Chemistry

Alcohols

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 I. Introduction.
 Alcohols are oxygenated organic compounds.
 The general formula of saturated non-cyclic monoalcohol is CnH2n+2O or CnH2n+1OH.
It could be represented by R-OH where R is alkyl group of general formula CnH2n+1 .
 The functional group of alcohol is – OH (hydroxyl group).
Hydroxyl
 The carbon atom attached to the functional group is
Group
called functional carbon. R―OH

II. Classes of alcohols.

According to the number of alkyl groups attached to the functional carbon, we
distinguish three classes of alcohols. ( R, R′ and R ̋ could be identical or different).

Class of alcohol Primary alcohol Secondary alcohol Tertiary alcohol

Number of alkyl One alkyl group Two alkyl groups Three alkyl groups
groups attached to ( 2 hydrogen (1 hydrogen atom) (no hydrogen atoms)
the functional atoms)
carbon
R― CH― R′
General formula R-CH2OH |
OH

Example CH3-CH2OH

III. Isomerism.
Isomers are organic compounds having same molecular formula but different
structural formula.
Isomerism of alcohols starts from n > 2 .

 Type of isomerism :

1) Positional isomerism: they possess same chain of carbon but different position
of – OH (same name but different position of – OH) .
2) Skeletal isomerism: same position of – OH but different chain of carbon (same
position of – OH but different name).
3) Functional isomerism: they possess same molecular formula but different
functional group (different families).

Alcohol possesses a functional isomerism with ether ( R―O―R′).

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 IV- Nomenclature of alcohols (Systematic name ,IUPAC nomenclature).
1- For n ≤ 2 : alKane → alKanol
Example : CH3-CH2OH ethanol CH3OH : methanol

2- For n > 2 :
 The position of hydroxyl group should be mentioned x-alkanol with x
position of hydroxyl group.
 Choose the longest chain containing the functional group OH.
 Number the carbon atoms in such a way the functional carbon has the lowest
number.
 The branchings (ramifications) are named by alphabetical order.
4 3 2 1
CH3―CH―CH―CH2OH
2,3-dimethyl-1-butanol
| |
CH3 CH3

V- Physical properties of alcohols.

 Hydrogen bond is intermolecular (between two molecules); it is a bond between

hydrogen atom and a highly electronegative atom such as oxygen (O), nitrogen (N)
or fluorine (F).
 Physical properties of alcohols depend on hydrogen bond.

Hydrogen bond

 Due to the presence of 2 hydrogen bonds, alcohols possess a high boiling point (b.p)
and a great solubility in water.
 As molar mass of alcohols increases (number of carbon atoms increase), boiling point
increases too.
 When the number of branching increases, boiling point decreases.
 Boiling point of : (primary alcohol) > (secondary alcohol) > tertiary alcohol.
 The solubility of alcohols in water decreases with increase of carbon chain.

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VI- Chemical reactions of alcohols.
The reactivity of alcohols is determined by the group C―O―H .

A- Complete oxidation of alcohols

The oxidation is complete when carbon chain in alcohol is not conserved.

(3n+1)
CnH2n+2O(l) + O2(g) → n CO2(g) + (n+1) H2O(l)
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B- Mild oxidation of alcohols

 Mild oxidation of alcohols is a redox reaction which allows to identify the class of
alcohol.
 Mild oxidation means that oxidation takes place without breaking of carbon chain
(carbon chain is conserved, only hydroxyl group is oxidized).
 Tertiary alcohols don’t undergo mild oxidation due to the absence of hydrogen atom on
functional carbon.
 Alcohols are reductants where hydroxyl group is oxidized into carbonyl group ( - CO - )
or carboxyl group ( - COOH).
 In mild oxidation alcohol is in excess while in continuous mild oxidation alcohol is the
limiting reactant.
 The oxidation is realized in liquid state or in vapor state.
 Mild oxidation is realized by three ways: 1- catalytic oxidation (in presence of air).
2- catalytic dehydrogenation (in absence of air)
3- Oxidation by oxidant ( as Cr2O7 2- , MnO4 - …..)

Mild oxidation of alcohols .

a) Primary alcohol. H O O O
| [O] ‖ [O] ‖
R – C ―O―H R–C―H R – C – OH
|
H aldehyde carboxylic acid

b) Secondary alcohol.
H O
| [O] ∥
R–C–O―H R – C – R1
|
R1 Ketone

c) Tertiary alcohol.
R2
| [O]
R – C – OH no reaction
|
R1
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 1- Catalytic oxidation.

 This reaction is called flameless lamp.

 It is an exothermic reaction.

Controlled mild Cu
R – CH2OH + ½ O2 H2O + RCHO
oxidation
(or Pt) aldehyde (CnH2nO)
Continuous mild Cu
R – CH2OH + O2 H2O + RCOOH
oxidation
(or Pt) carboxylic acid
(O2 is in excess)
(CnH2nO2 )

 Carboxylic acid is identified by : 1- pH < 7.

