forming an ​ammonium ion​. Like ammonia, they are ​weak bases​.
The ​base dissociation constant ​K​b ​can be used to compare the ​strength ​of different
amine bases.

Base Formula K​b

Ammonia NH​3 ​1.8 × 10​−5

Methylamine CH​3​NH​2 ​4.4 × 10​−4

Ethylamine CH​3​CH​2​NH​2 ​5.4 × 10​−4

Propylamine CH​3​CH​2​CH​2​NH​2 6
​ .9 × 10​−4

- ↑ Chain length → ↑ Partial negative → ↑ H​+ ​acceptor → ↑ Base strength

Alkyl groups are capable of ​donating electron density​. This results in a build-up of ​partial negative
charge ​on the electronegative ​nitrogen atom​, allowing it to pick up ​H+​ ​more readily and also stabilise the
positive charge on the ammonium ion. The longer the chain, the greater the electron density donate.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 42 OF 65

Amides ​are also nitrogen containing compounds with a lone pair of
electrons.

- Amides are ​neutral ​compounds. The presence of the ​highly electronegative oxygen ​atom in the C=O
group
pulls electron density away from the nitrogen atom, which makes it more difficult to accept a H​+
 and stabilise a positive charge if nitrogen was to accept it.

REACTIONS OF CARBOXYLIC ACIDS AND

AMINES

- Carboxylic acid + reactive metal → salt + hydrogen gas - Carboxylic acid +

metal hydroxide/oxide → salt + water - Carboxylic acid + metal
carbonate/bicarbonate → salt + carbon dioxide + water - Amine + acid →
ammonium salt

When ​carboxylic acids ​react with ​amines​, the product formed will depend on the conditions. At ​low
temperatures​, a ​proton transfer ​(neutralisation reaction) proceeds between the carboxylic acid and amine,
forming a ​carboxylate ion ​(acid) and an ​alkyl ​(base).

At ​higher temperatures ​or in the presence of a suitable catalyst, an ​amide ​is produced with the ​elimination
of water ​(condemnation reaction), which forms the ​OH ​group on the acid and a hydrogen from the amine.

- Condensation reaction: Where two or more molecules ​combine ​to form a ​larger molecule ​with
the
simultaneous elimination ​of a small molecule such as water or
methanol.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 43 OF 65

PHYSICAL PROPERTIES OF
CARBOXYLIC ACIDS, AMINES AND
AMIDES
OUTCOMES
● explain the properties within and between the homologous series of carboxylic acids
amines and amides with reference to the intermolecular and intramolecular bonding present
● investigate the structural formulae, properties and functional group
including: – aldehydes and ketones (ACSCH127) – amines and amides – carboxylic
acids

BOILING POINT

Carboxylic acids, amines and amides are all ​polar molecules​. They can form ​hydrogen bonds ​with other
molecules.

- ↑ Alkyl chain → ↑ MM → ↑ Dispersion forces → ↑ BP

Amides do not ​exhibit ​a ​linear relationship ​between boiling point and molecular weight. This is because the
hydrogen bonding ​exhibited by the amides is extensive and are more complex.

Amides ​exhibit the ​highest boiling points ​compared to carboxylic acids and amines. ​Carboxylic acids ​have
higher boiling points ​than ​amines​.

- Carboxylic acids and amines have ​less atoms ​that can form hydrogen bonds. Each carboxylic acid
molecule can form ​two hydrogen bonds ​with another acid molecule through the double bonded oxygen
and OH group, forming a ​dimer ​(existing in pairs).

- Each amine molecule can only form ​one hydrogen bond ​with another ​amine
molecule​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 44 OF 65

Amines and amides can be classified into primary, secondary and tertiary depending on the number of ​alkyl
groups ​attached to the ​nitrogen​.
 - Primary amines have the highest boiling points, followed by secondary and then tertiary amines. The
same
trend occurs with amides.

SOLUBILITY

Small ​amines, amides and carboxylic acids ​dissolve completely ​in water. However, solubility
decreases as the hydrocarbon chain increases.

- ↑ Carbon chain length → ↑ Non-polar nature of compound → ↑ Dispersion forces domination → Water
cannot solvate the long hydrocarbon chain due to cohesive bonds → ↓
Solubility

Similar to alcohols, the trend is ​reversed ​for their solubility in ​organic

solvents​.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 45 OF 65

ESTERS
OUTCOMES
● investigate the production, in a school laboratory, of simple esters
FORMATION OF ESTERS
Esters are organic compounds with the functional group −COO −.
Esters are formed from the reaction of a ​carboxylic acid ​and an ​alcohol. ​The OH group on the
acid is replaced with an OR group from the alcohol. This reaction is called ​esterification ​(a
condensation reaction).
The reaction is ​extremely slow. Concentrated H​2​SO​4 ​(dehydrating agent) is used to remove
the water and catalyse the reaction.
[H​ O][ester]
Because it is all liquids, it has a ​equilibrium constant​: K​eq =
​ ​ 2​
[alkanoic acid][alkanol]
Esters are everywhere in nature and are used in a number of ​industrial applications​.
- Short chain esters are known for their distinctive, ​fruit like odours ​and many occur naturally
in ​fruits ​and the
essential oils ​for plants. - Due to their pleasant odours, they are commonly used as ​flavouring
(banana lollies) ​agents ​in processed
foods, as well as ​fragrances ​in perfumes and cosmetics. - Fats and oils are also naturally
occurring ​triesters ​derived from ​glycerol ​and ​fatty acids​.
IUPAC NOMENCLATURE OF ESTERS
1) The ​alkanol ​is changed to “alkyl” and is the first word of the esters name 2) The ​alkanoic
acid ​becomes the ​alkanoate ​and is the second word of the esters name
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 46 OF 65
For example, an ester that smells like
banana.

pentanol ​+ ​ethanoic acid ​→ ​pentyl ​ethanoate ​+

water
ESTERIFICATION

To increase rate of reaction:

- ↑ Temperature - ↑
Acid catalyst

To increase yield:

- Remove water - Concentrated H​2​SO​4 ​(catalyst and

dehydrating agent)

REFLUX

Esterification must be carried out under

reflux​.

