Organic chemistry

The substances or compounds are classified into two groups. All those, which
could be obtained from vegetables or animals, that means substances that were
produced by the living organisms, were classified as organic.

Organic chemistry is now defined as the chemistry of carbon compounds. Some

of the properties of organic compounds differ greatly from inorganic compounds.

 Usually combustible
 Generally having low melting or boiling point
 Less soluble in water
 Several organic compounds may exist for a given formula
 Reactions of organic compounds are molecular rather than ionic. Reaction
rate is slow.
 Molecular weight may be very high.
 Organic compound can serve as a source of food for bacteria.

Structural formulas and Isomerism:

Kekule’ derived the constant quadric valency (tetra valency) of carbon

and symbolic formula is  C 


The molecular formula shows the number of each kind of atom present in the
molecule but does not indicate their arrangement. In organic chemistry there are
many cases where a given formula represents two or more compounds that differ
in physical and chemical properties. Such compounds having the same
molecular formula but differing in physical and chemical properties are known as
isomers or isomerised, phenomenon itself being known isomerism.

Saturated and unsaturated compounds:

In an organic compound containing two or more carbon atoms, there are only
single bond linking any two adjacent carbon atoms than the compound is seemed
to be saturated like ethane (C2H6), n – propanol (C3H7OH), n – acetaldehyde
(C2H4O or CH3CHO).

H H H H H
    
H ­ C ­ C ­ H H ­ C ­ C ­ C ­ OH
    
H H H H H
Ethane n – propanol

H O
 ‖
H ­ C ­ C ­ H

H
n – acetaldehyde
On the other hand, if the compounds contain at least one pair of adjacent carbon
atoms linked by a multiple bond then that compound is set to be unsaturated like
ethylene (C2H2), acetylene (C2H2) tetraldehyde (C3H4O).

H ∖ ∕ H
C = C H ­ C  C ­ H
H ∕ ∖ H

Ethylene Acetylene

H O
H ∖  ‖
C = C ­ C ­ H

H ∕

Tetraldehyde

Organic compounds are classified into three major groups:

1 a. Aliphatic compounds – open chain or acyclic compounds
b. Alicyclic compounds – these are carbocyclic or ring compounds,
which resemble aliphatic compound in many ways.

2 Aromatic compounds – these are carbocyclic or ring compounds

containing at least one benzene ring. These are also the group of non-
benzenoid aromatic compounds.

3 Hetrocyclic compounds – These are cyclic (ring) compounds containing

other elements besides carbon in the ring. In a few cases even no carbon
atom is in the ring.

Aliphatic compounds:
Aliphatic hydrocarbons or saturated hydrocarbons:

Alkanes: The simplest organic compounds are the hydrocarbons composed of

carbon and hydrogen. The aliphatic hydrocarbon may be saturated or
unsaturated. The saturated one is called the alkanes.

Methane (CH4): It is formed by bacterial decomposition of vegetable matter in

absence of air. It represents 45 to 96% of natural gas from oil or gas wells. The
gas also occurs in coal seams and is responsible for explosion in mines.

Ethane (C2H6): Ethane occurs in natural gas (5 – 10 %), coal gas and in
petroleum. In cracking of heavy petroleum, ethane is a co – product.
Propane (C3H8) and Butane (C4H10): Propane occurs in petroleum and upto 5%
in natural gas. The gas is absorbed in active charcoal and released by steam.
There are two butanes, normal and iso butane found in natural gas upto 2%.

Pentane (C5H12): Normal, iso and neo pentane occurs in petroleum and upto 1%
in natural gas.

Properties:

Methane and other alkanes react with nitric acid in vapour phase at 350 – 400 C
to form Nitro alkanes.

