Table of Contents

Module 1: Chemistry of Carbon Compounds ................................................................................. 8

Functional Group Analysis, Reactions and Mechanisms ............................................................... 8
Homologous Series ..................................................................................................................... 8
Alkane Reactions ........................................................................................................................ 8
Halogenation ........................................................................................................................... 9
Cracking ................................................................................................................................ 10
Combustion ........................................................................................................................... 10
Alkene Reactions ...................................................................................................................... 11
With Br2(l)` ............................................................................................................................. 11
With Br2(aq) ............................................................................................................................ 12
With COLD Acidified Potassium Manganate (VII) ............................................................ 12
With HOT (and concentrated) Acidified Potassium Manganate (VII) ................................ 12
With Concentrated Sulphuric Acid (Hydration) ................................................................... 13
With Hydrogen Halides ........................................................................................................ 14
With Hydrogen (Hydrogenation) .......................................................................................... 14
Reactions of Alcohols ............................................................................................................... 15
With Main Oxidizing Agents ............................................................................................... 15
With Carboxylic Acid (Esterification) .................................................................................. 15
With Concentrated Sulphuric Acid (Dehydration) ............................................................... 16
With I2 and NaOH (Iodoform Test) ...................................................................................... 16
Reactions of Halogenoalkanes/Haloalkanes/Alkyl Halides...................................................... 17
Hydrolysis ............................................................................................................................. 17
Reactions of Carbonyl Compounds .......................................................................................... 18
With NaCN(aq)/H+(aq) (Nucleophilic Addition) ...................................................................... 18
Reduction .............................................................................................................................. 19
Qualitative Tests ................................................................................................................... 19
Reactions of Carboxylic Acids ................................................................................................. 20
With NaOH ........................................................................................................................... 20
With NaHCO3 ....................................................................................................................... 20
Metals .................................................................................................................................... 20
PCl5/PCl3/SOCl (Formation of Acyl Chlorides) ................................................................... 20
 Reactions of Esters .................................................................................................................... 21
Hydrolysis ............................................................................................................................. 21
Alkaline Hydrolysis of Fats (Saponification) ....................................................................... 21
Transesterification................................................................................................................. 22
Reaction of Primary Amines with Dilute Acid ......................................................................... 22
Reactions of Benzene (and Methylbenzene/Toluene) .............................................................. 23
Halogenation (Br2/FeBr3)...................................................................................................... 23
Nitration (Conc. H2SO4/Conc. HNO3) .................................................................................. 24
Reactions of Nitrobenzene ........................................................................................................ 25
Reduction (Sn/HCl) .............................................................................................................. 25
Reactions of Phenol .................................................................................................................. 25
With Acyl Halides................................................................................................................. 25
Bromination (Aqueous Bromine) ......................................................................................... 25
With Sodium Hydroxide ....................................................................................................... 28
Diazotization (NaNO2/HCl) .................................................................................................. 28
Coupling (with Diazonium Salt) ........................................................................................... 29
Acidic and Basic Character of Organic Compounds .................................................................... 29
Acidity of Alcohols, Phenols and Carboxylic Acids ................................................................ 29
(Aliphatic) Alcohol Acidity .................................................................................................. 30
Phenol Acidity ...................................................................................................................... 30
Acidity of Carboxylic Acids ................................................................................................. 31
Basic Character of Aliphatic Amines, Amides and Aromatic Amines ..................................... 32
Aliphatic Amines .................................................................................................................. 32
Aromatic Amines .................................................................................................................. 33
Amides .................................................................................................................................. 33
Amino Acids ............................................................................................................................. 34
Macromolecules ............................................................................................................................ 34
Addition Polymerization ........................................................................................................... 35
Formation of Polyethene ...................................................................................................... 35
Polyvinyl Chloride/Poly(chloroethene) ............................................................................. 36
Polytetrafluoroethene (PTFE) ............................................................................................... 36
Condensation Polymerization ................................................................................................... 36
Module 2: Analytical Methods and Separation Techniques ......................................................... 37
Uncertainty in Measurements ....................................................................................................... 37
A Few Definitions ................................................................................................................. 37
Titrimetric Methods of Analysis ................................................................................................... 37
Acid Base Titrations ............................................................................................................. 38
Primary Standards ................................................................................................................. 39
Redox Titrations.................................................................................................................... 39
Gravimetric Methods of Analysis ................................................................................................. 41
Precipitation Method ............................................................................................................. 41
Volatilization/Evolution Methods ......................................................................................... 42
Applications of Gravimetric Analysis .................................................................................. 42
Spectroscopic Methods of Analysis .............................................................................................. 42
The Interaction of Electromagnetic Radiation with Atoms and Molecules .............................. 44
UV/Vis Spectroscopy.................................................................................................................... 45
Infrared Spectroscopy ................................................................................................................... 47
Infrared Absorption Process ................................................................................................. 47
Preparation of A Sample ....................................................................................................... 49
Infrared Absorption and the Environment ............................................................................ 50
Monitoring Air Pollutants Using IR Spectroscopy ............................................................... 50
Mass Spectroscopy........................................................................................................................ 50
Principles................................................................................................................................... 50
Mass Spectra ............................................................................................................................. 52
Fragmentation Patterns ............................................................................................................. 53
Chromatographic Methods of Separation ..................................................................................... 54
Principles................................................................................................................................... 54
Thin Layer Chromatography..................................................................................................... 55
Paper Chromatography ............................................................................................................. 55
Column Chromatography.......................................................................................................... 56
Gas Liquid Chromatography..................................................................................................... 57
Phase Separations.......................................................................................................................... 58
Distillation................................................................................................................................. 58
Simple Distillation ................................................................................................................ 58
 Fractional Distillation ........................................................................................................... 59
Vacuum Distillation .................................................................................................................. 64
Steam Distillation...................................................................................................................... 65
Solvent Extraction ..................................................................................................................... 65
Procedure .............................................................................................................................. 66
Module 3: Industry and the Environment ..................................................................................... 67
Locating Industrial Plants ............................................................................................................. 67
Factors Influencing Location of an Industrial Plant ................................................................. 67
Health and Safety ...................................................................................................................... 67
Aluminium .................................................................................................................................... 67
Ore Purification ......................................................................................................................... 67
Production ................................................................................................................................. 68
Aluminium Uses ....................................................................................................................... 69
Environmental Effects of Aluminium Industry ........................................................................ 69
Crude Oil ....................................................................................................................................... 70
Separation Method .................................................................................................................... 70
The Fractions of Crude Oil and their Uses ............................................................................... 70
Reforming ............................................................................................................................. 71
Environmental Impact ............................................................................................................... 71
Ammonia....................................................................................................................................... 72
Production/Haber Process ......................................................................................................... 72
Explaining the Equilibrium Conditions .................................................................................... 73
Uses of Ammonia ..................................................................................................................... 73
Impact of Ammonia Industry on the Environment ................................................................... 73
Ethanol .......................................................................................................................................... 74
Production/Fermentation........................................................................................................... 74
Fractional Distillation ............................................................................................................... 74
Uses of Ethanol ......................................................................................................................... 75
Fuels ...................................................................................................................................... 75
Alcoholic Beverages ............................................................................................................. 75
Solvents ................................................................................................................................. 75
Social and Economic Impact of Alcohol Consumption ............................................................ 75
Chlorine......................................................................................................................................... 76
Production ................................................................................................................................. 76
The Diaphragm Cell .............................................................................................................. 76
Alternative Methods of Production ....................................................................................... 77
Advantages and Disadvantages............................................................................................. 78
Industrial Importance of Chlorine............................................................................................. 79
Bleaches ................................................................................................................................ 79
PVC (Polyvinyl Chloride)..................................................................................................... 79
Solvents ................................................................................................................................. 79
Aerosols and Refrigerants ..................................................................................................... 79
Anaesthetics .......................................................................................................................... 79
Impact of the Chlor-Alkali Industry on the Environment ......................................................... 79
Sulphuric Acid .............................................................................................................................. 79
Production ................................................................................................................................. 79
Step 1: Production of Sulphur Dioxide ................................................................................ 80
Step 2: Oxidation of Sulphur Dioxide to Sulphur Trioxide .................................................. 80
Step 3: Hydration of Sulphur Trioxide ................................................................................. 80
Step 4: Dilution of Oleum ..................................................................................................... 81
Industrial Importance of Sulphur Compounds .......................................................................... 81
Impact of the Sulphuric Acid Industry...................................................................................... 82
Water ............................................................................................................................................. 82
Importance of the Water Cycle ................................................................................................. 82
Methods of Water Purification.................................................................................................. 83
Importance of Dissolved Oxygen to Aquatic Life .................................................................... 83
Sources of Water Pollution ....................................................................................................... 84
Experiments for Certain Pollutants in Water ............................................................................ 84
Impact of Pollutants on the Aquatic Environment .................................................................... 85
The Atmosphere ............................................................................................................................ 85
How Ozone Concentration is Maintained ................................................................................. 85
Significance of CFCs in the Ozone Layer ................................................................................ 86
Effects of Ozone on Human Life .............................................................................................. 87
Ozone in the Stratosphere ..................................................................................................... 87
 Ozone in the Troposphere ..................................................................................................... 87
Importance of Maintaining Carbon Dioxide Concentration in the Atmosphere....................... 88
Some Definitions ...................................................................................................................... 89
Greenhouse Effect ................................................................................................................. 89
Global Warming.................................................................................................................... 90
Photochemical Smog ............................................................................................................ 90
Effects of Products of Combustion of Hydrocarbon-Based Fuels ............................................ 91
Atmospheric Concentrations of the Oxides of Nitrogen........................................................... 92
Nitrogen Cycle ...................................................................................................................... 92
Recycling of Nitrogen Oxides .............................................................................................. 92
Acid Rain .............................................................................................................................. 93
Methods of Control and Prevention of Atmospheric Pollution ................................................ 94
Prevention ............................................................................................................................. 94
Control .................................................................................................................................. 94
Solid Waste ................................................................................................................................... 95
Reduce, Reuse, Recycle ............................................................................................................ 95
Waste Reduction ....................................................................................................................... 95
Glass ...................................................................................................................................... 95
Paper ..................................................................................................................................... 95
Plastic .................................................................................................................................... 96
Steel....................................................................................................................................... 96
Aluminium ............................................................................................................................ 96
Impact of Solid Wastes on the Terrestrial Environment ........................................................... 96
Disposal Methods.................................................................................................................. 96
Functional Group Analysis, Reactions and
Mechanisms
Homologous Series
• A functional group is a group of atoms within a molecule that has a characteristic
chemical behaviour.
• A homologous series is a group of molecules of the same general formula, carrying the
same functional group and exhibiting similar chemical properties.

Alkane Reactions
Alkanes undergo substitution reactions.

• Bond breaking can occur through two methods, homolytic and heterolytic bond
breaking. Homolytic bond breaking is symmetrical, while heterolytic bond breaking is
unsymmetrical.
 Note the difference in arrows used! One-headed ‘fishhook’ arrows are used to show homolytic
bond breaking while double headed arrows are used to show heterolytic bond breaking.

• The opposite pathway is true, bond formation can be symmetrical or unsymmetrical.

Halogenation
• Halogenation is the substitution of a hydrogen atom of an alkane with a halogen.
o This occurs through free radical substitution.
• Free radical substitution relies on the high reactivity of radicals (species carrying an odd
number of electrons).
• Radicals can abstract an atom from a molecule. Abstraction is the removal of an atom
or group from a molecule by a radical.
• The halogenation reaction has three stages (using chlorine as an example):
Initiation
Irradiation of the halogen with UV light initiates the homolytic breakage of the covalent bond in
some of the halogen molecules. A few halogen radicals are formed.

Propagation
A reactive halogen radical collides with a molecule of the alkane, abstracting a hydrogen atom
from it to produce the hydrogen halide and an alkyl radical.

The alkyl radical goes on to react with another halogen molecule, releasing a halogen radical and
forming a haloalkane. The halogen radical goes on to continue propagation, leading to a chain
reaction.
Termination
When two radicals collide, they can form a bond and end a reaction cycle, ending the chain
propagation. As the number of radicals at any time is very small, these reactions are infrequent.

Cracking
• Cracking involves the breakdown of saturated hydrocarbon molecules (alkanes) into
smaller (usually more useful) products (e.g. a smaller alkane and alkene) through the
application of heat, pressure and catalysts.
• Thermal cracking utilizes high temperatures (450-750°C) and pressures (up to 70 atm)
o Thermal cracking operates through free radical mechanisms.
• Catalytic cracking utilizes zeolites (complex aluminosilicates of the form Al2O5Si
associated with positive ions) along with lower temperatures (~500°C) and moderately
low pressures.
o The mechanism includes ionic intermediates.
• Note that cracking occurs in a fairly random manner, with only relative proportions of
alkenes to alkane products being generally modifiable based on conditions.

Combustion
• Combustion reactions are exothermic reactions of hydrocarbons with oxygen to produce
carbon dioxide and water (complete combustion) and occasionally carbon monoxide and
carbon as well (incomplete combustion).
• Complete combustion reactions follow a fairly repetitive equation structure as follows:
𝑦 𝑦
𝐶𝑥 𝐻𝑦 + (𝑥 + ) 𝑂2 → 𝑥𝐶𝑂2 + 𝐻2 𝑂
4 2
Alkene Reactions
• Alkenes are more reactive than alkanes due to the presence of a carbon-carbon double
bond.
• The electrons of the 𝜋 molecular orbital are of a higher energy than those of the 𝜎
molecular orbital. Alkanes are less reactive than alkenes because they lack this more
reactive bond.
• The 𝜋-bond of the alkene can act as a nucleophile, donating electrons to electrophiles in
electrophilic reactions.
o Unsurprisingly, alkenes undergo electrophilic addition reactions, where a
molecule is added across the double bond, giving a single product.

With Br2(l)`
• This reaction involves the addition of bromine dissolved in an organic solvent (like
tetrachloromethane, CCl4) to an alkene (like ethene)
• The product is a vicinal dihaloalkane (a dihaloalkane with both halogen substituents on
adjacent carbons). Here it is 1,2-dibromoethane.

A dipole is induced in the highly polarizable bromine molecule by the electron rich 𝜋 bond.
The partially positive bromine acts as an electrophile, attacking the double bond.
The result is the bromonium ion.

The remaining bromide ion attacks the bromonium ion from the opposite side, compensating for
the positive charge.

• The bromine starts out as red-brown but becomes decolorised throughout the reaction.
With Br2(aq)
• When an alkene reacts with bromine dissolved in water, the result is a bromoalkanol and
HBr, where the bromine substituent and the hydroxyl group are on adjacent carbons
(across the double bond).
o The reaction mechanism is similar to the previous one except that water becomes
attracted to the intermediate bromonium instead of the bromide ion.
o The OH- from the water combines with the bromonium instead, releasing a proton
which combines with the remaining bromide ion.
• The bromine water starts out as brown but becomes decolorised throughout the reaction.

With COLD Acidified Potassium Manganate (VII)

• The mixture will turn from purple to colourless, as the electron rich double bond of the
alkene acts as a reducing agent.
• The product will be a vicinal diol, also called a glycol, which has the hydroxyl groups on
adjacent carbons.

• This can be considered a partial oxidation.

With HOT (and concentrated) Acidified Potassium Manganate (VII)

• The alkene undergoes extended oxidation, in two main stages.
Stage 1: The carbon-carbon double bond is broken and replaced with two carbon-oxygen double
bonds on two separate carbonyl compounds.

The identities of R1 R2, R3 and R4 dictate the outcome of the following steps.
Stage 2: Further oxidation
If a product is a ketone (both R groups attached to the carbonyl group are alkyl groups), it will
not undergo further oxidation.
If a product is an aldehyde (one of the R groups on the carbonyl group is a hydrogen), it will be
further oxidized to a carboxylic acid.

If a product is formaldehyde/methanal (both R groups are hydrogen), it will be oxidized first to

methanoic acid, then to carbon dioxide and water.

