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2.

2 Module 2: Alcohols, Halogenoalkanes and Analysis


2.2.1 Alcohols
General formula alcohols CnH2n+1OH
The alcohols have relatively low volatility due to
their ability to form hydrogen bond between
alcohol molecules.
The smaller alcohols (up to 3 carbons) are
soluble in water because they can form
hydrogen bonds with water. The longer the
hydrocarbon chain the less soluble the
alcohol.

H +

Uses of alcohols
Ethanol is alcohol in alcoholic drinks. Ethanol is commonly used as a solvent in the form of methylated spirits.
Methanol is used as a petrol additive to improve combustion and is increasing important as a feedstock in
the production of organic chemicals;

Forming ethanol

Comparing two methods for producing ethanol: Fermentation or industrial formation from ethene

Fermentation
glucose
ethanol + carbon dioxide
C6H12O6
2 CH3CH2OH + 2 CO2

Type of reaction: Fermentation

From ethene reacting with steam


The conditions needed are:
Yeast
No air
temperatures 30 40oC

Reagent: ETHENE - from cracking of


fractions from distilled crude oil
CH2=CH2 (g) + H2O (g)

CH3CH2OH (l)

Type of reaction: Hydration/addition


The optimum temperature for fermentation is around 38oC
At lower temperatures the reaction is too slow.
At higher temperatures the yeast dies and the enzymes
denature.
Fermentation is done in an absence of air because the
presence of air can cause extra reactions to occur.
It oxidises the ethanol produced to ethanoic acid (vinegar).
Advantages
sugar is a renewable resource
production uses low level technology / cheap equipment
Disadvantages
Batch process which is slow and gives high production
costs
ethanol made is not pure and needs purifying by fractional
distillation
Depletes land used for growing food crops

Definition: Hydration is the addition of water


to a molecule
Essential Conditions
high temperature 300 C
high pressure 70 atm
strong acidic catalyst of conc H3PO4
Advantages:
faster reaction
purer product
continuous process (which means cheaper manpower)
Disadvantage:
High technology equipment needed (expensive initial
costs)
ethene is non-renewable resource (will become more
expensive when raw materials run out)
High energy costs for pumping to produce high
pressures

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Classifying Alcohols

H
H

H
O

H
H

H
H

Propan-1-ol
Primary

Propan-2-ol
Secondary

Primary alcohols are alcohols


where 1 carbon is attached to
the carbon adjoining the
oxygen

methylpropan-2-ol
Tertiary

Secondary alcohols are alcohols


where 2 carbon are attached to the
carbon adjoining the oxygen

Tertiary alcohols are alcohols


where 3 carbon are attached to
the carbon adjoining the oxygen

Oxidation reactions of the alcohols


The exact reaction, however, depends on the
type of alcohol, i.e. whether it is primary,
secondary, or tertiary, and on the conditions.

Potassium dichromate K2Cr2O7 is an oxidising agent


that causes alcohols to oxidise.
Partial Oxidation of Primary Alcohols

Reaction: primary alcohol


aldehyde
Reagent: potassium dichromate (VI) solution and dilute
sulphuric acid.
Conditions: (use a limited amount of dichromate) warm
gently and distil out the aldehyde as it forms:

+ [O]

CH3CH2CH2OH + [O]

An aldehydes name ends


in al
It always has the C=O bond
on the first carbon of the
chain so it does not need
an extra number

Ethanal

Observation: the
orange dichromate ion
(Cr2O72-) reduces to
the green Cr 3+ ion

+ H2O

CH3CH2CHO + H2O

propan-1-ol

propanal

Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent
When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO
Full Oxidation of Primary Alcohols
Reaction: primary alcohol
carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute
sulphuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distill off product after the reaction
has finished)

Propanoic acid

CH3CH2CH2OH + 2[O]
propan-1-ol

+ 2 [O]

+ H2O

CH3CH2CO2H + H2O

Observation: the
orange dichromate
ion (Cr2O72-) reduces
to the green Cr 3+ ion

Propanoic acid

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Oxidation of Secondary Alcohols


Ketones end in -one
Reaction: secondary alcohol
ketone
Reagent: potassium dichromate(VI) solution and
dilute sulphuric acid.
Conditions: heat under reflux

When ketones have 5Cs


or more in a chain then it
needs a number to show
the position of the double
bond. E.g. pentan-2-one

Propanone

+ [O]
H

Observation: the
orange dichromate
ion (Cr2O72-) reduces
to the green Cr 3+ ion

+ H2O

H
H

Propanone

propan-2-ol

There is no further oxidation of the ketone under these conditions.


Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group

Esterification
Carboxylic acids react with alcohols, in the
presence of a strong acid catalyst, to form
esters and water.

H+
Carboxylic Acid + Alcohol

O
H3C

C + H

OH

H+

C O

CH3CO2H + CH3CH2OH

C O

+ H2O

CH3CO2CH2CH3 + H2O

Ethanoic acid Ethanol

Esters have two parts


to their names, eg
methyl propanoate.

The bit ending in anoate


comes from the carboxylic
acid and includes the C in
the C=O bond.

Ester + water

The bit ending in yl comes from


the alcohol that has formed it
and is next to the single bonded
oxygen.
The reaction is reversible. The
reaction is quite slow and needs
heating under reflux, (often for
several hours or days). Low yields
(50% ish) are achieved. An acid
catalyst (H2SO4) is needed.

Ethyl Ethanoate

Reaction of alcohols with Dehydrating agents


Reaction: Alcohol

Alkene

Dehydration Reaction: removal of a


water molecule from a molecule

Reagents: Concentrated Sulphuric or Phosphoric acids


Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination

H
H

H
H

H
C

propan-1-ol

+ H2O

Propene

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Some 2o and 3o
alcohols can give
more than one
product, when the
double bond
forms between
different carbon
atoms

Butan-2-ol

But-1-ene

H H
C

H
C

Butan-2-ol can form both alkenes


although more but-2-ene would be
formed

But-2-ene
H

But-2-ene could also exist as E and Z


isomers

Producing alkenes from alcohols provides a possible route to polymers without using monomers derived from oil

2.2.2 Halogenoalkanes
Naming Halogenoalkanes

Based on original alkane, with a prefix indicating halogen atom:


Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I.

Cl

H
H

Br

Substituents are listed alphabetically


1-bromopropane

2-chloro-2-methylbutane

Classifying halogenoalkanes
Halogenoalkanes can be classified as primary, secondary or tertiary depending
on the number of carbon atoms attached to the C-X functional group.
H

Br

PRIMARY Halogenoalkane
One carbon attached to the
carbon atom adjoining the
halogen

Br

SECONDARY Halogenoalkane
Two carbons attached to the
carbon atom adjoining the
halogen

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Cl

TERTIARY Halogenoalkane
Three carbons attached to the
carbon atom adjoining the halogen

Nucleophilic substitution reactions


Substitution: swapping a halogen atom for another atom or groups of atoms
Nucleophile: electron pair donator e.g. :OH-, :NH3, CN:Nu represents any nucleophile they
always have a lone pair and act as
electron pair donators

The Mechanism: We draw (or outline) mechanisms to


show in detail how a reaction proceeds

Nu:-

The nucleophiles
attack the positive
carbon atom

Nu + X-

We use curly arrows in mechanisms (with


two line heads) to show the movement of
two electrons

The carbon has a small


positive charge because
of the electronegativity
difference between the
carbon and the halogen

A curly arrow will always start


from a lone pair of electrons or
the centre of a bond

The rate of these substitution reactions depends on the strength


of the C-X bond
The weaker the bond, the easier it is to break and the faster the reaction.