350 – 400 C
CH4 + HNO3 CH3NO2 Nitro methane

Homologous series: Methane (CH4), Ethane (C2H6), Propane (C3H8), Butane

(C4H10), etc. are closely resemble one another. All are practically insoluble in
water, stable, chemically inert but give substitution products with chlorine etc. If
the alkanes are arranged in ascending order of molecular weights, they are found
to be corresponding to a general formula CnH2n+2, i.e. for n carbon atoms in a
molecule, there are 2n+2 hydrogen atoms. Each member differs from the next by
CH2. A series of compounds, having similar structure and hence similar
properties, which can be expressed by a general formula; conjunctive member
differing by CH2 group is called homologous series. The individual members are
called homologs.

Functional groups: Replacing a hydrogen of a methane by chlorine will get

chloromethane or methyl chloride (CH3Cl), a very reactive compound which may
be converted into many other compounds like

AgNO3
CH3NO2

KOH
CH3OH
Cl2
CH4 CH3Cl
NH3
CH3NH2

KCN
CH3CN
In these compounds, the CH3  group remains intact. CH3  group is a
monovalent organic radical termed methyl. Similarly from ethane we have ethyl
chloride, ethyl alcohol, etc. C2H5  group is ethyl radical. General name of
alkane’s radical is alkyl radical and it is denoted by R. An alkyl radical is named
from the alkane by replacing –ane with –yl.

Nomenclature: Unbranched alkanes with more than four carbon atoms have
names derived from Latin or Greek numerals like n – pentane, n – hexane, n –
heptane etc. For branched molecules, the IUPAC system is followed. Here the
largest continuous chain is named according to the number of carbon atom,
which consecutively numbered. The compound is designed as a derivative if this
hydrocarbon.

CH3

CH3 ­ CH ­ CH2 ­ CH2 ­ CH3 (2 – methyl) pentane

CH3

CH3 ­ CH ­ CH2 ­ C ­ CH3 2,2,4 trimethyl pentane
 
CH3 CH3

General reactions:
1. Halogenations: Halogens react with alkane in presence of light or at
elevated temperature (above 300 C) and form halogenated alkanes.
Almost no reaction occurs in the dark or that ordinary temperature. The
order of reactivity is F>Cl>Br>I.

2. Nitration: Alkanes form nitro alkanes on heating with nitric acid but
oxidation products predominate and the yield of mono nitro alkane is low.

Example: Methane and nitric acid yields only 13 % Nitromethane at 475 C.
But if nitration is carried out in vapour phase with nitric acid or nitrogen dioxide
at 400 – 450 C, mono Nitromethane are the main products.

3. Sulfonation: Concentrated sulphuric acid does not react with alkanes even
at elevated temperature (this is utilised in petroleum refinery). With hexane
and higher homologs, fuming sulphuric acid is give alkane sulfonic acid
(R-SO3H), but oxidation takes place. The reaction with n–alkane is sluggish
but with branched alkanes fairly rapid.

4. Oxidation: An alkane readily burns in sufficient air or oxygen to form CO2

and water.

3n+1
CnH2n+2 + O2 nCO2 + (n+1) H2O
2

Reaction is highly exothermic. (Hence the use of natural gas and petroleum as
fuels, isomerism).
5. Biological oxidation: Hydrocarbons are oxidised by certain bacteria under
aerobic condition. The oxidation proceeds through several steps. This is
called omega oxidation.

Bacteria
2CH3CH2CH3 + O2 2CH3CH2CH2OH

Unsaturated hydrocarbon:

Unsaturated hydrocarbons contain less hydrogen then alkanes. Olefins or

alkenes have a C=C bond in their molecules. The simplest molecule is ethylene.
They are represented by the general formula CnH2n.

Ethylene: Ethylene occurs in coal gas (3 – 4 % by volume). It makes flame.

Hydrogenation: In a presence of a catalyst such as platinum, palladium or

nickel, alkene acts as a molecule of hydrogen at moderate temperature and
pressure and forms an alkane.