But actually, the methanoic acid is further oxidized to carbon dioxide and water:

With Concentrated Sulphuric Acid (Hydration)

• The reaction of concentrated sulphuric acid with an alkene has two main possible steps
based on the temperature of the acid.
o Most simply, the product of the reaction (when heated) is the alkanol. The acid
acts as a catalyst.
• The reaction actually proceeds by the addition of the sulphuric acid across the double
bond to form an alkyl hydrogensulfate

This goes on to react with water to produce the alkanol.

With Hydrogen Halides
• For this example, HBr will be added to propene
• HBr is a polar molecule, as bromine is far more electronegative and attracts the electrons
of the covalent bond far more strongly.
o Bromine carries a partial negative charge while hydrogen carries a partial
positive charge

o It is the partially positive

hydrogen atom that acts
as an electrophile to
initiate the reaction with
an electrophilic attack of
the electron-rich 𝜋 bond
• Two possible carbocations
(positively charged hydrocarbon
ions) are formed, one is
secondary and the other is
primary.
• The primary carbocation is less
stable than the secondary
carbocation, and as such, the
secondary form is more likely to
be formed.
• The more highly substituted a
carbon atom carrying the positive charge is, the more stable the carbocation will be
o That is, the more carbon atoms to which the carbon atom carrying the positive
charge is, the more stable the carbocation will be.
o This phenomenon occurs due to hyperconjugation
• The regioselectivity of this reaction is explained by Markovnikov’s Rule, which states
that the hydrogen will be added to the less substituted carbon while the halogen goes to
the more substituted carbon.
o The major product (the product created in the highest proportion) will be that
resulting from the formation of the most stable carbocation.
o The hydrogen will go the carbon already attached to the most hydrogens.

With Hydrogen (Hydrogenation)

• Product is an alkane.
• The reaction involves an insoluble metal catalyst like palladium (Pd-C), platinum (PtO2)
or nickel (Ra-Ni)
 o Occurs at 150°C
• Vegetable oils often contain high proportions of polyunsaturated and mono-unsaturated
fats (oils), and tend to be liquids at room temperature.
o You can "harden" (raise the melting point of) the oil by hydrogenating it in the
presence of a nickel catalyst.
o The relatively high temperatures tend to switch some cis carbon-carbon double
bonds into trans double bonds, which will remain in the final product if not
hydrogenated. Trans fats are associated with high LDL blood levels.

Reactions of Alcohols
• An alcohol is designated as primary, secondary and tertiary based on the number of
carbons to which the carbon carrying the hydroxyl group is joined (just like the
carbocations).
o The following reactions can follow different mechanisms or outcomes based on
the type of alcohol we are using in the reaction.

With Main Oxidizing Agents

With H+/K2Cr2O7
Type of With H+/K2Cr2O7
With H+/KMnO4 (Hot, or Heated
Alcohol (Cold)
Under Reflux)
Primary Carboxylic Acid Aldehyde Carboxylic Acid
Secondary Ketone Ketone Ketone
Tertiary No Oxidation No Oxidation No Oxidation

With Carboxylic Acid (Esterification)

• When heated under reflux with concentrated sulphuric acid and a carboxylic acid, an
alcohol forms an ester.
With Concentrated Sulphuric Acid (Dehydration)
• This is essentially the reversal of the hydration of an alkene. The product is the alkene
and water.
o This occurs at 180°C

With I2 and NaOH (Iodoform Test)

• The iodoform (CHI3) test involves adding iodine solution to a small volume of the
sample, followed by just enough sodium hydroxide to decolourise the iodine. Some
gentle heating may be necessary.
o The positive result is the formation of a pale yellow precipitate.
• A positive result is given by an alcohol of the form on the
right. These include:
o Ethanol
o Secondary alcohols where a methyl group is attached
to the carbon carrying the hydroxyl group
o NO tertiary alcohols.
• A positive result is also given by carbonyl compounds of the
form on the right. These include:
o Ethanal and
o Methyl ketones

Step 1: Formation of NaIO by reaction

between I2 and NaOH.
Step 2: (If the sample is an alcohol) Oxidation of the alcohol by NaIO to
form a carbonyl compound.
Step 3: Substitution of the hydrogen atoms of the methyl group with
iodine atoms.
Step 4: Cleavage of the carbon-carbon bond to release triiodomethane
(iodoform) from the rest of the molecule by hydroxide ions.
Reactions of Halogenoalkanes/Haloalkanes/Alkyl Halides
• Halogenoalkanes undergo mainly nucleophilic substitution reactions.
• Like alcohols, halogenoalkanes can be primary, secondary or tertiary based on the
number of carbon atoms connected to the carbon carrying the halogen substituent.
o The reaction follows a different mechanism based on what kind of alkyl halide is
being used.

Hydrolysis
• Usually alkaline hydrolysis, which requires an alkaline solution like NaOH(aq)
• The products of this reaction are an alcohol and the hydrohalic acid (the hydrogen halide
dissolved in water)
• Primary (and usually secondary) haloalkanes undergo a particular mechanism called
SN2 (short for substitution, nucleophilic, bimolecular).
o Substitution- The halogen substituent is being substituted by a hydroxyl group.
o Nucleophilic- A nucleophile (electron rich/negatively charged species) initiates
the reaction
o Bimolecular- TWO molecules are involved in the rate determining step.
o In this mechanism, bond breaking and making occurs in a concerted manner,
and both occur at the same time with the formation of a transition state.

After nucleophilic attack (rds) by the hydroxide ion from NaOH,

the transition state is formed, which has a transiently pentavalent
carbon atom loosely associated with both the hydroxide ion and the
bromide ion.
Bromide is a better leaving group because it is more stable than
the hydroxide ion. As such, it is displaced, or ‘substituted.’

• Tertiary (and sometimes secondary) haloalkanes typically undergo a type of reaction

called the SN1, where the 1 stands for unimolecular (only one molecule is involved in the
rate determining step).
 o Due to steric hindrance by the alkyl substituents, the SN2 mechanism which
requires space on the opposite side of the carbon atom carrying the halogen to
initiate the reaction cannot occur.
o The rate determining step is instead a unimolecular step, the spontaneous
ionization of the haloalkane to give a carbocation and the halide ion.
o Bond making and bond breaking occur in a stepwise manner

Reactions of Carbonyl Compounds

• As you know, the carbonyl group is a polar group, as the highly electronegative oxygen
atom pulls more strongly on the electrons in the carbon-oxygen double bond.
• Carbonyl compounds include aldehydes and ketones.

With NaCN(aq)/H+(aq) (Nucleophilic Addition)

• The product of this reaction is a hydroxynitrile, otherwise known as cyanohydrins.
• The reaction is usually carried out with acidified sodium or potassium cyanide because
the actual nucleophilic species (hydrogen cyanide) is actually a highly poisonous gas.
Step 1: NaCN reacts with H+ from acid to form HCN and sodium ions.
+ +
𝑁𝑎𝐶𝑁(𝑎𝑞) + 𝐻(𝑎𝑞) → 𝐻𝐶𝑁(𝑎𝑞) + 𝑁𝑎(𝑎𝑞)

Step 2: The cyanide ion acts as a nucleophile, attacking the partial positive charge on the carbon
of the carbonyl group. The pi bond is broken and the cyanide joins the chain as an extra carbon
with a nitrile group.

The result is a negatively charged ion.

Step 3: A hydrogen atom from hydrogen cyanide or from an acid in solution combines with the
ion to form the hydroxynitrile. In this case, it is 2-hydoxypropanenitrile.
 • This mechanism produces a racemic mixture (a 50/50 mixture of two optical
isomers/enantiomers). This occurs for all aldehydes and unsymmetrical ketones which
undergo this reaction.
o The carbon of the carbonyl group is the chiral carbon.

Reduction
• Reduction of carbonyl compounds is basically the addition of a hydrogen atom (an
electron is gained).
o This reduction can occur through the usage of different reagents including H2/Pt
(hydrogen gas over a platinum catalyst), LiAlH4 (lithium
tetrahydridoaluminate) or NaBH4 (lithium tetraydridoborate)
o Aldehydes are reduced to primary alcohols while ketones are reduced to
secondary alcohols.

Using LiAlH4
• This reducing agent is more reactive than NaBH4.
• The reaction is usually carried out in carefully dried ethoxyethane (diethyl ether) because
it reacts violently with water and alcohols.
• An acid is added to the reaction mixture afterwards to release the alcohol from a complex
ion.

Using NaBH4
• This is a gentler reducing agent.
• The reaction is carried out with the carbonyl compound dissolved in an alcohol.

Qualitative Tests
The following reactions allow us to distinguish between aldehydes, ketones and other organic
compound based on the observations.

Reagent Aldehyde Ketone

Brady’s Reagent (2,4-

Red/Orange precipitate formed Red/Orange precipitate formed
DNP)

Tollens’ Reagent
Silver mirror formed on
(Diamine silver (I) No reaction
reaction container
hydroxide)
 No reaction (mixture remains
Fehling’s Solution Red precipitate formed
deep blue)

Diute Acidified
Change from purple to No reaction (mixture remains
Potassium Manganate
colourless purple)
(VII)

Reactions of Carboxylic Acids

• Carboxylic acids are weak acids, meaning they have pH near (but lower than) 7,
dissociate incompletely in aqueous solution (most of the
molecules of acid do not ionize) and have lower Ka (acid
dissociation constant).

With NaOH
• The result is the formation of an alkanoate/carboxylate salt,
that is, the hydrogen ion is substituted for a sodium ion, along
with water.
• It is a neutralization reaction, giving a salt and water.

With NaHCO3
• The result is the same as above except with the added product of carbon dioxide.

Metals
• The result is a carboxylate salt and hydrogen gas. The metal must be above hydrogen in
the reactivity series (remember that?), so no reaction with copper.

PCl5/PCl3/SOCl (Formation of Acyl Chlorides)

Essentially, the OH group is being replaced with a chlorine substituent.

Carboxylic Acid Plus… Products

PCl5 Acyl Chloride + POCl3 + HCl
PCl3 Acyl Chloride + H3PO3
SOCl2 (thionyl chloride) Acyl Chloride + SO2 + HCl
Reactions of Esters
Hydrolysis
• Alkaline hydrolysis (also called saponification) produces the sodium salt of the
carboxylic acid, and the alcohol that originally composed the ester.
• The ester is heated with sodium hydroxide.

• Acid hydrolysis produces the carboxylic acid and alcohol without any production of salt.
• The ester is heated with an acid.

Alkaline Hydrolysis of Fats (Saponification)

• Fats (triacylglycerols or triglycerides) are molecules comprising 3 hydrocarbon chains
joined via ester bonds to a glycerol molecule.
• The fats/oils are mixed and heated with sodium hydroxide or another suitable alkali (eg
potassium hydroxide)
• The products are glycerol (C3H5(OH)3) and a soap (a sodium or potassium salt of a long
chain fatty acid acyl chain).
Transesterification
• An ester is placed in a large excess of alcohol in the presence of an acid or base.
o The alkoxy groups can be exchanged between the ester and the alcohol.

• The alkoxy group is an alkyl group bonded to an oxygen atom, or an alkanol with the
hydrogen removed.
o Note that only the portion of the ester originating from the alcohol can exchange
with the alcohol. The central carbonyl group and the alkyl group from the
carboxylic acid cannot participate.
• When transesterification is carried out between a
triglyceride and an alcohol (with the help of an NaOH
catalyst), the result is an acyl ester and glycerol. The
acyl ester is used as a biodiesel.

Reaction of Primary Amines with Dilute Acid

• Just like alcohols and carbocations, amines can also be classified as primary, secondary
or tertiary based on the number of R groups bound to the nitrogen of the amine group.
o Primary amines take the form RNH2, where R is an alkyl substituent or
hydrocarbon chain bound to the nitrogen of the amine group.
o As such, this refers to the degree of substitution of the nitrogen atom.
• The product of the reaction is a primary amine salt.

• When a primary amine reacts with a carboxylic acid however, the result is an amide.
Reactions of Benzene (and Methylbenzene/Toluene)
• Benzene actually undergoes electrophilic substitution reactions, contrary to the
addition reactions that would be expected of an unsaturated carbon compound. This is
due to the delocalization of electrons in the Benzene ring.
• Benzene and methylbenzene (also called toluene) undergo the same kind of reactions, as
they are of similar reactivities (despite toluene being slightly more reactive thanks to the
electron donating methyl substituent, but we’ll get to that later).

Halogenation (Br2/FeBr3)
• In this reaction, FeBr3 (or AlBr3) acts as a Friedel-Crafts Catalyst.
• Halogenation using another halogen, like chlorine, follows a similar pattern.
o The catalyst would be FeCl3 or AlCl3.
 The reaction is essentially the same for toluene.

Nitration (Conc. H2SO4/Conc. HNO3)

• The electrophile in this reaction is actually the nitronium ion, which is formed from the
reaction between concentrated sulphuric acid and nitric acid.
o The nitric acid is protonated by the sulphuric acid. This proton compound then
decomposes to form the nitronium ion.

Similar to the previous reaction, it culminates in a deprotonation of an intermediate.

Reactions of Nitrobenzene
Reduction (Sn/HCl)

The nitrobenzene is reduced to phenylamine/aniline.

Technically, the reaction only forms phenylammonium ions, and must be treated with NaOH
solution (sodium hydroxide) to convert it to aniline.

Above is the progression of reactions for the synthesis of aniline.

Reactions of Phenol
With Acyl Halides
• Phenol reacts with acyl halides to form an ester and the hydrogen halide.

Bromination (Aqueous Bromine)

• Phenol is more reactive than toluene or benzene because the hydroxyl group is an
activating group, and as such does not require a catalyst to be halogenated.
 Note that the products are 2,4,6-tribromophenol and 3HBr.

A brief aside on activating and deactivating groups, and inductive and resonance/conjugative
effects:
• Activating groups are electron donating groups, meaning that they donate electrons to
the benzene ring, increasing the electron density of the ring, stabilizing the carbocation
intermediate (lowering the activation energy for its formation) and increasing the
likelihood of electrophilic attack.
• Deactivating groups are electron withdrawing groups, meaning that they pull electrons
from the benzene ring, decreasing electron density of the ring, destabilizing the
carbocation intermediate (increasing the activation energy for its formation) and
decreasing the likelihood of electrophilic attack.

• Electron withdrawal or donation is mediated by a combination of inductive and

resonance effects.
o An inductive effect is the withdrawal or donation of electrons through a 𝜎 bond
due to electronegativity.
▪ It is a local shift in the electron density in a 𝜎 bond due to electron
withdrawing or donating groups elsewhere in the molecule.
▪ Halogens, hydroxyl groups, carbonyl groups, cyano groups, and nitro
groups inductively withdraw electrons through the 𝜎 bond linking the
substituent to a benzene ring (negative inductive effect).
▪ Alkyl groups inductively donate electrons through the hyperconjugative
effect, where electron density from the C-H bond is donated to the
𝜋 ∗ orbital of the benzene ring (positive inductive effect).
 o A resonance (also called conjugative) effect is the withdrawal or donation of
electrons through a 𝜋 bond due to overlap of the p orbital of the substituent with
the p orbital of the aromatic ring.
▪ Carbonyl, cyano, and nitro substituents, for example, withdraw electrons
from the aromatic ring by resonance. The p electrons flow from the ring to
the substituent, leaving a positive charge in the ring.
▪ Conversely, halogen, hydroxyl, alkoxyl and amino substituents donate
electrons to the aromatic ring by resonance. Lone-pair electrons flow from
the substituents to the ring, placing a negative charge on the ring.
• In all groups except for halogens, the resonance effect outweighs the inductive effect.
o Alkyl groups like the methyl group only have a weak inductive electron donating
effect, so a molecule like toluene is only slightly more reactive than benzene.
Why does the bromination of phenol occur in this manner (on the 2, 4 and 6 positions?)
 • Certain groups have orienting effects, meaning that when
they are present, they direct the addition of other groups to
certain more likely positions relative to themselves.