Bond enthalpy /
kJmol-1

The iodoalkanes are the fastest to substitute and the


fluoroalkanes are the slowest. The strength of the C-F bond is
such that fluoroalkanes are very unreactive

C-I

238

C-Br

276

C-Cl

338

C-F

484

Nucleophilic substitution with aqueous hydroxide ions


Change in functional group:
halogenoalkane
alcohol
Reagent: potassium (or sodium) hydroxide
Conditions: In aqueous solution; Heat under reflux
Mechanism:Nucleophilic Substitution
Type of reagent: Nucleophile, OH-

H
H3C
-HO:

C
H

H3C

+ KOH

OH

+ KBr

1-bromopropane

propan-1-ol

OH + :Br -

The aqueous conditions


needed is an important point.
If the solvent is changed to
ethanol an elimination
reaction occurs

H
Br

Br

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Comparing the rate of hydrolysis reactions


Water is a poor nucleophile but it can
react slowly with halogenoalkanes in a
substitution reaction. Use reflux OR heat
for more than 20 minutes

Hydrolysis is defined as the splitting of a molecule ( in this


case a haloalkane) by a reaction with water
CH3CH2X + H2O

CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a haloalkane and the


halide leaving group combines with a silver ion to form a
SILVER HALIDE PRECIPITATE.
The precipitate only forms when the halide ion has left the
haloalkane and so the rate of formation of the precipitate can
be used to compare the reactivity of the different haloalkanes.

CH3CH2I + H2O

CH3CH2OH + I- + H+

Ag+ (aq) + I-(aq)

AgI (s) - yellow precipitate

The quicker the precipitate is formed, the faster the


substitution reaction and the more reactive the haloalkane

AgI (s) - yellow precipitate


AgBr(s) cream precipitate
AgCl(s) white precipitate

The iodoalkane forms a precipitate with


the silver nitrate first as the C-I bond is
weakest and so it hydrolyses the quickest

The rate of these substitution reactions depends on the strength


of the C-X bond . The weaker the bond, the easier it is to break
and the faster the reaction.

Uses of halogenoalkanes

Cl

Chloroethene and tetrafluoroethene are


the monomers used to produce the
plastics PVC and PTFE

H
C

Polytetrafluoroethene (PTFE) is very


resistant to heat and chemical corrosion. It
is found on nonstick cookware.

Cl

poly(chloroethene) PVC
F

F
C

chloroethene
Poly(chloroethene): is used to make
insulation on electrical wires, window
frame coverings. It is waterproof, an
electrical insulator and doesnt react
with acids.

forms faster

C
F

Tetrafluorethene

Poly(tetrafluorethene)

Chlorofluorocarbons (CFCs)
CFCs were developed for use as aerosols,
refrigerants, and in air-conditioning due their low
reactivity, volatility and non-toxicity.

Many of these uses have now been stopped


due to the toxicity of halogenoalkanes and also
their detrimental effect on the ozone layer in the
atmosphere

Legislation to ban the use of CFCs was supported by chemists and chemists
have now developed alternative chlorine-free compounds
HFCs (Hydro fluoro carbons) e.g..
CH2FCF3 are now used for refrigerators
and air-conditioners. These are safer
as they do not contain the C-Cl bond

CO2 is now used as a blowing agent for producing


expanded polymers instead of CFCs

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2.2.3 Modern Analytical Techniques


Infrared spectroscopy
Complicated spectra can be obtained than
provide information about the types of bonds
present in a molecule

Certain bonds in a molecule absorb infra-red radiation at


characteristic frequencies causing the covalent bonds to
vibrate
ABOVE 1500 cm-1 Functional group identification

BELOW 1500 cm-1 Fingerprinting


Complicated and contains many
signals picking out functional group
signals difficult.
This part of the spectrum is unique for
every compound, and so can be used
as a "fingerprint".