Ni
R-CH=CH-R’ + H2 R-CH2-CH2-R’

Addition of halogen: In an inert solution, such as CCl4 (Carbon Tetrachloride),

an alkene combines with two atoms of halogen at ordinary temperature and
yields a viciual dichloride. The order of reactivity is F>Cl>Br>I.
CH2=CH2 + Br2 CH2 Br-CH2 BR
If an alkene is passes into concentrated hydro iodic acid or hydrobromic acid at
ordinary temperature and to a solution of hydrochloric acid in acetic acid at higher
temperature, an alkyl halide results. The order of reactivity is HI>HBr>HCl>HF.

CH3-CH2 -CH2I (10%)

n-propyl iodide

CH3-CH=CH2 + HI

CH3-CHI-CH3 (90%)
Iso-propyl iodide

A hydrogen of a hydrogen halide acts to the more hydrogenated and the halogen
to the less hydrogenated carbon linked double bond.

Addition of hypo halous acid: If an alkene is passed through aqueous hypo

chlorous acid at ordinary temperature, a cholo hydrin results. As per the rule, the
halogen attaches itself to the more hydrogenated carbon.

CH3-CH=CH2 + HOCl CH3 -CHOH-CH2 Cl

Propylene chlorohydrin
Addition of sulphuric acid: Cold, concentrated sulphuric acid readily absorbs
an alkene to pass into it. Alkyl hydrogen sulphate is mainly formed which remains
dissolved in the acid.
HSO4
|
H2O
CH3-CH=CH2 + H2SO4 CH3 -CH-CH3 CH3 -CHOH-CH3
Hydrolysis
Isopropyl Isopropyl alcohol
hydrosulphate

Hydration: Direct addition of water to the double bond of alkene is possible

under specified condition. For an example, ethylene and steam at 300 C under
65 atmospheric pressure passed over tungsten oxide or phosphoric acid on silica
produce ethyl alcohol.

CH2=CH2 + H2O CH3 -CH2OH

Oxidation: Dilute alkaline KMnO4 at low temperature oxidises an alkene to a

dihydric alcohol or a glycol. Air oxidises propylene to Acrolein at 300 – 350 C in
presence of cupric oxide catalyst.

R-CH=CH2 + O + H2O KMnO4 R-CHOH-CH2OH

Glycol

CH3-CH=CH2 + O2 CuO OHC - CH=CH2 + H2O

Acrolein

Addition of Ozone: If ozonised oxygen is let into the solution of an alkene in an

inert solvent like petroleum ether at low temperature, an ozonide is formed
quantitatively. It is unstable, on hydrolysis, two aldehydes or ketone results. By
identifying them the position of the double bond in an ethylinic compound may be
located. The process is called ozonalysis.

R−CH=CH−R’ + O3 R− CH − O− CH −R’
| |
O O
 H2O
R−CHO + R’CHO + H2O2

Diolefins (CnH2n-2): Of diolefins, the most important are isoprin

(CH2=C(CH3)CH=CH2) and 1,3 butadiene (CH2=CH – CH =CH2). A hydrocarbon,
with two double bond is known as diene. Isoprin is originally obtained by the dried
distillation of natural rubber. It is now made from Iso amide alcohol.

Acetylene or alkynes have a triple bond (CC) in their molecules. They are more
unsaturated then the alkenes. The simplest molecule is CnH2n-2. They are highly
reactive and they do not occur in nature.
Acetylene: Acetylene occurs in coal gas (0.06%). It is a bye product of
petroleum creaking.

Reactions:

Hydrogenation: At ordinary pressure, hydrogen and acetylene, in presence of

fine nickel at 100 C or platinum at room temperature, forms ethylene and then
ethane.

HCCH H2 CH2=CH2 H2 CH3 – CH3

Addition of halogen: Acetylene and chlorine combines at room temperature in

presence of lime with explosive violence producing hydrochloric acid and carbon.

