UNIT TWO CAPE

CHEMISTRY
WORKBOOK
2
MODULE
ONE (1)

3
Structure and Formulae (Module 1)
a) explain the occurrence of carbon compounds with straight chains, branched chains
and rings (refer to catenation, tetravalency, hybridisation and resonance of carbon
atoms)
b) explain the meaning of homologous series (chemical and physical characteristics)
c) distinguish between empirical, molecular and structural formulae
d) be able to write structural formulae (displayed, condensed and skeletal forms) of
compounds
e) be able to apply IUPAC rules to named organic compounds
f) define structural formulae with examples (include chain, functional group and
positional isomers)
g) define and explain stereoisomerism (geometrical and optical)
h) be able to determine the possible isomers from given molecular formulae
i) define the terms electrophile, nucleophile and functional group giving at least 2
examples of each
j) understand inductive and mesomeric effect
k) define the terms homolytic fission and heterolytic fission and give examples
l) understand different types of reactions

Introduction to organic chemistry

Carbon can form vast numbers of organic compounds. This occurs because of carbon
atoms’ ability to bond to themselves in long chains. This ability is called catenation.
Catenation occurs because of the tetravalency of carbon (i.e. its valency is 4 and
carbon being a small atom, therefore it forms strong bonds with itself)
These chains can be straight chains:-

4
 branched chains:- And rings

Carbon can form 4 covalent bonds, but this is not apparent when analysing its
electronic configuration of 1s2 2s2 2p2. Only the last 2 electrons are unpaired which
can be used to form covalent bonds. However only TWO covalent bonds can be
formed!!!
In order to form 4 covalent bonds, it must have FOUR unpaired electrons.

One of the 2s electrons would absorb energy and be promoted to the vacant 2p orbital
to form a new EXCITED electronic configuration 1s2 2s1 2p3! The 3 electrons in the 2p
subshell and the 1 electron in the 2s orbital are all now unpaired, so now carbon can
form 4 covalent bonds.

This happens spontaneously since the energy released by forming 4 bonds compensates
for the energy absorbed in promoting an electron to a higher energy level. Also the
formation of 4 bonds is more favourable than forming 2 covalent bonds.

The combination of the usage of the ONE s electron and the THREE “p” electrons in
bond formation results in a hybrid and the process is called hybridisation.

Organic compounds are placed in groups called homologous series.

Homologous series have several characteristics
1. All compounds have the same general formula
2. Same functional group
3. Similar chemical properties
4. Graduating physical properties as the number of carbon atoms increases
5. The masses of consecutive members differ by 14 g or by a –CH2 group.

5
A functional group is an atom or a group of atoms responsible for the chemical
properties of a compound
Bonds must be first broken before a chemical reaction can take place. In organic
chemistry, bonds can be broken in two ways.
a) homolytic fission and b) heterolytic fission
Homolytic fission :- breakage of a covalent bond with atoms of similar or same
electronegativity resulting in the formation of free radicals. Each atom retain one
electron from the covalent bond.
NB Free radicals are highly reactive species with an unpaired electron

Heterolytic fission :- breakage of a covalent bond with atoms of different

electronegativities with the formation of a cation and an anion. The more
electronegative atom retains both electrons from the covalent bond.

Terminology
● Electrophile:- an electron loving species to negatively charged centres e.g. H+, Cl+,
Br+, I-, NO2+

● Nucleophile:- a nucleus loving species i.e. attracted to positively charged centres e.g.
OH-, H2O, NH3, CN-, halide ion
● Hydrolysis – the splitting of a molecule using water or in some cases the reaction of
a molecule with water as opposed to simple dissolution

Molecules can be illustrated in several ways, via empirical formula, molecular

formula, structural or displayed formula, condensed formula or skeletal formula.

1. Empirical formula refers to the simplest whole number ratio of atoms in a

compound. e.g. CH2

2. Molecular formula refers to the actual number of atoms in a compound e.g. C2H4

6
3. Structural / displayed formula refers to the diagrammatic representation of an
organic molecule showing the arrangement of atoms

e.g.

4. Condensed formula refers to the groups of atoms arranged around each carbon
atom in the compound. It does not show the arrangement of the atoms. The condensed
formula can be determined from the structural formula e.g. butane is C4H10 and the
structural formula

Therefore the condensed formula is CH3CH2CH2CH3

5. Skeletal formula refers to the bare structure of the compound where carbon and
single hydrogen atoms are not shown. It is shown by a series of straight lines and
bends. An open end represents a –CH3 group which a “bend” represents a –CH2 group.
If a double bond is present, the number of hydrogen atoms would decrease
appropriately. Other functional groups are shown explicitly.

butane is shown as and butan-2-ol is represented by

Isomerism

There are two main types:- structural isomerism and stereoisomerism

Structural isomerism occurs when 2 or more compounds have the same molecular
formulae but their atoms are arranged differently

There are 3 categories of structural isomerism

a) chain b) functional c) positional
CHAIN ISOMERISM
7
Chain isomers have same molecular formula but differ in the length of the longest
carbon atom chain
Example:

2-methylpropane
POSITION ISOMERIS
Positional isomerism is caused by the difference in the position of functional group in
the same chain is termed as   position isomerism.
Example:

1,2-dichlorobenzene 1,3- dichlorobenzene

ONL ISOMERISM
Functional isomers have same molecular formula but different functional group.
  
Example:
Ethyl Alcohol            Dimethyl Ether   

Stereoisomerism occurs when 2 or more compounds have the same molecular and
structural formulae but the atoms are arranged differently in space
Stereoisomerism can be either a) geometric / cis-trans isomerism or
b) optical isomerism

Geometric isomerism occurs in unsaturated compounds

8
With the presence of the multiple bond, rotation about the C=C bond is difficult without
breaking the bonds between them

Example

Both (a) and (b) have the molecular formula CHClCHCl but the atoms are arranged
differently in space
In (a) similar atoms either the Cl or the H are on OPPOSITE sides of THE DOUBLE
BOND. This configuration is called “cis”. While in (b) similar atoms are on the SAME
side of THE DOUBLE BOND, this configuration is called “trans”

So compound (a) is trans-1,2-dichloroethene and

compound (b) is cis-1,2-dichloroethene
Optical isomerism occurs when there is no symmetry about a carbon atom in a
compound

For example Imagine a carbon atom with four different atoms or groups of atoms
attached to it

There is no line of symmetry one can draw for this molecule

9
Therefore the molecule is asymmetric. Since there is no line of symmetry about the
central carbon atom, that carbon atom is said to be CHIRAL.
Mirror images of compounds with chiral carbon atoms are said to be
non-superimposable. Think of trying to fit your left hand directly on top of your right
hand. You would realise that they don’t fit neatly on each other.

Mirror images of compounds with chiral carbon atoms are called enantiomers.
The dotted line represents the mirror line.

Note When showing chiral carbon atoms they MUST be indicated with an asterix
next to it. (*)
Enantiomers are identical in every way in terms of chemical and physical properties
EXCEPT that one rotates plane polarised light to the left and the other rotates plane
polarised light to the right by the same degree.
If there are equal concentrations of both enantiomers in a mixture, there would be no
observed optical activity and the mixture would called a racemic mixture or a
racematate.

One final concept to understand is that some atoms or groups of atoms are electron
withdrawing (pull electrons towards themselves) and others are electron donating (push
electrons away from themselves). Atoms or groups of atoms with electronegative atoms
are electron withdrawing and thus have a negative inductive effect (-I), while the others
like alkyl groups are electron donating and have a positive inductive effect (+I).
Mesomeric effect is the same as the inductive effect but it occurs in multiple
bonds, while inductive effect occurs in single bonds.
Optical Isomers
● Isomers are compounds with the same molecular formula but different structural
formulas
o They generally have different chemical and physical properties
10
● Optical isomers, are a special case of isomer in which the structural formula looks
the same when drawn in 2 dimension but the 3-D structure is different
1. Optical isomers have chiral centers – carbon attached to four different
substituent groups
2. Optical isomers come in pairs – they are mirror images of each other
3. Optical isomers rotate plane polarized light but otherwise have the same
chemical and physical properties
▪ Both isomers rotate light the same amount but in opposite directions

1. Chiral center: The bolded carbon atoms in the structures below are chiral centers

a. Carbons with two or three hydrogen atoms attached to them are not chiral
centers
b. Carbons with a double bonded oxygen atom cannot be chiral centers
c. A molecule can have more than one chiral center (called a diasetereomer)

2. Optical Isomers come in pairs

a. With normal isomers – there can be more than two for the same chemical
formula:
i. For example: C5H12

b. With optical isomers – there are only two per chiral carbon and they are
called enantiomers of each other.
i. When naming compounds that have chiral centers it is necessary to
use (+)/(-) or R/S or D/L in the front of the name to denote which
direction light is rotated (however, this is not necessary for IB)
c. Mirror images: You cannot superimpose the following two structures on
each other

i. for example, make the methyl (CH3) groups line up and notice that
the -Cl and –OH groups are not in the same place in both isomers
11
 3. Rotate plane polarized light…what does that mean?
a. Polarized light: light waves vibrating in only 1 plane
i. Usually light waves are vibrating in all planes
b. When plane polarized light travels through a crystal, the plane it was
vibrating in has rotated
Click here for picture and more explanation

Worksheet on intro to organic chemistry

Write your answers on the spaces provided or circle the most suitable letter

1. What is tetravalency?
………………………………………………………………………

2. How many structural isomers have the molecular formula C4H10?

(a) 1 (b) 2 (c) 3 (4)

3.
a) Draw the fully displayed formula corresponding to CH2ClCHClCH3

b) On the fully displayed formula you drew above, indicate the chiral carbon atom with
an asterix.

c) Draw the two enantiomers resulting from the chiral carbon atom you indicated above
in part b)

12
4. Using this condensed molecular formulae CH2ClCH2CH3
Which type of structural isomerism can it exhibit?
………………………….…………………

5 i). Which compounds would exhibit optical isomerism?

a) CH4 b) C2H6 c) CH3CHClBr (d) CH3CH2Cl

ii) Draw the optical isomers for the compound you have chosen in 5 i)

6. But-2-ene is said to show “stereoisomerism”. Draw the cis and trans isomers of
but-2-ene
7.

13
 I am trying to show a that three atoms of the tetrahedral make a plane, and the
other two stick out of the page – either behind or in front.

Empirical Formula Only gives ratio of elements

Molecular Formula Gives number of atoms in molecule but
does not give structure. Could be
isomers so name cannot be generated
from a molecular formula only
Lewis Structures Shows the location of all the electrons,
including lone pairs. Identifies isomer so
that name can be generated
Structural Formula – Condensed Usually written on one line in the order
that atoms are attached to give
structural information w/o taking up
space by drawing bonds. Does not give
information about stereoisomers.
Structural Formula- Bond-line Gives the general shape of the molecule.
Formula Condensed b/c hydrogen atoms are left
off and corners represent carbon atoms.
No lone pairs are shown. Can be used to
generate a name for the compound but
doesn’t show stereoisomers unless used
with Dash-wedge formula.
Structural Formula - Dash-Wedge
Formula

Functional Groups and Their Properties

Group Polarity Volatility/M.P./B. Soluble Acid-base Common
P. in Water Behavior Compounds
Alkanes Non-pol ● Very volatile, No None Methane,
CnH2n+2 ar smaller propane,
14
 molecules are butane,
gases octane
● B.P. increases (gasoline)
with size due to Wax
increased
dispersion forces
and larger mass
Alkenes/Alkyne Non-pol ● Have similar b.p No None
s ar to alkanes w/
CnH2n /CnH2n-2 same # of
carbons but a
few degrees
lower since they
have fewer
electrons = less
dispersion forces
Haloalkanes Slightly ● Most Slightly None PVC
R–X Polar – haloalkanes are CFCs
non-pol liquids at room Teflon
ar temp
● Only CH3Cl,
CH3Br and
CH3CH2Cl are
gasses
● Dispersion
forces are more
important than
dipole-dipole
forces
● B.P decreases
with # of
substituents
since temporary
dipole is
stronger for long
chains and
attractions are
more effective
when molecules
can pack closely
Alcohols Polar ● Volatile when Yes, Weakly Ethanol,
R- OH bond pure but often decrease acidic and isopropyl
capable mixed w/ H2O s w/ basic alcohol,
of ● Higher boiling length of (amphoteri menthol
H-bonds points than carbon c) like
alkanes b/c of chain water b/c
hydrogen of –OH
bonding
15
 ● Volatility and
B.P increase as
length of chain
increases
Ethers Polar ● Volatile First
R-O-R bonds, ● Lower boiling anesthetic –
no points than diethyl ether
H-bonds alcohols b/c no
hydrogen
bonding
Amines Polar ● Low volatility Yes Basic b/c Amino acids
R-NH2 or R2NH bonds, ● High boiling of lone pair, Ammonia
or R3N capable points b/c of R-NH2 even
of H-bonding more basic
H-bonds than NH3
Aldehydes Polar ● B.P. is higher Yes, Carbonyl Formaldehyd
R-CHO carbonyl than that of decrease can act as e
group similarly sized s w/ a base
(C=O) alkanes b/c of length of
H-bond dipole-dipole carbon
can forces. chain
form ● B.P. is lower
between than alcohols
carbonyl since
and dipole-dipole
water forces are
weaker than
H-bonds.
● B.P. increase
with size of
carbon chain
Ketones Polar ● See aldehydes Yes, Carbonyl Acetone (nail
R-CO-R carbonyl decrease can act as polish
group s w/ a base remover)
(C=O) length of
H-bond carbon
can chain
form
between
carbonyl
and
water
Carboxylic Polar, ● Low volatility Yes Acid Acetic acid -
Acids capable ● Higher boiling decrease Methanoic vinegar
R-COOH of points b/c of s w/ is stronger
hydroge hydrogen length of than
n bonds bonding carbon ethanoic
chain
16
 b/c of R
group.

Esters Polar, no ● More volatility Small

COOR H-bonds than carboxylic esters: Polyester
H-bond acids and lower yes, Fatty acids
can boiling points solubility
form b/c can’t decrease
between H-bond s w/ size
carbonyl ● Liquids at room of chain
and temp for smaller
water molecules
Amides Polar, ● High m.p. b/c of Yes Amine part Proteins
amine hydrogen of amide is (polypeptide)
can bonding basic Nylon
hydroge ● Amides are
n bond liquids or solids
at room temp

Hybridization of Carbon

17
18
19
Production of alkanes and alkenes (Module 1)
a) understand that all organic compounds ultimately come from crude oil
b) understand that crude oil is a mixture of organic compounds
c) know that fractional distillation is used to obtain various fractions which would
contain alkanes and alkenes
d) list at least three fractions that are obtained from crude oil distillation
e) know that the amount of gasoline and diesel from distillation does not meet the
demand
f) understand that cracking is used to obtain more gasoline fractions from the heavier
fractions which are not in such high demand
g) know the types of cracking that can be used
h) know the conditions present for each type of cracking
i) be able to give a full equation or complete a partial equation for the cracking of a
given alkane

Fractional Distillation of Crude Oil

BOILING POINTS AND STRUCTURES OF HYDROCARBONS
The boiling points of organic compounds can give important clues to other physical
properties. A liquid boils when its vapor pressure is equal to the atmospheric pressure.
Vapor pressure is determined by the kinetic energy of molecules. Kinetic energy is
related to temperature and the mass and velocity of the molecules. When the
temperature reaches the boiling point, the average kinetic energy of the liquid particles
is sufficient to overcome the forces of attraction that hold molecules in the liquid state.
Then these molecules break away from the liquid forming the gas state.
Vapor pressure is caused by an equilibrium between molecules in the gaseous state and
molecules in the liquid state. When molecules in the liquid state have sufficient kinetic
energy, they may escape from the surface and turn into a gas. Molecules with the most
independence in individual motions achieve sufficient kinetic energy (velocities) to
escape at lower temperatures. The vapor pressure will be higher and therefore the
compound will boil at a lower temperature.
BOILING POINT PRINCIPLE:
Molecules which strongly interact or bond with each other through a variety of
intermolecular forces can not move easily or rapidly and therefore, do not achieve the
20
kinetic energy necessary to escape the liquid state. Therefore, molecules with strong
intermolecular forces will have higher boiling points. This is a consequence of the
increased kinetic energy needed to break the intermolecular bonds so that individual
molecules may escape the liquid as gases.
THE BOILING POINT CAN BE A ROUGH MEASURE OF THE AMOUNT OF ENERGY
NECESSARY TO SEPARATE A LIQUID MOLECULE FROM ITS NEAREST NEIGHBORS.
MOLECULAR WEIGHT AND CHAIN LENGTH TRENDS IN BOILING POINTS
A series of alkanes demonstrates the general principle that boiling points increase as
molecular weight or chain length increases (table 1.).
Table 1. BOILING POINTS OF ALKANES

 Boiling Point  Normal State

 Formula  Name C at Room
Temp. +20 C
 CH4  Methane  -161  gas
 CH3CH3  Ethane  - 89  
 CH3CH2CH3  Propane  - 42  
 CH3CH2CH2CH3  Butane  -0.5  
 CH3CH2CH2CH2CH3  Pentane  + 36  liquid
 CH3(CH2)6CH3  Octane  +125  
QUES. State whether the compounds above will be a gas or liquid state at room
temperature (20 C). Hint: If the boiling point is below 20 C, then the liquid has already
boiled andthe compound is a gas.
The reason that longer chain molecules have higher boiling points is that longer chain
molecules become wrapped around and enmeshed in each other much like the strands
of spaghetti. More energy is needed to separate them than short molecules which have
only weak forces of attraction for each other.
FOCUS ON FOSSIL FUELS
Petroleum refining is the process of separating the many compounds present in crude
petroleum. The principle which is used is that the longer the carbon chain, the higher
the temperature at which the compounds will boil. The crude petroleum is heated and
changed into a gas. The gases are passed through a distillation column which becomes
cooler as the height increases. When a compound in the gaseous state cools below its
boiling point, it condenses into a liquid. The liquids may be drawn off the distilling
column at various heights.
Although all fractions of petroleum find uses, the greatest demand is for gasoline. One
barrel of crude petroleum contains only 30-40% gasoline. Transportation demands
require that over 50% of the crude oil be converted into gasoline. To meet this demand
21
some petroleum fractions must be converted to gasoline. This may be done by
"cracking" - breaking down large molecules of heavy heating oil; "reforming" - changing
molecular structures of low quality gasoline molecules; or "polymerization" - forming
longer molecules from smaller ones.
For example if pentane is heated to about 500 C the covalent carbon-carbon bonds
begin to break during the cracking process. Many kinds of compounds including
alkenes are made during the cracking process. Alkenes are formed because there are
not enough hydrogens to saturate all bonding positions after the carbon-carbon bonds
are broken.
 

Cracking of Alkanes
Cracking
What is cracking?
Cracking is the name given to breaking up large hydrocarbon molecules into smaller
and more useful bits. This is achieved by using high pressures and temperatures
without a catalyst, or lower temperatures and pressures in the presence of a catalyst.
The source of the large hydrocarbon molecules is often the naphtha fraction or the gas
oil fraction from the fractional distillation of crude oil (petroleum). These fractions are
obtained from the distillation process as liquids, but are re-vaporised before cracking.

22
There isn't any single unique reaction happening in the cracker. The hydrocarbon
molecules are broken up in a fairly random way to produce mixtures of smaller
hydrocarbons, some of which have carbon-carbon double bonds. One possible reaction
involving the hydrocarbon C15H32 might be:

Or, showing more clearly what happens to the various atoms and bonds:

This is only one way in which this particular molecule might break up. The ethene and
propene are important materials for making plastics or producing other organic
chemicals. The octane is one of the molecules found in petrol (gasoline).

Catalytic cracking
Modern cracking uses zeolites as the catalyst. These are complex aluminosilicates, and
are large lattices of aluminium, silicon and oxygen atoms carrying a negative charge.
They are, of course, associated with positive ions such as sodium ions. You may have
come across a zeolite if you know about ion exchange resins used in water softeners.
The alkane is brought into contact with the catalyst at a temperature of about 500°C
and moderately low pressures.
The zeolites used in catalytic cracking are chosen to give high percentages of
hydrocarbons with between 5 and 10 carbon atoms - particularly useful for petrol

23
(gasoline). It also produces high proportions of branched alkanes and aromatic
hydrocarbons like benzene.
The zeolite catalyst has sites which can remove a hydrogen from an alkane together
with the two electrons which bound it to the carbon. That leaves the carbon atom with
a positive charge. Ions like this are called carbonium ions (or carbocations).
Reorganisation of these leads to the various products of the reaction.