Reflux ​is a technique that involves heating a reaction mixture in a vessel fitted with a ​cooling condenser ​so
that the volatile reactants and products are returned to the reaction mixture without any loss.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 47 OF 65
PURPOSE OF REFLUXING

Component Purpose

Reaction flask Contains volatile reactants and products

Condenser Prevents the volatile reactant or product from escaping before the reaction has reached
equilibrium by cooling the reactant vapour into a liquid. Water enters at the base and
leaves from the top

Boiling chips To provide a surface upon which bubbles form, promoting even boiling

Open top To avoid dangerous pressure build-up inside the apparatus

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 48 OF 65

SOAP
 S
OUTCOMES
● investigate the structure and action of soaps and detergents

STRUCTURE OF SOAPS

Soaps are ​surfactants ​which, when dissolve in water, help to remove dirt, oil and foreign matter from
surfaces.

Soaps are ​salts of fatty

acids

- Fatty acids are ​carboxylic acids ​with long hydrocarbon chains (10+) - The salt of a fatty acid
consists of a ​negatively charged carboxylate ion ​(called the ​head​) with a l​ ong
hydrocarbon chain ​(called the ​tail​) and a p
​ ositively
charged ​ion.

In water the ​sodium ​or ​potassium ​ions float free and do not play a part in the cleaning actions of soaps.
It is the ​negatively charged fatty acid ion ​which is responsible for the cleaning action.

- The charged head is ​hydrophilic ​(water loving) due to its ​polar

nature ​- The tail is ​hydrophobic ​(water hating) due to its ​non-polar
nature

SAPONIFICATION

Soaps are produced from the ​hydrolysis ​of ​fats and oils ​(lipids) in a basic solution such
as NaOH.

Fats and oils are known as ​fatty esters​, ​triglycerides ​or

triesters​.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 49 OF 65
When esters are heated in the presence of a strong base such as NaOH or KOH, the ester is broken down to
give the ​alcohol ​and a ​carboxylate ion​.

- This reaction is known as ​saponification​. It is a type of hydrolysis reaction, involving the

breaking ​of a
chemical bond ​by the ​addition of
water

The general reaction for saponification of a triglyceride

is:

HOW SOAPS WORK

Soap is a ​surfactant ​(​surf​ace ​act​ive
a​ge​nt​s)

- This means it functions by reducing the ​surface tension ​of water and ​binding to grease and dirt ​to
emulsifies
them.

The ​hydrophobic ​part of the soap molecule is ​long, non-polar hydrocarbon chain​. It is ​strongly
repelled ​by water molecules.

When soap molecules are added into water, they form an ​oriented monolayer ​(with tails sticking out of the
water) at the surface in order to satisfy the interaction of both the ​hydrophobic ​and ​hydrophilic ​portions of
the soap molecule. This effectively ​breaks the hydrogen bonding b ​ etween molecules of water and thus
reduces the surface tension ​of water.

The components ​self-assemble ​into the most ​stable arrangement​, which consists of ​spherical structures
with the carboxylate groups forming a ​negatively-charged spherical surface​, with the hydrocarbon chains
inside the core of the sphere.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 50 OF 65

The spheres are called ​micelles​. The hydrophobic tails are shielded from the water by the polar
heads, which minimises the repulsive forces in the system.
1. DISSOLUTION

Soap molecules must be first dissolve in water. The hydrophilic head of a soap ion interacts with water
molecules via ​ion-dipole interactions ​and h
​ ydrogen bonding​.

2. ADSORPTION

Grease and oil consists of non-polar

molecules.

- The hydrophobic tails of the soap ions ​dissolve in the grease ​due to ​dispersion forces ​and
orientates
themselves.

Surfactant molecules continue to ​absorb ​into the grease, decreasing the surface tension of water at the
interface between the grease and water.

The hydrophilic heads interacting with water via ​ion-dipole ​forces effectively pull the grease off the
surface.

3. EMULSIFICATION

With ​agitation​, the grease layer breaks into smaller, ​spherical droplets (micelles)​, with the hydrophilic
surfactant head groups interacting with the water via ​ion-dipole forces​, and the hydrophobic surfactant tails
adsorbed into the grease. This forms a ​dispersion ​of grease droplets in water (an ​emulsion​).

The negative charged heads on the soap repel each other, preventing the grease and dirt from joining
together and keeping them dispersed throughout the solution. Therefore, the grease and oil can be simply
rinsed away, leaving a clean surface.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 52 OF 65

SYNTHETIC
DETERGENTS
OUTCOMES
● investigate the structure and action of soaps and detergents

PROBLEMS WITH SOAP

- The soap ion must be ​dissolved ​in water to have a cleaning effect - As salts of
weak acids, in low pH, soaps are converted into ​uncharged fatty acids

+ HCl​ → CH​ (CH​ )​ COOH ​ + NaCl​

CH​3​(CH​2​)​16​COO​− ​Na​+​(aq) ​ (aq) ​ 3​ 2​ 16​ (s) ​ (aq)
 Soluble fatty acid ion + acid → Insoluble fatty acid molecule + ionic
salt

- Soaps can also form ​insoluble salts ​(scum) in ​hard water ​(water with high concentration of ​divalent
metal
ions ​such as Ca​2+ ​and
Mg​2+​)

+ Mg​2+​ → [CH​ (CH​ )​ COO​−​ + 2Na​+​

2CH​3​(CH​2​)​16​COO​− ​Na​+​(aq) ​ (aq) ​ 3​ 2​ 16​ ]​2​Mg 2+​
​ (s) ​ (aq)

Soluble fatty acid ion + divalent metal ion → insoluble salt + sodium or potassium
ion

SYNTHETIC DETERGENTS

- All such ​synthetic ​surfactants are known as ​detergents ​- They have a similar structure to soaps, with
a long non-polar hydrocarbon tail and a polar head. However,
they vary in the ​structure of the polar head
group​.

ANIONIC DETERGENTS

All anionic detergents have a ​negatively charged polar

head.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 53 OF 65
The main structural difference between anionic detergents and soap is the presence of a ​sulfate ​(R − SO​2 −
​
O​−​) or ​sulfonate group ​(R − O − SO​2 ​− O​−​) instead of a ​carboxylate ​(R − COO​−​).

EFFECTIVENESS IN HARD OR ACIDIC

WATER

Anionic detergents ​don’t form insoluble precipitates​. They form salts that are all soluble. However, the
effectiveness is still ​reduced in hard and acidic water​. The positive ions in hard water/acidic water will
attract ​the ​negative head ​of the detergent.