HCCH + Cl2 2HCl + 2C

Addition of hydrogen halide: Acetylene acts with hydrogen halide in two stages
and form a vinyl halide and then gem – dihalide. The order of reactivity is
HI>HBr>HCl.

HCCH HCl CH2=CHCl HCl CH3 – CHCl2

Vinyl Ethylidine
chloride chloride

Formation of acetylides: Acetylene forms metallic compounds called acetylides.

The hydrogen atom is replaced by certain metals. If acetylene is passed through
an Ammonical solution of a silver or copper salt then Ag2C2 and Cu2C2 results.

HCCH + 2AgNO3 AgCCAg + 2HNO3

Silver acetylide

Alcohol
If one or more hydrogen atoms of an alkane are replaced by a corresponding
number of hydroxyl group (–OH), an alcohol or alkanol is obtained.

CH3OH - Methanol
CH3CH2OH - Ethanol

If a hydrogen atom of an alkene is replaced by a hydroxyl group, an unsaturated

alcohol results.

CH2=CH-CH2OH - Allyl alcohol

The general formula of saturated monohydric alcohol is CnH2n+1OH or R–OH.

–OH group is called functional group. They are primary, secondary or tertiary
according as the –OH group is attached to a primary, secondary or tertiary
carbon atom.
CH3 – CH2OH Primary alcohol (Ethanol)

CH3 – CHOH – CH3 Secondary alcohol (Iso propyl alcohol)

CH3
|
CH3 – C – OH Tertiary alcohol (Tertiary Butanol)
|
CH3

Nomenclatures:
Alcohols are used in three ways.

1. Their common names are derived from the alkyl group to which the
hydroxyl group is linked and the word alcohol.

2. A systematic IUPAC names of alcohols are obtained by replacing the

terminal ‘e’ of the parent alkane by ‘ol’. Which indicates the hydroxyl group
in molecule. The position of the –OH group in the carbon chain is shown
by a number so also the position of a substitute group in a branch chain if
any. The number in the first case lines between the first part (Methan,
Ethan, Propan, etc. & ol).

OH
|
CH3 – C – CH3 2 Methyl propan – 2 – ol
|
CH3

3. Alcohols are regarded as derivatives of methyl alcohol, which is called

Carbinol. The alkyl groups replacing its hydrogen atoms are mention first.

Isomerism:
Two isomerism are possible in monohydric alcohol.

1. The carbon skeleton (or nucleus) of the alkyl group to which the hydroxyl
group is attached may be different. Such isomerisms are known as
nuclear isomerism.

CH3 – CH2 – CH2 – CH2OH

CH3
|
CH3 – C – OH
|
CH3
 2. The carbon skeleton of the alkyl group remains the same but the
functional –OH group occupies different position in the chain. This is called
position isomerism.

CH3 – CH2 – CH2OH Normal butyl alcohol

CH3 – CH – CH2 – CH3 Secondary butyl alcohol

|
OH

Methyl alcohol:
Synthesis gas CO+2H2 is made from the natural gas, steam and CO2 by heating
to 800 C in presence of Nickel catalyst. Water gas is obtained by passing steam
over red hot coke. Thus methanol was produced.

800C
3CH4 + 2H2O +CO2 4CO + 8H2
Ni

(CO + H2) + H2 ⇌ CH3OH

Properties:
Methanol is a mobile, inflammable liquid with a pleasant smell and burning taste.
It is poisonous causing blindness and death depending on the dose. Methyl
alcohol is largely converted into formaldehyde for the plastic industry.

Ethyl alcohol:
Ethanol is manufactured by the fermentation of sugar solution with yeast from
ethylene.
C12H22O11 +H2O Invertase C6H12O6 + C6H12O6 Zymase 2C2H5OH +2CO2
Sucrose Glucose Fructose

Ethylene of petroleum refinery is absorbed under pressure in 90 – 95 % H2SO4 at

50 – 80 C. Ethyl hydrogen sulphate and diethyl sulphate are thus formed. The
mixture is diluted with 1 – 2 volumes of water and heated to 70 C for 2 hours to
hydrolysed these to ethanol.