Thermal cracking
In thermal cracking, high temperatures (typically in the range of 450°C to 750°C) and
pressures (up to about 70 atmospheres) are used to break the large hydrocarbons into
smaller ones. Thermal cracking gives mixtures of products containing high proportions
of hydrocarbons with double bonds - alkenes.
Thermal cracking doesn't go via ionic intermediates like catalytic cracking. Instead,
carbon-carbon bonds are broken so that each carbon atom ends up with a single
electron. In other words, free radicals are formed.

Reactions of the free radicals lead to the various products.

24
Alkanes (Module 1)
a) state the general formula of alkanes
b) understand the concept of hydrocarbon and saturated / saturation
c) apply the general formula of alkanes and give the molecular formulae and the names
of the first ten members of the homologous series
d) describe the reactions of alkanes (include the chemical equations for the reactions):-
i) combustion (include colour of the flame)
ii) halogenation
e) list and understand the general uses of alkanes being based on their reactivity
f) understand why alkanes are not very reactive
g) understand that a mechanism for a chemical reaction is a suggested series of steps
from the beginning of a reaction to the end of a reaction
h) understand why the conventional equation for the reaction of methane and chlorine
does not explain why small amounts of ethane are produced and detected at the end of
the reaction
i) be able to state the name of the mechanism by which alkanes use and describe the
mechanism (use methane and chlorine as an example but other examples should be
known)

Alkanes
(a) General formula CnH2n+2
(c) Alkanes are the simplest family of hydrocarbons - compounds containing carbon and
hydrogen only. They only contain carbon-hydrogen bonds and carbon-carbon single
bonds. The first six are:
25
 methane CH4
ethane C2H6
propane C3H8
butane C4H10
pentane C5H12
hexane C6H14
heptane C7H16
octane C8H18
nonane C9H20
decane C10H22

(b) Alkanes are saturated meaning that they have only single bonds

(d) Alkanes undergo two types of reactions:- combustion and halogenation.

They burn with a clean blue flame to form carbon dioxide and water
e.g.
They react with halogens in the presence of uv light to form a substituted alkane and a
hydrogen halide

e.g. .
(e) and (f) Alkanes contain only carbon and hydrogen. Their electronegativities are very
similar which means the C-H bond is essentially non-polar. Non-polar do not attract
either electrophiles or nucleophiles which are the species which undergo a reaction.
Hence alkanes are generally unreactive.

26
(g) In the chlorination of methane, small amounts of ethane gas is always detected.
This does not make any sense based on the simple series of substitutions.

It means the reaction occurs by some different means. A mechanism is proposed for
the process. A mechanism is a proposed series of small steps from start to finish of
a chemical reaction.
Alkanes undergo free radical substitution mechanism.
There are 3 stages.

Initiation
The chain is initiated (started) by uv light breaking a chlorine molecule into free
radicals (homolytic fission)
Cl2 2Cl

Propagation reactions
These are the reactions which keep the chain going.
CH4  +  Cl CH3  +
 HCl

CH3  +  Cl2 CH3Cl  +  Cl

Termination reactions
These are the combination of any two free radicals
2Cl
Cl2

27
 CH3  +  Cl
CH3Cl

CH3  +  CH3
CH3CH3
Worksheet
1. Explain the term “saturated”
………………………………………………………………………….
2. By use of equations give a possible occurrence of when a molecule of octane is
cracked
………………………………………………………………………..
3. Alkanes are generally used as fuels. Give a reason why this is done
…………………………………………………………………………..
4. Give a balanced equation for the complete combustion of octane
………………………………………………………………………
5. 0.00382 mol of a hydrocarbon X was burnt in oxygen and 1.68 g of carbon dioxide
was formed and 0.756 g of water was formed.
a) Calculate the empirical formula of hydrocarbon X

b) Suggest a molecular formula for hydrocarbon X

28
6. Give the mechanism for the reaction of ethane and chlorine gas in the presence of
uv light.

………………………………………………………………………..………………………………………
………………………………..………………………………………………………………………..……
…………………………………………………………………..……………………………………………
…………………………..………………………………………………………………………..…………
……………………………………………………………..…………………………………………………
……………………..………………………………………………………………………..………………
………………………………………………………..………………………………………………………
………………..………………………………………………………………………..……………………
…………………………………………………..…………………………………

Alkenes (Module 1)
a) state the general formula of alkenes
b) know and identify the functional group in alkenes
c) understand that alkenes are much more reactive than alkanes and explain why this
is so

29
d) appreciate that alkenes are not used as fuels but as building blocks to produce other
chemicals
e) describe the chemical reactions of alkenes (with conditions)
i) combustion (include colour of flame) ii) halogenation
iii) oxidation (hot and cold) iv) hydration v) hydrohalogenation
vi) hydrogenation (include production of trans-fat which are harmful)
and give equations for each chemical reaction
f) state the name of the mechanism by which alkenes use and describe the mechanism
using ethene and bromine as an example
g) define Markovnikov’s Rule and apply it to the prediction of products for the reaction
of hydrogen halides and UNsymmetrical alkenes

ALKENES
Alkenes are a family of hydrocarbons (compounds containing carbon and hydrogen
only) containing ONE carbon-carbon double bond. They contain a multiple bond and
thus are called UNSATURATED molecules. The first two are:
ethene C2H4
propene C3H6
You can work out the formula of any of them using the general formula: CnH2n
The functional group is the double bond C=C

Reactivity of alkenes vs alkanes

Alkenes have an electron rich centre i.e. partially negative region, the double bond or Π
bond. Alkanes do not have either a partially positive or negative region. Therefore
alkenes are susceptible to electrophilic attack but alkanes are NOT susceptible to either
electrophile or nucleophile attack. Hence alkenes are more reactive than alkanes.

Since alkenes are reactive compounds, they are NOT used as fuels like alkanes but as
building blocks in the petro-chemical industry.

Reactions of alkenes (using ethene as an example)

30
1. Combustion
With oxygen or air to carbon dioxide and water (in excess oxygen) if oxygen is limited,
carbon monoxide and water are the products
e.g. C2H4 + 3O2 🡪2CO2 + 2H2O alkenes burn with a smoky yellow flame

2. Addition (all unsaturated compounds undergo addition reactions)

a) Hydrogenation
Ethene reacts with hydrogen in the presence of a finely divided nickel catalyst at a
temperature of about 150°C. Ethane is produced.

Some margarine is made by hydrogenating carbon-carbon double bonds in animal or

vegetable fats and oils. You can recognise the presence of this in foods because the
ingredients list will include words showing that it contains "hydrogenated vegetable
oils" or "hydrogenated fats".
If there are two or more carbon-carbon double bonds in each chain, then it is said to be
polyunsaturated. However, there are possible health benefits in eating
mono-unsaturated or polyunsaturated fats or oils rather than saturated ones - so you
wouldn't want to remove all the carbon-carbon double bonds.
One of the problems arises from the hydrogenation process.
The double bonds in unsaturated fats and oils tend to have the groups around them
arranged in the "cis" form.
The relatively high temperatures used in the hydrogenation process tend to flip some of
the carbon-carbon double bonds into the "trans" form. If these particular bonds aren't
hydrogenated during the process, they will still be present in the final margarine in
molecules of trans fats.
The consumption of trans fats has been shown to increase cholesterol levels
(particularly of the more harmful LDL form) - leading to an increased risk of heart
disease.
b) THE HALOGENATION OF ALKENES
Ethene and chlorine / bromine
In each case you get an addition reaction. For example, bromine adds to give
1,2-dibromoethane.

31
The reaction with bromine happens at room temperature. If you have a gaseous alkene
like ethene, you can bubble it through either pure liquid bromine or a solution of
bromine in an organic solvent like tetrachloromethane. The reddish-brown bromine is
decolourised as it reacts with the alkene.

Using bromine water as a test for the presence of a multiple bond

If you shake an alkene with bromine water or bromine liquid (or bubble a gaseous
alkene through bromine water), the solution becomes colourless. Unsaturated
compounds decolourise bromine water.
c) ALKENES and HYDROGEN HALIDES
Addition to symmetrical alkenes
All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom
joins to one of the carbon atoms originally in the double bond, and a halogen atom to
the other.
For example, with ethene and hydrogen chloride, you get chloroethane:

Conditions
The alkenes react with gaseous hydrogen halides at room temperature. If the alkene is
also a gas, you can simply mix the gases. If the alkene is a liquid, you can bubble the
hydrogen halide through the liquid.
Addition to unsymmetrical alkenes
Orientation of addition
If HCl adds to an unsymmetrical alkene like propene, there are two possible ways it
could add. However, in practice, there is only one major product.

This is in line with Markovnikov's Rule which says:

When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes
attached to the carbon with the greater number of hydrogen atoms attached to it
already.

32
In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group
has 2 hydrogen atoms and the CH group only has one hydrogen atom attached.
d) Oxidation of alkenes
Alkenes react with potassium manganate(VII) solution in the cold. Manganate(VII) ions
are a strong oxidising agent, and in the first instance oxidise ethene to ethane-1,2-diol
(old name: ethylene glycol).
:

Oxidation of alkenes with hot concentrated acidified potassium manganate(VII)

solution
The formula below the general form of all alkenes. The R groups represent alkyl groups.

The hot conc. potassium manganate(VII) solution oxidises the alkene by breaking the
carbon-carbon double bond and replacing it with two carbon-oxygen double bonds.
Two fragments are produced.

The products are known as carbonyl compounds because they contain the carbonyl
group, C=O. Carbonyl compounds can also react with potassium manganate(VII), but
how they react depends on what is attached to the carbon-oxygen double bond. So we
need to work through all the possible combinations.
Carbonyl compounds which have two hydrocarbon groups attached to the carbonyl
group are called ketones. Ketones aren't that easy to oxidise, and so there is no further
action. If the groups attached either side of the original carbon-carbon double bond
were the same, then you would end up with a single ketone. If they were different, then
you would end up with a mixture of two.
For example:

Please note that if one of the R groups attached to the carbon atom is a hydrogen
atom, then it would form the corresponding carboxylic acid. If both R groups are
hydrogen atoms then it is further oxidised to carbon dioxide and water.

33
This breakage of double bonds can be used to determine the position of double
bonds in a molecule.
e) Hydration

In the lab, ethanol is produced by reacting ethene with concentrated sulphuric acid
with concentrated sulphuric acid at 170 °C.
In industry, ethanol is manufactured by reacting ethene with steam. The reaction is
reversible.

Only 5% of the ethene is converted into ethanol at each pass through the reactor. By
removing the ethanol from the equilibrium mixture and recycling the ethene, it is
possible to achieve an overall 95% conversion.
A flow scheme for the industrial preparation looks like this:

Alkenes react via the electrophilic addition mechanism

Using ethene and bromine as an example:-
Note: The arrows show the movement of the electrons towards a positively
charged region.
In the first stage of the reaction, one of the bromine atoms becomes attached to both
carbon atoms, with the positive charge being found on the bromine atom. A bromonium
ion is formed.

The bromonium ion is then attacked from the back by a bromide ion formed in a
nearby reaction.
34
Worksheet
1 a)

Circle one functional group in the molecule above.

b) Draw the structural formula when retinol reacts with excess bromine in
tetrachloromethane

c) Describe what would be observed in the reaction

…………………………………………………………………………………………………………………
……………………………………….
d) Describe what would be observed if excess acidified potassium manganate VII was
used instead of excess bromine.
…………………………………………………………………………………………………………………
……………………………………….
e) Calculate the molar mass of retinol (H = 1, O = 16, C = 12)

35
f) Using just a portion of the retinol molecule

i) Show the mechanism of the reaction of retinol and bromine.

ii) Show the structural formula of the product when retinol is reacted with hydrogen
gas

iii) Show the structural formula of the product when retinol is reacted with steam

v) What volume of carbon dioxide would be produced if 1 mole of retinol was

completely burnt in air? Remember 1 mole of any gas occupies 24 dm3 at rtp

Benzene and derivatives of benzene (Module 1)

a) State formula of benzene and discuss its structure (delocalised electrons/ pi system,
a planar molecule)
b) describe the reactions of benzene:-
i) nitration ii) halogenation
c) state the name of the mechanism that benzene and its derivatives undergo
d) describe the mechanisms involved in:-
i) nitration ii) halogenation

36
e) compare and explain the difference in reactivity of methylbenzene vs benzene and
use conditions of nitration as an example
f) use methylbenzene and a derivative of methylbenzene to show how different
conditions can influence the products formed for a reaction

The Kekulé structure for benzene, C6H6

What is the Kekulé structure?
Kekulé was the first to suggest a sensible structure for benzene. The
carbons are arranged in a hexagon, and he suggested alternating double
and single bonds between them. Each carbon atom has a hydrogen
attached to it.
This diagram is often simplified by leaving out all the carbon and
hydrogen atoms!

In diagrams of this sort, there is a carbon atom at each corner. You have to
count the bonds leaving each carbon to work out how many hydrogens there are
attached to it.
In this case, each carbon has three bonds leaving it. Because carbon atoms form four
bonds, that means you are a bond missing - and that must be attached to a hydrogen
atom.
Problems with the Kekulé structure
Although the Kekulé structure was a good attempt in its time, there are serious
problems with it . . .
Problems with the chemistry
Because of the three double bonds, you might expect benzene to have reactions like
ethene - only more so!
Ethene undergoes addition reactions in which one of the two bonds joining the carbon
atoms breaks, and the electrons are used to bond with additional atoms.
Benzene rarely does this. Instead, it usually undergoes substitution reactions in which
one of the hydrogen atoms is replaced by something new.

37
Problems with the shape
Benzene is a planar molecule (all the atoms lie in one plane), and that would also be
true of the Kekulé structure. The problem is that C-C single and double bonds are
different lengths.
C-C 0.154 nm

That would mean that the hexagon would be irregular if it had the Kekulé structure,
with alternating shorter and longer sides. In real benzene all the bonds are exactly the
same - intermediate in length between C-C and C=C at 0.139 nm. Real benzene is a
perfectly regular hexagon.
Problems with the stability of benzene
Real benzene is a lot more stable than the Kekulé structure would give it credit for.
Every time you do a thermochemistry calculation based on the Kekulé structure, you
get an answer which is wrong by about 150 kJ mol-1. This is most easily shown using
enthalpy changes of hydrogenation.

Hydrogenation is the addition of hydrogen to something. If, for example, you

hydrogenate ethene you get ethane:
CH2=CH2  +  H2 CH3CH3
In order to do a fair comparison with benzene (a ring structure) we're going
to compare it with cyclohexene. Cyclohexene, C6H10, is a ring of six carbon
atoms containing just one C=C.

When hydrogen is added to this, cyclohexane, C6H12, is formed. The "CH" groups
become CH2 and the double bond is replaced by a single one.
The structures of cyclohexene and cyclohexane are usually simplified in the same way
that the Kekulé structure for benzene is simplified - by leaving out all the carbons and
hydrogens.

38
In the cyclohexane case, for example, there is a carbon atom at each corner, and
enough hydrogens to make the total bonds on each carbon atom up to four. In this
case, then, each corner represents CH2.
The hydrogenation equation could be written:

The enthalpy change during this reaction is -120 kJ mol-1. In other words, when 1 mole
of cyclohexene reacts, 120 kJ of heat energy is evolved.
Where does this heat energy come from? When the reaction happens, bonds are broken
(C=C and H-H) and this costs energy. Other bonds have to be made, and this releases
energy.
Because the bonds made are stronger than those broken, more energy is released than
was used to break the original bonds and so there is a net evolution of heat energy.
If the ring had two double bonds in it initially (cyclohexa-1,3-diene), exactly twice as
many bonds would have to be broken and exactly twice as many made. In other words,
you would expect the enthalpy change of hydrogenation of cyclohexa-1,3-diene to be
exactly twice that of cyclohexene - that is, -240 kJ mol-1.

In fact, the enthalpy change is -232 kJ mol-1 - which isn't far off what we are
predicting.

Applying the same argument to the Kekulé structure for benzene (what might be called
cyclohexa-1,3,5-triene), you would expect an enthalpy change of -360 kJ mol-1, because
there are exactly three times as many bonds being broken and made as in the
cyclohexene case.

39
In fact what you get is -208 kJ mol-1 - not even within distance of the predicted value!
This is very much easier to see on an enthalpy diagram. Notice that in each case heat
energy is released, and in each case the product is the same (cyclohexane). That means
that all the reactions "fall down" to the same end point.

Heavy lines, solid arrows and bold numbers represent real changes. Predicted changes
are shown by dotted lines and italics.
The most important point to notice is that real benzene is much lower down the
diagram than the Kekulé form predicts. The lower down a substance is, the more
energetically stable it is.
This means that real benzene is about 150 kJ mol-1 more stable than the Kekulé
structure gives it credit for. This increase in stability of benzene is known as the
delocalisation energy or resonance energy of benzene. The first term (delocalisation
energy) is the more commonly used.
Why is benzene so much more stable than the Kekulé structure suggests? To explain
that needs a separate article! Follow the first link below.

REACTIONS OF BENZENE

40
41
42
43
44
45
46
Alcohols and Phenols (Module 1)
a) give general formula of alcohols
b) apply IUPAC rules to naming alcohols (stating the position of the functional group)
c) understand the differences between primary, secondary and tertiary alcohols and
give examples
d) list and describe the chemical reactions of alcohols:-
i) oxidation ii) dehydration iii) esterification iv) iodoform test
v) reaction with metals
and the chemical equations for i), ii), iii) and v) only
e) understand the concept of the breathalyser test
f) show how one can distinguish experimentally between primary, secondary and
tertiary alcohols
g) give general formula of phenols
h) explain difference between phenols and alcohols (aromatic vs aliphatic)
i) describe reactions of phenols:- a) reaction with aqueous bromine
b) reaction with acyl halides c) reaction with sodium hydroxide
and given chemical equations for the reactions
j) explain why alcohols do not react with sodium hydroxide but phenols do
k) be able to give and explain the order of acidity of water, ethanol and phenols
ALCOHOLS CnH2n+1OH
They can be classified as
primary (1°), secondary (2°) and tertiary (3°) alcohols.

General shape of an alcohol

R
|
R—C—OH

47
 |

Reactions of alcohols (R-OH)

1. Reaction with sodium to form a salt and hydrogen gas.

2C2H5OH + 2Na 🡪 2C2H5O-Na+ + H2
sodium ethoxide

2. Reaction with hydrogen halides to form alkyl halides (use concentrated HCl for
alkyl chloride) to form alkyl halides
R—OH + HX 🡪 R—X + H2O

3. Reaction with conc. sulphuric acid

With excess acid at 170 °C, the corresponding alkene is formed
C2H5—OH 🡺 C2H4 + H2O
4. Reaction with organic acids to form esters with conc. sulphuric acid present as
a catalyst O
//
R—COOH + R1—OH 🡪 R—C—O—R1 + H2O

NB Reaction with PBr3 and PI3 to form alkyl bromides and alkyl iodides
respectively (heating under reflux)
R—OH + PBr3 🡪 3R—Br + H3PO3
R—OH + PI3 🡪 3R—I + H3PO3

5. Reaction with oxidising agents to form initially aldehydes and then carboxylic
acids for primary alcohols. It forms a ketone with secondary alcohols and there
is no reaction with tertiary alcohols

primary R—OH Na2Cr2O7 / KMnO4 R—COOH

warm, H+
O
//
secondary R—OH Na2Cr2O7 / KMnO4 R—C—R

48
 warm, H+

Breathalyser Test

A driver suspected of driving under the influence of alcohol is given a device containing
orange crystals of potassium dichromate lightly soaked in dilute sulphuric acid. The
driver is then asked to exhale into the device. The alcohol vapour is oxidised by the
crystals which are at the same time reduced to the green Cr3+ ion. The intensity of the
green colour is calibrated to alcohol concentration in the blood which is shown as a
digital readout.

Iodoform Test (this is used to test for the presence of a methyl ketone or the group
shown below)

Secondary alcohols containing the group below or a methyl ketone to the right (as well
as ethanol) react with iodine in alkaline solution to form the yellow ppt CHI3 (iodoform)
which is the basis of the iodoform test.

OH O H H
| || | |
CH3—C-- OR CH3 – C – R OR H – C – C – OH
| | |
H H H

Checkpoint A

49
Draw out the structures for the compounds below and state whether they would give a
positive or negative test with the iodoform reaction.