Phosphate is an example of a builder that can be added to soften the

water.

CATIONIC DETERGENTS

All cationic detergents have a ​positively charged polar head​. The positive head is usually a ​quaternary
ammonium ion​. They are also known as ​fatty amine salts​.

Generally cationic detergents are not very good cleaning agents due to the ​strong attraction ​of cationic
detergents to ​negatively charged surfaces​. (Most surfaces are negatively charged).
This attraction however can be beneficial in certain
situations.

- Many fabrics acquired acquire a negative charge when they become

wet. - Cationic detergents are used in ​fabric softeners a
​ nd ​hair
conditioners​.

The strong attraction of cationic detergents to negatively charged surfaces can be ​detrimental ​in other
situations.

- Cationic detergents are particularly ​toxic ​to ​microorganisms​. They are attracted to the negative
surface of
bacteria and damage or kill bacteria that are involved in their decomposition. They therefore have
very low biodegradability​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 54 OF 65

NON-IONIC DETERGENTS

All non-ionic detergents have ​uncharged polar heads​. The polar heads consists of polar groups such as
ethoxylates​. Although these surfactants are ​uncharged​, the polar head groups are still attracted to the
highly polar water molecules forming numerous hydrogen bonds.
Non-ionic detergents ​don’t foam ​as much as other detergents. Hence, they can be used in dish
washers.

ENVIRONMENTAL IMPACTS OF
SURFACTANTS

Detergents are ​synthetic​, whereas soaps are made from naturally occurring biological materials (fats and
oils). Thus detergents are ​less biodegradable​.

- The enhanced stability of detergents means they persist in the environment, causing damage to the
mucus
membrane in wildlife and resulting in ​excessive frothing ​in the water ways. This leads to less
sunlight penetration. - Toxic to aquatic life.

Anionic detergents often contain ​builders ​such as ​sodium triphosphate

(Na​5​P​3​O​10​).

- The builders react with minerals in hard water and form soluble molecules. - High levels of phosphates
entering the rivers and waterways can lead to ​eutrophication ​(turning a lake into
swamp, algae etc)
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 55 OF 65

REACTION
PATHWAYS
OUTCOMES
● draft and construct flow charts to show reaction pathways for chemical synthesis,
including those that involve more than one step

FLOWCHART OF REACTIONS

[Deleted sorry. Mod 8 might have some flowcharts for

rxns]
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 56 OF 65

POLYMER
 S
OUTCOMES
● model and compare the structure, properties and uses of addition polymers of ethylene
and related monomers, for example: – polyethylene (PE) – polyvinyl chloride (PVC) – polystyrene (PS) –
polytetrafluoroethylene (PTFE) (ACSCH136)
● model and compare the structure, properties and uses of condensation polymers, for
example: – nylon – polyesters

POLYMER

A polymer is a ​long chain molecule ​made up of repeating units, called ​monomers ​joined by covalent
bonds. The process of linking monomer units is called ​polymerisation​.

Polymers may be natural or synthetic:

- Natural polymers are made by living organisms. Eg. Hair, starch, cellulose, DNA and silk -
Synthetic polymers are manufactured. Eg. Plastics like polyethylene, polyvinyl chloride and
nylon.

ADDITIONAL POLYMERS

Addition polymers ​are polymers made by adding ​unsaturated molecules ​to each other, ​without the
elimination of any atoms​.

- Additional polymerisation is a type of addition reaction, in which one of the bonds in the C=C double
bond is
broken to form two new single bonds.

A simple way of representing polymers is by writing the ​repeat units ​in ​square brackets ​followed by the
subscript n ​where n is the ​number of monomer units ​in the polymer.
Addition polymers are all ​synthetic​, they do not exist in
nature.

CONDENSATION POLYMERS

Condensation polymers ​are polymers formed through the ​condensation ​reaction of d ​ ifunctional
monomers ​with the ​elimination of a small molecule ​such as water or methanol in the process.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 57 OF 65

- Monomers used to synthesise condensation polymers usually contain groups such as alcohol, carboxylic
and
amine.

Condensation polymers are found everywhere in

nature.

- ​Polysaccharides ​such as cellulose and starch are condensation polymers made from ​glucose
monomers.

POLYESTERS

Polyesters are condensation polymers in which the repeating units are joined by ​ester
links.

Polymers made from two different monomers are called

copolymers​.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 58 OF 65

POLYAMIDES

Polyamides are condensation polymers in which the repeating units are joined by ​amide
links​.

The ​nylon class ​refers to polyamides that have ​linear carbon chains ​in the
repeating units.
PROPERTIES OF POLYMERS

Physical properties of polymers are important in determining their uses. These

include:

- Melting point (softening point) -

Mechanical strength - Flexibility.

This is due to the ​chemical structure ​of the polymers which leads to different strengths of ​intermolecular
forces ​that is dependent on:

- Molecular weight or chain length -

Extent of chain branching - Presence
of side groups (eg. -OH)

CHAIN LENGTH

Polymers are ​extremely large ​covalent molecules. The dominant intermolecular force is
dispersion.

The length of a polymer (and its molecular weight) depends on the ​number of monomers ​the polymer
contains. The ​melting point​, ​rigidity ​and h
​ ardness ​of a polymer ​increases ​with an increase in ​chain
length​.

CHAIN BRANCHING

Polymers are able to form ​branched ​and ​unbranched ​chains. Unbranched chains are able to pack more
closely in an ​orderly fashion​, forming a ​rigid crystalline solid.
 CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 59 OF 65
Branched ​polymer chains are unable to align with each other, forming an ​amorphous ​solid that
has weak intermolecular forces between the chain.

CRYSTALLINITY AND AMORPHOUS

If the polymer chains have few branches, as in the case with ​HDPE​, the molecules can sometimes line up in
a regular arrangement, creating ​crystalline regions​. The regular arrangements brings the polymer chains
closer together. The IMF between closely packed chains are stronger, and the presence of ​crystalline
regions strengthens the material overall.

Crystalline regions in a polymer ​prevents ​the ​transmission of light ​through the material, making it appear
cloudy or opaque.

