Organic Chemistry

Topic 10

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 10.1 Fundamentals of organic
chemistry
Essential idea:
● Organic chemistry focuses on the chemistry of
compounds containing carbon.
Nature of science:
● Serendipity and scientific discoveries—PTFE and
superglue. (1.4)
● Ethical implications—drugs, additives and pesticides can
have harmful effects on both people and the
environment. (4.5)

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 10.1 Understandings:
● A homologous series is a series of compounds of the same
family, with the same general formula, which differ from
each other by a common structural unit.
● Structural formulas can be represented in full and
condensed format.
● Structural isomers are compounds with the same
molecular formula but different arrangements of atoms.
● Functional groups are the reactive parts of molecules.
● Saturated compounds contain single bonds only and
unsaturated compounds contain double or triple bonds.
● Benzene is an aromatic, unsaturated hydrocarbon.
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10.1 Applications and skills: (1)
● Explanation of the trends in boiling points of members of
a homologous series.
● Distinction between empirical, molecular and structural
formulas.
● Identification of different classes: alkanes, alkenes,
alkynes, halogenoalkanes, alcohols, ethers, aldehydes,
ketones, esters, carboxylic acids, amines, amides, nitriles
and arenes.
● Identification of typical functional groups in molecules eg
phenyl, hydroxyl, carbonyl, carboxyl, carboxamide,
aldehyde, ester, ether, amine, nitrile, alkyl, alkenyl and
alkynyl. 4
10.1 Applications and skills: (2)
● Construction of 3-D models (real or virtual) of organic
molecules.
● Application of IUPAC rules in the nomenclature of
straight-chain and branched-chain isomers. Identification
of primary, secondary and tertiary carbon atoms in
halogenoalkanes and alcohols and primary, secondary
and tertiary nitrogen atoms in amines.
● Discussion of the structure of benzene using physical and
chemical evidence.

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 10.1 Guidance:
● Skeletal formulas should be discussed in the course.
● The general formulas (eg CnH2n+2) of alkanes, alkenes,
alkynes, ketones, alcohols, aldehydes and carboxylic
acids should be known.
● The distinction between class names and functional
group names needs to be made. Eg for OH, hydroxyl is the
functional group whereas alcohol is the class name.
● The following nomenclature should be covered:
○ non-cyclic alkanes and halogenoalkanes up to
halohexanes.
○ alkenes up to hexene and alkynes up to hexyne.
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Homologous Series

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 Homologous Series
Family of compounds

Same general formula

- Alkanes, CnH2n+2

- Alkenes, CnH2n

- Alcohols, CnH2n+1OH

Similar chemical
properties

Gradation in physical
properties
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Homologous Series and Boiling
Points
● What do you think will be the trend in melting/boiling
points as you go down a homologous series?

● Why?

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Alkane Boiling Point versus carbon number

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ional Distillation

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 Fractional
Distillation
Crude oil separated into fractions
based on density & boiling
points.

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 Types of Formula
● Empirical Formula C4H8O
C4H8O

● Molecular Formula C4H8O

C4H8O

● Full Structural Formula

○ Aka displayed formula
CH2=CHCH2CH2OH CH2=C(CH3)CH2OH

● Condensed Structural Formula

○ Note the ‘=‘ used for the C=C double bond

● Skeletal formula
○ Not required but v. useful
○ Used in data booklet for complicated structures
○ Do not use in exam answers!
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 Key Points
● Organic chemistry is the chemistry of carbon containing
compounds

● A homologous series is a family of organic compounds

differing only by the length of their carbon chains

● The melting and boiling point increases as you go down a

homologous series

● Displayed formulas show the unambiguous arrangement of

atoms in a compound

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 Isomers
● Compounds with the same
molecular formula but
different structural formula
● The 20 different C4H8O
compounds from last
lesson are isomers of each
other
● These are all structural
isomers
○ Same number of each
atom, but bonded in a
different order
● You would have even more
if you included geometric
and optical isomers
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Structural Isomers of the Alkanes
● The (non-cyclic) alkanes have the general formula CnH2n+2

● Draw full and condensed structural formulas for every

isomer of every one of the alkanes up to n = 6
○ If you finish early, draw each as a skeletal formula

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Did you get them all?