1. propan-1-ol

2. butan-1-ol

3. butan-2-ol

Checkpoint B
Write equations to show the reactions of:-
i) propanol + ethanoic acid
..................................................................................................................
ii) ethanol + calcium metal

.................................................................................................................

iii) butanol and xs conc. sulphuric acid at 170 °C

.................................................................................................................

Checkpoint C

Why must the crystals used for the breathalyser test be soaked with dilute sulphuric
acid or any acid at all?
…………………………………………………………………………………………………………………
……………………………………….
50
How to distinguish primary, secondary and tertiary alcohols
Reagent 1o alcohols 2o alcohols 3o alcohols
Lucas Reagent No visible reaction Solution turns Solution turns
(ZnCl2 in conc. HCl) cloudy in 3-5 cloudy immediately
minutes
Acidified potassium Changes from Changes from Remains orange
dichromate orange to green orange to green
(product forms (product has NO
silver mirror with reaction with either
Tollens’ reagent or Tollen’s or Fehling’s
brick-red ppt with reagent)
Fehling’s reagent)
END OF ALCOHOLS

PHENOLS

Phenols are aromatic alcohols e.g.

Reactions of phenols
1. Reaction with bromine water
A white ppt is immediately formed when bromine water is added to a solution of phenol
in water. The ppt smells of antiseptic.

51
2. Reaction with an acyl chloride like ethanoyl chloride
Phenol reacts with ethanoyl chloride at room temperature. Phenyl ethanoate is formed
together with hydrogen chloride gas.

3. Reaction with sodium hydroxide (note that aliphatic alcohols do NOT react with

sodium hydroxide)
Phenols are more acidic than alcohols and thus can react with strong bases like sodium
hydroxide.

Checkpoint D
You are given four unlabelled bottles. You are told that the labels were accidentally
removed, but the substances are phenol, ethanol,
propan-2-ol and 2-methylbutan-2-ol. Suggest a procedure with named reagents how
you would identify the four bottles.

…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
……………………………………………………………………………….………………………………
…………………………………………………………………………………………………………………

52
…………………………………………………………………………………………………………………
……………………………………………….
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
……………………………………………………………………………….………………………………
…………………………………………………………………………………………………………………
……………………………………………………………………………………
Relative acidities of water, ethanol and phenol

Both ethanol and phenol dissociate into their ethoxide and phenoxide ion respectively
and release a proton when dissolved in water therefore both substances can act as
acids. Note R represents any aliphatic chain, while Ar represents a benzene ring.

R—OH + H2O R—O- (aq) + H3O+(aq)

Ar—OH + H2O Ar—O- (aq) + H3O+(aq)

However they have varying orders of acidity, in fact increasing order of acidity is
ethanol, water and then phenol.

The strength as an acid depends on the stability of the anion formed. The greater
the charge is spread over the ion, the more stable the ion is and the more readily it is
formed. The more stable the anion, the more readily it is formed i.e. the more readily a
proton is donated i.e. the stronger the acid.

53
When water ionises, it forms a hydroxide and a hydroxonium ion, both of which have
no features that neither increase or decrease its stability, therefore in terms of acidity it
is intermediate of the two.
pKa values can be used to express acidity of molecules
The smaller the value, the more acidic the substance is:
Ethanol pKa = 16.0, Water pKa = 15.7, Phenol pKa = 10.0
END OF PHENOLS
Practice questions
1.

54
2.

55
 i) What functional groups are present in a molecule of aspirin?
………………………………………………………………………

2. Aspirin when taken as a pain reliever orally causes stomach irritation. Explain why
this would occur.
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…

3. Draw the organic product that would be formed for the reaction of aspirin and
sodium hydroxide

4 . Draw the organic product that would be formed for the reaction of salicylic acid and
sodium hydroxide

5. Draw the structures of the ethoxide ion and the propoxide ion arising from
propan-2-ol.

6. Which of the two ions from question 5 would most likely be the least acidic?
Suggest a reason for your answer.

56
Halogenoalkanes (Module 1)
a) give general formula of halogenoalkanes or alkyl halides
b) understand the differences between primary, secondary and tertiary alkyl halides
c) describe the chemical reactions of alkyl halides:- i) hydrolysis
ii) reaction with cyanide ions iii) reaction with ammonia gas
and give chemical equations for the reaction
d) appreciate that alkyl halides with an alcoholic solution of sodium hydroxide forms
the alkene and not the alcohol
e) state the name of the mechanism for the hydrolysis of alkyl halides
f) describe the mechanism for the hydrolysis of alkyl halides

Introduction

General formula = CnH2n+1X or simply R—X where R represents an alkyl group

They can be classified as primary, secondary or tertiary alkyl halides.

Primary alkyl halides have either 1 or no alkyl groups attached to the central carbon
atom.

Secondary alkyl halides have 2 alkyl groups (circled) attached to the central carbon
atom.

Tertiary alkyl halides have 3 alkyl groups (circled) attached to the central carbon atom

57
Aryl halides are compounds in which the halogen atom is attached directly to the
aromatic ring.

Please note that in alkyl halides, tertiary alkyl halides are more reactive than secondary
alkyl halides and primary alkyl halides are the least reactive. Aryl halides are even less
reactive than alkyl halides.

Reactions of alkyl halides

The point of attack would be the electron deficient carbon atom (due to the difference in
electronegativity) attached to the halogen atom, thus the attacking species would be a
nucleophile. All reactions need the present of heat i.e. reflux

1. Alcohol formation (R represents any hydrocarbon chain)

R—X + OH- 🡪 R—OH + X-
Primary and secondary alkyl halides undergo alkaline hydrolysis to the alcohol
while tertiary alkyl halides can be hydrolysed by water.
Aryl halides do not undergo hydrolysis except under VERY SEVERE conditions.
Industrially chlorobenzene is reacted with NaOH(aq) at 360 °C at a high pressure
then adding dilute HCl.

2. Amine formation
R—X + NH3(alc) heat in a sealed tube R—NH2 + HX
However the amine then reacts with the NH3 to form a secondary amine, which in
turn can react with more ammonia to form a tertiary amine etc.
However if an excess of ammonia is used, a better yield of the primary amine can be
58
 obtained.
3. Nitrile (cyanide) formation (can be used to increase the carbon chain by
one carbon atom)
R—X + CN aqueous alcohol
- R—CN + X-
Aqueous alcohol is used as the solvent, the alcohol dissolves the organic compound
while the water dissolves the sodium cyanide (source of cyanide ions)

Checkpoint A

1. State what type of alkyl halides (primary “P”, secondary “S” or tertiary “T”), the
following compounds are
a) chloroethane ………………. b) 2-chloropropane………………

c) 2-chloro-2-methylpropane…………………..

2. Complete the word equations for the following reactions

a) chloroethane + sodium hydroxide 🡪
…………………….................................................................................

b) 1-chloropropane + ……………………. 🡪 propylamine +

…………………………………………………………………….

3. Write the chemical equations for the word equations completed in question 2

a) …………………………………………………………………..

b) ……………………………………………………………………

59
4. Give a definition for the term electronegativity
…………………………………………………………………………………….
Halogenoalkanes undergo nucleophilic substitution mechanisms

Primary alkyl halides undergo SN2 reaction

(S= substitution, N = nucleophilic, 2 = bimolecular i.e. 2 species involved in forming the
intermediate)

Tertiary alkyl halides undergo SN1 reaction

(S= substitution, N = nucleophilic, 1 = unimolecular i.e. 1 species involved in forming
the intermediate)

Secondary undergo a mixture of the two.

SN1

The three methyl groups are electron donating (positive inductive effect (+I) and
this causes the electrons of the C-X bond to be pushed fully onto the halogen atom.
The causes the C-X bond to break and form a carbocation. The nucleophile is attracted
to the carbocation and the new substance is formed (am alcohol in this example)

SN2

60
The nucleophile (hydroxide ion) approaches the partially positive carbon atom from the
back (least hindrance) and it forms a bond between itself and the carbon atom, the
intermediate is the 5 co-ordinate species. The C-X bond then breaks. Since halogen
atoms are generally large, the nucleophile attacks the carbon atom from the back, this
results in an inversion of configuration.

Note: if alkyl halides are reacted with an alcoholic solution of sodium hydroxide, the
corresponding alkene is formed and NOT the alcohol.

Worksheet

1. Theoretically methane can be converted into ethanoic acid via the following steps
CH4 I CH3Cl II CH3CN III CH3COOH

State the reagents and conditions for step II

Step II
……………………………………………………………………………………

2. Difference in electronegativity values influences the magnitude of the positive charge

on the carbon atom in alkyl halides. The greater the difference, the more reactive the
alkyl halide.
Arrange the list C –Cl, C- I, C- Br in DECREASING reactivity

……………………………………………………………………..

61
Carbonyl compounds (Module 1)
a) know the two types of carbonyl compounds and be able to give general structural
formulae
b) apply IUPAC rules for the two types of carbonyl compounds
c) know how one can distinguish experimentally between the two types of carbonyl
compounds (refer to 2,4-DNPH, Tollen’s / Fehling’s reagent)
d) describe reactions of carbonyl compounds :- i) hydrogen cyanide (NaCN/HCl) ii)
Tollen’s reagent / Fehling’s reagent iii) KMnO4/H+
iv) LiAlH4 (ether) v) H2/Pt
e) state the name of the mechanism for the reaction of carbonyl compounds and
describe the mechanism using hydrogen cyanide as an example

CARBONYL COMPOUNDS

Introduction

Aldehydes and ketones can be referred to as carbonyl compounds as they both contain
the carbonyl >C=O, functional group.

62
They have the general formula of CnH2nO.

General shape of an aldehyde General shape of a ketone

R, R’ may be an alkyl or aryl group.

Nomenclature of aldehydes and ketons

Prefix Suffix of aldehydes - anal

# of carbon atoms Suffix of ketones - anone
1 – meth
2 – eth
3 – prop

e.g. H-CHO methanal

CH3-CHO ethanal
(CH3)2 C=O propanone

Checkpoint A

63
Give the names of the following carbonyl compounds based on the molecular formulae
a) C2H5 – CHO ……………………..
b) C4H9-CHO………………….
c) C2H5(CH3) – C=O ……………
d) H-CHO ……………..

How to distinguish between aldehydes and ketones

Reagent Aldehyde Ketone
2,4-DNPH Yellow or light Yellow or light
(2,4-dinitrophenylhydra orange ppt orange ppt
zine) also called Brady’s
reagent
Tollen’s reagent Silver mirror on No visible
inside of change
test-tube
Fehling’s reagent Brick-red ppt No ppt formed

Reactions of carbonyl compounds

Reagent Aldehyde Ketone
KMnO4/H+ These are Ketones are
oxidised to resistant to
carboxylic acids oxidation
Tollen’s reagent Aldehydes are No reaction
/ Fehling’s oxidised and a occurs
reagent silver mirror is
seen with
Tollen’s reagent
or a brick-red
ppt seen with
Fehling’s reagent

64
LiAlH4 (ether) These are These are
reduced to the reduced to the
primary alcoholsecondary
alcohol
H2/Pt These are These are
reduced to the reduced to the
primary alcohol secondary
alcohol
hydrogen A cyanohydrin or A cyanohydrin or
cyanide hydroxynitrile is hydroxynitrile is
(NaCN/HCl) formed formed
Haloform / Iodoform Reaction

This reaction is used to test for the presence of either

a methyl ketone CH3 or H

\ |
C=O H3C—C—
/ |
OH

Reagents: I2 and NaOH

Observations for positive reaction: fine yellow crystals

(iodoform) with a characteristic “hospital” smell

Checkpoint B

65
Mechanism for reaction of carbonyl compounds

The mechanism is called nucleophilic addition

The mechanism for the addition of HCN to propanone

66
In the first stage, there is a nucleophilic attack by the cyanide ion on the slightly
positive carbon atom.

The negative ion formed then picks up a hydrogen ion - for example, from a hydrogen
cyanide molecule to form a cyanohydrin

The mechanism for the addition of HCN to ethanal

As before, the reaction starts with a nucleophilic attack by the cyanide ion on the
slightly positive carbon atom.

It is completed by the addition of a hydrogen ion from, for example, a hydrogen cyanide
molecule.

Checkpoint C

67
68
Carboxylic acids and derivatives (Module 1)
a) give general formula of carboxylic acids
b) understand the structural formula of the functional group
c) describe chemical reactions of carboxylic acids:-
i) reaction with metals ii) reaction with bases
iii) reaction with carbonates iv) esterification v) PCl5, PCl3, SOCl2
and give equations for reactions i) to iv)
d) describe properties of esters (sweet smell, low molecular mass)

69
e) apply IUPAC rules for naming esters
f) be able to state the starting compounds from the name of the ester only
g) describe the acid and base hydrolysis of esters and give equations
h) describe the process of saponification and give equations
i) describe the process of transesterification biodiesel production
j) be able to give and explain the order of acidity of alcohols, phenols and carboxylic
acids (include chlorosubstituted acids and refer to pH and pKa values)
CARBOXYLIC ACIDS AND DERIVATIVES

Structure of a typical carboxylic acid

This group is the functional group

This is an example of an aliphatic acid

Aromatic carboxylic acids have a carboxyl group attached directly to an aromatic ring.
Reactions of carboxylic acids

1. With highly reactive metals and inorganic bases/alkalis to form the salt and
hydrogen gas for highly reactive metals and a salt and water formed from
inorganic bases
2CH3COOH(aq) + Na(s) 🡪 CH3COONa(aq) + H2(g)
ethanoic sodium sodium hydrogen
acid ethanoate gas
2CH3COOH(aq) + NaOH(aq) 🡪 CH3COONa(aq) + H2O(l)
ethanoic sodium sodium water
acid hydroxide ethanoate

70
2. Amide formation
With ammonia to form an
ammonium
salt, which then decomposes
by heat
(remember this reaction is
done in reflux) to form an
amide
RCOOH + NH3 🡪 RCOO-NH4+
RCOO-NH4+ 🡪 RCONH2 + H2O
3. Ester formation
Reflux with alcohols in the presence of conc. sulphuric acid and 170 °C to form an
ester and water (Note esters are low molecular mass compounds, which have sweet
smells and are insoluble in water)
RCOOH + R1OH conc.H2SO4 RCOOR1 + H2O
4. Acid chloride formation
With chlorinating agents e.g.
dichlorosulphur (IV) oxide SOCl2
or phosphorous (V) chloride PCl5
to form an acid chloride
RCOOH + PCl5 or SOCl2
RCOCl + HCl

5. With carbonates and hydrogen

carbonates to give a salt,
carbon dioxide and water
2RCOOH + Na2CO3 🡪
2RCOO-Na+ + CO2 + H2O
RCOOH + NaHCO3 🡪 RCOO-Na+ + CO2 + H2O

6. Reduction
With LiAlH4 to form the corresponding alcohol
RCOOH LiAlH4 (in ether) RCH2OH

71
7. Anhydride formation
When 2 molecules of a carboxylic acid is reacted with a dehydrating agent such as
phosphorous (V) oxide P4O10, a molecule of water is eliminated and an acid
anhydride is formed.
2RCOOH distilled in P4O10 (RCO)2O

Checkpoint A

72
Reactions of acid derivatives

1. Hydrolysis
Acid chlorides are hydrolysed to give carboxylic acid and hydrogen chloride gas
RCOCl + H2O 🡪 RCOOH + HCl
Esters are also hydrolysed to give the original alcohol and if the reagent is a strong
mineral acid, then the carboxylic acid is formed
RCOOR1 + H+ 🡪 ROH + RCOOH
If the reagent is a strong alkali, then the original alcohol is formed and the salt of
the carboxylic acid RCOOR1 + OH- 🡪 ROH + RCOO-
2. Ester formation
Acid and aroyl chlorides react readily with alcohols and with phenols in alkaline
solutions respectively to form esters
CH3COCl (l) + C2H5OH (l) 🡪 CH3COOC2H5 + HCl
ethanoyl ethanol ethyl hydrogen
chloride ethanoate gas
CH3COCl + O-Na+ 🡪 O—C—CH3 + NaCl (s)
||
O
sodium phenoxide phenyl ethanoate
3. Amide formation
Amides are formed by reaction of acid chlorides with ammonia and with primary and
secondary amines
RCOCl + NH3 🡪 RCONH2 + HCl
RCOCl + R2NH 🡪 RCONR2 + HCl
4. Anhydride formation
When an acid chloride is heated with the sodium salt of a carboxylic acid, the acid
anhydride is formed
RCOCl + RCOO-Na+ 🡪 (RCO)2O + NaCl
NB acid anhydrides react in a similar way to acid chlorides; they form esters with
alcohols and phenols and they form amides with ammonia and primary and
secondary amines.
Checkpoint B

73
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………

Saponification (alkaline hydrolysis of fats/oils)

When fats/oils are hydrolysed by an alkali, “soap” is produced.

How is a fat/oil molecule formed?

By the reaction of glycerol and long chain fatty acids (carboxylic acids with hydrocarbon
chains containing 12 or more carbon atoms)
Glycerol is propane-1,2,3-triol

Long chain fatty acids could be: C15H31COOH palmitic acid (saturated), C17H35COOH
stearic acid (saturated)
C17H33COOH oleic acid (unsaturated)
74
When a fat/oil molecule is hydrolysis by an alkali, the glycerol is formed as well as the
sodium salt of the long chain fatty acid. The sodium salt of the acid is the soap.

Transesterification biodiesel production

Biodiesel production is the act of producing the biofuel, biodiesel, through either
transesterification or alcoholysis. The process involves reacting vegetable oils or animal
fats catalytically with a short-chain aliphatic alcohols (typically methanol or ethanol).

The vegetable oil is reacted with alkali in the presence of ethanol or methanol as a
catalyst under reflux, which produces the esters of the fatty acids and glycerol. The
biodiesel is the collection of the esters produced.

75
Checkpoint C

What advantages would there be for the use of biodiesel or biofuel in general?
………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………….......
Explanation of relative acidities of acids and chlorine substituted acids

Carboxylic acids are only partially ionised in aqueous solution owing to the
predominantly covalent nature of the molecule are only weak in comparison with
mineral acids. RCOOH + H2O RCOO- + H3O+

The relative strength of acids is attributed to the stability of the acid anion.
The more stable the acid anion, the stronger the acid.

The longer the hydrocarbon acid, the WEAKER the acid. However, the more
electronegative atoms i.e. Cl atoms present in the aliphatic chain the STRONGER the
acid.

Acidic strength of aliphatic acids decreases in the order

(Cl)3CCOOH > CH(Cl)2COOH > CH2ClCOOH > CH3COOH > CH3CH2COOH

In aliphatic acids, the more electron withdrawing groups present, this represents a
spreading of the charge on the oxygen atom (from the anion formed from dissociation in
aqueous solution). Therefore trichloroethanoic acid is more acidic than
dichloroethanoic acid etc.
Propanoic acid is a weaker acid than ethanoic acid since there is an alkyl group (-CH3)
76
which is electron donating and thus increasing the charge on the oxygen atom, making
the anion formed from dissociation more unstable i.e. a weaker acid than ethanoic acid.

NB The lower the pKa value, the stronger the acid.

Note that aliphatic alcohols are the weakest acids, then phenols are stronger and
finally carboxylic acids show the highest acidity.

The acid anion of carboxylic acids are therefore the most stable, then the acid anion
from phenols and finally the acid anion from ethanol.

Checkpoint C

77
Amines (Module 1)
a) state general formula of amines
b) distinguish between aliphatic and aromatic amines
c) describe the chemical reactions of primary amines with dilute acid
d) describe the production of phenylamine from nitrobenzene (using Sn/HCl conc.)
e) describe the formation of an azo compound
f) state uses of azo compounds
g) give the structural formula of an amide
h) state and explain the order in basic character of aliphatic amines, amides and
aromatic amines (refer to pH and pKb)
i) give the general structural formula of amino acids
78
j) explain the acid-base properties of amino acids (refer to zwitterions
Amines

Introduction
Amines are alkyl derivatives of ammonia, and may be classified as primary, secondary
or tertiary amines.