Amorphous region ​will form where the polymer chains are ​randomly tangled ​and unable to pack very
closely. In some polymer materials, the entire solid is amorphous. Amorphous polymers are usually more
flexible ​and ​weaker ​and are often ​transparent​. (​LDPE​) Increasing the percentage crystallinity of a material
makes it stronger and less flexible. This also makes the material less transparent because ​crystalline
regions scatter light​. There are more crystalline regions in unbranched polymers
There are ​crystalline ​and ​amorphous ​regions in all
polymers.

SIDE GROUPS

Side groups can be introduced to make a material more ​rigid ​and ​brittle​. This results in a ​harder
polymer​.

CROSS-LINKING

Polymer chains are held together by ​intermolecular forces ​or they can be linked by ​covalent bonds ​called
cross-links ​to form a large extended network.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 60 OF 65

Polymers with only intermolecular forces between their chains are called ​thermoplastic ​polymers. They
soften when heated ​as the intermolecular forces are relatively weak and easily broken to allow the chains to
move between one another. This property allows polymers to be ​remoulded

Polymers with cross-links are called ​thermosetting ​polymers. Since covalent bonds are very string, cross
links limit movement between polymer chains, making the polymer more ​rigid, hard ​and ​heat resistant​.
These polymers cannot be remoulded (like XLDPE).
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 61 OF 65
 TYPES OF
POLYMERS
POLYETHYLENE (PE)

Polyethylene (polyethene) is the most popular plastic in the world. It has a very simple
structure.

Ethene is an ​unsaturated molecule ​because a ​double carbon-carbon bond​. When ethene polymerases,
the ​double bond breaks ​and new covalent bond are formed between carbon atoms on nearby monomers.
The polyethene formed does not contain any double bonds.

Ethene is one of the most ​simple ​and ​versatile monomers​. It is easily able to undergo addition
polymerisation

LOW DENSITY POLYETHYLENE (LDPE)

(4)

LDPE is produced under ​high temperatures ​and ​pressures​. Under these harsh conditions, the polymer is
formed too rapidly ​for the molecules to be neat and symmetrical. The products usually contain too many
small chains (branches) that divide off the main polymer.

The molecules in the polymer ​cannot pack closely together ​thus reducing the dispersion
forces.

The arrangement of the polymer molecules can be described as disordered or

non-crystalline.

- Flexible, chemically inert, good elongation -

Low melting point/thermoplastic - Lightweight,
good puncture resistance - Waterproof

Used in: Milk carton lining, bowls, flexible water pipes,

bottles

HIGH DENSITY POLYETHYLENE (HDPE)

(2)

Highly specialised transition metal catalyst, known as ​Ziegler-Natta catalysts ​are used to avoid the need for
high pressure. Due to the polymer being produced under a lower pressure, the conditions are milder and
there are fewer branches.

The ​lack of branches ​allows the molecules to ​pack together tightly ​increasing the ​density ​and the
hardness ​of the polymer formed. The arrangement of the polymer molecules is more ordered, resulting in
crystalline sections​.

Used in: Food packaging, dustbins, crates, drums, water

pipes

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 62 OF 65

POLYVINYL CHLORIDE (PVC)

PVC (polychloroethene) is made out of ​vinyl chloride ​monomers. The ​chlorine atoms ​introduce ​dipoles ​into
the long molecules. This increases the IMF between molecules, which leads to a ​higher melting point​. A
PVC item burning in a flame will not continue to burn when it is removed from the flame. It is used in products
such as conveyor belts, cordial bottles, water pipes and the covering of electrical wires.

Pure PVC ​is very ​hard ​and ​brittle​. ​Additives ​are incorporated into PVC to improve its flexibility, thermal
stability and UV stability. In a fire, PVC decomposes to form toxic and corrosive hydrogen chloride.

POLYSTYRENE (PS)

First commercial production by IG Farben; used in disposable household products, plastic model kits,
laboratory containers, insulation and packaging.
Benzene rings are covalently bonded to every second carbon atom in the polymer chain. This causes
polystyrene to be a ​hard ​but quite ​brittle ​plastic with a ​low density​. It is used to make food containers,
picnic sets, refrigerator parts, and CD and DVD cases. Polystyrene is made from ​styrene ​(ethylbenzene
monomers).

Polystyrene (polyethylbenzene) is commonly manufactured as a ​foam​. Foamed polymers are formed by

blowing a gas ​through melted polymer materials. Foaming can ​drastically change the physical
properties ​of a polymer material. 95-98% air

Polystyrene foam is produced by introducing pentane into melted polystyrene beads. The beads swell up to
produce the lightweight, insulating, shock-absorbing foam that is commonly used for takeaway hot drink
containers, bean bag beans, packaging materials and safety helmet linings. Once polystyrene has been
converted to a foam, it is difficult to recycle.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 63 OF 65

POLYTETRAFLUOROETHYLENE
(PTFE)

Polytetrafluoroethene is used in cookware fabrics, wiper blades, nail polish, industrial coatings. (aka
Teflon, or Fluon). Made out of ​tetrafluoroethene ​monomers.

Tetrafluoroethene is formed when all the hydrogen atoms in ethene are replaced by highly electronegative
fluorine ​atoms.

It has quite exceptional properties that are very different from those of polyethene. It can be used to make
non-stick frying pans, medical implants, gears and clothing. The electronegative fluorine atoms reduce the
strength of intermolecular bonds with other substances.

- Non-stick - Heat resistant -

Chemical resistant - Good
mechanical properties - Low
friction coefficient - Flame
resistant - High melting point

POLYETHYLENE TEREPHTHALATE
(PET)

Polyesters are a ​class of polymers ​that are formed through the process of condensation polymerisation.
Polyesters are formed by combining monomers that contain ​carboxylic acid ​and ​hydroxyl ​functional
groups. They are typically formed by reacting a dicarboxylic acid monomer with a diol monomer.

This is the most often polymer used to make polyester fabric. PET is synthesised by reacting
benzene-1,4-dioic acid monomers with ethane-1,2-diol monomers.

PET has a range of uses including recyclable drink bottles and food packaging. PET is a strong material
because the ester groups are polar, so that there are dipole-dipole attractions between the polymer chains.
Benzene rings make it stiff and strong, resistant to deformation.

CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 64 OF 65

NYLON 6,6
Nylon stockings created shopping frenzy in the USA in the 1940s. It is also used in clothing, parachutes,
kitchen utensils, toothbrushes, fishing lines, guitar strings, seatbelts.