A computer will compare the IR


spectra against a database of known
pure compounds to identify the
compound

e.g. C=O 1640 1750 cm-1


O-H (acid) 2500- 3300 cm-1

Use an IR absorption table provided in exam


to deduce presence or absence of particular
bonds or functional groups
use spectra to identify particular functional groups limited to data

Bond

Wavenumber

C-O

1000-1300

C=O

1640-1750

C-H

2850 -3100

O-H
Carboxylic acids

2500-3300
Very broad

N-H

3200-3500

O-H
Acohols, phenols

3200- 3550
broad

presented in wavenumber form e.g. an alcohol from an absorption peak


of the OH bond,

Spectra for
butanal
O
H3C CH2 CH2 C

2000

1500

C=O
Absorption or trough in between 1640-1750 cm-1 range indicates
presence of C=O bond
Always quote the wave number range from the data sheet
Spectra for
ethanoic acid

O-H absorptions tend


to be broad

O
Absorption or trough in
between 2500-3300 cm-1 range
indicates presence of O-H
bond in an acid

H3C

C
OH

C=O
Modern breathalysers measure ethanol in the breath by analysis using infrared spectroscopy

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Mass spectrometry
Mass spectrometry is used in the determination of relative isotopic masses of an element.
The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes
Fig: spectra for Magnesium from
mass spectrometer

100

% abundance

80

78.70%
For each isotope the mass
spectrometer can measure a m/z
(mass/charge ratio) and an abundance

24Mg+

60
40

25Mg+

10.13%

20
24

25

26Mg+

If asked to give the species for a peak


in a mass spectrum then give charge
and mass number e.g. 24Mg+

11.17%
26

m/z

R.A.M = (isotopic mass x % abundance)


100

Use these equations to


work out the R.A.M

For above example of Mg


R.A.M = [(78.7 x 24) + (10.13 x 25) + (11.17 x 26)] /100 = 24.3
R.A.M = (isotopic mass x relative abundance)

If relative abundance is used instead of


percentage abundance use this equation

total relative abundance

Mass spectrometers have been included in planetary space probes so that elements on other
planets can be identified. Elements on other planets can have a different composition and
abundances of isotopes.
Mass spectromemeters can also be used to monitoring levels of environmental pollution, such as
lead.

Measuring the Mr of an organic molecule

If a molecule is put through a mass spectrometer


it will often break up and give a series of peaks
caused by the fragments. The peak with the
largest m/z, however, will be due to the complete
molecule and will be equal to the Mr of the
molecule. This peak is called the parent ion or
molecular ion

Spectra for C4H10


Mass spectrum for butane
43

Molecular ion
C4H10+

29
58

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Fragmentation

Molecular ion formed:

When organic molecules are passed through a mass


spectrometer, it detects both the whole molecule and
fragments of the molecule.

M [M]+. + e

The molecule loses an electron and


becomes both an ion and a free radical

Several peaks in the mass spectrum occur due to fragmentation.


The Molecular ion fragments due to covalent bonds breaking: [M]+. X+ + Y.

This process produces an ion


and a free radical. The ion is
responsible for the peak

Relatively stable ions such as carbocations R+ such as CH3CH2+ and


acylium ions [R-C=O]+ are common. The more stable the ion, the greater
the peak intensity.
The peak with the highest mass/charge ratio will be normally due to the
original molecule that hasnt fragmented (called the molecular ion) . As
the charge of the ion is +1 the mass/ charge ratio is equal to Mr.
Equation for formation molecular ion

Mass spectrum for butane

C4H10 [C4H10]+. + e

43

m/z 58

Equations for formation of fragment ions from molecular ions

29

C4H10 = 58

[C4H10]+. [CH3CH2CH2]+ + .CH3 m/z 43


[C4H10]+. [CH3CH2]+ + .CH2CH3

m/z 29

Equation for formation molecular ion


Mass spectrum for butanone

CH3CH2COCH3 [CH3CH2COCH3]+. + e

The high peak 43


at 43 due to
[CH3CO]+
stability of acyl
group

29
[CH3CH2]+

m/z 72

Equations for formation of fragment ions from molecular ions


[CH3CH2COCH3]+. [CH3CH2CO]+ + .CH3 m/z 57

[CH3CH2CO]+
+.
57 [CH3CH2COCH3]

72

[CH3CH2COCH3]+. [CH3CO]+ + .CH2CH3 m/z 43


[CH3CH2COCH3]+. [CH3CH2]+ + .COCH3 m/z 29

A mass spectrum is essentially a fingerprint for the


molecule that can be identified by computer using a
spectral database.

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