2- turning red a litmus solution.
 Aldehyde turns pink a Schiff ’s reagent which is colorless.
 Continuous mild oxidation takes place in two steps:

Cu
First step : R – CH2OH + ½ O2 RCHO + H2O

Second step : R – CHO + ½ O2 Cu RCOOH

2- Catalytic Dehydrogenation (removing of H2).

 This reaction is endothermic.

 The catalyst is heated continuously.
Cu
R – CH2OH RCHO + H2
300˚C

3- Oxidation by oxidant.

 The oxidant could be potassium permanganate (KMnO4), potassium dichromate

(K2Cr2O7), Potassium chromate ( K2CrO4) in acidic medium…………
 KMnO4 → K + + MnO4 - (MnO4 – has a violet or purple color).
 K2Cr2O7 → 2 K + + Cr2O7 2- (Cr2O7 2- has a yellow-orange color).
 In continuous mild oxidation of primary alcohol by an oxidant, reflux heating
apparatus is used to condense all vapors such that all aldehyde is oxidized to
carboxylic acid.
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 ½ oxidation equation : ( R – CH2OH → RCHO + 2 H + + 2 e -) × 5
Controlled mild
½ reduction equation: ( MnO4 - + 5 e - + 8 H + → Mn 2+ + 4 H2O ) × 2
oxidation
Overall equation:
(by using KMnO4
5 R – CH2OH + 2 MnO4 - + 6 H + → 5 RCHO + 2 Mn 2+ + 8 H2O
as oxidant)
½ oxidation equation : ( R – CH2OH + H2O → RCOOH + 4 H + + 4 e -) × 5
Continuous mild
½ reduction equation: ( MnO4 - + 5 e - + 8 H + → Mn 2+ + 4 H2O ) × 4
oxidation
Overall equation:
(KMnO4 is in
5 R – CH2OH + 4 MnO4 - + 12 H + → 5 RCOOH + 4 Mn 2+ + 11 H2O
excess)

 Continuous mild oxidation takes place in two steps.

First step : 5 R – CH2OH + 2 MnO4 - + 6 H + → 5 RCHO + 2 Mn 2+ + 8 H2O
Second step :
½ oxidation equation : ( R ̶ CHO + H2O → RCOOH + 2 H + +2 e -) × 5
½ reduction equation : ( MnO4 - + 5 e - + 8 H + → Mn 2+ + 4 H2O) × 2
Overall equation: 5 RCHO + 2 MnO4 - + 6 H + → 5 RCOOH + 2 Mn 2+ + 3 H2O

 If K2Cr2O7 is used :
½ reduction equation: Cr2O7 2- + 6 e - + 4 H + → 2 Cr 3+ + 7 H2O

1- Catalytic Oxidation.

 This reaction is called flameless lamp.

 It is an exothermic reaction.

Cu
Controlled mild R – CHOH – R1 + ½ O2 H2O + RCOR1
oxidation Ketone (CnH2nO)
Continuous mild
R – CHOH – R1 + ½ O2 Cu RCOR1 H2O
oxidation +
(O2 is in excess)

 Continuous mild oxidation of secondary alcohol stops at the level of formation of

ketone due to the absence of hydrogen atom on functional carbon.
 Ketone does not turn pink a Schiff ’s reagent.

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 2- Catalytic Dehydrogenation.

 This reaction is endothermic.

 The catalyst is heated continuously.

R – CHOH – R1 Cu RCOR1 + H2
300˚C

3- Oxidation by oxidant.

 Oxidant could be potassium permanganate (KMnO4) , potassium dichromate (K2Cr2O7)

or potassium chromate ( K2CrO4) in acidic medium……
 KMnO4 → K + + MnO4 - (MnO4 – has a violet or purple color ).
 K2Cr2O7 → 2 K + + Cr2O7 2- (Cr2O7 2- has a yellow-orange color).
 Continuous mild oxidation of secondary alcohol stops at the level of formation of
ketone due to the absence of hydrogen atom on functional carbon.

Controlled mild ½ oxidation equation: (R – CHOH – R1→ RCOR1 + 2 H + + 2 e -) × 5

oxidation ½ reduction equation: ( MnO4 - + 5 e - + 8 H + → Mn 2+ + 4 H2O ) × 2
(by using KMnO4 Overall equation:
as oxidant) 5 R– CHOH– R1 + 2 MnO4 - + 6 H + → 5 RCOR1 + 2 Mn 2+ + 8 H2O
Continuous mild
oxidation Overall equation:
(KMnO4 is in 5 R – CHOH – R1+ 2 MnO4 - + 6 H + → 5 RCOR1 + 2 Mn 2+ + 8 H2O
excess)

Mild oxidation is used to identify the class of alcohol.