CH3NH2 (primary ) methylamine (CH3)2NH (secondary) dimethylamine

(CH3)3N (tertiary) trimethylamine

Aromatic amines have a amine group (—NH2) directly attached to the ring

C6H5NH2 phenylamine

Reactions of primary amines with HCl

RNH2 (whether aliphatic or aromatic + HCl 🡪 RNH3+Cl-

79
An acid-base reaction and a salt is produced.

Reactions of ethylamine and phenylamine with nitrous acid and bromine

1. Ethylamine reacts with nitrous acid to produce nitrogen gas, a mixture of alkenes
and alcohols.
2. Phenylamine reacts with nitrous acid (formed in situ by the reaction of sodium
nitrite and hydrochloric acid) below 10 °C to form an aromatic diazonium salt
C6H5—NH2 + NaNO2 + HCl 🡪 C6H5 –N≡N+ Cl- + 2H2O
phenylamine benzenediazonium chloride
3. Ethylamine does NOT react with bromine
4. Phenylamine reacts rapidly with bromine water to form 2,4,6-tribromophenylamine
and hydrogen bromide
NH2 + 3Br2 NH2 + 3HBr

Preparation of phenylamine

C6H5—NO2 industrial Fe + acid C6H5—NH2

lab: Sn + HCl (aq)
nitrobenzene phenylamine

Uses of azo compounds

80
All azo compounds have the functional group

e.g.
Primary uses are as dyes or pigments. Some are even used as acid-base indicators.
Relative basicities of ammonia, ethylamine and phenylamine

RNH2 + H2O
RNH3 + OH
+ -

Increasing order of relative basicity :- phenylamine < ammonia < ethylamine

Bases are electron donors or proton acceptors. The nitrogen atom in amines or
ammonia possess a lone pair of electrons which is available for donation.
In ethylamine, there is a methyl group attached to the nitrogen atom (i.e. an electron
donating group) this represents a localising or concentrating of negative charge and
thus the lone pair is readily available for donation i.e. it is a strong base.
In phenylamine, there is an aromatic ring attached to the amine group, this ring
possesses a pi system of delocalised electrons which represents a SPREADING of
negative charge. This spreading of charge makes the lone pair of electrons LESS
available for donation. This results in phenylamine being a weaker base than
ethylamine.
Ammonia possesses no features to increase or decrease the availability of the lone pair
of electrons for donation i.e. to act as a base. This results in its basicity being
intermediate of ethylamine and phenylamine.

81
Checkpoint A

…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
……………………………………………

Amides

All have the functional group

Amide can be formed from amines from the reaction

RCOOH + NH3 🡪 RCONH2 + H2O

Amino acids
General structure

82
All amino acids can form zwitterions and exhibit buffering properties.

zwitterion

Checkpoint B
Show via equations how a zwitterion can act as a buffer

83
Practice Questions

84
[2]

85
Macromolecules (Module 1)
a) define a monomer and a polymer
b) list the 2 types of polymers
c) describe the characteristics of addition and condensation polymerisation (refer to
polythene, polyvinyl chloride, polytetrafluorethene, terylene, nylon 6.6, proteins, starch)
d) be able to predict the type of polymer formed from given monomers
e) deduce the repeat unit of a polymer
f) be able to identify proteins and carbohydrates as naturally occurring polymers (refer
to starch, cellulose, pectin, proteins)
g) illustrate the connection between carbohydrates and their monomers
POLYMERISATION

Polymerisation is the formation of a large molecule from the combination of small

molecules.

Types of polymerisation

1. Addition
This is the straightforward addition of small molecules to form a large molecule. The
monomers used in addition polymerisation are alkenes or derivatives of alkenes.

2. Condensation
In this process, with the addition of 2 or more monomers, there is always the
evolution of a small molecule usually water or ammonia. Each monomer has AT
LEAST two functional groups.

86
Types and uses of polymers

Addition polymers (alkenes and other unsaturated compounds undergo addition

polymerisation)
Name Monomer Polymer (repeating Uses
unit)
Poly(ethene) or Ethene Polythene has 40% of
polythene CH2=CH2 polyalkane market. Low
density polythene has a low
m.p. and it is used for
making plastic bags and
toys. High density
polythene is used for
kitchenware, food boxes,
bowls etc
Poly(chloroethene) Chloroethene or PVC is more rigid than
PVC vinyl chloride polythene. Used as a
CH2=CHCl building material e.g.
guttering, electrical
insulation and pipes
Poly(tetrafluoroethe Tetrafluoroethe Used for coating surfaces to
ne) Teflon ne reduce friction e.g.
non-stick frying pans
CF2=CF2

Condensation polymers (compounds with two functional groups undergo

condensation polymerisation)

The difficulty of disposing polyalkanes

1. Plastics are man-made, therefore no natural organism can degrade them, i.e.
non-biodegradable, thus dumping does not solve the problem.
2. Plastics are also chemically inert, very unreactive, therefore no none reaction can be
used to dispose of them, however due to new technologies, there are biodegradable
plastics.
87
3. Very difficult to not use plastics as they have many uses where glass would be either
non-economical or unsafe. This establishes our great need for polyalkanes.
4. Incineration is not the answer either, as this introduces noxious fumes into the
atmosphere which may do more harm than good to the environment.
Naturally occurring macromolecules:- proteins are natural polyamides and
carbohydrates are natural polysaccharides.

Comparison of properties of a monomer and its polymer (using glucose and starch)

Property Glucose Starch Explanation

Solubility Soluble in Insoluble in water Low molecular mass of glucose
water (forms a colloid) coupled with –OH groups present
makes it soluble. However the high
molar mass of starch prevents the
formation of enough hydrogen
bonds for it to dissolve in water
Reducing Forms a No ppt is formed Monomeric glucose possesses free
sugar brick-red ppt –OH groups which can reduce the
with either Cu2+ ion, while starch does not
Benedict’s or possess these –OH groups.
Fehling’s
solution
Forms a No ppt is A blue-black colour Iodine is integrated within the
complex formed. is formed because of structure of starch which is absent
with iodine the starch-iodine in glucose.
complex

ADDITION POLYMERS

i) Formation of addition polymers

Addition polymers are formed from alkenes and are discussed in 12.3 Alkenes and
Epoxyethane.

Alkenes can be made to join together in the presence of high pressure and a suitable
catalyst. The π-bond breaks and the molecules join together. No other product is

88
formed, and so this is known as addition polymerisation. Since the polymers are
made from alkenes they are also known as polyalkenes.

ethene 🡪 polyethene

The product of this addition process is a very long hydrocarbon chain.

Addition polymers can be made from any alkene:

Eg propene poly(propene)

Eg but-2-ene poly(but-2-ene)

89
Many useful polymers are addition polymers made by this process:

● polyethene is used in plastic bags and in crates

● polypropene is used in plastic tubing

● polychloroethene (polyvinylchloride) is used in waterproof clothing and records

● polyphenylethene (polystyrene) is used in packaging

The most favourable conditions for the polymerisation of alkenes can be deduced from
Le Chatelier's principle, if two points are noted:
- the reaction involves breaking -bonds only, and many -bonds are made. The
reaction is thus exothermic.
- The reaction involves a reduction in the total number of moles:
90
Since the reaction is exothermic, the best yield is obtained at low temperature. Since
the number of gas moles decreases, the best yield is obtained at high pressure.

Addition polymerisation reactions are carried out at high pressure in the presence of a
suitable catalyst.

ii) Properties of addition polymers

Addition polymers (polyalkenes) are long chain hydrocarbons which are saturated and
non-polar. Their structure results in their having a number of characteristic properties:

a) Since the hydrocarbon chains are often very long, the Van der Waal's forces between
the chains are often very strong and the polymers have relatively high melting and
boiling points. Since the chain length is variable, most polymers contain chains of a
variety of different lengths. Thus the Van der Waal's forces are of variable strength
and these polymers tend to melt gradually over a range of temperatures rather than
sharply at a fixed temperature. As the chains are not rigidly held in place by each
other, polymers tend to be reasonably soft.

b) Since the chains are non-polar, addition polymers are insoluble in water. Since the
intermolecular forces between the molecules are strong and the chains are often
tangled, they are generally insoluble in non-polar solvents as well. In fact the long
saturated hydrocarbon chains result in polyalkenes being very unreactive generally,
as they cannot react with electrophiles, nucleophiles or undergo addition reactions.

This results in their widespread use as inert materials - they are very useful as
insulators, as packaging and in making containers.

However their low reactivity means that they are not easily decomposed in nature
and as a result have a very long lifetime. Such substances are said to be
non-biodegradable, and constitute an environmental hazard as they are very
persistent in nature and thus difficult to dispose of.

91
c) The density and strength of addition polymers varies widely. They depend to a
certain extent on the length of the hydrocarbon chain, but depend much more
strongly on the nature and extent of the branching on the chain.

Polymers which have very few branches are very compact and the chains can thus
pack together very efficiently:

These polymers tend to have a very high density. Since the chains are closely
packed, the Van der Waal's forces between the chains are strong and these polymers
tend to be stronger and harder as well.

Polymers which are highly branched cannot pack together as well, and there tend to
be large spaces in the structure:

These polymers have a much lower density. Since the chains are not closely packed,
the van der Waal's forces between the chains are weaker and these polymers tend to
be weaker and softer.

CONDENSATION POLYMERS

i) Polyesters

It has been shown that if a carboxylic acid or acyl chloride is reacted with an alcohol,
then an ester is formed and a water molecule is lost.
92
Eg ethanoyl chloride + ethanol 🡪 ethyl ethanoate + HCl

Eg benzoic acid + methanol 🡪 methyl benzoate + H2O

These are examples of condensation reactions – combination of two or more molecules

followed by the elimination of a small molecule.

It follows that if a dicarboxylic acid is reacted with a diol, then the -COOH group at
each end of the dicarboxylic acid should join to an -OH group, and the -OH group at
each end of the diol should join to a -COOH group. It should therefore be possible for
all the molecules to link together and form a polymer.

Eg benzene-1,4-dicarboxylic acid and ethan-1,2-diol

benzene-1,4-dicarboxylic acid ethan-1,2-diol

These two compounds can link together to form a polymer, and water is given off:

93
This polymer can be represented by the following repeating unit:

The overall equation can be represented as:

The monomer units are linked together by the ester group:

94
Polymers containing this type of linkage are therefore known as polyesters.

The above polymer is known as terylene. It is used in fire-resistant clothing (eg racing
drivers)

The same polyester can also be formed by the combination of a diacyl chloride and a
diol:

Eg benzene-1,4-diacyl chloride and ethan-1,2-diol

These two monomer units link together to form the same polymer. The only difference is
that HCl instead of H2O is given off.

The overall equation can be represented as:

The polymerisation reaction with diacyl chlorides produces a much better yield than the
corresponding polymerisation reaction with dicarboxylic acids. This is because acyl
chlorides are more reactive than carboxylic acids and also because the HCl produced is
gaseous and thus escapes, making the reaction more difficult to reverse.
95
Thus dicarboxylic acids are generally converted to diacyl chlorides (by addition of PCl5)
before a polymerisation is carried out.
Another example of polyester formation is:

Ethanediacyl chloride and propan-1,2-diol

ii)
Polyamides

It has been shown that if a carboxylic acid or acyl chloride is reacted with a primary
amine, an N-substituted amide is formed:

Eg propanoic acid + ethylamine == N-ethylpropanamide + H2O

Eg ethanoyl chloride + 1-aminopropane 🡪 N-propylethanamide + HCl

It follows that if a dicarboxylic acid is reacted with a diamine, the -COOH group at each
end of the dicarboxylic acid with join to an -NH2 group, and the -NH2 group at each end
96
of the diamine will join to a -COOH group. It should therefore be possible for each of the
molecules to join together and form a polymer.

Eg hexanedioic acid + 1,6-diaminohexane

These two compounds can link together to form a polymer, and water is given off.

The polymer can be represented by the following repeating unit:

The overall equation can be represented as:

97
The monomers are linked together by the amide, or peptide link:

Polymers containing this type of linkage are therefore known as polyamides.

The above polymer is known as nylon 66. It is a man-made fibre used in clothing

The same polyamide can be formed by the combination of the diacyl chloride and the
diamine:

These two monomer units link together to form the same polyamide. The only difference
is that HCl is given off instead of water.

The overall equation can be represented as:

The polymerisation reaction with diacyl chlorides gives a much better yield than with
the corresponding dicarboxylic acid for the same reasons as with the polyesterification

98
reaction. Dicarboxylic acids are therefore converted to the corresponding diacyl chloride
(by addition of PCl5) before the polymerisation is carried out.

Another example of polyamide formation is:

Butanedioyl chloride and 1,2 diaminopropane

Polyesters and polyamides are collectively known as condensation polymers because

they are the product of condensation reactions.

iii) Properties and uses of condensation polymers

Condensation polymers tend to consist largely of straight chains with few branches.
This is because they are formed by reactions with heterolytic mechanisms, which are
much less random than homolytic mechanisms. Addition polymers are formed by free
radical addition mechanisms which always lead to a variety of products and
consequently much more branching.

Since there are few branches in condensation polymers, they are usually linear and can
thus pack closely tegether. Condensation polymers are therefore more rigid than
addition polymers and have a higher tensile strength.

The strength of the intermolecular forces between the different chains in polyamides is
further enhanced by the presence of hydrogen bonding.

99
Polyamides are therefore generally very strong. In some natural polyamides, such as
proteins, intramolecular hydrogen bonding is possible and the molecule curls up to
form a helical structure:

Polyamides and polyesters are both used largely in high-strength synthetic fibres.

Polyesters are used as wool and cotton substitutes in clothing (esp jumpers, T-shirts,
shirts etc) and also in carpets and rugs. Bullet-proof vests and some flame-retardant
clothing are made from polyesters.

Polyamides are more elastic and used in underwear, fishing nets and other synthetic
fibres.

Perhaps the most important difference between condensation polymers and addition
polymers is that condensation polymers are made up of chains containing polar bonds;
i.e. C-N and C-O bonds which link every polymer unit. These polar carbon atoms can be
readily attacked by nucleophiles and as a result the polymers can be broken up and the
constituent monomers reformed. Condensation polymers are hence biodegradable, and
so clearly constitute a smaller environmental hazard than addition polymers, whose
chains are made up entirely of non-polar C-C bonds and which are hence
non-biodegradable.

The break-up of these polymers is carried out in aqueous solution and can be classed
as hydrolysis reactions:

Polyesters are best hydrolysed in strongly alkaline conditions, in which they undergo
saponification:

100
Polyamides are best hydrolysed in strongly acidic conditions:

The biodegradability of condensation polymers may compromise their effectiveness,

since physical and chemical durability is one of the reasons for their widespread use. A
balance must be struck between practical durability and long-term biodegradability.

Practice Questions

101
102
103
MODULE 2

104
Uncertainty in Measurements (Module 2)
a) understand the concept of errors in measurement and their importance in analytical
chemistry (refer to measurements using thermometers or beakers or measuring
cylinder or rulers i.e. reporting values with a margin of error)
b) understand and explain the main types of errors that can occur:- random (statistical
fluctuations either too high or too low)
systematic (reproducible inaccuracies in the same direction i.e. always either too high
or too low)
c) know how random and systematic errors can be minimised (random errors can be
reduced by conducting more measurements and obtaining an average, but systematic
errors can only be eliminated if the cause is known) e.g. if a scale was incorrectly
zeroed, it would give a constant error
d) know and explain the differences between accuracy and precision
e) know that a measurement is only valid if it is both accurate and precise
f) be able to calculate the mean and standard deviation from a series of data points
g) know and appreciate the role of standards and calibration curves in measurement
h) know the uncertainty in measurements using thermometers, burettes, pipettes,
measuring cylinders, volumetric flasks, top loading and analytical balances
i) be able to state which type of instrument should be used depending on the accuracy
required

Precision vs Accuracy
Accuracy is the degree of closeness of a measured or calculated quantity to its actual
(true) value. Precision, is the closeness of the values to each other. The results of
calculations or a measurement can be accurate but not precise; precise but not
accurate; neither; or both. A measurement system or computational method is called
valid if it is both accurate and precise.
Errors made in measurements can be either random or systematic.
Random errors can be minimised as it usually is related to experimental technique e.g.
reading the value of a burette or pipette. Generally random errors result in a spread of
105
data around the mean. This is called variability or the standard deviation of the
data. Systematic error (or bias) is more difficult to eliminate, since it is usually
equipment error that causes the problem. If the equipment is not regularly calibrated,
or changes in the environment or even using improper observational skills, systematic
error can occur. Systematic errors cause the mean of the value to differ significantly
from the “true” value. Systematic errors are usually in one direction i.e. either greater
or less than the true value. It is a constant error that occurs.
In analytical chemistry, a calibration curve is a general method for determining
the concentration of a substance in an unknown sample by comparing the
unknown to a set of standard samples of known concentration.
The calibration curve is a plot of how the instrumental response, the so-called
“analytical signal,” changes with changing concentration of analyte (substance to be
measured).

Most analytical instruments produce a signal even when a blank (matrix without
analyte) is analyzed. This signal is referred to as the noise level
LOD – limit of detection is the lowest quantity of a substance that can be
distinguished from the absence of that substance (a blank value) within a stated
confidence limit (generally 1%)
LOQ – Limit of Quantification Just because we can tell something from noise does not
mean that we can necessarily know how much of the material there actually is. The
LOQ is the limit at which we can reasonably tell the difference between two different
values.
Note, the gradient of the slop indicate sensitivity of the device. The higher the
gradient, the more sensitive the device.
Example
It is often difficult to understand the concept of detection limit. The following example may
help to clarify some of the concepts defined above.
Suppose you are at an airport with lots of noise from jets taking off. If the person next to
you speaks softly, you will probably not hear them. Their voice is less than the LOD. If
they speak a bit louder, you may hear them but it is not possible to be certain of what
they are saying and there is still a good chance you may not hear them. Their voice is
>LOD but <LOQ. If they speak even louder, then you can understand them and take
action on what they are saying and there is little chance you will not hear them. Their
voice is then >LOD and >LOQ. Likewise, their voice may stay at the same loudness, but
106
the noise from jets may be reduced allowing their voice to become >LOD. Detection limits
are dependent on both the signal intensity (voice) and the noise (jet noise).
Mean

In mathematics, an average, or central tendency of a data set refers to a measure of

the "middle" or "expected" value of the data set. There are many different descriptive
statistics that can be chosen as a measurement of the central tendency of the data
items.

Standard deviation

Sample standard deviation. The formula is:

Example
The owner of the Ches Tahoe restaurant is interested in how much people spend at the
restaurant.  He examines 10 randomly selected receipts for parties of four and writes
down the following data.   44,   50,   38,   96,   42,   47,   40,   39,   46,   50
He calculated the mean by adding and dividing by 10 to get

Calibration is the comparison between measurements - one of known magnitude

or correctness made or set with one device and another measurement made in as
similar a way as possible with a second device.
107
Calibration Technique of a Pipette
One of the easiest ways of calibrating a pipette is via gravimetric calibration.
In gravimetric calibration you are measuring the weight of water a pipette
dispenses. This weight must then be converted into a volume by using the physical
property of water density. 
Volume (ml) = Weight of water dispensed ( mg ) / density of water (mg/ml)
The density of water is a well-known constant at known temperatures, and thus the
mass of the dispensed sample provides an accurate indication of the volume dispensed.
Remember the density of water is temperature dependent.

Worksheet
1.

108
Titrimetric (volumetric) methods of analysis (Module 2)

109
a) know and explain the basic principles upon which titrimetric analyses are based
(using the concentration of one solution to determine to concentration of an unknown
sample)
b) know and understand the concepts of indicator, end point and equivalence point
c) explain the concept of standardisation and why it is necessary
d) know at least 4 characteristics of primary standards and be able to list 4 primary
standards
e) know at least 3 types of titrations that do not require indicators (refer to
potentiometric, conductimetric and thermometric)
f) be able to perform calculations on data from conductimetric and thermometric
titrations
g) perform calculations on data obtained from titrimetric analyses
h) cite examples of the use of titrimetric analysis in the quantification of various
substances (refer to vinegar, household cleaners, vitamin C tablets, aspirin, antacids)
Titrimetric (volumetric) methods of analysis (Module 2)

110
Titrant is the reagent of known concentration and it reacts with the other solution
called the analyte or titrand.

The endpoint is the point at which the titration is complete, as determined by an

indicator’s colour change.

The equivalence point is the volume of added titrant at which the number of
moles of titrant is equal to the number of moles of analyte.