Nylon is formed when a monomer containing an ​anime group ​on each end reacts with a monomer with a
carboxyl ​group on each end, a ​polyamide ​can form.

The term ‘nylon’ refers to the group of ​polyamides​, in which the monomers are linear carbon chains. A
common example is nylon-6,6 which is named so because the dicarboxylic acid monomer has a chain of 6
carbons and the diamine monomer also has a chain of 6 carbon atoms.

Nylon can be ​easily drawn into fibres ​that have high ​tensile ​strength. These fibres are used to
produce strong lightweight material for clothes.
CHEMISTRY MODULE 7: ORGANIC CHEMISTRY PAGE 65 OF 65
 CHEMISTRY
MODULE 8
Applying Chemical Ideas
CHEMISTRY MODULE 8 – APPLYING CHEMICAL
IDEAS

ANALYSIS OF INORGANIC
SUBSTANCES

Inquiry question: ​How are the ions present in the environment identified and
measured?

● analyse the need for monitoring the environment

● conduct qualitative investigations – using flame tests, precipitation and complexation reactions as
appropriate – to test for the presence in aqueous solution of the following ions: – cations: barium (Ba​2+​),
calcium (Ca​2+​), magnesium (Mg​2+​), lead(II) (Pb​2+​), silver ion (Ag​+​), copper(II) (Cu​2+​),
iron(II) (Fe​2+​), iron(III) (Fe​3+​) – anions: chloride (Cl​–​), bromide (Br​–​), iodide (I​–​), hydroxide
(OH​–​), acetate (CH​3​COO​–​), carbonate (CO​32–​ ​ ),

sulfate (SO​42–​
​ ), phosphate
3–​
(PO​4​ )
● conduct investigations and/or process data involving:
– gravimetric analysis – precipitation titrations
● conduct investigations and/or process data to determine the concentration of coloured species and/or
metal ions in aqueous solution, including but not limited to, the use of: – colourimetry – ultraviolet-visible
spectrophotometry – atomic absorption spectroscopy

ANALYSIS OF ORGANIC
SUBSTANCES

Inquiry question: ​How is information about the reactivity and structure of organic compounds
obtained?

● conduct qualitative investigations to test for the presence in organic molecules of the following
functional groups: – carbon–carbon double bonds – hydroxyl groups – carboxylic acids (ACSCH130)
● investigate the processes used to analyse the structure of simple organic compounds addressed in the
course, including but not limited to: – proton and carbon-13 NMR – mass spectroscopy (ACSCH19) –
infrared spectroscopy (ACSCH130)

CHEMICAL SYNTHESIS AND

DESIGN

Inquiry question​: What are the implications for society of chemical synthesis and
design?
● evaluate the factors that need to be considered when designing a chemical synthesis process, including
but not limited to: – availability of reagents – reaction conditions (ACSCH133) – yield and purity
(ACSCH134) – industrial uses (eg pharmaceutical, cosmetics, cleaning products, fuels) (ACSCH131)
environmental, social
and economic issues

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 1 OF 48

ION
IDENTIFICATION

OUTCOMES
● analyse the need for monitoring the environment

CHEMICAL MONITORING AND MANAGEMENT

Chemical monitoring and management are needed to ensure the ​health ​and ​wellbeing ​of both ​plants ​and
animals​. Monitoring also allows for more effective management.
For example, the ​destruction of UV-protective ozone​, caused by widespread use of
chlorofluorocarbons (CFCs)

- ​Hazardous ions ​in the environment such as mercury have also been identified and monitored using
chemical
techniques. - ​Nutrients ​required by humans and other living organisms have also been discovered
through environmental
monitoring.

OUTCOMES
● conduct qualitative investigations – using flame tests, precipitation and complexation reactions as
appropriate – to test for the presence in aqueous solution of the following ions: – cations: barium (Ba​2+​),
calcium (Ca​2+​), magnesium (Mg​2+​), lead(II) (Pb​2+​), silver ion (Ag​+​), copper(II) (Cu​2+​),
iron(II) (Fe​2+​), iron(III) (Fe​3+​) – anions: chloride (Cl​–​), bromide (Br​–​), iodide (I​–​), hydroxide
(OH​–​), acetate (CH​3​COO​–​), carbonate (CO​32–​ ​ ),

sulfate (SO​42–​
​ ), phosphate
3–​
(PO​4​ ) ​QUALITATIVE ION ANALYSIS

- ​Precipitate​: Insoluble ionic salt formed when 2 ionic solutions are mixed together. - ​Qualitative
analysis​: Identification of the constituents of components in a sample. - ​Quantitative analysis​:
Measurement/determination of the amount (expressed in a concentration) of the
constituent. - ​Destructive testing: ​Test that irreversibly alter the
composition of a sample.
CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 2 OF 48
PRECIPITATION REACTIONS
SOLUBILITY RULES
Precipitation reactions ​are useful for the rapid identification of ions.
- Solutions of specific ions are added to the unknown aqueous sample. - The ​formation ​or
absence ​of a precipitate can be used to ​determine the ion present​.
Rule Exceptions
All ​Group 1 ​(Li​+​, Na​+​, K​+​, Rb​+​, Cs​+​) and ​ammonium ​(NH​4+​​ ) are soluble
NONE
All ​nitrate ​(NO​3-​​ ) and ​acetate ​(CH​3​COO​-​) salts are soluble NONE
All ​chloride ​(Cl​-​) and ​bromide ​(Br​-​) salts are soluble Ag​+​, Pb​+ ​(Hg​+​)
All ​iodide ​(I​-​) salts are soluble Ag​+​, Pb​+​, Hg​+
All ​sulfate ​(SO​42-​ +​ 2+​ 2+​ 2+​
​ ) salts are soluble Ag​ , Pb​ , Ba​ , Ca​ , Sr​ , Hg​
2+​ +

All ​hydroxide ​(OH​ ) salts are insoluble Group 1 and NH​4​ salts are soluble. Ba​2+​, Ca​2+ ​are slightly
-​ +​

+​
All ​carbonate ​(CO​32-​ 3-​
​ ) and ​phosphate ​(PO​4​ ) are insoluble Group 1 and NH​4​ salts are soluble