These positions are named as shown above.

With Sodium Hydroxide

• The products are sodium phenoxide and water.

Diazotization (NaNO2/HCl)
• The reaction produces benzene diazonium chloride, sodium chloride and water.
o This occurs at 0-5°C, as diazonium salts will decompose at higher temperatures to
form phenol, nitrogen gas and a proton.
• Technically, the sodium nitrite and hydrochloric acid react to form nitrous acid, which
then goes on to react with the aniline molecule.
Coupling (with Diazonium Salt)
• If we take a diazonium salt like the one formed above and mix it with phenol in an
alkaline medium (i.e. solution containing NaOH), the result will be coupling to form an
azo compound.
o HCl is also formed as the chloride ion is released.
o The NaOH is necessary to convert the phenol to the phenoxide ion, which can
then go on to react with the salt.
o The reaction also occurs at 0-5°C due to the volatility of the reactants.

As shown above, the reaction also occurs between aniline (phenylamine) and the benzene
diazonium chloride salt, forming a yellow dye instead.

• The azo compounds are used as dyes or as intermediates in organic synthesis.

Acidic and Basic Character of Organic

Compounds
Acidity of Alcohols, Phenols and Carboxylic Acids
• The acidity of a compound is measured by the acid dissociation coefficient (Ka) of the
compound, an equilibrium constant which indicates the extent to which a compound
dissociates to produce protons in aqueous solution.
o The greater the Ka, the stronger the acid.
o The smaller the pKa, the stronger the acid.
o Stronger acids produce solutions of lower pH.
• Since the defining factor of a Bronsted-Lowry Acid is its ability to donate a proton to
another compound, a stronger acid is a compound which more easily dissociates to
release a proton.
• The tendency of an acid to dissociate depends on the stability of its conjugate base, i.e.
the molecule formed when a hydrogen atom dissociates from the molecular form of the
acid.
o When the conjugate base is more stable, it takes less energy to form,
dissociation of the hydrogen requires less energy, and the acid is more acidic.
 • You can explain the acidity of a compound on two main bases:
o The stability of the conjugate base (due to resonance or delocalisation for
example)
o The electron withdrawing or donating character of any present
groups/substituents
o These contribute to the ease with which the H+ is released and how readily it is
recombined with the residual anion.

• The syllabus only requires a comparison of

alcohols, phenols and carboxylic acids.
o Alcohol > Phenol > Carboxylic Acid
o This hierarchy of acid strength

(Aliphatic) Alcohol Acidity

• Alcohols are weakly acidic, and sometimes
dissociate into a proton and the alkoxide ion.
• Alcohols are slightly less acidic than water.
• Oxygen is highly electronegative, and pulls more strongly on the electrons of the OH
bond than the hydrogen.
o As such, the OH bond is strained, and hydrogen can dissociate occasionally. This
is relatively uncommon however, as the bond is not significantly weakened.

• When an electron donating group (EDG) is added, the acidity decreases (pKa
increases).
o For example, alkyl groups are EDGs. As such, tertiary alcohols are weaker than
secondary alcohols, which are weaker than primary alcohols.

Phenol Acidity
• Phenol is more acidic than aliphatic alcohols (by about a million times).
o The phenoxide ion is more stable than any alkoxide ion due to the presence of the
aromatic ring.
o The negative charge on the oxygen atom of the phenoxide ion is delocalised
around the ring.
 ▪ One of the lone pairs of the oxygen overlaps with the band of delocalized
electrons on the benzene ring, resulting in a delocalisation of the negative
charge.
▪ Electron density is moved away (on average) from the hydrogen atom due
to the electron donating resonance effect of the hydroxyl group, further
straining the bond, and increasing the likelihood of dissociation.
• The substituent attached to the phenol also
affects the acidity.
• Electron withdrawing groups take
electron density away from the benzene
ring, in turn reducing electron density in
the benzene ring and in the O-H bond. The hydrogen atom thus requires less energy to
dissociate.

Acidity of Carboxylic Acids

• Despite having similar OH groups to alcohols, carboxylic acids are more acidic.
• Instead of forming alkoxide ions when dissociated from the proton, carboxylic acids form
carboxylate ions, which are more stable than alkoxide ions due to the delocalization of
the negative charge on the oxygen.
• As you can see on the left, the carboxylate ion (in this
case acetate) has two resonance forms, which
increases stability.
• The charge is spread over 3 atoms instead of 1,
making it less likely to attract hydrogens and reform
the molecular form.

• The C-O 𝜋 bond overlaps with the p orbital of the other oxygen, forming a delocalized
electron band.
o Formation of this ion requires less energy and is more favourable.
• In addition, while in the molecular form, the electronegative oxygen in the carbon-
oxygen double bond exerts an electron withdrawing inductive effect, decreasing electron
density in the O-H bond.
o This weakens the bond, making it easier to break.

Chlorosubstituted Acids
• Chlorosubstituted carboxylic acids are those with a chlorine substituent.
 • Chlorine (and any halogen substituent) is strongly inductively electron withdrawing
substituent, and as such will intensify polarization elsewhere in the molecule
• Chlorosubstituted carboxylic acids are stronger acids, as the electronegative halogen
substituent will pull electron density away from the COO- group, further delocalising the
negative charge and increasing the stability of the ion.
• The pulling of electron density will also weaken the OH bond in the molecular form,
making the bond easier to break.

Aside: Why would ethanoic acid still be a stronger acid than phenol?
• The question arises since both molecules exhibit some resonance effects resulting in the
delocalization of a negative charge on oxygen.
• However, look at the atoms over which the charge is delocalized.
o In phenoxide ion (formed by dissociation of phenol), those atoms are carbon
atoms in the benzene ring. The oxygen carrying the charge is still the most
electronegative and will attract the electrons most strongly. The negative charge
will still be more concentrated on this atom, making it more likely to attract
hydrogen and reform phenol.
o In ethanoate (or any carboxylate ion), the negative charge is delocalised over a
carbon atom and another oxygen atom. Charge is more evenly distributed and
less concentrated, increasing its stability and decreasing the likelihood of
reformation of the carboxylic acid.

Basic Character of Aliphatic Amines, Amides and Aromatic

Amines
• Bases, when soluble, produce solutions with high pH.
• Stronger bases have higher Kb but lower pKb.
• The Bronsted-Lowry definition of bases is that they act as proton acceptors.
o Alkalis are soluble in water, and just like acids, the strength of a base is correlated
to the extent of its dissociation in water.
o Strong bases will ionize to produce solutions with high concentrations of OH-
ions (Arrhenius base definition). Weak bases only partially ionize.
• Aliphatic Amines > Aromatic Amides > Amides
o All of the contributing factors to acid strength are reversed here- a less
delocalized electronic structure will lead to greater base strength since the
purpose of the base is to attract hydrogen ions.

Aliphatic Amines
• Amines are basic due to the lone pair available on the nitrogen atom which is available
for accepting protons.
o As such, anything that increases the availability of the lone pair on the nitrogen
atom increases its strength as a base.
 • The degree of substitution of an amine influences its strength as a base. Remember that
alkyl substituents are EDGs, and their positive inductive effect will push electron
density towards the nitrogen, making the nitrogen’s lone pair more available to form
dative covalent bonds with protons.

Aromatic Amines
• Arylamines/Aromatic Amines are less basic
than alkylamines/aliphatic amines because the
nitrogen lone-pair electrons are delocalized
by interaction with the aromatic ring’s 𝝅
electron system and are less available for
bonding to H+.
• Activating groups, or electron donating
groups, increase the electron density of the
benzene ring and the 𝝅 electron system.
• This increases the availability of the lone pair
on the nitrogen of the amine substituent, allowing it to accept a proton.

Amides
• Amides are less basic than both aromatic and aliphatic
amines.
• The lone pair on nitrogen is delocalised (conjugative
effect). This orbital overlaps with the adjacent 𝜋 bond
electrons, forming a delocalised band.
o The lone pair becomes less available to accept
protons.
Amino Acids
• These are organic compounds containing an amine group and a carboxylic acid functional
group.
• The carboxylic acid group is deprotonated to the
carboxylate anion, while the amine group is protonated
and exists as the ammonium cation.
o Amino acids exist in solution primarily as dipolar
ions, also called inner salts or zwitterions.
o A zwitterion is a molecule containing an equal
number of positively and negatively charged functional groups. They have both
an intramolecular positive and negative charge (which are equal in magnitude).
o Amino acids are amphiprotic, meaning they can both accept and donate
electrons.

• In aqueous acid solution, an amino acid zwitterion is a base that accepts a proton onto
its CO2- group to yield a cation.

• In aqueous base solution, the zwitterion is an acid that loses a proton from its NH3+
group to form an anion.

Macromolecules
• A macromolecule is a large molecule comprising a large number of atoms.
• A polymer is a macromolecule comprised of many identical or similar molecular
subunits known as monomers arranged in a regular, organized manner.
• Polymerization is the process by which many small molecules called monomers are
combined to produce a polymer.
o The two types of polymerization are:
 o Addition polymerization, where monomers combine without the loss of atoms or
the formation of by-products.
o Condensation polymerization, where monomers combine with the loss of atoms
or a small molecule (eg HCl, H2O)

Addition Polymerization
• Characteristics:
o All monomers are the same.
o The empirical formula of the polymer is the same as the monomer as no atoms
are lost during formation.
o The polymer is the only product formed.

Formation of Polyethene
• The polymerization of ethene is described via a radical process, that is, initiation,
propagation and termination, as with radical substitution of alkanes.
• Involves the use of a Ziegler-Natta Catalyst and high pressures.
o Two forms of polyethene are possible:
▪ Low density polyethene is formed using high pressure and high
temperature. Used in plastic bags and insulation cables.
▪ High density polyethene is formed using lower temperatures and
pressures. Used in buckets and bottles.
• A chain initiator radical (usually oxygen) reacts with ethene to form a new radical

• Chain propagation occurs via the reaction of this new radical with another ethene
molecule.

• Chain termination occurs with the reaction of two radicals.

Polyvinyl Chloride/Poly(chloroethene)
• Polyvinyl chloride (PVC) is formed from
multiple chloroethene monomers, and is
used in pipes and window frames.

Polytetrafluoroethene (PTFE)
• PTFE (also called Teflon) is formed from
several tetrachloroethene monomers, and is
used in non-stick coatings and insulation

Condensation Polymerization
• Characteristics:
o Always forms two products, the polymer and a small molecule.
o The polymer is either a copolymer (a polymer produced from two or more
monomer species), or produced from monomers with two different functional
groups.
o The empirical formula of the polymer is different from the monomer.
o The monomers must have two functional groups.
• The two most important reactions of condensation polymerization are:
o The formation of an amide from the reaction between a carboxylic acid group
and an amine group.
o The formation of an ester from the reaction between a carboxylic acid group and
a hydroxyl group.
Uncertainty in Measurements
A Few Definitions
• Calibration is the comparison of an instrument’s performance to a standard of known
accuracy.
o It is also the act of checking or adjusting (by comparison with a standard) the
accuracy of a measuring instrument.
• Detection Limit of an instrument is a measure of the smallest concentration/value
which can be determined with a specified precision or reproducibility.
• Sensitivity of an instrument related to how the variation in the output of that instrument
can be apportioned, qualitatively or quantitatively to different sources of variation.

Titrimetric Methods of Analysis

• Titration is an analytical technique in which the unknown concentration of a chemical
species in a solution (called the analyte) is determined by reacting the species completely
with a reagent in a solution of known concentration (known as the titrant).
o The reagent in the solution of known concentration is called the standard.
o The precise point where all moles of analyte have reacted with all moles of
standard is called the equivalence point.

• The equivalence point is detected by either a visual/colour change or a physical

method.
o The point at which this visual or physical change is observed in a titration is
called the end point.
o The end point does not always coincide with the equivalence point, leading to a
difference called the titration error.
• The visual/colour change may result purely from the reaction between the analyte and
standard, or from an indicator, an auxiliary reagent added to either the titrant or analyte.
• The physical change may be a change in temperature, pH or electrical conductivity.
o Experimentally, we add the titrant to the analyte (usually from a burette into a
flask containing the analyte) until the end point is observed.
Acid Base Titrations
• In a simple acid/base titration, the equivalence point is where the acid is completely
neutralized by the added base (or vice versa, depending on the identity of the analyte and
standard).
o At neutralization between a strong acid and a
strong base, the pH is 7.
o At neutralization between a strong acid and a weak
base, the pH is <7.
o At neutralization between a weak acid and a strong
base, the pH is >7.
• How do we determine the equivalence point?
o Indicators- add an indicator to the solution in the
flask. A suitable indicator must be used, which
undergoes a colour change at or close to the pH of
the solution at equivalence point.

pH at
Suitable
Acid Strength Base Strength Equivalence
Indicator
Point
Bromothymol
Blue, Phenol
Strong Strong 7
Red,
Phenolphthalein
Strong Weak <7 Methyl Orange
Weak Strong >7 Phenolphthalein
None- use back
Weak Weak Variable
titration instead

o pH Meter- The actual pH of the reaction mixture can be detected and plotted
using a pH Meter. This is called a potentiometric titration.
o Conductometer/Electrical Conductivity Meter- a
conductometer can be used to measure the conductivity of
the reaction mixture throughout the titration. Conductivity
decreases to a minimum at the equivalence point, as all
the ions in solution have reacted, leaving only slightly
ionizable water.
▪ This is called a conductimetric titration.
o Thermometer- Neutralization reactions are exothermic, and as such, the
temperature of a reaction mixture will reach a maximum at the equivalence point.
▪ This is called a thermometric titration.
Back Titrations in Acid/Base Analysis
• Back titration (or indirect titration) is a method where an analyte is added to a solution
containing an excess of standard.
o The quantity of unreacted standard is then quantified by titration against a
second standard.
o The quantity of the first standard which has reacted is calculated through
subtraction, and the quantity of the analyte can be calculated through knowledge
of the reaction.
• When is back titration used?
o The analyte is insoluble in water
o The analyte is volatile
o The reaction between analyte and standard is slow
o A direct titration would be a weak acid/weak base titration, where the end point
is not sharp.