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 Key Points
● Structural isomers have the same number of each atom
but they are connected differently
● When naming compounds
● The longest carbon chain forms the prefix
● The functional group tells you the suffix
● Sometimes numbers need to be used to tell you
where this functional group is
● Side chains and other groups are named according to
what they are, how many there are and their position

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Meet the Families

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 Refresh
● Draw the three isomers
containing the alcohol functional
group of formula C4H9OH*.
*You haven’t formally met this yet
but alcohol is -OH
Reviewing Your Notes
You should spend 60
seconds reviewing your
notes from last lesson
before attempting this.
Your notes and mind-
map must be ready for
me to inspect.
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 How to name organic
compounds
1. Identify the longest straight chain

1. Identify the functional group

1. Identify the side chain

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Nomenclature - from Pearsons

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 Volatility
● How easily a substance changes into a gas
● High volatility means a low boiling point

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 Volatility
● Depends on the type of functional group

● Polar functional groups cause dipole-dipole attraction

which increases boiling point

● Functional groups that form hydrogen bonds have

even higher boiling points

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Volatility

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Which will have the higher boiling point?
C2H5OH or C3H8
ethanol Mr =46, BP = 78℃
propane Mr =44, BP = -42℃

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Solubility in water
▶ Length of carbon chain
▶ The nature of the functional group

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Solubility in water
▶ The nature of the functional group
▶ Solubility is determined by the extent to which this
group can interact with water
▶ By forming hydrogen bonds, for example

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Solubility in water

▶ Soluble or insoluble…why?

▶ Alcohols, Carboxylic acids,

Aldehydes, Ketones

▶ Do you think this will hold true for

all sizes of these molecules?

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 Solubility in water
▶ Insoluble or soluble…why?
▶ Halogenoalkanes are not soluble because they do not
form hydrogen bonds with water.

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 Example
● Which will have the lowest boiling point?
(Draw out the structure first).

CH3CH2CH(CH3)CH3

(CH3)4C

CH3CH2CH2CH2CH3

CH3CH2OCH2CH3

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Homework

▶ Memorise the functional groups and their naming

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Alkanes

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 Reviewing Your Notes
You should spend 60
Refresh seconds reviewing your
notes from last lesson
▶ The following is a computer-generated before attempting this.
representation of the molecule, methyl
2-hydroxy benzoate, better known as oil
of wintergreen.

a) Deduce the empirical formula of H

methyl 2-hydroxy benzoate and draw
the full structural formula, including
any multiple bonds that may be H C H
present…The computer-generated C C
representation shown does not
distinguish between single and
multiple bonds. C C
H
b) Name all the functional groups H C O
present in the molecule.
H H
C C
O O 34H
35
Combustion of Alkanes

▶ The alkanes really don’t do much

▶ Combustion is of one of two notable reactions (this is why we
use them for fuels)

▶ Complete combustion:
▶ alkane + oxygen → carbon dioxide + water

▶ Incomplete combustion:
▶ Alkane + oxygen → carbon + carbon monoxide + carbon dioxide
+ water
▶ The amounts of C, CO and CO2 will vary depending on
conditions 36
Combustion

Complete: C3H8+ 5O2-->3CO2 + 4H2O

In limited O2 : 2C3H8 + 7O2--> 6CO + 8H2O

Even less O2: C3H8 + 2O2--> 3C + 4H2O

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 Carbon Monoxide and Carbon

1. Combines irreversibly with

haemoglobin in the blood
▶ Prevents it from carrying oxygen

2. Smoke
▶ Particulates
▶ Smog
▶ Global dimming

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Why Good Fuels?
▶ To do:
▶ Use Table 13 in the data booklet to help you determine the
trend in energy released per gram by combustion of the
alkanes.