Ba​2+
−
Solution PO​4 2−
​ ​SO​4 2− ​ ​OH​− ​Cl​− ​Br​− ​I​− ​CH​3COO​
​ ​CO​3 −2 ​
Colourless
White insoluble White
insoluble
White ​soluble
White ​soluble
White ​soluble
White ​soluble
Ca​2+ ​White insoluble White
insoluble
White ​soluble
White ​soluble
White ​soluble
White ​soluble
Mg​2+ ​White
insoluble
White ​soluble
White insoluble
White insoluble
White ​soluble
White ​soluble
White ​soluble
White ​soluble
Pb​2+ ​White insoluble White
insoluble
White insoluble
White insoluble
Bright Yellow
White ​soluble
Cu​2+ ​Blue Blue
insoluble
Blue ​soluble ​Green
insoluble
Blue insoluble
Blue ​soluble
Blue ​soluble
Not stable Blue ​soluble
Fe​2+ ​Pale green Green
insoluble
Green ​soluble
Grey insoluble
Green insoluble
Green ​soluble
Green ​soluble
Green ​soluble
Green ​soluble
Fe​3+ ​Yellow ​Pink
insoluble
Yellow ​soluble
Not stable
Brown insoluble
Brown ​soluble
Brown ​soluble
 Not stable Brown ​soluble
Ag​+ ​Colourless Yellow
insoluble
White insoluble
Yellow insoluble
Not stable
White insoluble
Pale yellow insoluble White ​soluble

- Ag​+ ​halides ​precipitates ​decompose ​with ​exposure to light ​to form Ag​(s)​. This is observed

as ​darkening ​of
the solid.
CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 3 OF 48
COMPLEXATION REACTIONS

Complexation reactions are commonly used to ​identify transition metal cations ​(due to their d
orbitals).

- This includes Ag​+​, Cu​2+​, Fe​2+​, Fe​3+ ​and Pb​2+

A complexation reaction occurs when a ​coordination compound ​or ​complex

forms​.

- These consist of a central metal ion (typically a transition metal) ​coordinated ​to molecules or ions
(polar &
lone pair of electron molecules). - The coordinating species are called ​ligands​. They are
typically neutrally or negatively charged. (E.g.
H​2​O,NH​3​,Cl​−​,CN​−​)

Coordination complexes are usually ​coloured a

​ nd are indicated by the formula being enclosed in
square brackets. E.g. [Cu(OH​2​)​6​]​2+ ​and [CuCl​4​]​2−​.
COMPLEXATION REACTIONS AND ION IDENTIFICATION

HYDRATED TRANSITIONAL METAL ION

When transition metal ions ​dissolve in water​, a complexation reaction

occurs:

​ (l) ​→ [Fe(OH​2​)​6​] ​(aq) 2+

FeCl​2(aq) ​+ 6H​2O​ ​ ​+ 2Cl (​ aq) −
​

- Water molecules (​ligands​) coordinate to the transition metal centre - ​Charge ​stays the same as
the original cation - Hydrated transition metal centres often have ​characteristic colours ​that can be
used to identify them.

IDENTIFICATION WITH COMPLEXATION

Complexation reactions can be also used in conjunction with precipitation reactions to ​identify
ions​.

Sliver halides ​can be distinguished due to their different complexation reactions with
ammonia:

- AgCl is ​soluble ​in ​dilute ​ammonia​: ​AgCl​(s) ​+ 2NH​3(aq) ​⇌ [Ag(NH​3)​​ 2​] ​(aq) +​ ​+ Cl ​(aq) −​ ​- AgBr is

soluble ​in ​concentrated ​ammonia: AgBr​(s) ​+ 2NH​3(aq) ​⇌ [Ag(NH​3​)​2​] ​(aq) ​+ ​+ Br (​ aq) −​ ​- AgI is
insoluble ​in any concentration of ammonia

This test can be used to distinguish between ​Ag​+ ​and ​Pb​2+​. ​(PbCl​2 does
​ not dissolve in
ammonia)
 CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 4 OF 48
Complexation reactions can also be used as ​confirmatory
tests​:

- ​Iron (III) ions ​react with thiocyanate (SCN​-​) to produce blood red [Fe(SCN)]​2+ ​- ​Copper (II) ions
react with ammonia to form pale blue Cu(OH)​2(s) ​which then dissolves to form deep blue
[Cu(NH​3​)​4​]2+
​

o ​Ammonia initially reacts with water to produce the OH​-​: NH​3(aq) +

​ H​2​O​(l) ​→ NH​4 (aq) +
​ ​+ OH ​(aq)
−

FLAME TESTING

A flame test is used to ​qualitatively ​identify some ​metal ions ​in a sample. It can be used to ​distinguish
between ​cations ​that undergo similar precipitation reactions. For example, Ba​2+ ​and Ca​2+ ​or Group 1 metals.
However, ​not all metals ​produce a diagnostic flame colour.

ATOMIC EMISSION

The flame colour arises from ​atomic emissions ​of the

metal.

- The heat of the flame ​excites ​electrons into higher energy

levels - Atomic emission occurs when an electron in a
higher energy
level returns to a lower energy level (​relaxation​) -
During relaxation, a ​wavelength ​of light matching the ​energy
difference ​between the levels is emitted.

Wavelength is ​inversely proportional ​to

energy:

hc​
E=​ λ

- The greater difference → shorter λ

The colour of the flame produced in the flame test results from a
combination ​of the most intense wavelengths emitted in the
visible regions.
Metals that ​do not produce a characteristic flame colour ​typically
have atomic emissions that fall outside the visible region.

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 5 OF 48

CHARACTERISTIC FLAME
COLOUR

Metal Ion Colour

Ba​2+ ​Yellow-green (apple green)

Ca​2+ ​Orange-red (brick red)

Mg​2+ ​No characteristic flame colour

Pb​2+ ​Grey-blue

Cu​2+ ​Green (halide = blue green)

Fe​2+​/Fe​3+ ​Orange-brown

Ag​+ ​No characteristic flame colour

LIMITATIONS OF THE FLAME TEST

- Flame tests are only useful for some ​metal cations.

- Destructive - Can be ​ambiguous ​which metal ion is
present
 o ​The flame colours may be similar (e.g. Rb and Cs produce the same colour as K) ​o ​Different
oxidation states ​of the same metal cannot be distinguished (e.g. Fe​3+ ​and Fe​2+​) - Inconclusive results
can be caused by ​interference ​created by other metal ions present in the sample. (e.g.
Ba flame masks Cu, Li and
Sr)
o ​Interference can sometimes be removed by using coloured glass filters. For example, ​blue
cobalt
glass ​can be used to filter out the bright yellow light produced by Na, a common
impurity.