Primary Standards
• These are compounds which meet the following criteria:
o Stable, so that it can be easily weighed under atmospheric conditions and not
change during storage.
o Easy to obtain in highly purified form
o Soluble in the titration medium in which it is to be used
o High formula weight to reduce weighing errors
o The reaction between the primary standard and the compound being standardized
should be fast and quantitative (go to completion)
o Inexpensive
• For standardization of acids:
o Na2CO3
o NaHCO3
• For standardization of permanganate solutions:
o Oxalic Acid - (COOH)2
o Sodium Oxalate – (COONa)2
• For standardization of thiosulfate solutions:
o Potassium Iodate - KIO3

Redox Titrations
• In a redox reaction, one reactant is oxidized and the other reactant is reduced.
o Analytes which are readily oxidized or reduced can be analysed quantitatively by
titrimetric analysis, where the standard is an oxidizing or reducing agent.
Potassium Permanganate
• Acidified MnO4- solution is a strong oxidizing agent, where manganese (VII) accepts 5
electrons and is reduced to manganese (II)
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − ↔ 𝑀𝑛2+ + 4𝐻2 𝑂
 • The permanganate ion is deep purple, and so titrations with colourless or faintly
coloured analytes do not require indicators, they are self-indicating.
• Potassium permanganate is not a primary standard, as it is contaminated with an
insoluble brown solid manganese dioxide (MnO2)
o Potassium permanganate must first be standardized before usage, usually with
sodium oxalate.
Iodometric Titrations
• Iodine (I2) is an oxidizing agent and readily takes two electrons from a reducing agent to
form two iodide ions.
• Iodine is soluble in fairly concentrated solutions of potassium iodide, where the triiodide
ion is formed:
o 𝐼2 + 𝐼 − ↔ 𝐼3−
o Triiodide is also an oxidizing agent and is reduced by two electrons to form three
iodide ions
o Iodine tends to evaporate when in aqueous solution, but this problem is avoided
when iodine is dissolved in potassium iodide solution and the triiodide ion forms.
• Starch is the indicator for titrations involving iodine.
o I2 dissolved in KI is red. When dilute starch solution is added, it becomes deep
blue.
• Iodine solutions are commonly standardized using sodium thiosulfate.
o Na2S2O3 is not a primary standard as it is commonly a pentahydrate but is
efflorescent, so it also loses water.
o Sodium thiosulphate is standardized using the primary standard potassium iodate
(in acid solution).
Preparing a standard solution
Gravimetric Methods of Analysis
• Gravimetric analysis is quantitative analysis by weight.
o It involves isolating and weighing an element or a definite compound of the
element in as pure a form as possible.
o Usually, the element to be determined is transformed into a pure stable compound
which can be readily converted into a suitable form for weighing.
• Advantages of Gravimetric analysis:
o It is accurate and precise with modern analytical balances
o Possible sources of error can be easily checked (precipitates may be examined for
impurities, and filtrates can be tested for completion of precipitation)
o It involves direct measurement, so no calibration is required. It is an absolute
method.
o It is inexpensive to carry out (can sometimes only require a crucible and heat)

Precipitation Method
• The constituent being determined is precipitated from solution in a form which is so
slightly soluble that no appreciable loss occurs when the precipitate is separated by
filtration and weighed.
• Requirements for the precipitation:
o The precipitate must be so insoluble that no appreciable loss occurs when it is
collected by filtration. The quantity remaining in solution does not exceed the
minimum detectable by the ordinary analytical balance.
o The precipitate must be granular; the size of the particles must be sufficiently
large so that they do not pass through the filtering medium and are not diminished
by the washing process.
o The precipitate must be convertible to a pure substance of definite chemical
composition (such as through evaporation)
• Apparatus for gravimetric analysis:
o Analytical Balance: a balance for determination of weights to 4dp
o Laboratory Oven: for drying reagents and precipitates
o Desiccators: a large glass vessel in which a drying agent (like silica gel or CaCl2)
is placed.
o Weighing paper
o Vacuum Source: an aspirator pump or
water pump
o Sintered Glass Crucibles, porosity #4:
cylindrical glass funnel used for filtration
and weighing.
▪ The base is a porous disc which has
been subjected heat and pressure.
o Suction/Buchner funnel
o Suction filter flask
Volatilization/Evolution Methods
• These methods depend essentially upon the removal of volatile constituents, which can
happen in several ways, including heating/ignition and treatment with a chemical
reagent which renders a constituent volatile.
o The determination of the amount of water of crystallization in a hydrate can
occur by heating a sample of the hydrated salt in a silica crucible and recursively
weighing the residue until a constant mass is reached.
o The purity of a carbonate compound can be determined by reacting the
compound with excess acid. This reaction releases gaseous carbon dioxide.
▪ The evolved CO2 is made to react with an absorbent like NaOH. The
change in mass of the absorbent is used to determine the quantity of carbon
dioxide that has reacted.

Applications of Gravimetric Analysis

• To analyse and establish the purity of compounds used as standards in other types of
analysis and for calibration of instruments.
• To determine the concentrations/percentages of specific substances in mixtures and
materials such as foodstuffs, drugs and soils.
• To maintain quality control of fertilizers; the three numbers displayed on the label of a
fertilizer indicate the percentages of nitrogen (N), phosphorus (P) and potassium (K);
phosphorus is present in the fertilizer as phosphate ion (PO43-); the percentage of
phosphate ion in the fertilizer can be verified by converting the phosphate in a known
quantity of fertilizer to the insoluble compound magnesium ammonium phosphate
hexahydrate (MgNH4PO4.6H2O).
• To monitor the concentrations of particles in air; many air quality monitors contain
filters made of Teflon or fibreglass to trap particles; the filters must be carefully
conditioned before use and weighed to a high degree of accuracy both before and after
use in the monitor; the difference in the weight of the filter before and after use gives the
mass of the particulate matter collected.

Spectroscopic Methods of Analysis

• Spectroscopy is the study of the interaction of matter with electromagnetic radiation.
• Max Planck discovered that atoms and molecules emit energy only in certain discrete
quantities, or quanta.
o A quantum is the smallest quantity of energy that can be emitted or absorbed in
the form of electromagnetic radiation.
o The energy of a quantum depends on its frequency (f, but sometimes written as
v):
▪ 𝐸 = ℎ𝑓, where h is Planck’s constant, 6.626×10-34 Js.
𝑐
▪ Since 𝑐 = 𝑓𝜆, 𝑓 = 𝜆
ℎ𝑐
▪ 𝐸= 𝜆
• Electrons can only exist at specific energy levels. When they are closer to the nucleus,
they are in a lower energy state. When they are further away, they are in a higher energy
state
o The electron is in its ground state when it is in its lowest possible energy level.
o However, when absorbing energy, an electron can move to a higher energy level,
entering an excited state.

• As mentioned previously, energy can only be absorbed in discrete quantities known as

quanta.
o So, when an electron absorbs a quantum of energy E, it transitions to a higher
energy level (excited state); but to return to that original energy level (ground
state), it emits a quantum of equal energy.
• It is therefore said that energy levels in atoms and molecules are quantized.

Region of EM Spectrum Wavelength (m)

Radio >1
Microwave 10−3 𝑡𝑜 1
Infrared 7 × 10−6 𝑡𝑜 10−3
Visible 4 × 10−7 𝑡𝑜 7 × 10−7
Ultraviolet 4 × 10−7 𝑡𝑜 10−9
X-Ray 10−9 𝑡𝑜 10−12
Gamma < 10−12
The Interaction of Electromagnetic Radiation with Atoms and
Molecules
• The energy levels in atoms and molecules are quantized, and so they have exact values.
The differences between any two energy levels are therefore also quantized. This means
that:
o the electrons in atoms and molecules can have only certain specific energies;
o if a bond connects two atoms, that bond behaves as a spring with a fixed natural
frequency of oscillation so molecules can vibrate and rotate only with specific
frequencies.
• When photons with a range of energies fall on a material:
o any photons whose energy corresponds exactly to the difference in two electron
energy levels will be absorbed and the electron will be promoted into its higher
level
o any photons whose frequency corresponds exactly to the frequency of oscillation
of a bond between atoms will be absorbed and the amplitude of the oscillation
will increase.
• In both of these cases, the photons are resonating with a part of the system. A graph of
energy transmitted against frequency of the incoming radiation will show a dip at the
resonant frequency.
o Each resonance will be characteristic of the particular atom or bond that is
stimulated.
• Different regions of the electromagnetic spectrum cause transitions between different
types of energy levels:
Change Occurring Type of Radiation Absorbed
Rotational Microwave
Vibrational Infrared
Electronic Visible and Ultraviolet
UV/Vis Spectroscopy
• As stated before, when electromagnetic radiation having energy exactly equal to the
difference between the excited and ground states is absorbed by an atom or molecule, it
passes to a higher energy state.
• In UV/Vis spectroscopy the transitions that result in absorption of electromagnetic
radiation in this region are transitions between electronic energy levels.
o An electron is promoted from an occupied orbital to an unoccupied orbital of
higher potential energy.
o The most probable transition is from the highest occupied molecular orbital to
the lowest unoccupied molecular orbital, as this transition has the lowest
energy.
• For most molecules, the lowest-energy occupied molecular orbitals are the 𝝈 orbitals,
which correspond to 𝝈 bonds. 𝝅 orbitals lie at somewhat higher energy levels, and
orbitals that hold lone pairs, the nonbonding (n) orbitals, lie at even higher energies.
o The unoccupied, or antibonding orbitals (𝜋* and 𝜎*), are the orbitals of highest
energy.

• In all compounds (except alkanes), electrons may undergo several possible transitions
of different energies:

However, only the bottom three are actually within the UV-Vis region: 𝒏 → 𝝅∗ , 𝒏 →
𝝈∗ and 𝝅 → 𝝅∗ .
(𝜎 𝑡𝑜 𝜋 ∗ is impossible based on selection rules)
Why aren’t some compounds UV/Vis active?
• To say some compounds are not UV/Vis active is to say that they do not absorb light in
the ultraviolet-visible region of the electromagnetic spectrum.
• Above, the important transitions involve 𝝅 antibonding orbitals and non-bonding
orbitals. As such, if a compound does not have either 𝝅 bonds or lone pairs, they will
not absorb in the UV/Vis region.
o UV/Vis inactive compounds include alkanes which lack both pi bonds and lone
pairs.
• Compounds which absorb in the UV/Vis region contain certain groups called
chromophores or lone pairs of electrons.
o Chromophores are groups in a molecule producing absorption of light.
o These include the carbon-carbon double bond, carbonyl group, amide group,
amine group, carbon-carbon triple bond, acyl chloride group and nitro group

• Auxochromes are groups of atoms which, when attached to chromophores, have a

hyperchromic effect, i.e. they increase the intensity of the absorption of the chromogen.
• If substances do not absorb strongly in the UV/Vis region, they can be made to react with
reagents to produce coloured derivatives. These reagents are called chromophoric
reagents, such as:
o 1,10-phenanthroline (forms red complex with iron (II) ion)
o Dimethylglyoxime (forms red complex with nickel (II) ion)

Beer-Lambert’s Law
• The greater the number of molecules capable of absorbing light of a given wavelength in
solution, the greater the extent of light absorption.
o And the more effectively a molecule absorbs light of a given wavelength, the
greater the extent of light absorption.
o As such, the concentration of a molecule and the identity of the molecule in
solution affect the extent of light absorption.
 • There are two empirical laws which describe the absorption of light by compounds in
solution:
o Lambert’s Law- the fraction of incident light absorbed by a homogenous liquid
depends on the length of the absorbing medium, also called the path length (l).
o Beer’s Law- the fraction of incident light absorbed by a homogenous liquid is
proportional to the number of absorbing molecules
o The combination of these laws is the Beer-Lambert Law, which states:
𝐼
▪ 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 (𝐴) = log10 𝐼0 = 𝜀𝑐𝑙
▪ Where 𝐼0 is incident light intensity, 𝐼 is intensity of transmitted light, 𝜀 is
molar extinction coefficient, c is concentration and l is path length
• For UV/Vis spectroscopy, the source of UV light is a deuterium discharge lamp.
o The source of visible light is a tungsten filament lamp.

• The sample for analysis is usually dissolved in a solvent which does not absorb light at
the same wavelength as the sample. This is usually ethanol, water or hexane.
• The sample is typically placed in a glass, quartz (transparent down to 200nm) or
calcium fluoride (transparent down to 100nm) cuvette and placed in the relevant slot of
the spectrophotometer.

Infrared Spectroscopy
Infrared Absorption Process
• The absorption of infrared radiation is, like other absorption processes, a quantized
process.
• The frequencies of infrared radiation that match the natural vibrational frequencies of
the bonds of the molecule in question are absorbed, and this energy increases the
amplitude of the vibrational frequencies of the bonds in most covalent molecules.
o Only those bonds that have a dipole moment that changes as a function of time
are capable of absorbing infrared radiation.
o A bond must present an electrical dipole that is changing at the same frequency
as the incoming radiation for energy to be transferred.
• Since every bond has a different natural frequency of vibration, and because two of the
same bond exist in different environments in two different compounds, no two molecules
of different structure have exactly the same infrared spectrum.
• Infrared spectra also allow us to determine structural information about a molecule- that
is, we can infer the functional groups present in
a molecule based on the peaks in the infrared
spectrum, as certain types of bonds will exhibit
similar absorptions.
• As seen on the right, IR spectra are usually
plotted as transmittance (amount of light passing
1
through) against wavenumber (𝜆 (𝑖𝑛 𝑐𝑚))
• There are different modes of vibration, that is,
molecules can undergo a set of either stretching or bending vibrational motion which
can be infrared active.
o If a vibrational mode is infrared active, it means that the dipole moment of the
molecule changes as a result of this motion over time.
o This can only occur in polar molecules, and excludes non-polar molecules like
N2 or Argon.

o A vibrational mode can be IR inactive however if no dipole moment change is

effected, like in CO2, where symmetric stretching does not change the net dipole
moment of the molecule.
 • A diatomic molecule can be considered as two vibrating masses connected by a spring.
The natural frequency of vibration of a bond can be thought to obey Hooke’s Law.
o Stronger bonds vibrate at higher frequencies.
• The region between 1300 and 600 cm-1 of the infrared spectrum is called the fingerprint
region, as the absorption peaks are difficult to interpret. It is unique to every compound
and allows us to confirm the identity of the compound by comparing this region (and the
full spectrum).
• The IR spectrum alone cannot be used to determine the structure of a compound,
however apart from being overlaid with known IR spectra. It can only hint the presence
of certain functional groups, and must be used with other data like molecular formular,
elemental composition and other types of spectra.

Preparation of A Sample
Solids
KBr pellet
• Mix the finely ground sample with powdered KBr (potassium bromide)
• Press the mixture under high pressure.
o The KBr melts at high pressure and seals the sample into a matrix.
• The resulting KBr pellet is placed into the instrument.
o KBr is used since it is IR transparent down to 400cm-1,
which is just at the lower end of the range of detection
for most IR spectrophotometers.
OR the Nujol mull
• The compound is ground with Nujol (mineral oil) to create a
suspension of the sample dispersed in the oil.
• The suspension is then placed between two KBr or NaCl plates.
o This method is disadvantageous as the mineral oil is IR
active at 2924, 1462 and 1377 cm-1.

Liquids
• A drop of liquid organic compound is placed between two polished NaCl of KBr plates,
then pressed gently to form a thin liquid film between the plates.
• The compound must be free of water.
In modern FT-IR spectrometers, the sample does not need to be prepared, and can simply be
placed on an ATR (attenuated total reflection) crystal made of diamond, zinc selenide or
germanium.
Infrared Absorption and the Environment
• Radiation from the Sun which reaches the Earth’s atmosphere is approximately 3% UV
light, 44% visible light and 53% infrared light. The visible radiation is absorbed by
the Earth’s surface.
o This absorption of energy warms the surface, and the surface then emits lower
energy IR radiation back towards space.
• The gases nitrogen, oxygen and argon make up more than 99% of the Earth’s
atmosphere. These gases do not absorb either visible or infrared radiation as they are
completely non-polar.
• However, the small percentages of carbon dioxide and water vapour present in the
atmosphere absorb the infrared radiation from the Earth’s surface. This causes heating of
the atmosphere, and also makes the surface of the Earth warmer.
o This heating is known as the greenhouse effect- greenhouse gases trap some of
the heat radiated from the earth’s surface.
o Greenhouse gases include carbon dioxide, methane and nitrous oxide, all of
which are IR active.

Monitoring Air Pollutants Using IR Spectroscopy

• FT-IR (Fourier Transform Infrared) spectrometers can determine levels of several gases
concurrently over a pathlength extending between 50 and 1000 meters.
o In the field, the FT-IR sends beams of IR radiation towards retro-mirrors that
send each beam back to its receiver. Gases travel through these beams and take in
some energy as they do, and so will show up in the measured absorbance.
• Laser-based IR spectroscopy has also been used to monitor the composition of
atmospheric gases.

Mass Spectroscopy
Principles
• Know the diagram on the right, it is a block
diagram representing mass spectroscopy.
• The mass spectrometer has five
components:
o Sample Inlet brings the sample from the lab to the low pressure spectrometer.
o Ion Source where sample molecules are transformed into gas phase ions. These
are then accelerated under a magnetic field.
o Mass analyser separates sample ions based on their mass-to-charge (m/z) ratio.
o Detector counts the ions
o Data system records and processes the output to produce a mass spectrum, a
graph of relative abundance versus m/z ratio.
• Ions are usually produced through electrical ionization.
o A beam of high-energy electrons is emitted from a filament that is heated to
several thousand degrees Celsius.
o These high-energy electrons strike the stream of molecules that has been
admitted from the sample inlet system.
o The electron–molecule collision strips an electron from the molecule, creating a
cation.
o A repeller plate, which carries a positive electrical potential, directs the newly
created ions toward a series of accelerating plates. A large potential difference,
ranging from 1 to 10 kilovolts (kV), applied across these accelerating plates
produces a beam of rapidly traveling positive ions.
o One or more focusing slits direct the ions into a uniform beam

• The ions are accelerated and pass into the mass analyser (usually a magnetic sector mass
analyser), where they are separated according to the m/z ratio
𝑚 𝐵2 𝑟 2
o = , describes the path taken based on this ratio and the strength of magnetic
𝑧 2𝑉
field (B) or potential difference (V).