Standard solutions (solutions of known concentration) must be used in a titration. A

primary standard which is the substance used to make a standard.
Characteristics of primary standards
1. High purity
2. Stability (low reactivity)
3. Low hygroscopicity (absorbing water to atmosphere) and efflorescence (releasing
water to the atmosphere)
4. High solubility (if used in titration)
5. High equivalent weight
6. It should be nontoxic
7. It should be readily available (inexpensive)
8. It should be environmentally friendly

Examples of primary standards are:- sodium carbonate, oxalic acid and its salts,
sodium chloride, potassium hydrogen phthalate, benzoic acid)

Type of titrations (d o not need an indicator)

● Redox titration is a type of titration based on a redox reaction between the
analyte and titrant. (usually the redox reagent acts as its own indicator)
● Potentiometric is related to the use of a potentiometer can also be used. This is
an instrument which measures the electrode potential of the solution. These are
used for titrations based on a redox reaction; the potential of the working
electrode will suddenly change as the equivalence point is reached.

111
 ● Conductimetric analysis uses the change of conductivity of the solution, either a
maximum or minimum shows the end point
● Thermometric uses the change in temperature to indicate the end point
● Back titrations are like normal titrations, except that a known excess of a
standard reagent is added to the solution being titrated. The solution is then
titrated back, taking into account the addition of the excess. Back titrations are
useful if the end point of the reverse titration is easier to identify than the end
point of the normal titration. (exception must should be known as well)

Use of titrimetric analyses

Quantification of various substances e.g. vinegar, household cleaners, vitamin C

tablets, aspirin, antacids)

Worksheet
1. Titration reveals that 11.6 mL of 3.0 M sulfuric acid are required to neutralize the
sodium hydroxide in 25.00 mL of NaOH solution. What is the molarity of the NaOH
solution?

2.

Example of a back titration calculation

2.75 g sample of dolomite containing CaCO3 and MgCO3 is dissolved in 80 cm3 of 1 M
HCl solution. The solution is then diluted to 250 cm3. 25 cm3 of this solution requires
20 cm3 of 0.1M NaOH solution for complete neutralisation. Calculate the % composition
of the sample.

a) # of mol of NaOH used = 20 / 1000 x 0.1 = 0.002 mol NaOH

112
b) NaOH + HCl 🡪 NaCl + H2O
therefore # of mol of HCl that remained in 25 cm3 = 0.002
therefore # of mol HCl that remained in 250 cm3 = 0.02
therefore # of mol of HCl that reacted = ((80/1000) x 1)) – 0.02 = 0.06

c) CaCO3 + MgCO3 + 4HCl 🡪 CaCl2 + MgCl2 + 2CO2 + 2H2O

therefore 0.06 / 4 mol of both CaCO3 and MgCO3 was present = 0.015

d) 0.015 mol of CaCO3 = 0.015 x (40 + 12 + 48) = 1.5g

0.015 mol of MgCO3 = 0.015 x (24 + 12 + 48) = 1.25g

e) 1.5/2.75 x 100 = 54.5% CaCO3

1.25 / 2.75 x 100 = 45.5% MgCO3

113
114
Magnesium oxide is not very soluble in water, and is difficult to titrate directly. Its
purity can be determined by use of a 'back titration' method. 4.06 g of impure
magnesium oxide was completely dissolved in 100 cm3 of hydrochloric acid, of
concentration 2.0 mol dm-3 (in excess). The excess acid required 19.7 cm3 of sodium
hydroxide (0.20 mol dm-3) for neutralisation. This 2nd titration is called a
'back-titration', and is used to determine the unreacted acid. [atomic masses: Mg =
24.3, O = 16)
(a) write equations for the two neutralisation reactions.

115
(b) calculate the moles of hydrochloric acid added to the magnesium oxide.

(c) calculate the moles of excess hydrochloric acid titrated.

(d) calculate the moles of hydrochloric acid reacting with the magnesium oxide.

(e) calculate the moles and mass of magnesium oxide that reacted with the
initial hydrochloric acid.

(f) hence the % purity of the magnesium oxide.

Gravimetric methods of analysis (Module 2)

a) explain the principles upon which gravimetric analyses are based (refer to
precipitation and volatilisation methods)

116
b) describe the function of various pieces of apparatus used in gravimetric analyses
(refer to suction flasks, suction funnels, silica crucibles, sinter glass crucibles and oven
/ furnaces)
c) perform calculations on data obtained from gravimetric analyses
d) cite examples of the use of gravimetric analysis in quality control (refer to estimation
of SO2 in soft drinks, estimation of pollutants in air

Gravimetric analysis describes a set of methods in analytical chemistry for the

quantitative determination of an analyte based on the mass of a solid.
In most cases, the analyte must first be converted to a solid by precipitation with an
appropriate reagent. The precipitate can then be collected by filtration, washed, dried to
remove traces of moisture from the solution, and weighed. The amount of analyte in the
original sample can then be calculated from the mass of the precipitate and its
chemical composition. When the precipitating reagent is added, there is a period of
induction (time taken before the first sign of precipitate is seen) and then nucleation
(when a minimum amount of ions come together to form a stable solid) occurs. Large
crystals are preferred to small crystals as they are more easily filtered, digestion
(heating of the solid and mother liquor [liquid containing the solid]) encourages the
formation of large crystals.
For filtration, a vacuum pump is used (large conical flask connected to a tap via an
aspirator), sintered crucible are used (small crucible with very high melting point,
inert) which can withstand high pressures used in vacuum filtration. A rubber
policeman (glass rod with a hard rubber scrapper on one end) is also used to transfer
residues of solid or precipitate onto glass surfaces. The precipitate is rinsed with cold
distilled water and then heated in an oven to remove all traces of water and then cooled
in a dessicator (air tight container which contains silica to absorb any water vapour
present) before weighing.
In other cases, the volitilisation method would be used. For example with a hydrated
salt, the aim is to determine the number of moles of water of crystallisation present. It
would be heated multiple times to remove the water ( and the difference in mass can
then be used to determine the amount of water present and thus the number of moles
of water needed for one mole of the anhydrous salt.
NB Sometimes the element being analysed is in one form, but must first be converted to a
different form before quantitative analysis can take place. Usually an acid would be used
to convert the analyte which is a solid to an aqueous solution which can then be
precipitated by an known amount of precipitating reagent. Either HCl or HNO3 is used, if
the substance is a carbonate, the acid can be dilute, otherwise the concentrated version
of the acid is used.
Gravimetric method of calibrating a pipette
117
The mass of a small empty beaker is measured and recorded using an analytical
balance.
The temperature of the water used is measured and recorded.
Then using 10ml pipette, the liquid is drawn up and run into the small beaker and the
mass of the beaker is measured and recorded.
The previous step is repeated until there are 5 mass readings with water present.
The relationship between density of water and its temperature is well known and the
temperature recorded is used to obtain the density of the water used.
The mean mass of the water delivered by the pipette is converted to volume using the
relationship of density with mass and volume.
The standard deviation of the data is calculated.
Thus the mean volume and the standard deviation comprises the capacity of the pipette
used.

Checkpoint A
1. State briefly what steps one would take to determine the amount of water in a
sample of hydrated magnesium sulphate crystals

…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………
…………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………
…………………………

2. Imagine you are given a sample of sea water and asked to determine the amount of
chloride ions present. You decide to use the precipitation method, suggest a suitable
reagent to use to form the precipitate……………………….

Diagram of SOME apparatus used in gravimetric analysis

118
The sintered glass filter can withstand the high pressures used in vacuum filtration.

Uses of gravimetric analysis in quality control

Measurement of the “essential” elements in plant foods (phosphorus, for example, is

converted into the insoluble salt, magnesium ammonium phosphate)
Estimation of pollutants in the air, such as sulphur dioxide (by conversion to insoluble
barium sulphate)
Estimation of sulphur dioxide (used to prevent microbial spoilage) in soft drinks, such
as orange juice.
Estimation of chloride ions in water supplies
(by conversion to insoluble silver chloride).

Worked Example of gravimetric analysis question

119
A compound of Iron (Fe) and Chlorine (Cl) is soluble in water. An excess of Silver Nitrate
(AgNO3) was added to precipitate the chloride ion as silver chloride. If a 134.8 mg
sample of the compound gave 304.8 mg of AgCl, what is the formula of the compound?

Answer:
Note 1000 mg = 1g Ar Fe = 56, Cl = 35.5 Ag = 108
🡪determine # mol AgCl = mass AgCl / molar mass AgCl = 0.3048 / (143.5)
= 0.0021
🡪 Ratio AgCl : Cl- = 1: 1 therefore # mol Cl- = 0.0021
🡪 Mass of Cl- = # mol x relative atomic mass of Cl = 0.0021 x 35.5 = 0.0746g
🡪 Mass of iron ions = mass of sample – mass of Cl- ions = 0.1348 – 0.0746
= 0.0602 g
🡪 # mol iron = mass of iron / relative atomic mass iron = 0.0602 / 56 = 0.0011
🡪 Ratio of mol of iron : chloride = 0.0011 : 0.0021 🡺 1: 2
🡪 Therefore formula of compound = FeCl2

Checkpoint B
1. A 2.00g sample of limestone was dissolved in dilute hydrochloric acid and all the
calcium present in the sample was converted to Ca2+(aq). Excess ammonium oxalate
solution, (NH4)2C2O4(aq), was added to the solution to precipitate the calcium ions as
calcium oxalate, CaC2O4(s). The precipitate was filtered, dried and weighed to a constant
mass of 2.43g. Determine the % calcium in the limestone sample. Note: Ca2+(aq) +
C2O42-(aq) 🡪 CaC2O4(s)
Ca = 40, N = 14, C = 12, H = 1, O = 16, Ag = 108, Cl = 35.5, Fe = 56

120
2.

Note the dry precipitate would have the formula CaC2O4

Spectroscopic methods of analysis (Module 2)

a) explain the nature of electromagnetic radiation
b) know the approximate wavelength ranges of the X-ray, UV/VIS, IR and
radiofrequency regions of the EM spectrum
c) appreciate the relative energies and dangers associated with exposure to high energy
wavelengths
d) perform calculations using the equation E = hν = hc / λ
e) appreciate that energy levels in atoms and molecules are quantised

UV-VIS Spectroscopy
a) explain the origin of absorption in UV/VIS spectroscopy
b) explain why some species will absorb light in the uv/vis region but some others will
not
c) describe the basic steps involved in analysing samples by uv/vis spectroscopy (also
mention use of complexing agents to form coloured compounds, as well as sensitivity
and detection limits)
121
d) state the Beer-Lambert Law and be able to use the equation to calculate the
concentration of a given species in solution (implies the use of standards and
calibration curves)
e) list examples of the use of uv/vis spectroscopy in the quantitation of substance (refer
to iron tablets, glucose and urea in blood, cyanide in water)

Introduction to spectroscopy
Electromagnetic radiation can be described in terms of a stream of photons, which are
massless particles each travelling in a wave-like pattern and moving at the speed of
light. Each photon contains a certain amount (or bundle) of energy, and all
electromagnetic radiation consists of these photons.
The electromagnetic (EM) spectrum is just a name that scientists give a bunch of types
of radiation when they want to talk about them as a group. Radiation is energy that
travels and spreads out as it goes-- visible light that comes from a lamp in your house
and radio waves that come from a radio station are two types of electromagnetic
radiation.
Other examples of EM radiation are microwaves, infrared and ultraviolet light, X-rays
and gamma-rays. Hotter, more energetic objects and events create higher energy
radiation than cool objects. Only extremely hot objects or particles moving at very high
velocities can create high-energy radiation like X-rays and gamma-rays.
EM waves are typically described by any three of the following physical properties: the
frequency, , and wavelength, λ, and photon energy, E.
Frequencies range from about a million billion Hertz (gamma rays) down to a few Hertz
(radio waves). Wavelength is inversely proportional to the wave frequency, so gamma
rays have very short wavelengths that are fractions of the size of atoms, whereas radio
wavelengths can be as long as a several thousand kilometers. Photon energy is directly
proportional to the wave frequency, so gamma rays have the highest energy around a
mega electron volt and radio waves have very low energy around femto electron volts
(femto = 10 − 15).
These relations are illustrated by the following equation E = h and its variations
below:-
    or         or    

Where: c = 3 x 108  m s-1 (speed of light in vacuum) &

h = 6.626 ×10−34 Js-1 (Planck's constant).
122
Checkpoint A
1.

2.

123
High energy EM radiation e.g. ultraviolet rays, X-rays and gamma rays are very
dangerous to living tissue. These energetic rays have to ability to disrupt and destroy
DNA in tissue which can result in mutations or even death. All three types of rays
would result in electronic transitions and even ionisation.
In atoms, energy levels do NOT form a continuum. In fact, these energy levels are
discrete or quantised. For example, energy levels may be at 5J, 10 J, 20 J but
never 5.1J, 5.2 J, 10.3 J etc. There are no “in between” energy levels or values.

UV-VIS Spectroscopy
The absorption of ultraviolet or visible radiation corresponds to the excitation of outer
electrons and thus electronic transitions.

When an atom or molecule absorbs energy, electrons are promoted from their ground
state (lowest energy level) to an excited state.

124
Absorption of ultraviolet and visible radiation in organic molecules is restricted to
certain functional groups (chromophores) that contain valence electrons of low
excitation energy. Chromophores generally contain either П or lone pair(s) of electrons

Electronic transitions generally seen are n* and * transitions. In essence
molecules containing lone pairs of electrons OR  electrons would absorb uv-vis
radiation.

All other transitions either do NOT occur or are TOO SMALL to be considered. Below is
a diagram that shows the various electronic transitions.

Checkpoint B

Underline the molecules in the list below which would absorb uv-vis radiation. O2,
C6H6, NH3, CH4, C2H4, HCl

Sample preparation

UV-VIS samples are usually liquids or solutions. They are placed in a “cell” or cuvette
which is a rectangular block, with two sides frosted and the other two sides clear and
one end open and the other closed. The frosted sides can be touched but not the clear
sides.

125
 Cells are made of fused synthetic silica.

Solutions or liquids are placed in the cell in increasing concentrations. A “blank”

(which contains everything else but the analyte in question) is first used to use
as a reference point.

Sometimes, complexing agents must be added to provide colour to the analyte

which allows it to be analysed via uv-vis more easily. For example iron present in
aqueous samples can be determined  spectrophotometrically by complexation
with a suitable complexing agent. The absorbance of the metal-ligand complex is
usually measured in the visible region and is related to metal ion concentration.
Colorimetric determination of iron can be done using several known complexing
agents. Among the routinely used is 1,10-phenanthroline (phen) which reacts
with Fe2+ to form an orange-red complex. Also dimethylglyoximeis is a
complexing agent using to determine the amount of nickel present.
    The procedure depends on the construction of a calibration curve from standard
Fe2+, followed by measurement of the unknown Fe2+ concentration from the
curve.

Using absorbance to determine the concentration of an analyte

The Beer-Lambert Law

ε = molar absorbtivity
ℓ = cell length in cm (usually 1 cm in length)
c = molar concentration of solution
A = absorbance

126
Spectrophotometer
The basic parts of a spectrophotometer are a light source, a holder for the sample, a
diffraction grating or monochromator to separate the different wavelengths of light, and
a detector. The radiation source is often a Tungsten filament (300-2500 nm), a
deuterium arc lamp which is continuous over the ultraviolet region (190-400 nm), and
more recently light emitting diodes (LED) and Xenon Arc Lamps for the visible
wavelengths. The detector is typically a photodiode. Photodiodes are used with
monochromators, which filter the light so that only light of a single wavelength reaches
the detector.

The dual-beam design greatly simplifies this process by simultaneously measuring P

and Po of the sample and reference cells, respectively. Most spectrometers use a
mirrored rotating chopper wheel to alternately direct the light beam through the sample
and reference cells. The detection electronics or software program can then manipulate
the P and Po values as the wavelength scans to produce the spectrum of absorbance or
transmittance as a function of wavelength.
Schematic of a dual-beam uv-vis spectrophotometer

Applications of UV-VIS spectroscopy

UV/VIS spectroscopy is routinely used in the quantitative determination of solutions of
transition metal ions and highly conjugated organic compounds, of iron in iron tablets,
glucose and urea in blood and cyanide in water

Solutions of transition metal ions which are too pale to give a reasonable absorbance
can be complexed with various ligands to form more intense colours (i.e., absorb visible
light) because d electrons within the metal atoms can be excited from one electronic
state to another. The colour of metal ion solutions is strongly affected by the presence
of other species, such as certain anions or ligands. For instance, the colour of a dilute
solution of copper sulphate is a very light blue; adding ammonia intensifies the colour
and changes the wavelength of maximum absorption (λmax)

127
Checkpoint C

2.

128
129
…………………………………………………………………………………………………………………
……………………………………….………………………………………………………………………
………………………………………………………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….
…………………………………………………………………………………………………………………
……………………………………….

130
Infrared Spectroscopy (Module 2)
a) explain the origin of absorption in IR spectroscopy
b) describe the basic steps involved in analysing samples by IR spectroscopy (include
reference to preparation of solids)
c) appreciate the limitations associated with the use of IR spectroscopy (refer to
usefulness of IR data when combined with other data)
d) be able to deduce the functional groups present in organic compounds from IR
spectra (groups such as:- -OH, -NH2, -C=O, -C=C-, -COOH,
-CONH2) (make use of IR spectra data)
e) cite examples of the use of IR spectroscopy in the monitoring of air pollutants (refer
to carbon dioxide and sulphur dioxide)

Infrared Spectroscopy

Energies in infra-red radiation correspond to the energies involved in bond vibrations.

In order for a molecule to be IR active, it must be associated with changes in the

permanent dipole i.e. only molecules which have a dipole (partially positive and
negative charges) would undergo IR absorption

What causes some frequencies to be absorbed?

Each frequency of light (including infra-red) has a certain energy. If a particular
frequency is being absorbed as it passes through the compound being investigated, it
must mean that its energy is being transferred to the compound.
Energies in infra-red radiation correspond to the energies involved in bond vibrations.
Bond stretching
In covalent bonds, atoms aren't joined by rigid links - the two atoms are held together
because both nuclei are attracted to the same pair of electrons. The two nuclei can
vibrate backwards and forwards - towards and away from each other - around an
average position.
The diagram shows the stretching that happens in a carbon-oxygen single bond. There
will, of course, be other atoms attached to both the carbon and the oxygen. For
example, it could be the carbon-oxygen bond in methanol, CH3OH.
131
The energy involved in this vibration depends on things like the length of the bond and
the mass of the atoms at either end. That means that each different bond will vibrate in
a different way, involving different amounts of energy.
Bonds are vibrating all the time, but if you shine exactly the right amount of energy on
a bond, you can kick it into a higher state of vibration. The amount of energy it needs to
do this will vary from bond to bond, and so each different bond will absorb a different
frequency (and hence energy) of infra-red radiation.
Bond bending
As well as stretching, bonds can also bend. The diagram shows the bending of the
bonds in a water molecule. The effect of this, of course, is that the bond angle between
the two hydrogen-oxygen bonds fluctuates slightly around its average value. Imagine a
lab model of a water molecule where the atoms are joined together with springs. These
bending vibrations are what you would see if you shook the model gently.

Again, bonds will be vibrating like this all the time and, again, if you shine exactly the
right amount of energy on the bond, you can kick it into a higher state of vibration.
Since the energies involved with the bending will be different for each kind of bond,
each different bond will absorb a different frequency of infra-red radiation in order to
make this jump from one state to a higher one.

Vibrational modes of CO2 vs SO2

CO2 SO2
Type of molecule linear Non-linea
r
Polar vs non-polar Non-polar polar
Vibrational mode (symmetric Non IR IR active
stretch) active

132
Vibrational mode (asymmetric IR active IR active
stretch)
Vibrational mode IR active IR active
(bending)

Since SO2 is a polar molecule essentially all modes of vibration causes a cause in the
dipole and thus would be IR active. However a linear molecule like CO2 would be
non-polar but specific vibrational modes where the dipole is no longer symmetrical
would result in IR absorption.
Uses of IR spectroscopy include the monitoring of air pollutants examples carbon
dioxide and sulphur dioxide and in forensic analysis
CHARACTERISTIC INFRARED ABSORPTION FREQUENCIES
Bond Compound Type Frequency range, cm-1
2960-2850(s) stretch
Alkanes
C-H 1470-1350(v) scissoring and bending

CH3 Umbrella Deformation 1380(m-w) - Doublet - isopropyl,

t-butyl
3080-3020(m) stretch
C-H Alkenes
1000-675(s) bend
Aromatic Rings 3100-3000(m) stretch
C-H Phenyl Ring Substitution Bands 870-675(s) bend
Phenyl Ring Substitution Overtones 2000-1600(w) - fingerprint region
3333-3267(s) stretch
C-H Alkynes
700-610(b) bend
C=C Alkenes 1680-1640(m,w)) stretch
CC Alkynes 2260-2100(w,sh) stretch
C=C Aromatic Rings 1600, 1500(w) stretch

133
 C-O Alcohols, Ethers, Carboxylic acids, Esters 1260-1000(s) stretch

C=O Aldehydes,
Esters
Ketones, Carboxylic acids, 1760-1670(s) stretch

Monomeric -- Alcohols, Phenols 3640-3160(s,br) stretch

O-H Hydrogen-bonded -- Alcohols, Phenols 3600-3200(b) stretch
Carboxylic acids 3000-2500(b) stretch
3500-3300(m) stretch
N-H Amines
1650-1580 (m) bend
C-N Amines 1340-1020(m) stretch
CN Nitriles 2260-2220(v) stretch
1660-1500(s) asymmetrical stretch
NO2 Nitro Compounds
1390-1260(s) symmetrical stretch
v - variable, m - medium, s - strong, br - broad, w - weak

The table is used in conjunction with an IR spectrum to determine what functional

groups are present in an organic molecule.