ADDITIONAL TESTS FOR ION IDENTIFICATION

SOLUTION PH

Conjugates of strong acids/bases will dissolve to produce a solution with neutral pH. Conjugate bases
of weak acids/bases will produce a non-neutral pH.

Basic Ion (pH > 7) Neutral Ion (pH = 7)

Hydroxide (OH​-​) Chloride (Cl​-​)

Acetate (CH​3​COO​-​) Bromide (Br​-​)

Carbonate (CO​32-​ -​
​ ) Iodide (I​ )

Phosphate (PO​43-​ 2-​

​ ) Sulfate (SO​4​ )

ACID CARBONATE REACTION

Carbonate anions (CO​32-​

​ ) can be identified through the addition of an ​acid​. Bubbles will be observed. A

lime water ​test can be used to confirm the presence of CO​2(g)​.

2H ​(aq) ​+ ​+ CO​3 (aq) ​2− ​→ H​2​O​(l) ​+ CO​2(g)

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 6 OF 48

FLOWCHARTS

- To create a flowchart effectively, go from ​least ​soluble to ​most ​soluble. - It is

important to include ‘​in excess​’ for flowcharts with more than 1 ion in a sample.
 o ​Include filtering out precipitates as well.

CATIONS
CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 7 OF 48
ANION
 GRAVIMETRIC
ANALYSIS

OUTCOMES
● conduct investigations and/or process data involving:
– gravimetric analysis

WHAT IS GRAVIMETRIC ANALYSIS

Gravimetric analysis uses the ​mass of product ​(precipitate) formed through a precipitate reaction to
quantify a ​target ion​. It is used in applications such as monitoring water quality, determining the mineral
composition of soil and product testing.

Gravimetric analysis is typically performed with the following

steps:

1) A ​known quantity ​of sample is ​dissolved ​in water 2) The target ion is
precipitated ​from the solution using a suitable reagent 3) The precipitate
is collected by ​filtration​, then washed, dried and weighed

The reagent used in the precipitation reaction must react ​selectively ​with the ​target ion ​and form a
highly insoluble precipitate ​in order to give accurate results. The selective reagent can be chosen using the
solubility rules​, while the solubility of the resulting precipitate can be found by examining the ​solubility
product constant (K​sp​).
Undesired precipitation reactions can be prevented through ​experimental
design​.

The amount of the target ion present is usually expressed as a ​mass percentage ​of the original
sample.

GRAVIMETRIC ANALYSIS ASSUMPTIONS

(VALIDITY)

- Only the target ion precipitates out

o ​Selective reagent ​o ​Remove or prevent the precipitation
of other salts - All the target ion precipitates out
o ​Selective reagent (Highly insoluble precipitate, really small
K​sp​) ​o ​Added in excess

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 9 OF 48

- All of the precipitate is collected and in a pure form ​o ​Filtration (quantitative filter paper) ​o
Wash precipitate with warm distilled water multiple times ​o ​Ensure it is dry when measuring its
mass
SULFATE CONTENT OF FERTERLISER
Fertilisers (a solid mixture) commonly contain ​ammonium sulfate ​(NH​4​)2​ ​SO​4​, as a sulfur
source for plants. The sulfate content of fertiliser can be determined gravimetrically through the
addition of Ba​2+ ​to form a highly insoluble BaSO​4​.
3- ​ -​
Barium can precipitate with CO​32-​ -​
​ , Cl​ , PO​4​ and OH​ anions as well. To precipitate out:
3​
- CO​3​ : Add acid in excess - PO​4​ and OH​ : Acidify solution (Don’t use H​2​SO​4​) - Cl​-​: Add AgNO​3
2-​ -​

in excess
If other anions precipitate with Ba, the mass of the residue collected will increase. Therefore, a
higher w/w % will be calculated than actually present.
EXAMPLE QUESTION 1
The following results were obtained for the gravimetric analysis of sulfate ions in several
fertiliser samples
Sample A B
Mass of fertiliser sample used (g) 13.5 1.5
Mass of BaSO​4 ​collected (g) 1.642 0.0870
There are two methods:

A ​m(BaSO​n(BaSOn(SOm(SO% of ​44​SO) ) = 4​​ = ​4 4​) ) in n(BaSO= 0.679520932 = fertiliser

0.00703663719 1.642 ​4​) g
m(SO​ )
= = 0.00703663719 g ​ 13.5 mol ​4​
 = 5.01%

mol

B ​m(BaSO​% m(SO% of of ​4​SOSO) ​4 =

​ ​4 4​) in in 0.0870 = BaSOfertiliser 0.0870 ​4 ×
​ = 41.17% g
mm(SOm(SO​ ) ​ ) ​ = = 2.4%
mm(BaSO= ​ 1.5 = ​4​0.035814768 ​4​ 4​ ) ​
96.07
233.37 ​
= 41.17%

g
PROS AND CONS OF GRAVIMETRIC ANALYSIS
ADVANTAGES
- It is ​very accurate​, if the gravimetric analysis is carefully designed (assumptions) and
conducted. - It does not require ​speciality equipment ​to perform. - It does not require the
construction of a ​calibration curve​, which can be time consuming
DISADVANTAGES
- The target ion of interest must be able to form a ​sufficiently insoluble precipitate ​for
accurate results (A
limitation of the technique)
CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 10 OF 48
- The precipitate must be ​highly pure
o ​Impurities can be adsorbed to the surface of the precipitate or trapped within the
precipitate,
resulting in increased mass and inaccurate results - It is ​extremely time
consuming ​compared to modern analytical techniques - ​Concentration ​of the target ion must be
high enough to produce a precipitate that can be accurately
weighed.

PRECIPITATION
TITRATIONS

OUTCOMES
● conduct investigations and/or process data involving:
– gravimetric analysis – precipitation titrations

TITRATION
Precipitation titration are commonly used in the quantification of ​halides ​(Cl​-​, Br​-​, I​-​). In these procedures,
silver ions ​are usually the titrant and consequently they are known as ​argentometric titrations​.