• The most abundant ion formed in the ionization chamber gives rise to the tallest peak in
the mass spectrum, called the base peak. This peak is assigned 100% relative
abundance.
 o The molecular ion (𝑴+• ) is the radical cation formed from the removal of an
electron from the molecule in study.
▪ The heaviest peak (highest m/z ratio) is usually the molecular ion.
▪ Molecular ions tend to be unstable, and break down into fragments of
smaller mass. As such, the molecular ion does not tend to be the base
peak.
▪ The molecular ion will have the same mass as the compound being
analysed.
▪ Sometimes the molecular ion is so unstable that it is not detected (it
breaks down before reaching the detector)

Mass Spectra
• If mass spectroscopy is carried out on a sample of a single species atoms (one element),
the peaks will correspond to isotopes of the element.
o Ionizing the atoms will produce cations with an m/z ratio corresponding to the
mass of the isotope (as the ions have majorly +1 charge).

e.g. The mass spectrum of Zirconium. There are five isotopes.

• When mass spectroscopy is carried out on a molecule, the peaks produced correspond to
fragments as well as the molecular ion.
Using Peaks Above 𝑴+•
• A small peak (low relative abundance) 1 m/z unit to the right of the main molecular ion
peak is the (𝑀 + 1)+• peak
• The M+1 peak is due to the presence of the carbon-13 isotope in the molecule.
o Carbon-13 makes up 1.11% of all carbon atoms.
• Using the M+1 peak can allow us tor determine the number of carbon atoms in a
molecule:
100 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑎𝑏𝑢𝑛𝑑𝑎𝑛𝑐𝑒 𝑜𝑓 𝑀+1 𝑝𝑒𝑎𝑘
o # 𝑜𝑓 𝐶 𝑎𝑡𝑜𝑚𝑠 = 1.11 × 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑎𝑏𝑢𝑛𝑑𝑎𝑛𝑐𝑒 𝑜𝑓 𝑀+ 𝑝𝑒𝑎𝑘
• +•
Using peaks above the 𝑴 peak also allows us to determine the presence of other atoms
with two or more isotopes in the molecule, mainly chlorine and bromine.
 Atom/Substituent Isotopes Abundance
Ratio
Chlorine Chlorine-35 Chlorine-37 ~3:1
(75.5:24.5)
Bromine Bromine-79 Bromine-81 ~1:1
(50.5:49.5)

• As you can see in the table above, both of the halogens have major isotopes separated by
2 atomic mass units.
o As such, two peaks with different isotopes would also be separated by 2 m/z units.
o The peak 2 m/z units to the right of the molecular ion peak is called the M+2
peak.
o Based on the ratio of abundance between the M+ and M+2 peaks, we can infer the
presence of chlorine or bromine.
▪ If chlorine is present, the M+ will be 3 times taller than M+2
▪ If bromine is present, the M+ and M+2 will be approximately the same
heights
Fragmentation Patterns
• The electron beam is energetic enough to displace electrons from the molecules, but it is
also capable of breaking some of the bonds in the molecule.
• The positively charged fragments are also accelerated in the ionization chamber, sent
through the analyzer, detected, and recorded on the mass spectrum.
o These fragment ions appear at m/z values corresponding to their individual
masses.
• They can also be produced if the molecular ion has a shorter lifetime that 10-5 seconds
(the radical cation disintegrates)
The Nitrogen Rule
• This rule states that if a compound has an even number of nitrogen atoms (including
zero), its molecular ion will appear at an even mass value.
• On the other hand, a molecule with an odd number of nitrogen atoms will form a
molecular ion with an odd mass.
▪ The Nitrogen Rule stems from the fact that nitrogen, although it has an
even mass, has an odd-numbered valence.
Stevenson’s Rule
• The most probable fragmentation is the one that leaves the positive charge on the
fragment with the lowest ionization energy.
o In other words, fragmentation processes that lead to the formation of more stable
ions are favoured over processes that lead to less stable ions. (Doesn’t that sound
familiar?)
• When the loss of more than one possible radical is possible, a corollary to Stevenson’s
Rule is that the largest alkyl radical will be lost preferentially.
Common Fragmentation Patterns

• Benzene and alkylbenzenes have mass spectra showing the molecular ion as the base
peak, as the benzyl cation is relatively very stable due to delocalization of the positive
charge throughout the ring.

Chromatographic Methods of Separation

Principles
• Chromatography is the non-destructive separation of chemical substances by selective
sorption. Components are distributed between two phases, one of which is a stationary
phase, while the other is a mobile phase, which moves in a definite direction.
o Sorption refers to a physical and chemical process by which a substance becomes
attached to another, through absorption and adsorption.
• Chromatography involves passing the analyte in a mobile phase (the moving material)
across a second stationary material called the stationary phase.
o The separation is based on the differential affinities of the components of the
analyte mixture for the stationary phase compared to the mobile phase.
o Some materials will travel more quickly than others, leading to eventual complete
separation into the components.
• Elution is the process of washing out a compound through a column using a suitable
solvent called an eluent.
o The methods we are concerned with will only use isocratic elution (same
composition of the solvent mixture throughout the process)
 • Adsorption is the process by which particles (atoms, ions or molecules) adhere to a solid
surface. In chromatography, particles move from the fluid mobile phase and adhere to the
stationary phase, forming a film of the adsorbate.
• Partitioning is the distribution of a solute between two immiscible solvents based on
solubility.
• Chromatography is classified into adsorption and partition chromatography.

• This technique is used in forensic analysis, purification of samples, and pesticide

analysis.
Thin Layer Chromatography
• Thin layer chromatography (TLC) depends on the relative affinity of compounds
towards both the phases.
• The TLC plate is a thin piece of aluminium coated on one side with the stationary phase
(an adsorbent) like silica gel or alumina.
o Components of the samples will separate according to how much they adsorb on
the stationary phase versus how much they dissolve in the mobile phase.
• When colourless compounds like amino acids are being
separated, a locating/visualizing agent is sprayed onto the
chromatogram, which creates a coloured product.
o A 0.2% solution of ninhydrin in propanone
produces a purple colour with amino compounds
o Ammonia vapour forms a deep purple complex with
the Cu2+ ion.
o Spots containing a fluorescent substance become
visible when viewed in UV light.
Paper Chromatography
• This is a method of partition chromatography which uses filter paper strips as a carrier
or inert support
 o Based on partition between two
immiscible phases. The solutes
equilibrate between the two phases
according to their partition coefficients
(we’ll discuss this later).
▪ The first is usually water absorbed
on cellulose fibres in paper.
▪ The second is the organic solvent
which flows past the sample on
the paper.
• Retention Factor (Rf) is a property of a component of a mixture
when separated using paper chromatography. It is always the
same for a compound given the same mobile and stationary
phases are used.
𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑠𝑡𝑎𝑟𝑡/𝑜𝑟𝑖𝑔𝑖𝑛 𝑡𝑜 𝑐𝑒𝑛𝑡𝑒𝑟 𝑜𝑓 𝑠𝑝𝑜𝑡
o 𝑅𝑓 = 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑠𝑡𝑎𝑟𝑡 𝑡𝑜 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑓𝑟𝑜𝑛𝑡
o The solvent front is the point on the chromatogram
where the mobile phase travels furthest up the stationary
phase (filter paper in this case).

Column Chromatography
• The stationary phase is held in a narrow tube
through which the mobile phase is forced through
elution or the effect of gravity.
o This is an example of adsorption
chromatography.
• The column is packed with silica gel or alumina
completely saturated with a solvent. The solvent
is clearly the mobile phase while the silica or
alumina is the stationary phase.
• The different components of the sample have
differential affinities for the stationary and
mobile phases.
 • On continued elution (addition of solvent/eluent), the
components with higher affinity for the mobile phase
will pass through the column faster.
• What passes through is often called the eluate.

Gas Liquid Chromatography

• Separation occurs by partitioning a sample between a mobile gas phase and a thin layer
of non-volatile liquid coated on an inert support.
o The gaseous mixture is separated into its components by moving it over a
stationary sorbent.
• A gas chromatograph comprises the basic
following parts:
o Gas supply- this gas cylinder provides a
stream of eluent (the mobile phase, which
is a gas). This is usually an inert gas like
Helium, Nitrogen, Hydrogen or Argon.
o Sample injection system- A very small
sample size (1-10 𝜇𝐿) is injected.
o GLC Column- Contains a liquid phase
(like paraffin oil, glycol) on granular inert support like Celite.
o Detector- Feeds output to a recorder which produces the chromatogram. Includes
thermal conductivity detector and the flame ionization detector.
 • The time a compound spends in a column after it has been injected is called the retention
time.
o This value can be used to identify a compound given the same eluent flow rate
and components of the chromatograph.

Phase Separations
• Phase separation is simply concerned with methods of separating mixtures into their
constituent components, usually through changes of state (the states of matter are also
referred to as phases).
• Distillation is one form of phase separation, along with solvent extraction.
Distillation
• Distillation is a method of separation of components from a liquid mixture which
depends on the differences in boiling points of the individual components and the
distributions of the components between a liquid and gas phase in the mixture.
o It is split into two types, simple distillation and fractional distillation.

Simple Distillation
• This is used to separate:
o Liquid solutions of substances with widely differing boiling points (>25°C).
o Liquids from involatile solids or oils.

• In the apparatus, vapours rise from the solution in the flask being boiled. In simple
distillation, these are pure vapours since the components being separated have such
different boiling points. They pass into the Liebig condenser, which causes them to
condense and pass along as liquid to the conical flask. This deposited condensed liquid is
called the distillate.
 • One component is boiled away while the other remains in the original flask, resulting in
separation.
• It involves a single vaporization/condensation cycle.

Fractional Distillation
• This is used to separate:
o miscible liquids which have close boiling points (<25°C)
o chemically similar components (like ethanol and water)
• It is similar to simple distillation except that a fractionating column is placed between
the flask and the condenser.
o A fractionating column is a vertical tube packed with inert fragments that provide
a large surface area for the vapours rising from the flask to cool, condense and
then vaporise again.
▪ Doesn’t that sound similar to a column in chromatography? The difference
being that chromatography separated based on affinity for the stationary
phase versus the mobile phase, while fractional distillation does so based
on difference in boiling point.
• Fractional distillation involves a series of vaporization/condensation cycles.
o Thanks to the fractionating column, vapour rises up the column then condenses.
When it re-evaporates, it rises further up the column and condenses again.
o With each cycle, the vapour becomes enriched in the component with the lower
boiling point.
o Some condensed liquid which is richer in the less volatile component falls down
the column.
• The motive force for the separation is the drive towards thermodynamic equilibrium
between the different phases.
o This equilibrium is constantly
disturbed by colder descending
liquid and the hotter vapour
rising.
• At equilibrium, a temperature gradient
exists across the length of the column.
• The mode of action of fractional
distillation can be explained with
reference to Raoult’s Law.
Raoult’s Law
• Raoult’s Law states that the vapour pressure of a liquid component of a mixture is equal
to the vapour pressure of the pure liquid at the temperature of the mixture multiplied
by the mole fraction of the liquid present.
o 𝑝𝐴 = 𝑃𝐴0 × 𝑋𝐴
o Vapour pressure is the pressure exerted by the vapour of a liquid in equilibrium
with its liquid phase at a given temperature.
▪ It represents the tendency of a liquid to evaporate, as a higher vapour
pressure corresponds to a lower boiling point, as equilibrium leans
towards evaporation more than condensation. A lower vapour pressure
corresponds to a higher boiling point, as particles of the liquid are less
likely to escape.
o Mole fraction of a particular component of a mixture is the ratio of the number of
moles of that component to the total number of moles in the mixture.
𝑛𝑎
▪ 𝑋𝑎 = 𝑛 +𝑛 for a mixture containing a and b
𝑎 𝑏
• Raoult’s Law however only applies to ideal mixtures.
o An ideal mixture is one where the interactions between molecules of the different
components are the same as those between molecules of the pure substances.
o That is, intermolecular forces between unlike molecules are of equal strength to
those between like molecules.
o A corollary of Raoult’s Law is that for an ideal mixture, the total vapour pressure
of the mixture is equal to the sum of the partial pressures of the components,
𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝𝐴 + 𝑝𝐵

A graph of Vapour Pressure versus Mole Fraction Composition for an ideal mixture.
• For an ideal mixture, the enthalpy of mixing is zero.
o Enthalpy of mixing is the enthalpy change resulting from mixing two substances
due to the formation of intermolecular forces between unlike molecules and
breakage of intermolecular interactions between like molecules.
o Since the energy of the interactions between like and unlike molecules are equal,
the net change in energy is zero.
• No ideal mixture exists, but some are fairly close:
 o Water and methanol
o Propan-1-ol and propan-2-ol
o Butan-1-ol and butan-2-ol
o Hexane and heptane
o Benzene and toluene
Non-Ideal Solutions and Deviations from Raoult’s Law
• The more dissimilar the nature of the components of a mixture, the more the solution is
expected from the ideal.
o No ideal mixture exists, as stated above; as such, vapour composition graphs are
always, in reality, curves.
• Deviations from Raoult’s Law can be categorized as either positive or negative.

Positive Deviation from Raoult’s Law

• The vapour pressure of the mixture is higher than would be expected for an ideal
mixture.
• The boiling point of the mixture is therefore lower than would be expected for an ideal
mixture.
• Interactions between the unlike molecules are weaker than those between like molecules.
o Enthalpy of mixing is positive (endothermic, as more energy is taken in to break
stronger intermolecular forces)
• Deviation can be slight or extreme.

The maximum vapour pressure of the curve occurs at a particular composition called a
positive or pressure maximum azeotrope.
 The graph is essentially flipped to show boiling point. As the A-B interactions are weaker than
A-A or B-B interactions, molecules escape more easily than expected, i.e. at lower temperatures.
The red curve represents vapour composition while the blue curve represents the composition
of the liquid at that temperature.
That minimum point is called a minimum boiling point azeotrope. The vapour composition is
equal to the liquid composition.

Negative Deviation from Raoult’s Law

• The vapour pressure of the mixture is lower than would be expected for an ideal
mixture.
• The boiling point of the mixture is therefore higher than would be expected for an ideal
mixture.
• Interactions between the unlike molecules are stronger than those between like
molecules.
o Enthalpy of mixing is negative (exothermic, as more energy is released to form
stronger intermolecular forces)

The composition at which minimum vapour pressure is achieved is called the negative
azeotrope or the minimum pressure azeotrope.
That maximum point is called a maximum boiling point azeotrope. The vapour composition is
equal to the liquid composition for a mixture of this composition.

Relevance of Raoult’s Law to Fractional Distillation

• Recall that fractional distillation is based on a series of cyclical evaporation and
recondensation aided by a fractionating column to continually enrich the vapour in the
more volatile component.
• The boiling point composition curve on the
right allows us to demonstrate fractional
distillation.
o Firstly, thanks to that gap between
the liquid and vapour composition
curves, the liquid and vapour
compositions differ at one
temperature.
o This means that condensing the
vapours from the liquid of
composition 𝑦 at 𝑇𝑦 will produce a liquid of composition 𝑦1 , which has more of
component B, which is more volatile (lower boiling point).
▪ Think of the horizontal lines as representing evaporation/boiling, and
vertical lines representing condensation, going from left to right and from
top to bottom.
o This process of evaporation and condensing can be repeated to eventually procure
the pure components of the mixture.
• It is not always possible to gain the pure components from a mixture however, if
deviation of the mixture from Raoult’s Law is extreme.
o When thinking about the evaporation-condensation cycle using these composition
graphs, you move from peaks (higher points) to lower points to determine the
composition of the distillate.
 • Look at the graphs following.
The presence of azeotropes
means that at some point,
depending on the starting
composition of the mixture, no
further separation will be
possible since the compositions
of both the liquid and vapour
phases will be equal.
• When there is a minimum
boiling point azeotrope, it is
impossible to attain a pure
substance in the distillate through unaided fractional distillation methods.