Sample preparation for IR spectroscopy

Gaseous samples require little preparation beyond purification, but a sample cell with a
long path length (typically 5-10 cm) is normally needed, as gases show relatively weak
absorbances.
Liquid samples can be sandwiched between two plates of a high purity salt (commonly
sodium chloride, or common salt, although a number of other salts such as potassium
bromide or calcium fluoride are also used).
The plates are transparent to the infrared light and will not introduce any lines onto the
spectra. Some salt plates are highly soluble in water, so the sample and washing
reagents must be anhydrous (without water).
Solid samples can be prepared in four major ways. The first is to crush the sample with
a mulling agent (usually Nujol) in a marble or agate mortar, with a pestle. A thin film of
the mull is applied onto salt plates and measured.

134
The second method is to grind a quantity of the sample with a specially purified salt
(usually potassium bromide) finely (to remove scattering effects from large crystals).
This powder mixture is then crushed in a mechanical die press to form a translucent
pellet through which the beam of the spectrometer can pass.
The third technique is the Cast Film technique, which is used mainly for polymeric
materials. The sample is first dissolved in a suitable, non hygroscopic solvent. A drop of
this solution is deposited on surface of KBr or NaCl cell. The solution is then
evaporated to dryness and the film formed on the cell is analysed directly. Care is
important to ensure that the film is not too thick otherwise light cannot pass through.
This technique is suitable for qualitative analysis.
The final method is to use microtomy to cut a thin (20-100 micrometre) film from a
solid sample. This is one of the most important ways of analysing failed plastic products
for example because the integrity of the solid is preserved.
It is important to note that spectra obtained from different sample preparation methods
will look slightly different from each other due to differences in the samples' physical
states.

Limitations
Note that to determine the structure of an unknown compound, IR Spectroscopy can only
determine the functional groups present. In order to fully elucidate the structure, other
techniques are required such as:- Mass Spectroscopy and NMR (Nuclear Magnetic
Resonance) Spectroscopy.

Practice Questions

135
136
137
Mass Spectrometry (Module 2)
a) explain the basic principles of mass spectrometry (include a block diagram)
b) describe the process from injection of the sample to formation of the mass spectra
c)explain the significance of the bases peak, the (M+1) peak in mass spectra
d) be able to use mass spectral data to i) determine relative isotopic masses and
abundances ii) distinguish between molecules of similar relative molecular mass iii)
predict possible identities of simple organic molecules based on their fragmentation
patters iv) determine the relative atomic mass of an element
Module 2 Mass Spectroscopy

Diagram of a mass spectrometer

Stage 1: Ionisation
The sample is injected as a vapour and the atoms are bombarded by fast moving
electrons. This causes the molecule to fragment into two or more pieces. When a
molecule or part thereof fragments, one portion would be positively charged while the
second portion will be uncharged. All uncharged fragments are ultimately lost in the
machine as mass spectrometers only work with positive ions.
Stage 2: Acceleration
The ions are accelerated so that they all have the same kinetic energy.
Stage 3: Deflection
Generally only univalent ions are present, so the only variable would be their masses
and thus deflection is based on their mass on charge ratio (m/z) ratio.
138
Stage 4: Detection
The beam of ions passing through the machine is detected electrically.
What the mass spectrometer output looks like
The output from the chart recorder is usually simplified into a "stick diagram". This
shows the relative current produced by ions of varying mass/charge ratio.
The stick diagram for molybdenum looks like this:

You may find diagrams in which the vertical axis is labelled as either "relative
abundance" or "relative intensity". Whichever is used, it means the same thing. The
vertical scale is related to the current received by the chart recorder - and so to the
number of ions arriving at the detector: the greater the current, the more abundant the
ion. NB relative abundance = percentage
The origin of fragmentation patterns
The formation of molecular ions
When the vaporised organic sample passes into the ionisation chamber of a mass
spectrometer, it is bombarded by a stream of electrons. These electrons have a high
enough energy to knock an electron off an organic molecule to form a positive ion. This
ion is called the molecular ion - or sometimes the parent ion. The molecular ion is
often given the symbol M+

Fragmentation
The molecular ions are energetically unstable, and some of them will break up into
smaller pieces. The simplest case is that a molecular ion breaks into two parts - one of
which is another positive ion, and the other is an uncharged free radical.
The uncharged free radical will NOT produce a line on the mass spectrum. Only
charged particles will be accelerated, deflected and detected by the mass spectrometer.
These uncharged particles will simply get lost in the machine - eventually, they get
removed by the vacuum pump. The ion, X+, will travel through the mass spectrometer
just like any other positive ion - and will produce a line on the stick diagram.
All sorts of fragmentations of the original molecular ion are possible - and that means
that you will get a whole host of lines in the mass spectrum. For example, the mass
spectrum of pentane looks like this:

139
The molecular ion peak and the base peak
In the stick diagram showing the mass spectrum of pentane, the line produced by the
heaviest ion passing through the machine (at m/z = 72) is due to the molecular ion.
Note:  You have to be a bit careful about this, because in some cases, the
molecular ion is so unstable that every single one of them splits up, and none gets
through the machine to register in the mass spectrum. If there is no molecular
ion peak, it means that the original molecule is highly branched.

The tallest line in the stick diagram (in this case at m/z = 43) is called the base peak.
This is usually given an arbitrary height/value of 100, and the height of everything else
is measured relative to this. The base peak is the tallest peak because it represents the
commonest fragment ion to be formed - either because there are several ways in which
it could be produced during fragmentation of the parent ion, or because it is a
particularly stable ion.

Checkpoint A
Look at the mass spectrum of pentane above on the previous page.
1. Write the molecular formula of the fragment for m/z = 57.

2. What fragment would correspond to the m/z ratio of 72?

What is the M+1 peak?

If you have a complete mass spectrum, you will find a small line ONE m/z unit to the
right of the molecular ion peak. This is called the M+1 peak.

140
The M+1 peak is caused by the presence of ONE 13C isotope in the molecule.
13C is a stable isotope of carbon. Carbon-13 makes up 1.11% of all carbon atoms. If you
had a simple compound like methane, CH4, approximately 1 in every 100 of these
molecules will contain carbon-13 rather than the more common carbon-12. That means
that 1 in every 100 of the molecules will have a mass of 17 (13 + 4) rather than 16 (12 +
4).
Mass Spectrometry

141
Using mass spectra to distinguish between compounds
Suppose you had to suggest a way of distinguishing between pentan-2-one and
pentan-3-one using their mass spectra.
pentan-2-one CH3COCH2CH2CH3
pentan-3-one CH3CH2COCH2CH3
Each of these is likely to split to produce ions with a positive charge on the CO group.
In the pentan-2-one case, there are two different ions like this:
● [CH3CO]+
● [COCH2CH2CH3]+
That would give you strong lines at m/z = 43 and 71.
With pentan-3-one, you would only get one ion of this kind:
● [CH3CH2CO]+
In that case, you would get a strong line at 57.
You don't need to worry about the other lines in the spectra - the 43, 57 and 71 lines
give you plenty of difference between the two. The 43 and 71 lines are missing from the
pentan-3-one spectrum, and the 57 line is missing from the pentan-2-one one

The two spectra look like this:

142
Using a mass spectrum to find a molecular formula
So far we've been looking at m/z values in a mass spectrum as whole numbers, but it's
possible to get far more accurate results using a high resolution mass spectrometer.
You can use that more accurate information about the mass of the molecular ion to
work out the molecular formula of the compound.
Accurate isotopic masses
For normal calculation purposes, you tend to use rounded-off relative isotopic masses.
For example, you are familiar with the numbers:
H
1 1
12 C 12
14 N 14
16 O 16
To 4 decimal places, however, these are the relative isotopic masses:
143
 1H 1.0078
12 C 12.0000
14 N 14.0031
16 O 15.9949
The carbon value is 12.0000, of course, because all the other masses are measured on
the carbon-12 scale which is based on the carbon-12 isotope having a mass of exactly
12.
Using these accurate values to find a molecular formula
Two simple organic compounds have a relative formula mass of 44 - propane, C3H8, and
ethanal, CH3CHO. Using a high resolution mass spectrometer, you could easily decide
which of these you had.
On a high resolution mass spectrometer, the molecular ion peaks for the two
compounds give the following m/z values:
C3H8 44.0624
CH3CHO 44.0261
You can easily check that by adding up numbers from the table of accurate relative
isotopic masses above.
A possible exam question
A gas was known to contain only elements from the following list:
1H 1.0078
12 C 12.0000
14 N 14.0031
16 O 15.9949
The gas had a molecular ion peak at m/z = 28.0312 in a high resolution mass
spectrometer. What was the gas?

Practice Questions

144
.

145
END OF MASS SPECTROSCOPY

146
Practice Questions

147
2.

148
Chromatographic methods of separation (Module 2)
a) explain the principles upon which chromatographic methods are based (refer to
adsorption and partition between mobile and stationary phases
b) know and describe the different types of chromatography (refer to paper (including
two-way), thin layer and gas-liquid)
c) define the terms solvent front, retention factor, retention time, visualising agent
d) be able to calculate the retention factor of a substance
e) describe the steps involved in separating and quantifying the components of a
mixture (refer to Rf values and retention times)
f) list at least 2 examples of commonly used stationary phases (refer to cellulose, silica
gel, alumina)
g) cite at least 3 applications of chromatographic methods of separation (refer to
pesticide analysis, forensic testing, purification of natural products)

Theoretical principles of chromatography

This is based on the partition of components of a mixture between a stationary phase

and a mobile phase. The different components experience slightly different adsorption
forces with the stationary phase and different solubilities in the mobile phase.
Differences in both phases result in separation of the components in the mixture.
149
There are several types of chromatographic methods:- paper, thin layer, column and
gas-liquid.

Chromatographic Stationary phase Mobile

method phase
Paper cellulose Any solvent
Thin layer Dried slurry of Any solvent
powdered alumina or
silica on a glass plate
Column Dried slurry of Any solvent
powdered alumina or
silica packed into a
column
Gas-liquid Inert powder coated Nitrogen gas
with an involatile oil

Paper chromatography

The mixture is placed as a spot roughly 1 inch from the edge of the chromatography
paper. The paper is then dipped into a suitable solvent such as water or ethanol. The
solvent travels up (if it is ascending chromatography) and via adsorption forces and
solubility, the components separate. The retention factor (Rf) can be calculated for
each component.
Rf = distance traveled by component
distance traveled by solvent front

The solvent front is the distance travelled by the solvent up(or down) the paper. All
components have their own retention factor values, these values can therefore be used
to identify substances. In order for this to be useful, the procedure must be

150
standardized i.e. carried out inside a glass tank with a lid to exclude draughts and the
solvent would need to be buffered.

A variation of the process is called two-way paper chromatography. After one solvent
is used, the paper is placed with the left side to the bottom and a second solvent is used
for chromatogram development. The spots are more widely dispersed and can be
recognised from their position on the final chromatogram.

This method is used to determine the identity of amino acids, however they must be
first sprayed with a visualizing agent called ninhydrin or iodine vapour to form
coloured spots.

151
Thin Layer Chromatography (TLC)

Similar to paper chromatography, however the stationary phase is on a glass plate and
is a dried slurry of powdered alumina or silica. Good separation can be routinely
achieved on these glass plates and this method can be used to investigate the several
products formed from the nitration of phenol.

Column chromatography
Similar to TLC but the stationary phase is packed into a column.

152
Gas-Liquid Chromatography (GLC)
The column used in GLC is coiled and very thin. It is packed with an inert powder
which is coated with an involatile oil. The column is in an oven which is maintained at
a constant, pre-set temperature. The sample analysed must be in the vapour phase at
the temperature at which the column is operated.

153
Components of the mixture analysed are identified by either their retention times or
by spectroscopic analysis. The retention times of the components are calibrated using
known pure substances under identical, specified conditions. The retention time is
the time taken for a component to be detected after the sample has been injected into
the column.

The chromatogram from GLC shows not only the retention time of a substance but also
its concentration which is related to the height and width of its peak.

Applications of chromatographic methods

1. Pesticide analysis
2. Forensic testing
3. Purification of natural products

END OF CHROMATOGRAPHIC METHODS OF SEPARATION

Practice Question

154
155
Phase Separation (Module 2)
a) discuss chemical principles upon which simple and fractional distillation are based
(refer to vapour pressure, Raoult’s Law)
b) know and explain the differences between real and ideal mixtures
c) be able to construct and interpret boiling point composition curves of both ideal and
real mixtures
d) be able to explain the formation of azeotropic mixtures
e) be able to list at least 2 examples each of azeotropic mixtures for both negative and
positive deviation
f) discuss advantages and disadvantages of using vacuum distillation
g) discuss the principles upon which steam distillation is based
h) discuss advantages and disadvantages of steam distillation
i) know at least 2 uses of steam distillation
156
j) be able to perform simple calculations based on steam distillation
k) state and discuss the basic principles of solvent extraction (refer to partition
coefficient)
l) be able to perform simple calculations based on partition coefficient
m) be able to select appropriate methods of separation based on the physical and
chemical properties of a mixture
n) cite at least 2 examples of the application of distillation methods used in various
industries (refer to petroleum, rum and fragrance industries)

PHASE SEPARATIONS

The evaporation of a liquid in a closed container

Particles will gain kinetic energy and break away from the surface of the liquid.
As the gaseous particles bounce around, some of them will hit the surface of the liquid
again, and be trapped there. There will rapidly be an equilibrium set up in which the
number of particles leaving the surface is exactly balanced by the number rejoining it.
In this equilibrium, there will be a fixed number of the gaseous particles in the space
above the liquid.
When these particles hit the walls of the container, they exert a pressure. This pressure
is called the saturated vapour pressure of the liquid.
Saturated vapour pressure and boiling point
A liquid boils when its saturated vapour pressure becomes equal to the external
pressure on the liquid.
If the liquid is in an open container and exposed to normal atmospheric pressure, the
liquid boils when its saturated vapour pressure becomes equal to 1 atmosphere (or
101325 Pa or 101.325 kPa or 760 mmHg). This happens with water when the
temperature reaches 100°C.
But at different pressures, water will boil at different temperatures. For example, at the
top of Mount Everest the pressure is so low that water will boil at about 70°C.
Depressions from the Atlantic can easily lower the atmospheric pressure so that water
will boil at 99°C - even lower with very deep depressions.

157
Raoult's Law

The vapour pressure of a solution with a non-volatile solute e.g. water with salt in it is
equal to the vapour pressure of the pure solvent at that temperature multiplied by its
mole fraction

In equation form, this reads: p = xsolv x P0solv

In this equation, Po is the vapour pressure of the pure solvent at a particular
temperature. xsolv is the mole fraction of the solvent.
You calculate this using: xsolv = moles of solvent / total number of moles
Suppose you had a solution containing 10 moles of water and 0.1 moles of sugar. The
total number of moles is therefore 10.1
🡺 The mole fraction of the water is: xwater = 10 / 10.1 = 0.99

Explanation of why Raoult's Law works

Remember that saturated vapour pressure is what you get when a liquid is in a sealed
container. An equilibrium is set up where the number of particles breaking away from
the surface is exactly the same as the number sticking on to the surface again. Now
suppose you added enough solute so that the solvent molecules only occupied 50% of
the surface of the solution.
If you reduce the number of solvent molecules on the surface, you are going to reduce
the number which can escape in any given time. The net effect of this is that when
equilibrium is established, there will be fewer solvent molecules in the vapour phase –
which means that the saturated vapour pressure would be lower.
Limitations of Raoult's Law
Raoult's Law only works for ideal solutions. An ideal solution is defined as one which
obeys Raoult's Law.
Examples of ideal mixtures
There is no such thing as an ideal mixture. However, some liquid mixtures get fairly
close to being ideal. These are mixtures of two very closely similar substances.
Common examples include:
● hexane and heptane
● benzene and methylbenzene
● propan-1-ol and propan-2-ol

Ideal mixtures and enthalpy change of mixing

If the temperature rises or falls when you mix the two liquids, then the mixture isn't
ideal.

158
Vapour pressure / composition diagrams
Suppose you have an ideal mixture of two liquids A and B. Each of A and B is making
its own contribution to the overall vapour pressure of the mixture. The greater the mole
fraction, the greater the vapour pressure exerted.

Using a boiling point / composition diagram

B has the higher vapour pressure. That means that it will have the lower boiling
point. Remember this inverse relationship!!!!

If you boil a liquid mixture, you can find out the temperature it boils at, and the
composition of the vapour over the boiling liquid.
For example, in the next diagram, if you boil a liquid mixture C1, it will boil at a
temperature T1 and the vapour over the top of the boiling liquid will have the
composition C2.

All you have to do is to use the liquid composition curve to find the boiling point of the
liquid, and then look at what the vapour composition would be at that temperature.
Notice again that the vapour is much richer in the more volatile component B than the
original liquid mixture was.
The beginnings of fractional distillation
Suppose that you collected and condensed the vapour over the top of the boiling liquid
and reboiled it. You would now be boiling a new liquid which had a composition C2.
That would boil at a new temperature T2, and the vapour over the top of it would have a
composition C3. If you keep on doing this (condensing the vapour, and then reboiling
the liquid produced) you will eventually get pure B

159
Please note
Raoult's Law only works for ideal mixtures. In these, the forces between the particles in
the mixture are exactly the same as those in the pure liquids. The tendency for the
particles to escape is the same in the mixture and in the pure liquids. That is NOT
TRUE in non-ideal mixtures.
Positive deviations from Raoult's Law
In mixtures showing a positive deviation from Raoult's Law, the vapour pressure of the
mixture is always higher than you would expect from an ideal mixture. The deviation
can be small or it may be large. Large deviations shown a very distorted curve as
shown below.
REMEMBER HIGHER VAPOUR PRESSURE MEANS LOWER BOILING POINT!

Notice that mixtures over a range of compositions have higher vapour pressures than
either pure liquid. The maximum vapour pressure is no longer that of one of the pure
liquids.
Explanation
The fact that the vapour pressure is higher than ideal in these mixtures means that
molecules are breaking away more easily than they do in the pure liquids. That is
because the intermolecular forces between molecules of A and B are less than they are
in the pure liquids.
160
The classic example of a mixture of this kind is ethanol and water. This produces a
highly distorted curve with a maximum vapour pressure for a mixture containing
95.6% of ethanol by mass.

Negative deviations from Raoult's Law

In exactly the same way, you can have mixtures with vapour pressures which are less
than would be expected by Raoult's Law. In some cases, the deviations are small, but
in others they are much greater giving a minimum value for vapour pressure lower than
that of either pure component.

Explanation
These are cases
where the
molecules break
away from the
mixture less
easily than they
do from the pure liquids. New stronger forces must exist in the mixture than in the
original liquids. The example of a major negative deviation is a mixture of nitric acid
and water.
A large positive deviation from Raoult's Law: ethanol and water mixtures
If a mixture has a high vapour pressure it means that it will have a low boiling
point. The molecules are escaping easily and you won't have to heat the mixture much
to overcome the intermolecular attractions completely.
The implication of this is that the boiling point / composition curve will have a
minimum value lower than the boiling points of either A or B.

Suppose you are going to distil a mixture of ethanol and water with composition C1 as
shown on the next diagram. It will boil at a temperature given by the liquid curve and
161
produce a vapour with composition C2. . If you reboil that, it will produce a new vapour
with composition C3.