The main three titrations used are:

- Mohr’s method -
Volhard’s method -
Fajan’s method

MOHR’S METHOD (DIRECTION TITRATION)

Mohr’s method quantifies chloride, bromide and cyanide ions using ​direct titration ​with a standard silver
nitration solution.

Ag ​(aq) +​ ​+ X ​(aq) −​ ​→ AgX​(s)

Yellow ​potassium chromate ​(K​2​CrO​4​) is used as the

indictor:

- Silver ​preferentially ​precipitates with halide ions - When excess silver is added, it will react with
chromate ions to produce a reddish-brown precipitate
Ag​2​CrO​4(s)

2Ag ​(aq) +​ ​+ CrO​4 (aq) 2−

​ ​⇌ Ag​2CrO​
​ 4(s)

LIMITATIONS OF MOHR’S METHOD

The presence of ​multiple anions ​in a sample can lead to invalid results. Carbonate and phosphate
ions will precipitate with silver.

2Ag ​(aq) +​ ​+ CO​3(aq) ​2− ​→ Ag​2​CO​3(s)

3Ag ​(aq) +​ ​+ PO​4(aq) 3−

​ ​→ Ag​3PO​
​ 4(s)

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 11 OF 48

The conical flask must be ​thoroughly stirred ​during the titration to ensure the Ag​+ ​ions are evenly
distributed, so AgCrO​4 ​will not precipitate early.
The titration must be conducted at a ​pH
6.5-9.0

- At pH < 6.5, the chromate ion (a weak base) accepts H​+ ​to become HCrO​4-​​ , so there will not be
enough
chromate in solution to produce the end point colour change. HCrO​4-​ ​is also bright orange, which
obscures the endpoint. - At pH > 9.0, the concentration of OH​- ​is too high. It will form a precipitate with Ag
to produce AgOH which is
a brown precipitate. It also obscures the endpoint and increases the silver needed to
reach it.

Mohr’s method is suitable for the analysis of ​chloride ​and ​bromide ​ions, but not iodide or thiocyanate ions.
This is because the chromate ions are strongly adsorbed to the surface of AgI and AgSCN precipitates,
making the endpoint indistinct.

In this precipitation titration, the concentration of the indicator used is quite low as adding too much chromate
indicator will lead to an intense yellow colour which masks the end point. Hence the excess titrant required to
cause a colour change is ​relatively large​.

​
- 2Ag ​(aq) ​+ ​+ CrO​4(aq) ​2− ​⇌ Ag​2​CrO​4(s) ​- Small concentrations of CrO​42-
​ means that equilibrium lies towards

the LHS. To shift equilibrium towards the

​
RHS, a relatively large amount of Ag​+ needs to be
added.

This excess silver required to reach the end point leads to a ​systematic error​, which can be corrected using
a ​blank titration​.

- The same quantity of chromate indictor is to be used in the titration is added to a suspension of
calcium
carbonate ​(which imitates the white AgX precipitate). - AgNO​3 ​is added to the solution until a
colour change occurs. - The volume of AgNO​3 ​required to cause the colour change in the blank is the
excess volume required. This
volume is ​subtracted ​from the titration
volumes.

VOLHARD’S METHOD (BACK TITRATION)

Volhard’s method quantifies anions used in back titration

procedure.
 - A known ​excess quantity of AgNO​3 ​is added to the sample to precipitate ​all ​of the analyte
anions:

o ​Ag ​(aq) ​+ ​+ X (​ aq) ​− ​→ AgX​(s) ​- The excess AgNO​3 ​is determined by ​back
titration ​against ​KSCN​(aq) ​standard solution

o ​Ag ​(aq) +​ ​+ SCN ​(aq) −​ ​→ AgSCN​(s) -​ A small amount of ​Fe​3+ ​is added as the indictor.
When excess SCN​- ​is present, there will be a permanent
colour change.

o ​Fe ​(aq) 3+
​ ​+ SCN ​(aq) −
​ ​→ [Fe(SCN)] ​(aq)
2+

LIMITATIONS OF VOLHARD’S METHOD

The Volhard titration must be performed in ​low pH ​to prevent the precipitation of Fe​3+ ​indictor as Fe(OH)​3​.
At low pH, there is a relatively low [OH​-​], therefore the precipitate Fe(OH)​3 ​will not form.

The Volhard method is less valid if the ​first precipitate formed ​is more soluble than
AgSCN.

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 12 OF 48

- For example, AgCl (K​sp ​= 1.77 × 10​−10​) is more soluble than the AgSCN (K​sp =
​ 1.03 × 10​
−12​
). This means
that AgCl can dissolve during the titration leading to a greater titration volume
required.

To avoid this problem, the procedure can be

modified​.

- The first precipitate can be removed via ​filtration ​before titration. However, this can lead to
inaccuracies
and is less convent . - A dense organic liquid like nitrobenzene or chloroform can be added to
the conical flask to act as a ​barrier
between the precipitate and aqueous layer.

FAJAN’S METHOD (DIRECT TITRATION AND ADSORPTION

INDICATOR)

In the analysis of chloride, an ​anionic dye ​is added to the

sample.
 - A standard solution of AgNO​3 ​is added and the precipitation occurs:

o ​Ag ​(aq) +​ ​+ Cl ​(aq) −​ ​→ AgCl​(s) -​ Before the equivalence point, a small excess of chloride ions is
incorporated into the precipitate, so it carries
a ​negative charge​. The dye is repelled and ​remains in solution​. - After the equivalence point,
there is a small excess of silver ions. Therefore, the precipitate becomes slightly
positively charged​, and the dye ​adsorbs ​onto it, resulting in a precipitate colour
change.

The ​most suitable indicator ​depends on the

analyte.

PROS AND CONS OF FAJAN’S METHOD

The Fanjan’s method relies on a ​large precipitate surface area​, to allow sufficient dye to adsorb so the
colour change is easily visible.

- Dextrin (starch) can be added to prevent silver halide precipitates from aggregating - A high
concentration of spectator ions can also caused aggregation, so this method cannot be used with all
samples. - The analyte must also be concentrated enough, as the colour will not be seen if there is
too little precipitate.

The ​pH ​of the titration reaction must be carefully controlled as ​anionic dye indicators ​are conjugate bases
of weak acids. This means it will react with free H​+ ​and will not adsorb onto the surface of the precipitate.

CHEMISTRY MODULE 8: APPLYING CHEMICAL IDEAS PAGE 13 OF 48