• Where there is a maximum boiling point

azeotrope however, it is possible to attain pure
components in the distillate.

• However, in either case, if the mixture given

at the beginning is the azeotrope, no further
separation can occur.

Vacuum Distillation
• This involves carrying out distillation in an environment of reduced pressure (lower
than atmospheric pressure).
o Vacuum distillation is preferred when the compounds being separated are soluble
in water and miscible.
• Boiling occurs when vapor pressure of a liquid or solution equals or exceeds the
external/applied pressure.
o Naturally, if the external pressure is reduced, a lower vapour pressure is required
for boiling, which can be achieved at a lower temperature.
o The boiling point is decreased.
• This is used to separate mixtures of compounds with high boiling points or compounds
that decompose thermally at higher temperatures.
o In the petroleum industry, it is carried out to distil higher boiling point fractions
without causing thermal cracking.
 • Advantages:
o Less energy required for heating.
o Thermal decomposition is avoided for certain compounds.
Steam Distillation
• In steam distillation, temperature sensitive
components immiscible with water can be
separated.
• Steam is introduced into the mixture, but as
steam (water) and the mixture are immiscible,
they both exert vapour pressure as if the other
were absent.
• This increases the total vapour pressure of the
system.
• Since boiling occurs when the vapour pressure of a liquid just exceeds the
ambient/external pressure, the increase in vapour pressure will decrease the boiling
point, allowing distillation to occur at a lower temperature, which is perfect for
compounds that decompose near their boiling points.
• This method is used in separating:
o Eugenol from cloves
o Eucalyptus oil from eucalyptus
o Citrus oils from lemon/orange peel
• In steam distillation, the ratio of the moles of the two compounds in the distillate is equal
to the ratio of their vapour pressures:
𝑛 𝑝
o 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 = 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
𝑛
𝑤𝑎𝑡𝑒𝑟 𝑝𝑤𝑎𝑡𝑒𝑟

Solvent Extraction
• Also called liquid-liquid extraction, this is a technique in which a solution (usually
aqueous) is brought into contact with a second (usually organic) solvent immiscible with
the first, in order to bring about transfer of one or more solutes into the second solvent
based on differential solubility of the desired solute in either immiscible solvent.
• When a solute is shaken with a pair of immiscible liquids, it partitions between the two
liquids based on the partition law, or Nernst’s Distribution Law.
o This law states that, provided that its molecular state is the same in both liquids,
both solutions are dilute and that the temperature is constant, the ratio between
the concentrations of the solute in both solvents will be constant at equilibrium.
o 𝑋𝑎𝑞𝑢𝑒𝑜𝑢𝑠 ⇌ 𝑋𝑜𝑟𝑔𝑎𝑛𝑖𝑐 represents the equilibrium that exists.
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑙𝑎𝑦𝑒𝑟
o 𝑘𝑝𝑐 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑞𝑎𝑢𝑒𝑜𝑢𝑠 𝑙𝑎𝑦𝑒𝑟
o Where 𝑘𝑝𝑐 is the partition coefficient, an equilibrium constant for this system.
 • Solvent extraction is more efficient when a certain volume of the extracting solvent is
used in small successive portions rather than all at once.

Solvent extraction is usually carried out in a separatory funnel as above.

When the layers settle out, the tap can be opened to let out the bottom (denser) solvent.

Procedure
1. The organic compound/product in aqueous solution is shaken up with a small quantity of
organic solvent in a separatory funnel.
a. The tap is opened periodically during the shaking to release pressure caused by
the evaporation of solvent vapours.
b. Any solid impurities are filtered off.
2. The mixture is left to stand, allowing separation of the liquids into two distinct layers,
each of which can be drained separately through the tap. The organic layer, which
contains the organic product dissolved in the organic solvent, is kept and referred to as
the extract.
3. Since trace amounts of the desired organic product still remain in the aqueous layer, the
shaking and separation procedure is repeated at least twice, each time using fresh
solvent. All the product extracts are combined.
a. Recall that solvent extraction is more efficient if the solvent is used in successive
small portions rather than all at once.
4. The organic solvent may then be distilled off, leaving the pure solid.
Locating Industrial Plants
Factors Influencing Location of an Industrial Plant
• Suitability of terrain
• Vulnerability of an area to weather/natural disaster events
• Availability and Proximity of building materials
• Availability of safe disposal systems
• Availability of commodities like water
• Access to sufficient electrical power
• Proximity of skilled workers
• Effect on nearby community- providing employment versus using up productive
farmland.
Health and Safety
• Choosing processes and tools which are inherently safe
• Identifying hazards which cannot be eliminated, and instituting training on how to cope
with it
• Having plans for coping with large-scale emergencies like hurricanes and ensuring staff
has had chance for training and practice
• Ensuring that emergency exits are clearly marked
• Training staff in proper procedures including use of personal protective equipment (PPE)
• Having some staff qualified in first aid

Aluminium
Ore Purification
• Purification of aluminium ore occurs via the Bayer process.
• The constituent of interest of aluminium ore (bauxite) is aluminium oxide, and
amphoteric compound.
o The main impurities of bauxite are iron (III) oxide, silicon dioxide and titanium
oxide.
o Fe2O3 is basic while SiO2 is acidic.
STEP ONE (Digestion)
• Ground bauxite is mixed with hot sodium hydroxide solution in a process called
digestion.
o Amphoteric aluminium oxide reacts with the caustic soda to form soluble sodium
aluminate
 ▪ Al2O3(s) + 2NaOH(aq) → 2NaAlO2(aq) + H2O(l)
▪ Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2NaAl(OH)4(aq)
o Acidic silicon dioxide reacts with the caustic soda to form soluble sodium silicate
▪ SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
o Basic iron oxide remains unreacted and undissolved
STEP TWO (Filtration)
• The insoluble impurities like the iron oxide are filtered out as red mud, and only the
soluble products move on.
STEP THREE (Precipitation)
• The heated filtrate is stirred and cooled, causing the precipitation of aluminium
hydroxide crystals.
o NaAlO2(aq) + 2H2O(l) → NaOH(aq) + Al(OH)3(s)
o A crystal of aluminium hydroxide is usually used to seed the mixture and
jumpstart precipitation.
• Carbon dioxide is also pumped through the solution to trigger precipitation.
o 2[Al(OH)4]-(aq) + CO2(g) → 2Al(OH)3(s) + CO32-(aq) + H2O(l)
STEP FOUR (Filtration)
• The silicates remain in solution, leaving aluminium hydroxide (hydrargillite) crystals.
STEP FIVE (Calcination)
• The filter residue is heated in a rotary kiln at 1100 to 1300 degrees Celsius, which drives
off water, leaving near pure aluminium oxide (alumina).
o 2Al(OH)3(s) → Al2O3(s) + 3H2O(l)

Production
• This occurs through the Hall-Heroult Process.
o This process is essentially hydrolysis of the molten alumina.
o Alumina melts at 2050 degrees Celsius, which is very high and requires a lot of
power.
o This melting point can be decreased to around 960 degrees Celsius by dissolving
alumina in molten cryolite
(NaAlF6) and fluorspar (CaF2).
This also increases conductivity.
• The aluminium oxide is thought to
dissociate into aluminium ions and oxide
ions in solution.
• At the cathode (carbon lining), the half
equation is: O2-(l) + C(s) → CO(g) + 2e-
 • At the anode (carbon rods), the half equation is: Al3+(l) + 3e- → Al(l)
• The molten aluminium can then be let off through the outlet.
Aluminium Uses
• Physical properties include:
o Lustrous, silvery white colour
o Lightweight
o Relatively soft and malleable
o Low density
o High thermal and electrical conductivity
o Highly reflective when polished
• Chemical properties include:
o Natural formation of a thin coating of aluminium oxide on the surface on
exposure to air, which protects it from further oxidation (resistant to corrosion).
o Easily recyclable (100%)
Property Usage
Non-toxic Used for cans and food-grade packaging
Resistant to corrosion Used in window frames and kitchen utensils
Highly reflective under certain conditions Used in telescope mirrors and firefighter
garments
Thermally conductive Pots and pans
Lightweight Alloyed with Copper, manganese, magnesium
or silicon for use in the bodies of aircrafts and
spacecrafts

Environmental Effects of Aluminium Industry

• The red mud produced during extraction of aluminium oxide form bauxite in the Bayer
Process (1 tonne for each tone of alumina produced) is caustic, and can percolate into
groundwater of local areas.
o Sodium concentration and pH are increased.
• Fluoride gases are produced from the discharge of the cryolite in the electrolyte during
the Hall-Heroult Process.
o About 2% of the gases escape into the atmosphere, causing damage to plants and
entering the food chain.
• Perfluorocarbons, sulphur dioxide, carbon dioxide and carbon monoxide are
produced by the process, all of which are potent greenhouse gases, contributing to
global warming.
• The mining of bauxite is often preceded by destruction of vast areas of greenery and
vegetation or forests. This affects many habitats and wildlife.
o The final result of bauxite mining is a stripped landscape with a large empty pit.
o This can affect water flow across the landscape as well as aesthetic appeal.
 • Disposal of the used carbon cell linings is also a concern, as these contain highly alkaline
solutions, aluminium carbides, and cyanides, which may end up in landfills.

Crude Oil
Separation Method
• The separation of crude oil occurs through fractional distillation.
• Hydrocarbons, mainly alkanes, are the main and most important components of crude
oil. Longer chain hydrocarbons have higher boiling points than shorter chain
hydrocarbons.
o Since crude oil contains alkanes with chain lengths from 1 carbon to over 70, the
components can be separated based on their differences in boiling points.
• Industrial fractional distillation of
crude oil involves heating the oil at
the base of the fractionating column
to 300°C.
• The liquid that doesn’t boil is
simply piped off as residues. This
is the heaviest fraction.
• The rest of the liquid, which boils,
rises as vapours through the
fractionating column, across which
there is a temperature gradient- the
top being the coolest.
• A hydrocarbon compound will
condense when it reaches a part of
the column that is below its boiling
point, where is will be collected and
piped off.
• The vapours which don’t condense
are piped off at the top as refinery
gases. This is the lightest fraction.
The Fractions of Crude Oil and their Uses
Carbon Chain
Fraction Boiling Range Uses
Length
Refinery Gases <5°C C1 to C4 LPG for cooking
High octane gasoline,
Naphtha 20-180°C C5 to C9
diluting bitumen
Fuel for motor
Gasoline (Petrol) 40-200°C C5 to C10
vehicles
 Fuel for jet engines,
Kerosene (Paraffin
150-260°C C10 to C16 kerosene lamps
Oil)
(domestic heating)
Fuel for diesel
Diesel (Gas Oil) 260-340°C C14 to C20 engines (cars and
large vehicles)
Lubrication, wax,
polishes, candles,
Lubricating Oil >370°C C20 to C50
solvent for petroleum
jelly
Paraffin Wax >C40 Insulation
Road surfacing,
Bitumen/Tar/Asphalt >C70 waterproofing and
sealing

Reforming
• Reforming is a process in which straight-chain hydrocarbons (with a low octane rating)
are broken up and then reassembled into aromatic and branched-chain hydrocarbons
(with a high octane rating).
• These ‘higher octane ratings’ (meaning more highly branched compounds) are more
resistant to knocking, or the premature combustion of fuels in an engine implicated in
engine damage and overheating.

Environmental Impact
• All stages of the crude oil industry- exploration, extraction , transportation, refining and
use- are major sources of pollution.
• Exploration, or the search for crude oil, has significant impact on the environment.
o Seismic surveys are used to determine underground oil deposits. These surveys
require shock waves which are usually generated using explosions in the ocean or
underground.
▪ This destroys ecosystems and wildlife.
o Exploratory wells are drilled at prospective oil sites. If no oil is found, they can
sometimes be left abandoned.
• Extraction is the procurement of oil from the oil deposit discovered in the well.
o The surrounding land is cleared and levelled, which destroys flora, fauna and
habitats.
o If no water is nearby, large water wells are drilled, which is highly damaging.
o Well drilling expels both brine and oil into surrounding soil and water, which
damages plant life and aquatic life.
 • Transportation is also a potential environmental hazard.
o Oil tanker spills kill marine life and contribute to reduce air quality if they catch
ablaze.
▪ Birds can also be affected if the oil reaches their feathers.
▪ Coral reefs are killed due to blockage of sunlight.
▪ Polar bears freeze to death when they lose insulation due to their fur
being stuck down by oil.
o April 20th 2010, an explosion on the Deepwater Horizon drilling rig killed 11 of
the 126 crew members and spilled about 4.9 million barrels of oil into the Gulf of
Mexico.
• Refinery process releases toxic and hazardous air pollutants (many of which are
greenhouse gases).
o Carbon monoxide
o Nitrogen Oxides
o Benzene, toluene, ethylbenzene and xylene (BTEX compounds)
• Use of petroleum fractions as fuels releases compounds like carbon dioxide and
nitrogen oxides into the environment.

Ammonia
Production/Haber Process
• The Haber Process can be simplified as a reaction combining hydrogen and nitrogen to
form ammonia:
o N2(g) + 3H2(g) → 2NH3(g), Δ𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1 (exothermic reaction)

• Hydrogen gas is obtained via steam reforming, that is, reacting methane with steam
o CH4(g) + H2O(g) → CO(g) + 3H2(g)
o Nickel catalyst at 700-1100°C and 20 atm.
• Additional hydrogen is recovered from the steam through the water gas shift reaction.
o CO(g) + H2O(g) → CO2(g) + H2(g)
o Nickel oxide catalyst at 130°C.
• Nitrogen gas is procured from the fractional distillation of liquified air.
 • The purified nitrogen and hydrogen gases are the mixed and compressed to 150-250 atm
and passed over an iron catalyst at temperatures around 400°C.
o This combination produces a 10% yield of ammonia.
• The equilibrium gas mixture leaves the reactor, where it is then cooled.
o Ammonia condenses (as it has a much higher boiling point), but the nitrogen and
hydrogen remain gaseous, and can be recycled into the reactor while the
ammonia is piped off.
o Thanks to the recycling of gases, a ~97% yield can be obtained by maintaining
the position of the equilibrium to the right.
Explaining the Equilibrium Conditions
• N2(g) + 3H2(g) → 2NH3(g)
• The equilibrium needs to be shifted to the right to increase the yield.
• Le Chatelier’s principle (which states that if dynamic equilibrium is disturbed by a
change in conditions, the position of the equilibrium will shift to oppose the change in
conditions) allows us to determine the conditions necessary to produce the highest
theoretical yield.
o 4 moles of reactants gives 2 moles of reactants, so high pressures will shift the
equilibrium to the right. This is why high pressures are used in the Haber process.
▪ Though this is limited because high pressures are expensive to maintain,
and requires costly, high maintenance equipment.
o The reaction is exothermic (releases heat), and as such, lower temperatures will
shift the equilibrium to the right. However, low temperatures also slow the rate of
reaction.
▪ The reaction must proceed at a viable rate, and so, temperatures are kept
moderately high.
Uses of Ammonia
• Agriculture: Production of nitrogen fertilizers (usually as ammonium
nitrate/sulphate/phosphate by reaction with acids), which provide nitrogen in soluble
form to support plant growth.
• Chemical Industry: manufacture of nitric acid, plastics, pharmaceuticals, commercial
and household cleaners (like glass cleaner!)
• Ammonia is also used in the food and beverage industry as a nitrogen source for yeast
• Used as a refrigerant gas
Impact of Ammonia Industry on the Environment
• Carbon dioxide from the steam-reforming process is emitted, however it is often used in
urea production.
• The catalysts used in ammonia production need to be replaced every 2-6 years, which
can be an issue if not properly recycled.
• The use of ammonia in agriculture can be an environmental hazard:
 o Excess fertilizers entering natural waters results in eutrophication. This ends in
death of aquatic organisms.
o Fertilizer runoff can enter domestic water supply, polluting drinking water.
Nitrates of fertilizers are poisonous, especially to babies.
o Soil acidification results when ammonium ions in the soil are nitrified by
bacteria, releasing hydrogen ions. This acidity can af6fect plant growth.
o Smog particles are formed when ammonia combines with nitrogen oxides and
sulphur dioxides in the atmosphere