You can see that if you carried on with this boiling-condensing-reboiling sequence, you
would eventually end up with a vapour with a composition of 95.6% ethanol. If you
condense that you obviously get a liquid with 95.6% ethanol.
This particular mixture of ethanol and water boils as if it were a pure liquid. It has a
constant boiling point, and the vapour composition is exactly the same as the liquid.
It is known as a constant boiling mixture or an azeotropic mixture or an
azeotrope.
A large negative deviation from Raoult's Law: nitric acid and water mixtures
Nitric acid and water form mixtures in which particles break away to form the vapour
with much more difficulty than in either of the pure liquids. In the case of mixtures of
nitric acid and water, there is a maximum boiling point of 120.5°C when the mixture
contains 68% by mass of nitric acid. That compares with the boiling point of pure nitric
acid at 86°C, and water at 100°C.
Start with a dilute solution of nitric acid with a composition of C1 and trace through
what happens.

162
The vapour produced is richer in water than the original acid. If you condense the
vapour and reboil it, the new vapour is even richer in water. Fractional distillation of
dilute nitric acid will enable you to collect pure water from the top of the fractionating
column. As the acid loses water, it becomes more concentrated. Its concentration
gradually increases until it gets to 68% by mass of nitric acid. At that point, the vapour
produced has exactly the same concentration as the liquid, because the two curves
meet.
You produce a constant boiling mixture (or azeotropic mixture or azeotrope). If you
distil dilute nitric acid, that's what you will eventually be left with in the distillation
flask. You can't produce pure nitric acid from the dilute acid by distilling it.
Distilling nitric acid more concentrated than 68% by mass
This time you are starting with a concentration C2 to the right of the azeotropic mixture.

The vapour formed is richer in nitric acid. If you condense and reboil this, you will get a
still richer vapour. If you continue to do this all the way up the fractionating column,
you can get pure nitric acid out of the top.
As far as the liquid in the distillation flask is concerned, it is gradually losing nitric
acid. Its concentration drifts down towards the azeotropic composition. Once it reaches
that, there can't be any further change, because it then boils to give a vapour with the
same composition as the liquid. Distilling a nitric acid / water mixture containing more
than 68% by mass of nitric acid gives you pure nitric acid from the top of the
fractionating column and the azeotropic mixture left in the distillation flask.
Immiscible liquids
If you have two immiscible liquids in a closed flask and keep everything still, the vapour
pressure you measure will simply be the vapour pressure of the one which is floating on
top. There is no way that the bottom liquid can turn to vapour. The top one is sealing it
in. For the purposes of the rest of this topic, we always assume that the mixture is
being stirred or agitated in some way so that the two liquids are broken up into drops.
At any one time there will be drops of both liquids on the surface. That means that both
of them contribute to the overall vapour pressure of the mixture.

Total vapour pressure of the mixture

163
Assuming that the mixture is being agitated, then both of the liquids will be in
equilibrium with their vapours. The total vapour pressure is then simply the sum of the
individual vapour pressures:
. . . where po refers to the saturated vapour pressure of the pure liquid.
Notice that this is independent of the amount of each sort of liquid present. All you
need is enough of each so that both can exist in equilibrium with their vapour.
For example, phenylamine and water can be treated as if they were completely
immiscible.
At 98°C, the saturated vapour pressures of the two pure liquids are:
phenylamine 7.07 kPa
water 94.30 kPa
The total vapour pressure of an agitated mixture would just be the sum of these - in
other words, 101.37 kPa

Boiling point of the mixture

Liquids boil when their vapour pressure becomes equal to the external pressure.
Normal atmospheric pressure is 101.325 kPa.
Compare that with the figure we have just got for the total vapour pressure of a mixture
of water and phenylamine at 98°C. Its total vapour pressure is fractionally higher than
the normal external pressure.
This means that such a mixture would boil at a temperature just a shade less than
98°C - in other words lower than the boiling point of pure water (100°C) and much
lower than the phenylamine (184°C).
Exactly the same sort of argument could be applied to any other mixture of immiscible
liquids.
Important conclusion
Agitated mixtures of immiscible liquids will boil at a temperature lower than the boiling
point of either of the pure liquids. Their combined vapour pressures are bound to reach
the external pressure before the vapour pressure of either of the individual components
get there.
Steam distillation
This exploits the concept shown above and allows for organic compounds which would
normally decompose at high temperatures, to be separated at lower temperatures
minimising decomposition.
Steam is blown through the mixture and the water and phenylamine turn to vapour.
This vapour can be condensed and collected.
164
The steam can be generated by heating water in another flask (or something similar).
As the hot steam passes through the mixture it condenses, releasing heat. This will be
enough to boil the mixture of water and phenylamine at 98°C provided the volume of
the mixture isn't too great. For large volumes, it is better to heat the flask as well to
avoid having to condense too much steam and increase the volume of liquid in the flask
too much.
Steam distillation allows separation of components which would decompose at high
temperatures usually organic compounds. Vacuum distillation operates via the use of
low pressures allowing components to be separated which would otherwise decompose
at high temperatures.
Some other applications of steam distillation
Steam distillation can be used to extract some natural products - for example, to
extract eucalyptus oil from eucalyptus, citrus oils from lemon or orange peel, and to
extract oils used in perfumes from various plant materials.

Calculations involving steam distillation

The ratio of the moles of two liquids in the distillate is equal to the ratio of their vapour
pressures
e.g. phenylamine and water. NB A means phenylamine and W means water

nA = pA
nW pW

If the amount of water produced is 1 g and the amount of phenylamine is 0.212 g, and
the molar mass of water is 18g, what is the molar mass of phenylamine?

Note nW = mass of water (mW) AND nA = mass of phenylamine (mA)

molar mass of water (MW) molar mass of phenylamine (MA)

165
 mA / (MA) = 4.11 x 10-2 🡺 0.212 / M = 4.11 x 10-2
mW / MW 1/ 18

0.212 x 18 = 4.11 x 10-2

M 1

Therefore M = 0.212 x 18 = 92.8 g = 93 g

4.11 x 10-2

Solvent extraction
One solvent can be used to extract a solute from another solvent. This process is called
solvent extraction and this technique is very useful for extracting organic or even
inorganic solutes. For example, if iodine crystals are placed in water and then a
solvent like ether is added to the mixture and shaken in a separating funnel and left for
a few hours for equilibrium to be established, the majority of the iodine crystals would
be found in the non-aqueous layer. The ratio of the amounts of solute found in each
layer is a constant and this is called the partition coefficient.

partition coefficient (k) = CU CU = concentration of solute in upper layer

CL CL = concentration of solute in lower layer
Using the separating funnel, the lower layer is run off and collected and the solute then
separated from the solvent.

Sample calculation
The mass of iodine used in 0.9656 g and 50 cm3 each of water and ether was used in
the solvent extraction. After equilibrium was established, it was found that the upper
layer contained 0.0112 g and the lower layer contained 0.9544 g. What is the partition
coefficient for this system? CU / CL = 0.0112 / 0.9544 = 1.17 x 10-2
Examples of the application of distillation methods used in various industries
such as petroleum, rum and fragrance industries.

166
Questions

167
168
MODULE THREE (3)

169
Industrial plant site location
Industrial plants are manufactured for the sole purpose of producing materials and items either
used directly or indirectly in our everyday lives. However, the question that first arises is where
to build this industrial plant ? Near a school, near a beach, an airport, away from everything
and everybody? A place only accessible by helicopter? WHERE?

Some factors which influence a plant site

1. Proximity to raw materials
2. Easily accessible to the workforce
3. Proximity to good infrastructure (seaport, railway, airport, roads)
4. Type of terrain (flat, rugged or slightly rolling hills)
5. Distance from general populace

Checkpoint A
Think of the cement factory in St. Lucy, which of the factors listed above would be the most
important in relation to the location of the plant site and give reasons why.
……………………………………………………………………………………………………………………………
……………………………………………………………………………………………………………………………
…………………………………………………………………………………………

All industrial plants have general safety requirements. These requirements include head
covering, eye protection, feet protection, and ears as well. Industrial plants can be very
hazardous; falling objects, loud noises as well as fire protection and toxic fumes alerts. However
not all safety requirements have the same level of emphasis placed upon them

Checkpoint B
Compare a cement plant to a petroleum refinery plant. Which safety requirements would be the
most critical for each and why?
……………………………………………………………………………………………………………………………
……………………………………………………………………………………………………………………………
…………………………………………………………………………………………

170
 Production of aluminium
Bauxite, the most important ore of aluminium, contains only 30-54% alumina, Al2O3, the rest
being a mixture of silica, various iron oxides, and titanium dioxide.

The alumina must be purified before it can be refined to aluminium metal. In the Bayer process,
bauxite is digested by washing with a hot solution
of sodium hydroxide, NaOH, at 175 °C. This converts the alumina to aluminium hydroxide,
Al(OH)3, which dissolves in the hydroxide solution according to the chemical equation:
Al2O3 + 2 OH− + 3 H2O → 2 [Al(OH)4]−
The other components of bauxite which are not amphoteric like aluminium oxide do not
dissolve. However the silica is weakly acidic and dissolves to form silicate ions as well. The
mixture is then filtered to remove the solid impurities. The mixture of solid impurities is called
red mud, and presents a disposal problem. Next, the hydroxide solution is cooled, and a “seed”
of aluminum hydroxide is added and it results in large amounts of aluminium hydroxide
precipitating out of solution to form a white, fluffy solid. NB In some cases, carbon dioxide
gas is bubbled through the aluminate and silicate solution to form the solid aluminium
hydroxide Then, when heated to 1050°C, the aluminium hydroxide decomposes to alumina,
giving off water vapor in the process: 2 Al(OH)3 → Al2O3 + 3 H2O
The pure alumina so produced is then subsequently electrolysed in the Hall–Héroult process in
order to produce aluminium.

Below is the Hall-Heroult electrolytic cell

Cryolite (Na3AlF6) is added to molten alumina to become the electrolyte as its melting temperature
is reduced from 2050 ° to 950 °C. Aluminium is formed at the cathode Al3+ + 3e- 🡪 Al and oxygen at
the anode 2O2- -4e- 🡪 O2. Since the anode is made of carbon, the oxygen gas causes the anode to be
eroded because of carbon dioxide gas produced. This process requires a lot of energy and thus
should be located next to a hydroelectric power plant. Aluminium metal can also be recycled
171
without any loss of properties or quality. Only 5% of the initial energy needed for aluminium
production is used in the recycling process

Properties and related uses of Aluminium metal

Property Uses
Low density Used in aerospace and
transport industries i.e.
manufacture of car parts and
aircraft frames
High An oxide layer forms on the
corrosion surface of the metal and
resistance prevents any further corrosion.
This allows it to be used for car
parts, packaging material and
cooking utensils.
High Allows for use as overhead
electrical electric cables
conductivity
High Reflects infra-red radiation and
reflective visible light very well, so can be
nature used in firefighter suits

Checkpoint C

172
Crude Oil (Module 3)
a) explain the method used in the separation of the components of crude oil
b) discuss the uses of the components of crude oil as fuels and as raw materials for the
petro-chemical industry (also refer to catalytic cracking, fractional distillation and reforming
techniques)
c) assess the impact of the petroleum industry on the environment

First the crude oil is pumped from the earth or the sea and then it undergoes fractional
distillation to obtain the separate fractions or components.
Essentially the crude oil is heated in a long column containing trays. Each tray has a number of
bubble caps.

173
The way the distillation works is by becoming progressively cooler from the base to the top. All
the hydrocarbon fractions start off in gas form, as they have been heated to that point. The
gases then rise up the tower.
The gas mixture then encounters a barrier through which there are only openings called bubble
caps. The gas mixture is then forced to go through a liquid before
continuing upwards. The liquid in the first tray is at a cool enough
temperature to get the heaviest gas fractions to condense into liquid
form, while the lighter fractions stay gaseous.
In this way the heaviest hydrocarbon fractions are separated out
from the mixed gas. The remaining gas continues its journey up the
tower until it reaches another barrier. Here the bubble cap process
is repeated but at a lower temperature than before, which then filters out the next lightest set of
fractions.
This process continues until only the very lightest fractions, those of 1-4 carbon atoms, are left.
These stay in gas form and are collected at the top of the tower.

Some fractions are in heavier demand than other, for example the fractions diesel and petrol are
required in extremely large amounts while the heavier fraction are not in such high demand. A
process called cracking is then used to fragment the large molecules into smaller molecules
(forming even more diesel and petrol fractions).

The gasoline produced then undergoes reforming techniques to improve its octane rating.
Iso-octane or 2,2,4-trimethylpentane is the standard used to determine octane rating i.e.
octane is reformed into 2,2,4-trimethylpentane. In the final stages blending of fuels with

174
different octane ratings occurs to produce the retail gasoline for selling to customers to meet
certain specifications.

Checkpoint A

What is the basic property being exploited in fractional distillation?

……………………………………………………………………………………………………………………………
……………………………

Not only are the fractions used for the purposes as shown in the diagram above but are also used
as feedstock for the petro-chemical industry to produce plastics, detergents, solvents and fabrics.

Safety concerns in an oil refinery

1. Air pollution (release of several contaminants during the refinery process) as well as a
persistent and unpleasant odour
2. Fire and explosions due to flammable gases in a refinery
3. Noise pollution to the industrial equipment.
4. Risk of leaks on land or in the water (water leaks more relevant for underwater drilling)
Refer to BP incident April 2010

Checkpoint B

175
176
Ammonia (Module 3)
a) outline the steps in the manufacture of ammonia from its elements by the Haber Process
(include production of the starting materials and manufacturing conditions and also apply the
principles of chemical equilibrium and kinetics)
b) discuss the uses of ammonia (in agriculture and chemical industry)
c) assess the impact of the ammonia industry on the environment

HABER PROCESS
The Haber Process combines nitrogen from the air with hydrogen derived mainly from natural
gas (methane) into ammonia. The reaction is reversible and the production of ammonia is
exothermic.

A flow scheme for the Haber Process looks like this:

Hydrogen gas is obtained by reacting methane with steam over a nickel catalyst. This is called
steam reforming: CH4 + H2O → CO + 3 H2
Nitrogen gas is obtained via fractional distillation of liquid air
According to Le Chatelier’s Principle, a lower temperature and a higher pressure would
increase the yield of ammonia. However, too low a temperature would slow the rate of the
reaction and high pressures are costly as materials must be strengthened to withstand the
pressure to resist to risk of explosion. Thus a compromise is reached, where the temperature
is not too low nor too high and the pressure also not too high but high enough to shift the
equilibrium position to the right.
Under these conditions, the conversion rate to ammonia is 15%. However it occurs quickly and
unreacted gases are recycled to improve efficiency.
177
Checkpoint A

1. State how the following conditions would cause a shift in the position of equilibrium (left,
right or no change)
a) increase in temperature ………………………
b) decrease in pressure …………………………
c) a catalyst…………………………….

Uses of ammonia

1. Manufacture of fertilisers and/or used as a fertiliser itself

2. Ammonia used as a source of protein for livestock
3. Used in the manufacture of nitric acid, drugs and various textiles
4. Used in water treatment for control of pH

Environmental impact of ammonia industry

Atmospheric deposition
Ammonia gas which is emitted falls to the ground over land, often during rainfall. This results in
terrestrial eutrophication i.e. the enrichment of nitrogen content on land. This ultimately causes the
disruption of plant ecosystems, with a few common fast growing species to dominate over greater variety
of plants often of conversation value.
Eutrophication
Over-use of ammonium fertilisers. These fertilisers are water soluble and excess is leached from the soil
during rainfall or irrigation, causing the bacterial levels in nearby water bodies to increase substantially.
This large increase in bacteria robs the water body of adequate oxygen causing other aquatic life to die.
Acid soils
The overuse of fertilisers causes the soil to become acidic. Acidic soils cannot support several crops
needed today and the soil must be neutralised before anymore crops are planted. This neutralisation
must be done on a continuous basis to ensure the viability of the soil.
Air pollution

178
High concentrations of ammonia in air can damage vegetation such as lichen and moss. It also
contributes to the formation of haze in the atmosphere which reduces visibility and the formation of
particulate matter which can cause respiratory problems

Checkpoint B

Ethanol (Module 3)
a) explain the process of fermentation and distillation in the manufacture of alcoholic beverages
b) discuss the uses of ethanol (include fuel, pharmaceutical industry)
c) discuss the social and economic impact of alcohol production and consumption (include
physiological changes)
d) assess the impact of the alcohol industry on the environment

ETHANOL PRODUCTION AND CONSUMPTION

179
To manufacture alcoholic beverages, there are essentially two processes that must occur:
fermentation to produce the alcohol and then distillation to purify and increase the alcohol
content.

Yeast is added to a sugar source e.g. sugarcane, molasses, grapes etc with various nutrients
and the correct temperature and pH and in the absence of oxygen. Sugar is first broken down
into glucose and fructose by the enzyme sucrase. Eventually glucose molecules are respired
anaerobically to produce ethanol and carbon dioxide gas by the enzyme zymase.

C6H12O6 → 2C2H5OH + 2CO2

The ethanol content rises as high as 12% before the yeast cells are killed.

At this stage, distillation is required to further increase the ethanol content as well as to
produce pure amounts of ethanol for use to make alcoholic beverages. All alcoholic beverages
contain additives as well to improve the colour and the taste of the beverage, these additives are
closely guarded secrets known only to one or two persons.

Uses of ethanol
1. As a fuel (gasohol)
2. Alcoholic beverages
3. Antiseptic use
4. Base chemical for petro-chemical industry
5. Manufacture pharmaceutical drugs
Physiological effects of alcohol consumption

180
Practice Problems

181
Chlorine (Module 3)
a) describe the chemical processes involved in the electrolysis of brine using the diaphragm cell
b) discuss the economic advantages of chlorine production by the diaphragm cell method
(include sodium hydroxide and disadvantages as well)
c) discuss the industrial importance of the halogens and their compounds (bleaches, PVC,
halogenated hydrocarbons, solvents, aerosols, refrigerants, anaesthetics)
d) assess the impact of the chloro-alkali industry on the environment

CHLORINE PRODUCTION

In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a cathode

and an anode, preventing the chlorine forming at the anode from re-mixing with the sodium
hydroxide and the hydrogen formed at the cathode.
The salt solution (brine) is continuously fed to the anode compartment and flows through the
diaphragm to the cathode compartment, where the caustic alkali is produced and the brine is
partially depleted.
As a result, diaphragm methods produce alkali that is quite dilute (about 12%) and of lower
purity than do mercury cell methods. But diaphragm cells are not burdened with the problem
of preventing mercury discharge into the environment. They also operate at a lower voltage,
resulting in an energy savings over the mercury cell method, but large amounts of steam are
required if the caustic has to be evaporated to the commercial concentration of 50%.

182
Economic advantages
1. Less energy used because it operates at a lower voltage
2. No risk of releasing mercury into environment (i.e. less cost involved in expensive
recovery methods)
Economic disadvantages
Very dilute sodium hydroxide produced (12%) and industry requires 50%. Large amounts of
steam is required to concentrate the alkali.
The chlorine produced is usually not very pure and requires purification

Chlorine can also be produced via the flowing mercury cathode cell
The cathode is a thin layer of mercury and graphite is the anode.
The electrode reactions are:-
At cathode Na+ + e- 🡪 Na At anode 2Cl- -2e- 🡪 Cl2
However the sodium undergoes further reactions
a) Na + Hg 🡪 Na/Hg
b) 2Na/Hg + 2H2O 🡪 2NaOH + H2 + 2Hg

The product is chlorine and by-products are sodium hydroxide and hydrogen gas.

Importance of halogens and their compounds

183
These substances are used in the manufacture of:-
1. Bleaches 2. PVC 3. Solvents
4. Aerosols 5. Refrigerants 6. Anaesthetics
7. Purification of drinking water supplies 8. Herbicides/fungicides

Practice Question

What is the ratio of moles of NaCl used to moles of Cl2 produced?