▶ Use bond enthalpies to help you explain the trend noted

above.

▶ What do you think should be the characteristics of a good

fuel?

▶ Use the above to decide and explain which out of methane

and octane is a better fuel.
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Why so boring stable?

▶ There are at least two reasons why alkanes are so

unreactive

▶ Task: Think back to your knowledge of molecular

structure, and look at the tables of bond-enthalpies in
the data booklet to see if you can work out why.

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 Halogenation
▶ Alkanes will undergo halogenation if reacted with a halide in the presence of
u.v. light.
C2H6(g) + Br2(l) CH3CH2Br(g) + HBr(g)
u.v
ethane . bromoethane

▶ This reaction is an example of free radical

substitution

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Radicals

▶ Free radicals are species with unpaired electrons

▶ They are crazy reactive

▶ Halogensu.v
form radicals when hit by uv light of the right frequency:
.
▶ Cl2 2 Cl•

▶ The dot after the Cl represents the unpaired electron and tells us we have a
radical

▶ This process is called homolytic fission – the bond breaks equally with one
electron going to each chlorine

▶ Task: draw Lewis structures for the Cl2 molecule and each of the Cl•
radicals

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 Reaction Mechanism: Free▶ Radical
Initiation
Substitution
u.v
▶ Cl2 . 2 Cl• ▶ Radicals formed by homolytic fission

▶ Propagation
▶ Cl• + C2H6 → C2H5• + HCl ▶ These steps feed each other the radicals
▶ C2H5• + Cl2 → C2H5Cl + Cl• needed to continue

▶ Termination
▶ Cl• + Cl• → Cl2 ▶ Any two radicals can combine to
terminate the reaction
▶ Cl• + C2H5• → C2H5Cl
▶ Concentration of radicals is low so this is
▶ C2H5• + C2H5• → C4H10 a rare event

▶ A single radical can cause thousands of cycles of the propagation stage before it reaches
termination
▶ This same mechanism applies to all of the halogens
▶ The alkane can be substituted multiple times, until every H has been replaced

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Extension:

▶ Research the role of free radical reactions in the

depletion of the ozone layer

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Key Points

▶ Alkanes are pretty unreactive

▶ They release a lot of energy on combustion, and are

easy to handle which makes them good fuels

▶ Undergo free radical substitution to form

halogenoalkanes and a hydrogen halide in the
presence of UV light

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Alkenes

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Refresh
Reviewing Your Notes
You should spend 60
▶ Write an equation for the reaction seconds reviewing your
between methane and chlorine to form notes from last lesson
chloromethane. before attempting this.

Your notes and mind-

map must be ready for
▶ Explain this reaction in terms of a free- me to inspect.
radical mechanism.

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Alkenes and hydrogen (Hydrogenation)

▶ Alkene + hydrogen → alkane

▶ Reaction conditions:
▶ Hot, around 150°C
▶ Ni catalyst

▶ This is an addition reaction, in which the hydrogen

adds across the double bond
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Alkenes and hydrogen halides

▶ Alkene + hydrogen halide → halogenoalkane

▶ Reaction conditions:
▶ This reaction occurs very readily and needs no special
conditions

▶ This is an addition reaction, in which the hydrogen

halide adds across the double bond
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Alkenes and halogens

▶ Alkene + halogen → dihalogenoalkane

▶ Reaction conditions:
▶ This reaction occurs very readily and needs no special conditions

▶ If the halogen used is an aqueous solution of bromine

(bromine water), the orange-brown colour of bromine
solution is decolourised.
▶ This is the standard test for alkenes.