Ethanol
Production of ethanol occurs by fermentation of sugars, followed by distillation to increase the
concentration of ethanol produced.
Production/Fermentation
• Fermentation is the process by which sugars are oxidized by living organisms in the
absence of oxygen to release energy.
o Yeast (Saccharomyces cerevisiae) is a unicellular fungus which releases ethanol
and carbon dioxide as products of anaerobic respiration.
• Yeast is combined with a solution containing sugars and a nitrogen source (like
ammonia). The solution is kept in a fermenter under anaerobic conditions (oxygen
absent).
o The temperature is kept at a fairly low 25°C, as temperatures too high or low
adversely affect the activity of enzymes in the yeast.
o When ethanol concentration reaches 12-15% however, the activity of the yeast
stops as the enzymes are denatured by the toxic ethanol.
• To increase the concentration of alcohol in the solution to the wonderfully deleterious
levels found in spirits (even up to 40% alcohol by volume), fractional distillation must
be carried out.
Fractional Distillation
• We already discussed fractional distillation in a previous section.
• Ethanol is being separated from a mixture with water.
o Since these two compounds have boiling points within 25 degrees Celsius of each
other (water 100°C versus ethanol at 78.5°C), fractional distillation must be used.
• The mixture of ethanol and water has a minimum boiling point azeotrope (78.2°C) at
95.6% ethanol and 4.4% water however, meaning that the maximum concentration of
ethanol that can be procured from the 15% ethanol solution is 95.6% ABV.
• Absolute, or pure ethanol can be procured from the azeotropic mixture by combining
the azeotrope with an additional agent (called an entrainer) like cyclohexane.
o The resulting ternary azeotrope can be distilled to attain the pure ethanol.
Uses of Ethanol
Fuels
• Ethanol has a very clean (non-smoky) and exothermic combustion. As such, it is used as
a fuel additive.
o For example, E85 is a mixture of 85% ethanol and 15% gasoline commonly used
in many vehicles and gas-powered equipment.

Alcoholic Beverages
• This is the most familiar use of ethanol. Alcoholic beverages are the most commonly
consumed drugs.

Solvents
• Ethanol is used as a solvent for dissolving many organic compounds, including
pharmaceuticals, cosmetics, perfumes and paints
• It is also used as a disinfectant for wounds thanks to its antiseptic properties.

Social and Economic Impact of Alcohol Consumption

• Alcohol, when ingested in the form of alcoholic beverages for example, acts as a
depressant on the central nervous system.
• Small quantities of alcohol in the blood can cause pleasurable feelings of euphoria, and
relaxation of inhibitions.
• Short term physiological effects of alcohol consumption include:
o Loss of social inhibitions
o Slurred speech
o Slower response times and reflexes
o Memory loss
o Impaired communication
o Loss of consciousness
• Long term health effects of alcohol consumption include:
o Nervous disorders including Wernicke-Korsakoff Syndrome
o Increased risk of cardiovascular diseases
o Liver cirrhosis
• Blood alcohol level exceeding 0.45% is likely to result in death.
• Drinking in pregnant women can contribute to intrauterine growth retardation and foetal
alcohol spectrum disorder (adverse developmental effects on the baby)
Chlorine
Production
The Diaphragm Cell
• The production of chlorine occurs through the electrolysis of brine, a saturated solution
of sodium chloride.
o This process generates chlorine, sodium hydroxide and hydrogen.
• The ions present in brine solution are Na+, Cl- (from sodium chloride), H+ and OH- (from
the dissociation of water)
• At the anode, hydroxide ions would be preferentially discharged if not for the high
concentration of chloride ions. As such, chloride ions are discharged to produce
chlorine gas:
▪ 2Cl-(aq) → Cl2(g) + 2e-
o However, some (very few) hydroxide ions are also discharged, producing oxygen
gas as well:
▪ 4OH-(aq) → 2H2O(l) + O2(g) + 4e-
o The chlorine gas is thus contaminated with some oxygen gas, and must be
purified.
• Sodium ions and protons are attracted to the cathode. Protons are preferentially
discharged instead of sodium ions, leading to the production of hydrogen gas:
o 2H+(aq) + 2e- → H2(g)
• What is left in solution are sodium ions and hydroxide ions which are less likely to be
discharged.
o As such, sodium hydroxide is produced throughout the process.
 • Electrolysis is carried out in a diaphragm cell, which separates the anode and cathode
into compartments using a diaphragm made of a porous asbestos and polymer-fibre
mixture.
o The solution can pass between the compartments, but gases are kept apart.
▪ This separation of gases is necessary because a mixture of hydrogen and
chlorine gas can react explosively to form hydrogen chloride in the
presence of sunlight or UV radiation.
o The level in the cathode compartment is also kept lower than in the anode
compartment.
▪ This is so that the flow of solution can only occur from anode to cathode.
This ensures the chlorine gas doesn’t react with sodium hydroxide
formed, as this would produce a mixture of sodium chloride and sodium
hypochlorite, which may not be the desired products.
• As can be seen in the diagram, brine is piped into the anode compartment, chlorine is
piped off from the anode compartment, hydrogen is piped off from the cathode
compartment, and sodium hydroxide solution contaminated with sodium chloride is
drained from the anode compartment as well.
o Sodium chloride can be crystallized out of the contaminated sodium hydroxide
solution, after which the sodium hydroxide can be used as its own product and
sodium chloride can be recycled into chlorine production.

Alternative Methods of Production

Membrane Cell
• Similar to the diaphragm cell
except that the diaphragm is
replaced with a membrane
impermeable to anions while
remaining permeable to cations
like sodium.
o The membrane is made of
PTFE
(polytetrafluoroethylene)
mainly, preventing
chloride ions from
migrating from the anode
chamber to the anode
chamber.
o This ensures that the sodium hydroxide produced is not contaminated by
sodium hydroxide.
Mercury (Castner-Kellner) Cell
• The cathode is flowing mercury, which discharges sodium ions but reacts with the
resulting sodium metal to form mercury amalgam.
Advantages and Disadvantages
Method Advantages Disadvantages
Requires higher voltage.

Requires higher purity brine

Produces high purity, high solution.
Mercury Cell
concentration NaOH (50%)
Mercury release to the
environment is highly
hazardous.
Operates at a lower voltage
than mercury cell.
Alkali is slightly impure.
Brine can be low purity.
Diaphragm Cell
Asbestos may be released,
Asbestos is chemically stable, which is a known carcinogen.
relatively inexpensive and
abundant.
Very pure NaOH produced.
Brine must be high purity.
Uses less electricity.
Membrane Cell
NaOH is of lower
Non-toxic membrane and concentration (~32%)
materials.
Industrial Importance of Chlorine
Bleaches
• Chlorine based bleaches are used due to their powerful oxidizing action.
• They are used to whiten clothing, remove stains, disinfect surfaces and sterilize water.

PVC (Polyvinyl Chloride)

• Used in producing piping, insulation, window frames, clothing, bags, etc.

Solvents
• Chlorine is a substituent in common organic solvents like tetrachloromethane (now
phased out due to environmental risk) and chloroform.

Aerosols and Refrigerants

• Chlorofluorocarbons (CFCs) were primarily used as solvents, refrigerants and propellants
in aerosols. Similar to CCl4 however, they have been phased out for their deleterious
environmental impact, especially to the ozone layer.

Anaesthetics
• Halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) is a commonly used inhalational
anaesthetic.

Impact of the Chlor-Alkali Industry on the Environment

• Chlor-alkali plants using the diaphragm cell can sometimes release asbestos if it is not
properly handled. The inhalation of asbestos causes lung cancer over long periods.
• Those plants using the Castner-Kellner cell (mercury cell) can sometimes release
mercury into the environment.
o Mercury is toxic, and tends to bioaccumulate when introduced into ecosystems.
• PVC is non-biodegradable, and extended exposure to the elements causes PVC to emit
toxic pollutants which may enter water supplies.
• The burning of PVC releases toxic pollutants called dioxins, which create developmental
and reproductive issues.

Sulphuric Acid
Production
• Production of sulphuric acid occurs through the Contact Process.
• It has four main stages:
o Production of sulphur dioxide
o Oxidation of sulphur dioxide to sulphur trioxide
o Hydration of sulphur trioxide to oleum
 o Dilution of oleum to concentrated sulphuric acid

Step 1: Production of Sulphur Dioxide

• Sulphur dioxide is produced by one of two methods:
o Burning of sulphur in excess air:
▪ S(s) + O2(g) → SO2(g)
o Heating of sulphide ores like pyrite in excess air:
▪ 4FeS2(s) + 11O2(g) → 2Fe2O3(s) +8SO2(g)
• This all occurs at 1000°C.

Step 2: Oxidation of Sulphur Dioxide to Sulphur Trioxide

• The sulphur dioxide is cooled to ~450°C, mixed with air, then purified through gas filters.
• The sulphur dioxide and air mixture is then passed over a vanadium (V) oxide in silica
gel catalyst to form sulphur trioxide.
o 2SO2(g) + O2(g) ⇌ 2SO3(g)
o Δ𝐻 = -197 kJmol-1
• The vanadium (V) oxide catalyst is organized into layers of pellets to increase surface
area available for the gases to react on.
Equilibrium Conditions
• As the reaction is exothermic (releases heat), to shift the equilibrium to the right (by Le
Chatelier’s principle), the gases are cooled back to 450°C using a closed water circuit.
This is the lowest temperature that can be used without reducing the rate of the
oxidation reaction to uneconomical levels.
• 3 moles of gaseous reactants give 2 moles of gaseous products. As such, it is expected
that to shift the equilibrium to the right, higher pressures would be required.
o Higher pressures are not used because sulphur dioxide liquifies at elevated
pressures, and the cost of equipment and maintenance would be uneconomical.
o Near atmospheric pressure is used instead.
▪ A 99.5% conversion rate is achieved nonetheless, showing that the
improvement of increased temperatures is not worth the cost.

Step 3: Hydration of Sulphur Trioxide

• The hydration of sulphur trioxide does produce sulphuric acid (as SO3 is its acid
anhydride)
o The direct reaction is highly uncontrollable and exothermic, creating large
plumes of sulphuric acid spray instead of a solution.
o These plumes are highly dangerous, as they are corrosive to flesh and organic
matter, and cause blindness if they reach the eyes.
• Instead, hydration of sulphur trioxide is done indirectly, with the formation of an
intermediate called oleum, or fuming sulfuric acid.
 • The SO3 gas is dissolved in a solution of concentrated sulphuric acid to form oleum.
o H2SO4(l) + SO3(g) → H2S2O7(l)

Step 4: Dilution of Oleum

• The oleum is slowly diluted with water with continuous cooling to form concentrated
sulfuric acid.
o H2S2O7(l) + H2O(l) → 2H2SO4(l)

The above has some intermediary cleaning and drying steps that weren’t fully explained, but the
principle is the same.

Industrial Importance of Sulphur Compounds

• Sulphur dioxide is used as a bleaching agent for paper, sugar and flour, and as a
preservative in alcoholic drinks and dried fruits.
o And, as we saw above, the production of sulphuric acid!
• Sulphuric acid is used in the manufacture of fertilizers (combined with ammonia), dyes,
detergents, explosives, car batteries…
 • Sulphate salts
o Magnesium sulphate is a laxative
o Sodium sulphate is a drying agent

Impact of the Sulphuric Acid Industry

• Sulphur dioxide emissions during the production of sulphuric acid contribute to acid
rain.
o Some of it is recycled however, by reacting it with a solution of sodium or
ammonium hydroxides.
• In the case of sulphuric acid spills during transportation, the reaction of the acid with
metals can produce hydrogen gas (explosive).
• Sulphuric acid is used as a catalyst in the chemical industry, and is easily recyclable when
spent.

Water
Importance of the Water Cycle
• The water cycle or hydrological cycle is the cyclical process of evaporation and
condensation of water on the surface of the Earth.

• The water cycle is a self-purifying system that helps to maintain ecological balances.
Water is necessary for
o Drinking
o Domestic purposes
o Photosynthesis
o Digestion
o Excretion
o Agricultural Use
 o Solvent Use
o Industrial Use
o Electricity Generation
Methods of Water Purification
• Filtration is a very common method of water purification utilized in household and
small-scale settings. It involves mechanical separation of solids from water.
o Screen filters are made of metal, plastic or fibre to remove large debris.
o Carbon filters are made of pieces of charcoal activated with a positive charge,
allowing the removal of sediments, organic compounds and chlorine.
o Sand filters- made of layers of sand or other particulate materials.
o Membrane filtration- semi-permeable membrane coupled with high pressures,
which removes microscopic organisms and particles.
• Desalination- the removal of salts from sweater to produce fresh water for other use.
o Flash distillation
o Electrodialysis
o Ion exchange
o Reverse Osmosis
o Freeze Desalination
• Chemical Treatment
o Step 1: Clarification
▪ Coagulant (like aluminium sulphate) added to the water which causes
particulate contaminants to flocculate into larger particles which can be
easily filtered.
o Step 2: Disinfection
▪ Water is treated with chlorine or another disinfectant like bleach or ozone.
▪ This does not work against certain chlorine-resistant protozoans like
Giardia or Cryptosporidium, and the chlorine may form carcinogenic
compounds with organic materials in the water.
▪ Residual disinfectant may also remain in the water.
• UV Radiation
o UV radiation acts as a mutagen which is able to irreversibly damage the DNA of
organisms, rendering them incapable of causing harm.
Importance of Dissolved Oxygen to Aquatic Life
• Aquatic life relies on dissolved oxygen (DO) in the water for respiration, a process
essential for the continuation of life.
o Without adequate dissolved oxygen, aquatic animals will die as they will be
unable to carry out aerobic respiration.
• Oxygen gets into rivers, lakes and the sea through:
o Diffusion through the water surface from the air
o Diffusion from bubbles of trapped air or from photosynthesis of aquatic plants.
o Process of photosynthesis
 • The amount of DO in water depends on several factors:
o Temperature and pressure- higher temperature and lower pressure decrease
DO.
o Salinity- Saltwater has a lower DO content than freshwater.
o Stagnation- Stagnant water has less DO than flowing water.
o Bacterial content- these organisms remove oxygen from water.
• At DO levels of 3-5 ppm (parts per million), aquatic life is put under stress, and below 2
ppm, organisms start to die.
Sources of Water Pollution
• Water pollution is the discharge of pollutants and contaminants into bodies of water
without suitable treatment to remove unsafe compounds.

Pollutant Source
Nitrates Leaching of fertilizers
Leaching of fertilizers and phosphates from
Phosphates
detergents
Mercury from the chlor-alkali industry and
dumping of fluorescent bulbs
Heavy Metals
Lead from old water pipes and petrol
Cadmium from batteries
From metal extraction industries (silver, gold,
Cyanides
iron, steel)
Aluminium from clay extraction, trace
Other Metals
elements leaching through soil, nuclear waste
Pesticides and herbicides (like DDT) Washing from crop fields into water bodies
Petroleum residues Oil spills
Particles of clay and other materials washed
Suspended particles
from quarries, construction sites and homes

Experiments for Certain Pollutants in Water

Pollutant Test Positive Result
Add aqueous sodium hydroxide, then add
Ammonia gas released,
either zinc or aluminium powder
Nitrates which turns wet red litmus
blue
Warm gently.
Acidify with concentrated nitric acid and
add aluminium molybdate. Bright yellow precipitate
Phosphates
formed.
Warm gently.
 On addition of HCl, presence
of a white precipitate that
Add 1M hydrochloric acid.
redissolves in hot water.
Lead Ions
Add aqueous potassium iodide to
On addition of KI, bright
acidified water.
yellow precipitate formed.