Use this ratio to determine mass of NaCl in kg required to produce 2.5 x 1010 kg of Cl2

Sulphuric Acid (Module 3)

a) describe the Contact process for the manufacture of sulphuric acid (include principles of
chemical equilibrium and kinetics)
b) discuss the industrial importance of compounds of sulphur (SO2 in food preservation and
H2SO4)
c) assess the impact of the sulphuric acid industry on the environment

184
CONTACT PROCESS

The process can be divided into three stages:

1. Preparation and purification of sulphur dioxide
2. Catalytic oxidation (using vanadium pentoxide catalyst) of sulphur dioxide to sulphur trioxide
3. Conversion of sulphur trioxide to sulphuric acid
Purification of air and SO2 (using an electrostatic precipitator) is necessary to avoid catalyst poisoning
(i.e. removing catalytic activities). The gas is then washed with water and dried by sulphuric acid.
To conserve energy, the mixture is heated by exhaust gases from the catalytic converter by heat
exchangers.
Sulphur dioxide and oxygen then react in the manner as follows:
2 SO2(g) + O2(g) ⇌ 2 SO3(g) : ΔH = −197 kJ mol−1

To increase the reaction rate, high temperatures (450 °C), medium pressures (1-2 atm), and vanadium(V)
oxide (V2O5) are used to ensure a 96% conversion.
Hot sulfur trioxide passes through the heat exchanger and is dissolved in concentrated H2SO4 in the
absorption tower to form oleum:
H2SO4(l) + SO3(g) → H2S2O7(l)

Note that directly dissolving SO3 in water is impractical due to the highly exothermic nature of the
reaction. Acidic vapour or mists are formed instead of a liquid.
Oleum is reacted with water to form concentrated H2SO4.
The average percentage yield of this reaction is around 30%.
H2S2O7(l) + H2O(l) → 2 H2SO4(l)

Importance of compounds of sulphur in industry

1. SO2
Used as a food preservative in juices and jams. It creates an acidic and oxidising medium which
prevents the growth of any microbes.
2. Sulphuric acid
Used in the manufacture of fertilisers, manufacture of detergents, production of phosphoric acid, used
to help manufacture fabrics e.g. nylon, in petroleum refining, to manufacture dyes and as the battery
acid in car batteries.

Impact on the environment

185
Emissions of SO2 causes drastic changes in the atmosphere. It plays a major role in the formation of
acid rain via the reaction
SO2 + H2O 🡪 H2SO3 or even 2SO2 + O2 + 2H2O 🡪 2H2SO4
Acid rain damages or destroys buildings and vegetation and of course it is not healthy for the aquatic life
as it reduces the pH of the water decreasing their quality of life. It also can cause the mobilisation of
toxic ions in the soil which results in vegetation’s growth being affected.

SO2 emissions can cause respiratory problems as it is irritating and causes wheezing and shortness of
breath.

Practice Questions

186
a) describe the importance of the water cycle
b) discuss the methods of water purification (include desalination via reverse osmosis)
c) discuss the importance of dissolved oxygen to aquatic life
d) discuss the sources of water pollution (include nitrates, phosphates, heavy metals (lead and
mercury), cyanides, trace metals, pesticides, herbicides, petroleum reside, suspended particles)
e) assess the impact of the pollutants in part d) above on the aquatic environment

187
Module 3 Water & its importance

Water Cycle

Water cycle is essential for the continued supply of water on the earth’s surface. Our bodies are
made of about 65% water and thus all metabolic activities require water to be present. We
cannot easily make MORE water, so we must depend on the water cycle for our present supply
of it.

Water Purification
In many cases, the water obtained from nature is not pure enough for our needs, whether it is
drinking or bathing or even for industrial processes. Hence a series of purification steps must
be conducted in order for the water to be used for our various purposes.

Please note that desalination can also be considered a process of water purification via the use
of reverse osmosis

188
Sedimentation
The water, after coagulation, is left in settling basin further for sufficient period to allow sedimentation of
remaining materials. Sedimentation however considerably reduces microbial population of the water
aside from removing most of the suspended particles.

Filtration
After sedimentation, water is subjected to sand filters to remove flocks of living organisms. The process of
filtration is highly critical and important as it can remove protozoan cysts and also about 98-99% of
bacteria from water. The water may also be filtered through activated charcoal to remove potentially
toxic organic compounds and organic compounds that impart undesirable colour and/or taste to the
water.

Disinfection
Disinfection is the final step is municipal water purification and it ensures that no pathogenic
microorganisms are carried through water. For water supplies of small towns and localities sodium or
calcium hypochlorite (NaOCl or CaOCl2 respectively) may be used to disinfect water, but for larger cities,
however, chloroamine (as opposed to chlorine) is now the method for disinfection.

Importance of Dissolved Oxygen

189
All aquatic life depend on the amount of dissolved oxygen (DO) present. This allows all aquatic life to
conduct their metabolic processes essential to life. High levels of DO (above 90%) indicate “healthy”
water bodies. DO can also be related indirectly to biological oxygen demand (BOD), the higher the DO,
the lower the BOD. Once DO levels begin to drop, this usually indicates some form of pollution is
present in the water body.

Sources of water pollution

Pollutant Source Effect on environment

Nitrates Manmade fertilisers Drinking water that gets
contaminated with
nitrates can prove fatal
especially to infants that
drink formula milk as it
restricts the amount of
oxygen that reaches the
brain causing the ‘blue
baby’ syndrome as well
as eutrophication.
Phosphates Manmade fertilisers Eutrophication
and detergents
Heavy metals Use of lead pipes Lead affects the nervous
(e.g. lead and causes dissolved lead system and can
mercury) ions to form in the ultimately lead to death.
water, improper Mercury stunts physical
disposal of mercury development of
from industrial organisms
processes
Cyanides Improper disposal Acts as a poison
after used in making
fabrics
Trace metals mining waste and Hazardous effects on
tailings, landfills, or nervous systems and
hazardous waste physical development
dumps.
Pesticides and Run off from Accumulate up the food
herbicides backyards, farms and chain and cause
golf courses impairment of physical
development of aquatic
life
190
Petroleum From underground Similar to pesticides
residues storage tanks
Suspended Industrial processes Respiratory problems,
particles e.g. cement covers wide area in fine
manufacture dust

Practice Questions
1.

2.

191
The Atmosphere (Module 3)
a) explain how the concentration of ozone in the atmosphere maintained (photodissociation)
b) discuss the environmental significance of CFCs in the ozone layer (include reference to free
radical reactions in the upper atmosphere)
c) discuss the effects of ozone on human life ( refer to both stratosphere and troposphere and
part c above)
d) explain the importance of maintaining the balance of carbon dioxide concentration in the
atmosphere (refer to equilibrium concepts, carbon cycle and reforestation)
e) explain the following terms: green-house effect, global warming, photochemical smog (include
re-radiation of energy from the infrared region)
f) discuss the effects of the products of combustion of hydrocarbon-based fuels (consider CO,
SO2, oxides of nitrogen, lead compounds and volatile organic compounds)
g) explain how the atmospheric concentrations of the oxides of nitrogen may be altered (refer to
the nitrogen cycle and acid rain)
h) discuss methods of control and prevention of atmospheric pollution (for prevention include
alternative and cleaner fuels, improved technology and mass transit; for control include
sequestering, filters, washers and scrubbers)

THE ATMOSPHERE
192
Layers of Atmosphere
Earth's atmosphere can be divided into five main layers. These layers are mainly determined by whether
temperature increases or decreases with altitude. From highest to lowest, these layers are:
Troposphere
The troposphere begins at the surface and extends to between 7 km (23,000 ft) at the poles and 17 km
(56,000 ft) at the equator, with some variation due to weather. The lowest part of the troposphere is
warmest and temperature decreases with altitude. The tropopause is the boundary between the
troposphere and stratosphere.
Stratosphere
The stratosphere extends from the tropopause to about 51 km (32 mi; 170,000 ft). Temperature
increases with height, which restricts turbulence and mixing. The stratopause, which is the boundary
between the stratosphere and mesosphere.

Mesosphere
The mesosphere extends from the stratopause to 80–85 km (50–53 mi; 260,000–280,000 ft). It is the
layer where most meteors burn up upon entering the atmosphere. Temperature decreases with height in
the mesosphere.

Thermosphere
Temperature increases with height in the thermosphere from the mesopause up to the thermopause,
then is constant with height. The top of the thermosphere is the bottom of the exosphere, called the
exobase.

Exosphere
The outermost layer of Earth's atmosphere extends from the exobase upward. Here the particles are so
far apart that they can travel hundreds of km without colliding with one another.

193
Maintenance of ozone concentration in stratosphere

Ozone is produced by uv radiation which is plentiful in the stratosphere.

These four equations are the Chapman reactions which regulate the concentration of ozone in the
stratosphere. Note that hv represents uv light.

(1) Photodissociation causes the oxygen molecule to dissociate, (2) each oxygen atom then can combine
with an oxygen molecule to form ozone.
(3) Ozone molecules dissociate when in contact with uv rays reforming an oxygen molecule and oxygen
atom. (4) An ozone molecule and oxygen atom combine to form 2 oxygen molecules.

Significance of CFCs in ozone layer

CFCs and other contributory substances are commonly referred to as ozone-depleting
substances (ODS). Since the ozone layer prevents most harmful UVB wavelengths
(270–315 nm) of ultraviolet light (UV light) from passing through the Earth's atmosphere,
observed and projected decreases in ozone have generated worldwide concern leading to
adoption of the Montreal Protocol that bans the production of CFCs and halons
(halogenoalkane) as well as related ozone depleting chemicals such as carbon tetrachloride and
trichloroethane. It is suspected that a variety of biological consequences such as increases in
skin cancer, cataracts, damage to plants, and reduction of plankton populations in the ocean's
photic zone may result from the increased UV exposure due to ozone depletion. Ozone is also a
very powerful oxidising agent.

CFCs are non-toxic, low boiling, inert compounds and thus diffuse to the stratosphere where it
undergoes fission by uv light. An example of the reactions are shown below

Step 1 CFCl3 + hν → CFCl2 + Cl

Step 2 Cl + O3 → ClO + O2
Step 3 ClO + O3 → Cl + 2 O2
194
Steps 2 and 3 result in a chain reaction. Essentially CFCs result in the destruction of the
ozone layer. One chlorine atom can destroy 100,000 ozone molecules.
Effects of ozone on human life
a) Stratospheric ozone
Although the concentration of the ozone in the ozone layer is very small, it is vitally important to life
because it absorbs biologically harmful ultraviolet (UV) radiation coming from the Sun. UV radiation is
divided into three categories, based on its wavelength; these are referred to as UV-A (400–315 nm), UV-B
(315–280 nm), and UV-C (280–100 nm). UV-C, which would be very harmful to humans, is entirely
screened out by ozone at around 35 km altitude. UV-B radiation can be harmful to the skin and is the
main cause of sunburn; excessive exposure can also cause genetic damage, resulting in problems such
as skin cancer. The ozone layer screens out 95% of UV-B; for radiation with a wavelength of 290 nm, the
intensity at the top of the atmosphere is 350 million times stronger than at the Earth's surface.

b) Tropospheric ozone
The majority of tropospheric ozone formation occurs when nitrogen oxides (NOx), carbon monoxide (CO)
and volatile organic compounds (VOCs), such as xylene, react in the atmosphere in the presence of
sunlight. NOx, CO, and VOCs are called ozone precursors. Motor vehicle exhaust, industrial emissions,
and chemical solvents are the major anthropogenic (man-made) sources of these chemicals.

Ozone is known to have the following health effects at concentrations common in urban air:
● Irritation of the respiratory system, causing coughing, throat irritation, and/or an uncomfortable
sensation in the chest.
● Reduced lung function, making it more difficult to breathe deeply and vigorously. Breathing may
become more rapid and more shallow than normal, and a person's ability to engage in vigorous
activities may be limited.
● Aggravation of asthma. When ozone levels are high, more people with asthma have attacks that
require a doctor's attention or use of medication. One reason this happens is that ozone makes
people more sensitive to allergens, which in turn trigger asthma attacks.
● Increased susceptibility to respiratory infections.
● Inflammation and damage the lining of the lungs. Within a few days, the damaged cells are shed
and replaced much like the skin peels after a sunburn. Animal studies suggest that if this type of
inflammation happens repeatedly over a long time period (months, years, a lifetime), lung tissue
may become permanently scarred, resulting in permanent loss of lung function and a lower
quality of life.

195
Checkpoint A

Importance of carbon cycle

196
The element carbon is necessary for all organic material. Its presence is maintained by the
carbon cycle. On the previous page shows the various processes involved in the carbon cycle.

If all the carbon was present in the atmosphere as CO2, the greenhouse effect would be
enhanced to such a level, that life as we know it on Earth would cease to exist. If all the carbon
was locked in the sediments (rocks) or vegetation or animals, again life would cease as no more
photosynthesis would be able to occur and life would swiftly end.

In recent times, the balance of carbon has been disrupted by the extreme levels of fossil fuel
combustion, causing a dramatic increase in the level of CO2 in the atmosphere. CO2 is a
greenhouse gas and an increase in its levels causes an increase in the mean temperature of the
Earth. This has undesirable effects on weather patterns and countries’ climates.

In order to remove the excess carbon dioxide in the atmosphere, a concept such as carbon
sequestering can be used. Carbon sequestering is a geoengineering technique for long-term
storage of carbon dioxide or other forms of carbon to mitigate global warming. Carbon dioxide is
usually captured from the atmosphere through biological, chemical or physical processes.

Biological:- Reforestation i.e. the replanting of trees on marginal crop and pasture lands

Physical:- Biomass burial i.e. burying trees which are now dead which resulting in a mimicking
of the natural process of fossil fuel formation

Chemical:- Mineral sequestration i.e. the reaction of carbon dioxide with either magnesium
oxide or calcium oxide to form the respective carbonates.

The greenhouse effect

The greenhouse effect is a process by which radiative energy leaving a planetary surface is
absorbed by some atmospheric gases, called greenhouse gases. They transfer heat to other
components of the atmosphere, and also re-radiate energy in all directions, including back
down towards the surface. This transfers energy to the surface and lower atmosphere, so the
temperature there is higher than it would be if direct heating by solar radiation were the only
warming mechanism.

197
Higher levels of CO2 in present time (around 380ppm) causes an enhanced greenhouse effect
which results in an increase of the average temperature of the Earth than in the past with lower
levels of CO2 (315ppm)

Causes of global warming

● High levels of combustion of fossil fuels releasing CO2
● High amounts of methane gas from grazing animals and landfills
● Release of nitrous oxide from fertilisers
● Release of refrigerants for industrial processes
● Deforestation whether man-made or natural via the burning of forests in dry seasons

Effects of global warming

● Sea levels to rise

● Change the amount and pattern of precipitation, probably including expansion of subtropical
deserts
● Continuing retreat of glaciers, permafrost and sea ice.
● Other likely effects include changes in the frequency and intensity of extreme weather events,
species extinctions, and changes in agricultural yields.
● Warming and related changes will vary from region to region around the globe, though the
nature of these regional variations is uncertain.

Photochemical smog
Photochemical smog is the chemical reaction of sunlight, nitrogen oxides (NOx) and volatile
organic compounds (VOCs) in the atmosphere, which leaves airborne particles (called
particulate matter) and ground-level ozone.

Nitrogen oxides are released by nitrogen and oxygen in the air reacting together under high temperature
such as in the exhaust of fossil fuel-burning engines in cars, trucks, coal power plants, and industrial
manufacturing factories. VOCs are released from man-made sources such as gasoline (petrol), paints,
solvents, pesticides, and biogenic sources, such as pine and citrus tree emissions.

Effects of photochemical smog

● It can inflame breathing passages, decrease the lungs' working capacity, cause shortness of
breath, pain when inhaling deeply, wheezing, and coughing.

198
● It can cause eye and nose irritation and it dries out the protective membranes of the nose
and throat and interferes with the body's ability to fight infection, increasing susceptibility to
illness.

Checkpoint B

Effects of combustion of hydrocarbon based fuels

Pollutant Source/how Effects

s produced
carbon burning of oil, Increase of carbon dioxide in
dioxide coal and the atmosphere leads to the
natural gas "greenhouse effect".
When the energy from the
sun is reflected back from
the earth, the gas prevents
this energy from returning
to outer space and
ultimately causes
temperatures on Earth to
rise, similar to a
greenhouse.

199
sulphur burning of oil, the gas is absorbed in rain
dioxide coal or gasoline water which causes the
containing formation of acid rain.
sulphur
acid rain destroys vegetation
and damages marble and
limestone buildings.
carbon incomplete poisonous, prevents uptake
monoxide burning of fossil of oxygen by haemoglobin.
fuels
increases the formation of
carbon dioxide i.e.
enhancing the greenhouse
effect
Oxides of Internal Same as for sulphur dioxide
nitrogen combustion
engine, reaction
of nitrogen gas
with oxygen gas
Lead Leaded gasoline Forms volatile lead
compound specifically compounds or elemental
s tetraethyl lead lead. Lead acts as a
cumulative poison and it
can cause madness and
then death
CFCs Petro-chemical Forms radicals in the ozone
industry, layer which ultimately
aerosol destroys the ozone layer.
propellants This can cause an increased
incidence of skin cancers.

NOx concentration in the atmosphere

NOx is produced in the atmosphere by a variety of ways.
● Via lightning high temperature causes the reaction of nitrogen gas and oxygen gas to form
nitrogen monoxide
● In the internal combustion engine, the high temperature causes the nitrogen and oxygen
gases to react to form NOx

200
Once NOx is in the atmosphere, their concentrations can be affected by precipitation resulting
in acid rain. That is the reaction of NOx and water forming dilute solutions of nitric acid.

The formation of acid rain, the Haber Process and use of fertilisers also affects the nitrogen
cycle, the amount of nitrates present in the soil.

Methods of control and prevention of atmospheric pollution

Pollutant Method of control
Particulate For large particles:- Baghouses or similar
equipment are used which utilise
centrifugal forces to create a cyclone to
trap particles and collect them, removing
them from the air flow

For small particles:- Electrostatic

precipitators are used, these exploit the
fact that particles are usually charged
and by passing “dirty” air through
charged plates, the particles are attracted

201
 to the oppositely charged plate and the
air comes out clean
Gases Scrubbers (wet)
A wet scrubber uses an anti parallel flow
of water against the flow of gas (gas
travelling upward and water flowing
downward). Note the water is in very fine
droplets to increase surface area. The
pollutant then dissolves or reacts with
the water, allowing the air to become
“clean”.

Prevention of atmospheric pollution

● Use of alternative fuels (purely electric cars)
● Improved technology (improved catalytic converters, hybrid cars (use of electricity and
gasoline for propulsion)
● Mass transit (car pooling, use of public transportation) (although the cars or vehicles would
still cause pollution)
Checkpoint C

Solid Waste (Module 3)

a) distinguish among reduce, reuse and recycle
b) describe the process involved in waste reduction (consider reusing and recycling of glass,
paper, plastic, steel and aluminium; reduce)

202
c) assess the impact of the solid wastes on the terrestrial environment (refer to iron, glass,
plastic, paper, lead, biodegradable and non-biodegradable materials, nuclear waste, proper and
improper disposal techniques-dumps and sanitary landfills)
Unit 2 Module 3 Topic Solid Waste Management

The 3 R’s
Reduce :- decrease the amount of substance used for any given process e.g. using less
styrofoam containers

Reuse involving using the item for the same purpose or even a different purpose after the item
has been cleaned and dried e.g. reuse of glass bottles for more liquid or solid or even a different
substance altogether.
Recycle implies either or both the physical or chemical processing of an item for future use e.g.
the melting of an aluminium can to produce a new can.
Recycling
Glass
It must be first cleaned and all labels removed and then sorted in different colours and
chemical compositions. It is then melted and then reshaped into the new object.

Plastic
All plastics have a resin code which represents the type of chemical processing required for
recycling purposes. Thus all plastics must be cleaned, all labels removed and then sorted into
their different resin codes. Some plastics are merely heated while others undergo a type of
reverse polymerisation and then the melt is shaped into new plastics.
Aluminium
Aluminium metal is very good for recycling as 95% of the energy used to make virgin aluminium
is saved. The metal is melted and then easily reshaped into new objects.
Paper
Paper is first sorted for suitable use for recycling and then it is easily mixed with water to form
a paste and then rolled into large sheets. Paper is not infinitely recyclable.
Steel is one of the most recycled materials in the world. Roughly 75% of the energy is saved
when steel is recycled. Again it is a process of melting the scrap metal and reshaping it for
future uses.

203
Impact of solid waste on the terrestrial environment
1. Space required vs space present
2. Contamination of water supply or soil
3. Biodegradable vs non-biodegradable
4. Aesthetic aspect (unsightly and/or foul odour)

Incineration vs Landfill
1. Reduction of volume of space required but release of toxic fumes
2. High initial cost of construction of incinerator
3. For either incineration or landfill, areas for construction must be away from populace,
also to minimise risk of contamination
4. Inhalation of emissions from incinerator
5. Landfills produce methane gas which can be used as fuel but can cause water pollution

Practice Questions

204
205
206
207