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Alkenes and water

▶ Alkene + water → alcohol

▶ Reaction conditions:
▶ Water must be steam
▶ Phosphoric or sulphuric acid catalyst

▶ This is the process used to make industrial ethanol

▶ Fermentation from sugar would be far too expensive!
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52
Polymerisation
▶ Under the right conditions, alkene molecules will add to each
other creating a polymer

▶ In this case, 1-bromo-2-fluoroethene polymerises to form poly-

1-bromo-2-fluroethene

▶ Conditions:
▶ Vary from alkene to alkene but often include high pressure,
temperature and a catalyst

▶ The carbons in the C=C double bonds form the carbon chain,
everything else hangs off this chain
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54
Drawing polymers
▶ Draw three-monomer lengths of the polymers formed
by:

▶ Propene

▶ Styrene

▶ Pent-2-ene

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56
Polychloroethene

▶ PVC (poly vinyl chloride)

▶ Construction material
▶ Packaging
▶ Electrical cable sheathing
▶ Synthesis produces dioxin as a
byproduct
▶ Linked with reproductive disorders
and cancers
▶ Greenpeace advocates a global
phase out of PVC

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Polytetrafluoroethene
▶ PTFE
▶ Teflon
▶ Non-stick pans
▶ Gore-tex fabrics

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Key Points
▶ Alkenes undergo addition reactions with:
▶ Hydrogen
▶ Hydrogen halides
▶ Halogens
▶ Water (steam)

▶ Alkenes undergo addition polymerisation

▶ Alkenes are very economically important due to the

range of products they can make

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Alcohols

60
Refresh
▶ Which products can be potentially
obtained from crude oil and are
economically important?
Reviewing Your Notes
You should spend 60
seconds reviewing your
notes from last lesson
before attempting this.

I. Plastics Your notes and mind-

map must be ready for
II. Margarine
me to inspect.
III. Motor fuel

A. I and II only
B. I and III only
C. II and III only
D. I, II and III

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Alcohols as Fuels
▶ Alcohols combust more readily than equivalent
alkanes but release less energy since they are already
partially oxidised

Alcohol + oxygen → carbon dioxide + water

▶ Alcohols are used as fuels:

▶ As a fuel for cars – either pure or blended with petrol
▶ Methanol as fuel for competitive motorsports including
dragsters and monster trucks

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63
Oxidation of alcohols
▶ The most important reactions of the alcohols are their
oxidations

▶ A range of compounds will oxidise them so the oxidiser is

often represented as [O]

▶ One oxidising agent you need to know is potassium

dichromate, K2Cr2O7.
▶ When using this, orange Cr(VI) is reduced to green Cr(III)

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Oxidation reaction scheme

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66
Oxidation of primary alcohols
▶ Bottle of wine exposed to air
▶ Bacteria oxidize the ethanol
▶ To ethanoic acid which is the acid
in vinegar.

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 Oxidation of primary alcohols
▶ If we want to keep the aldehyde product
it is possible to distill it as it forms.

▶ If we want to keep the carboxylic acid as

product
▶ Leave it for a longer time
▶ Most efficiently done in a reflux condenser

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Oxidation of 2o and 3o alcohols
▶ 2o - Form ketones
▶ 3o – Are not oxidized

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Key Points

▶ Alcohols are highly combustible

▶ Primary alcohols oxidise to form aldehydes, which

oxidise to form carboxylic acids

▶ Secondary alcohols oxidise to form ketones

▶ Tertiary do not oxidise due to the 3 strong C-C bonds

surrounding the –OH carbon
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Halogenoalkanes

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 Halogenoalkanes

▶ CnH2n+1X
▶ Where X is a halogen
▶ The halogen can be replaced by other atoms
or groups
▶ Substitution reactions
▶ Halogenoalkanes can be used as synthetic
pathways leading to other important organic
products