Add iron (II) sulphate to the solution then A deep blue coloration
Cyanide
acidify with hydrochloric acid. (complex ion) is formed.

• Turbidity is the cloudiness of a mixture due to the presence of suspended particles.

o Testing for this is not a chemical experiment but a physical one.
o A turbidity tube can be used, or a nephelometer which measures the light
scattered from a sample.
Impact of Pollutants on the Aquatic Environment
• Nitrates and phosphates from the leaching of fertilizers can cause eutrophication in
water bodies. Eutrophication directly leads to the death of aquatic organisms through the
deprivation of dissolved oxygen.
• Heavy metals like mercury and lead can cause poisoning when ingested either directly
(from contaminated water) or indirectly (consuming an animal that has fed in a mercury-
contaminated ecosystem)
• Cyanides are highly toxic respiratory inhibitors which can cause death in small
quantities.
• Pesticides and herbicides like DDT can be toxic to aquatic life, and tend to
bioaccumulate in top carnivores.
• Suspended particles increase turbidity of the water, and can block the passage of light to
photosynthesizing aquatic flora.

The Atmosphere
The atmosphere is the blanket of air surrounding Earth held in place by the force of gravity.

How Ozone Concentration is Maintained

• Ozone (O3) is formed naturally by the action of UV light on oxygen in the stratosphere
(20-50km above earth).
o This reaction is a photodissociation reaction, in which light causes bond
breaking.
• The bond energy of O=O (the oxygen molecule) is 498 kJmol-1, which, by the equation
E=hf, corresponds to a frequency around 1015 Hz (within the UV range)
 o This means that the oxygen molecule can absorb UV radiation from the sun, and
this sometimes leads to the homolytic cleavage of the oxygen-oxygen bond.
o As oxygen has a double covalent bond, its homolytic cleavage forms di-radicals,
i.e. with two unpaired electrons:

• The oxygen radicals can then either:

o Recombine to form oxygen molecules (the reverse of the reaction above) OR
o Form a dative bond with a lone pair of electrons on an atom of an oxygen
molecule, forming ozone.

Resonance forms of ozone

• Ozone molecules also break down in UV light to reform the products.
• When no other factor is contributing to ozone decomposition, the formation of ozone is in
balance with the rate of breakdown of ozone, which maintains the concentration of
ozone in the stratosphere.
Significance of CFCs in the Ozone Layer
• Chlorofluorocarbons (CFCs) are commonly used as refrigerants, solvents and aerosol
propellants. While not harmful in their normal state (within the troposphere), upon rising
to reach the stratosphere, they cause severe damage to the ozone layer.
• CFCs interact with UV radiation, and, similar to oxygen molecules, undergo homolytic
cleavage at the C-Cl bond, which is the weakest (and most polar) in the molecule.
o This mechanism follows an initiation-propagation-termination pathway
(remember module 1?)
o This is the initiation step, and it forms a chlorine radical.
 o Next is the propagation step, where the chlorine radical reacts with ozone to
form the chlorine monoxide (ClO) radical and oxygen gas (degrading
ozone).

o ClO then reacts with ozone once more to form oxygen and reproduce the
chlorine radical. Chlorine acts as a catalyst as it is regenerated.

o ClO may also simply react with an oxygen radical to form the chlorine radical
and oxygen:

• Each chlorine radical (from a single CFC molecule) can catalyse the breakdown of about
100000 ozone molecules before a termination reaction occurs (simply a reaction
between two radicals).
Effects of Ozone on Human Life
Ozone in the Stratosphere
• The reactions involving the photo-activated formation and destruction of ozone rely on
absorption of light in the UV range of the sun’s radiation, and as such, absorbs
significant amounts of potentially harmful UV light.
o Recall that UV light, in excessive dosages, can damage the genetic material of
organisms.
o Increased UV exposure is linked to higher incidence rates of skin cancer and
cataracts in humans
• Ozone helps to exclude UV radiation. However, absorption of UV radiation from the sun
by the skin is necessary for about 90% of the Vitamin D production of the human body

Ozone in the Troposphere

• Ozone in the layer of the atmosphere right above earth’s surface is a respiratory irritant
and has some linkages to higher incidence of cardiovascular diseases.
• Ozone also contributes to the production of photochemical smog.
 o Nitrogen dioxide produced by car exhausts can undergo photolytic reactions in
the presence of UV light. Ozone is formed and NO2 is reproduced:

Importance of Maintaining Carbon Dioxide Concentration in the

Atmosphere
• The carbon cycle describes the movement of carbon between carbon reservoirs and
carbon sinks.
o There is a balance between the release of carbon from these reservoirs and the
uptake of carbon into those same reservoirs.
• The atmosphere is the most rapidly fluctuating carbon reservoir of them all.

Releasing CO2 into the Atmosphere Uptake of CO2 from the Atmosphere
Photosynthesis/Carbon fixation by plants and
Respiration (CO2 is a waste gas)
some bacteria.
Fuel Combustion (combustion reactions
release CO2 and H2O when complete)
Decomposition of organic matter
Release of CO2 from oceans (especially upon
Dissolution of CO2 in oceans (the reverse
warming)
reaction on the left)
2HCO3-(aq) ⇌ CO2(g) + H2O(l) + CO32-(aq)
Volcanic activity
As can be seen in the carbon cycle above, removal and adding of CO2 to the atmosphere occurs
in a cyclical nature.
Photosynthesis and respiration are balanced and the uptake and release of CO2 from oceans
is also balanced. If this balance is not disrupted, the level of CO2 in the atmosphere can remain
constant.
• Deforestation and combustion of fossil fuels are putting the carbon cycle out of balance.
o Deforestation reduces the global rate of photosynthesis by eliminating plants,
which is one of the only ways carbon is taken up from the atmosphere.
o Fossil fuel combustion causes the release of carbon dioxide.
o Global warming increases the temperature of oceans and shifts the equilibrium
of bicarbonate dissociation and formation in the direction of dissociation and
release of CO2.
• Reforestation efforts are necessary to restore the balance between photosynthesis and
respiration.
Some Definitions
Greenhouse Effect
• This is the phenomenon wherein radiation from the sun reflected from the earth as
longer-wave infrared is absorbed by certain greenhouse gases in the atmosphere which
re-radiate this energy back to earth’s surface (rather than allowing it to pass into space) to
contribute to warming of the earth.
Global Warming
• Global warming is the gradual increase in the temperature of earth’s surface as
contributed to by the greenhouse effect.
• Global warming is actually a major contributor to habitable conditions on earth, as
without it, the surface would be too cold for life to exist. It is the enhanced global
warming due to the emission of many greenhouse gases into the atmosphere (CO2, CH4,
CFCs, water vapour) which causes today’s concerns.

Photochemical Smog
• This is a mixture of pollutants (seen as a brown haze) that are formed when nitrogen
oxides and volatile organic compounds (VOCs) react in the presence of sunlight.
• Recall from above:

• Reactions of radicals (nitrogen oxide

and oxygen included) with
hydrocarbon compounds (VOCs)
released into the air cause the
formation of aldehydes, ketones and
PAN (peroxyacetylnitrate)
Effects of Products of Combustion of Hydrocarbon-Based Fuels
• The main products of the combustion of hydrocarbon based fuels are:
o Carbon monoxide
▪ This binds irreversibly with haemoglobin in the blood, out-competing
oxygen. This has adverse health effects like headaches, nausea, light-
headedness and potentially death.
o Sulphur dioxide
▪ Forms acid rain when it enters the upper atmosphere
▪ Causes respiratory and eye irritation
o Nitrogen oxides
▪ These are respiratory irritants which also contribute to the formation of
photochemical smog
▪ Their emission can be reduced using a catalytic conversion in vehicles.
▪ NO is considered a primary pollutant, which means it is directly emitted
from a source.
▪ NO2 is considered a secondary pollutant, as it forms from a reaction in
the atmosphere (oxidation). Secondary pollutants include ozone, PAN and
acid rain as well.
o Lead (A common addition to fuel to reduce knocking)
▪ Cause neurological and gastrointestinal problems.
o Volatile Organic Compounds
▪ Can be carcinogenic, or harmfully impact reproduction and development
Atmospheric Concentrations of the Oxides of Nitrogen
Nitrogen Cycle
• Nitrogen concentration in the atmosphere is regulated via the nitrogen cycle, which
involves the cyclical fixation of nitrogen into soil and dissolved media followed by
release into the atmosphere.

Releasing N2 into the Atmosphere Uptake of N2 from the Atmosphere

Denitrification, carried out by mainly
anaerobic bacteria to reduce nitrates in soil Haber process
and water to nitrogen gas.
Oxidation of ammonia/ammonium ions by Lightning, it produces high temperatures and
certain bacteria catalyses the formation of nitrogen oxides.
Combustion engines, as the high temperatures
and pressures can also catalyse the formation
of nitrogen oxides (NOx)
• The Haber process and the action of combustion engines have been new introductions to
the earth’s atmosphere, and have upset the balance of the nitrogen cycle, but not to a
deleterious degree.
o The true concern is the prevalence of nitrogen oxide compounds in the
atmosphere.

Recycling of Nitrogen Oxides

Reactions during thunderstorms and in car engines:
N2(g) + O2(g) → 2NO(g)
N2(g) + 2O2(g) → 2NO2(g)
Nitrous Oxide (N2O) is released along with N2 gas during the denitrification pathway.
 In the stratosphere, on exposure to UV light:
N2O(g) → NO(g) + N•(g)
N2O(g) → N2(g) + O•(g)
Nitric oxide (NO) can again be formed:
N2O(g) + O•(g) → 2NO(g)
This NO can catalyse the breakdown of ozone or undergo other reactions to form NO2.

Acid Rain
• Acid rain describes rain with a pH below 5, formed from the reaction between oxides of
sulphur and nitrogen in the atmosphere reacting with water vapour.
• Sulphur dioxides come from the burning of impure fuels containing sulphur, as well as
from volcanic eruptions.
Formation of Acid Rain
The formation of acid rain occurs in two stages, oxidation and deposition.

Oxidation
• This involves the oxidation of SO2 and NO2 to form acidic gases SO3 and NO2.
• Oxidation of SO2 can be catalysed by NO2 or by free radicals
o SO2(g) + NO2(g) → SO3(g) + NO(g)
▪ This reaction is followed by the regeneration of NO2:
2NO(g) + O2(g) → 2NO2(g)
o Oxidation with oxygen free radicals or ozone:
SO2(g) + O3(g) → SO3(g) + O2(g)
o Oxidation to sulphates by OH• (formed by the action of oxygen radicals with
water)
OH•(g) + SO2(g) → HSO3•(g), which is then oxidized to sulphuric acid.
• Nitric Oxide can also react with oxygen radicals or ozone to form acidic NO2 gas
 o NO(g) + O•(g) → NO2(g)
Acid Formation/Deposition
• This is simply how the acids form through reaction with water.
• Deposition can occur as dry deposition or wet deposition.
• Wet deposition- NO2 and SO3 react with water vapour in the atmosphere to form dilute
solutions of nitric, nitrous and sulphuric acid, which fall with the rain as acid rain.
o SO3(g) + H2O(l) → H2SO4(aq)
o 2NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq)
• Dry deposition- small particles of sulphates and nitrates can form in the atmosphere
when the acids react with ammonia in the atmosphere.
o These compounds and dry SO2 and SO3 gases can then react with water on moist
surfaces like wet buildings to form acids.
Methods of Control and Prevention of Atmospheric Pollution
Prevention
Alternative and Cleaner Fuels
• Biofuels are common alternative fuels which do not disrupt the carbon cycle. The waste
products from the production of biofuels (plants) can be reduced, reused and recycled.
o Examples of biofuels include biodiesel, ethanol, gasohol and biogas
• Fuel cells are electrochemical cells which convert some form of chemical fuel (like
hydrogen) into electrical energy.
o They only produce heat and water as waste products, making them essentially
zero emission fuel sources
o The hydrogen they require must be acquired through production like steam
reforming and electrolysis, which are both energy consuming.
Particular Technology
• Catalytic converters use platinum-rhodium catalysts to convert nitrogen oxides and
carbon monoxide to harmless nitrogen gas and non-toxic carbon dioxide.
Mass Transit
• When transportation is done en masse using public transportation, it reduces the need for
individual automobiles.
o This reduces air pollution and emissions from individual vehicles.

Control
Sequestering
• In sequestering, greenhouse gases like carbon dioxide are trapped by reaction with
substances like metallic oxides to form stable compounds like carbonates.
Filters
• Small particulate matter (like dust and smoke) are removed using filters like air filters
and electrostatic precipitators.
Washers
• Washers dissolve pollutants in a solvent to remove them from air exhaust.
Scrubbers
• Scrubbing makes use of alkalis or basic compounds to neutralize acidic gases in the
atmosphere.
• An example of this is flue-gas desulphurisation.

Solid Waste
Reduce, Reuse, Recycle
• Reducing/Waste reduction is the prevention of the creation of waste material.
• Reuse is simply using a material or item more than once.
• Recycling involves processing used materials into fresh products.

Waste Reduction
• Investing in more durable products
• Limiting the use of disposable products
• Repairing broken items instead of purchasing replacements
• Manufacturers can use minimal packaging
• Manufacturers can utilize all components of a raw material to reduce waste

Glass
• Waste glass can be sorted and melted to make new objects or added to freshly made
glass.
• Recycled glass can be used:
o To make new glass bottles
o To be included in concrete or ceramic
o As an abrasive in glasspaper

Paper
• Paper undergoes a process of sorting and grading, then pulping, then screening, de-inking
and refining and bleaching. After this, the recycled paper pulp can be converted into
sheets.
• While glass is infinitely recyclable, paper can only be recycles about 5-7 times as the
fibers will shorten and weaken.
Plastic
• Thermoplastics, or those that melt when heated, make up most of recycled plastic.

Steel
• Scrap iron or steel is simply melted and added to a furnace. This reduces carbon
emissions by about 60% when compared to newly produced iron.

Aluminium
• The aluminium is melted and added to a furnace then degassed to remove hydrogen. It is
then recast. Recycling aluminium reduces carbon emissions by 95% and energy
consumption by 95% compared with making aluminium from bauxite ore.

Impact of Solid Wastes on the Terrestrial Environment

Waste Impact on environment
Iron Iron rusts and can form pools of red waste, which reduce plant growth.
Broken glass does not degrade very quickly, and when broken can cause cuts
Glass
and abrasions in animals.
Animals may get tangled in plastic nets and suffocate, or attempt to ingest
Plastic plastics.
Toxic additives may also seep out of plastics to harm organisms.
Printing inks can contain heavy metals, residual bleaches and toxic organic
Paper compounds in small quantities. These can leach into soil and water when
paper gets wet.
This metal is poisonous, and when ingested in some form, it can reduce
Lead
neurological development and potentially lead to other complications.
Nuclear Radioactive waste can have extremely long half lives, and can contribute to
Waste burns, sterilization of animals and skin damage.

Disposal Methods
• Dumping: This is very common due to its ease, throwing garbage into streets, roadways
and gullies.
• Landfill: Waste can be buried in a landfill site, like an unused quarry or mine.
o Landfills can either be waste dumps or sanitary landfills
• Composting is allowing the natural breakdown of organic plant and animal material in
aerobic conditions
• Nuclear waste disposal can be achieved safely through:
o Vitrification: mixing with molten glass
o Adsorption: Addition to an ion-exchange resin which is then mixed with cement.
o Above ground disposal: The waste is placed into a steel cylinder, and an inert
gas is then added.

Good luck guys! (With love)