Controlled mild oxidation Continuous mild oxidation
Catalytic Catalytic Oxidation Catalytic Oxidation by
oxidation dehydrogenation by oxidant oxidation oxidant
Primary + + + + +
alcohol Aldehyde Aldehyde Aldehyde Carboxylic Acid Carboxylic acid
CnH2n+2O CnH2nO CnH2nO CnH2nO CnH2nO2 CnH2nO2

Secondary + + + _ _
alcohol Ketone Ketone Ketone
CnH2n+2O CnH2nO CnH2nO CnH2nO

Tertiary _ _ _ _ _
alcohol
CnH2n+2O

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 C- Esterification Reaction.

Esterification reaction is the reaction between alcohol and carboxylic acid to produce ester
and water where H from alcohol and OH from acid combined to give water.
Esterification reaction (forward direction)

+
H
RCO-OH + H-OR' RCOOR' + H2O
Heat
Hydrolysis reaction (reverse direction)

Characteristics of the reaction :

1- Slow (it takes longer time to produce)
2- reversible or limited ( n(ester)formed < n(ester)expected )
3- athermic (it neither releases nor absorbs heat).

Equilibrium constant (KC)

Water is one of the products
of the reaction and not a
The equilibrium constant KC of the esterification reaction is: solvent: we must include its
n(ester) n(water)
×
concentration in the
[ester][water] V V n(ester)×n(water)
KC = [acid][alcohol] = n(acid) n(alcohol) = equilibrium constant.
× n(acid)×n(alcohol)
V V

The ester is prepared experimentally using the reflux heating apparatus.

Labeled schema of the apparatus of reflux heating.

condenser

balloon
Alcohol
+ carboxylic acid
+ H2SO4 concentrated
+ boiling chips Water out
Water in

elevator
Heating mantle
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1- Purpose of using reflux heating apparatus.
Reflux: to not lose any of reactants or products during boiling (or to condensate the
evaporated gases and return them back to the medium).
Heating: to increase the rate of reaction (since reaction is slow and temperature is a
kinetic factor).

2- Role of boiling chips.

They are used to prevent bumping (or to regulate the boiling).

3- Justify why the top of the tube of the condenser must be opened ( it is not closed).

It is opened to avoid the explosion of gases (or to avoid increasing the pressure inside
the tube which will cause the tube to explode).

4- Identify the purpose of using a condenser with spheres instead of a straight condenser.
Because it permits better condensation of vapors due to the greater contact of surface
between the vapors and the condenser which is caused by the spheres.

5- Effect of temperature .
Temperature is a kinetic factor. When the temperature increases, the rate of the reaction
increases and then the equilibrium is reached faster.

6- Effect of catalyst.
When sulfuric acid H2SO4 is used in small quantity, it plays only the role of kinetic factor;
it increases the rate of the reaction to reach faster the equilibrium state.
It does not affect neither the yield nor the equilibrium constant KC (KC depends only on
temperature).

Note If the reaction takes place in absence of sulfuric acid, it will take place but in a
slow rate since H2SO4 acts as a catalyst which increases the rate of reaction but
it does not allow an impossible reaction to take place.

7- How could we accelerate the rate of reaction?

We could accelerate the rate of reaction by:

 adding a small amount of sulfuric acid.
 increasing the temperature of the medium (heating).

8- Yield of esterification.
𝑛(𝑒𝑠𝑡𝑒𝑟)𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 where n (ester) experimental = n(ester)formed at equilibrium
Yield =
𝑛(𝑒𝑠𝑡𝑒𝑟 )𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
n (ester) theoretical = n(ester)formed if the reaction is
complete and it is determined by stoichiometric ratio.
Percentage of yield = 100 × yield

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 the percentage yield of esterification reaction depends on the class of used alcohol.
For an equimolar mixture (same number of mol) of alcohol and carboxylic acid :
 Primary alcohol : yield = 67 %
 Secondary alcohol : yield = 60 %
 Tertiary alcohol : yield = 1 to 5 %

9- How could we increase the yield of reaction?

We increase the yield of the reaction by increasing the experimental amount of ester formed
by favoring the esterification reaction either:
a- by using one of reactant in excess which increases the rate of the forward direction.
b- by removing ester (by fractional distillation) or water (by using concentrated H2SO4
in greater amount playing the role of dehydrating agent) as they are formed.

10- Labeled schema of the apparatus of fractional distillation.

thermometer

Fractionating column condenser

Reacting mixture

distillate

D- Alcoholic Fermentation Of Sugar Juice (fructose or glucose).

This reaction takes place in absence of air to prevent the oxidation of ethanol.
enzyme
C6H12O6 2 CH3 – CH2OH + 2 CO2(g)

 Enzyme is a biological catalyst.

 Enzyme is specific.

Alcoholic degree: it represents the percentage by volume of ethanol in the solution.

V(ethanol)
Alcoholic degree = × 100
V(solution)

m(ethanol) n(ethanol)×M(ethanol)
With V(ethanol) = =
density (ethanol) density (ethanol)

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