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Carbon-halogen bond
▶ Is polar
▶ Carbon atom attached to the halogen
has a partial positive charge
▶ Electron deficient
▶ Attracts nucleophiles
▶ A nucleophile is a ‘nucleus-loving’
species that is attracted to positive
charges.
▶ Nucleophiles have either full negative
charges or delta-negative charges
▶ Water and hydroxide are both nucleophiles
▶ In this case we can also call the reaction
‘hydrolysis’

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74
Halogenoalkanes and strong bases
▶ A substitution reaction takes place, where the halogen atom is displaced by the
hydroxide ion
halogenoalkane + sodium hydroxide → alcohol + sodium chloride

▶ Conditions:
▶ Aqueous base
▶ Gently warmed (can at room temperature, but may be quite slow)
▶ This is a nucleophilic substitution.
▶ The C attached to the halogen is δ+ due to the high electronegativity of the halogen
▶ The OH- ion (our nucleophile) is attracted to the δ+ carbon
▶ A nucleophile is a species with a negative charge or a lone pair that is attracted to positive/delta-positive
atoms

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 Halogenoalkanes
▶ CFC
▶ Chlorofluorocarbons
▶ Use is now restricted
▶ CFCs remain active in the atmosphere for a long time,
even though no more are being used

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Condensation Reactions SL

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Condensation Reactions
▶ A reaction in which two molecules join together, and
produce a small molecule, usually water, as a by-
product.

▶ Other small molecules: HCl, NH3

▶ When water is the molecule loss then it is also a

dehydration reaction.

(Alternative name: addition-elimination reaction)

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Esterification – the reaction of alcohols and
carboxylic acids
▶ Carboxylic acids react with alcohols to make esters:
▶ The ester linkage is outline in red

▶ Carboxylic acid + alcohol ester + water

H+ cat

▶ Propan-1-ol + methanoic acid

▶ Propyl comes from the propanol and methanoate comes

from methanoic acid

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Esterification
Carboxylic acid + alcohol <-> ester + water
CH3COOH + CH3OH <-> CH3COOCH3 + H2O
Concentrated sulfuric acid as a catalyst

What are the names of the reactants and products?

Compare the bpts, volatility, and solubility of the
three. Explain.
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 Esters’ characteristics
Many have sweet, fruity smells
Used in food flavorings and perfumes
Used to soften plastics, add flexibility

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Triglycerides

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Condensation of Esters
● Esterification reaction can lead to polymerization
when the acid has two –COOH groups and the alcohol
has two –OH groups

● The chain can extend in two directions

● Forming a polymer known as a POLYester

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 Extension - Condensation to form
amide
Carboxylic acid + amine → amide + water

Example
ethanoic acid + methamine→methylethanamide + water

CH3COOH + CH3NH2 →

If the molecules have functional groups on both ends then polyamides can
be formed.

There are polyamides that are natural e.g. proteins and synthetic e.g. nylon.

84
Making nylon
http://www.youtube.com/watch?v=5k_4hMjYoMs

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Hexane-1,6-diamine + hexanedioic aicd → nylon 6,6 and water
Draw and name the products of the
following reactions:

▶ Ethanoic acid with ethanol

▶ Pentanoic acid with phenol (C6H5OH)

Ethyl ethanoate

Phenyl pentanoate
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Benzene

87
 Benzene
▶ Contains six sp2 hybridized C atoms bonded to each
other.

▶ Each C is bonded to a single H atom by a pi bond.

▶ The p orbitals of the hybrized C atoms overlap with

each other and form a continuous pi bond which lies
above and below the plane of the C atoms.

▶ This can be represented by two resonant structures or

one which shows delocalization of the ring.
88
 Pearsons page 205, 478
▶ ,

Cyclohexane Benzene

1, 3, 5 - cyclohexatriene 89
 Benzene
Benzene undergoes electrophilic substitution reactions.

The reactions have a high activation energy as the first step

leads to the disruption of the benzene ring.

90
 Pearsons page
167

▶ m

91