CH2=CH2 + H2SO4 CH3-CH2-O-SO3H H2O CH3CH2OH + H2SO4

Ethyl hydrogen sulphate

CH2=CH2 + H2SO4 (CH3-CH2)SO4 2H2O 2CH3CH2OH + H2SO4

Diethyl hydrogen sulphate

Ethanol with about 0.3% water is called absolute alcohol. Methylated spirit is the
rectified spirit containing unpalatable substances such as wood spirit (about
10%), pyridine or mineral naphtha etc. Industrial methylated spirit is rectified spirit
mixed with 5% methanol.
Propyl alcohol:
n – propyl alcohol occurs in fusel oil from which it may be recovered by fractional
distillation.

Ethylene, carbon monoxide and hydrogen are heated to 180 – 200 C under 200
atmospheric pressure in presence of cobalt catalyst.

H2
CH2=CH2 + CO + H2 CH3-CH2-CHO CH3CH2 CH2 CH2OH

n – butyl alcohol:
n – butyl alcohol is prepared by fermentation of molasses (or other
carbohydrates) with the soil bacteria (Clostridium acetobutylicum) at about 37C
for nearly 48 hours.

General reactions:
Replacement of hydroxyl group by halogen: An alcohol reacts with PCl3/PCl5
to form an alkyl halide. Yield generally follows the order primary > secondary >
tertiary.

3C2H5OH + PCl3 3C2H5Cl + H3PO4

Formation of ester: Alcohol reacts with carboxylic acids to form esters and
water on refluxing. The reaction is reversible and catalysed by strong acid. If the
water is absorbed as soon as form a high yield is obtained. For a given acid the
reactivity follows the order primary > secondary > tertiary.

3C2H5OH + CH3COOH CH3 –C –O– C2H5 + H2O

‖
O
How do you distinguish between primary, secondary and tertiary alcohol.

By oxidation, primary alcohols yield aldehydes and then acids. Both are having
the same numbers of carbon atoms as the parent alcohols with oxidising agents
like chromium trioxide and acetic acid.

CH3CH2CH2OH O CH3CH2CHO O CH3CH2COOH

Cr2O3
Acetic acid
Secondary alcohols form ketones with same numbers of carbon atom as the
original alcohol. But on further oxidation give acids with a lesser carbon atom.

CH3 – CH – CH3 O CH3 – C – CH3 + H2O 4O CH3COOH + CO2 + H2O

| ‖
OH O
Tertiary alcohol on oxidation produces ketones with lesser carbon atom. Further
oxidation results in acids with still lesser carbon atoms. These alcohols are
however difficult to oxidised.

(CH3 )3– OH O CH3 – C – CH3 + HCOOH 4O CH3COOH + CO2 + H2O

‖
O

Ethers:
If from two molecules of a monohydric alcohol, one molecule of water is
eliminated and ether is obtained.

R – OH + HO – R R–O–R + H2O

General formula of ether is CnH2n+2O. They are briefly indicated by R – O – R or

R – O – R’. The common names of ethers are derived from the alkyl group or
groups followed by the word “ether”. The smaller alkyl group in mixed ether is
usually mentioned first. In the IUPAC system, ether is regarded as an alkoxy
alkane. The larger alkyl group is considered as the parent alkane.

C2H5 – O – C2H5 - Ethoxy ethane

Diethyl ether:
It is prepared in the laboratory or factory by heating an excess of ethyl alcohol
and concentrated H2SO4 at about 140 C.

H2SO4
2C2H5OH C2H5 – O – C2H5 + H2O
 140 C

2nd method: From alkyl halide and sodium alkoxide on refluxing sodium ethoxide
and ethyl halide in alcohol, ether is formed in high yield. It is called Williamson’s
synthesis.

C2H5 – O – Na + C2H5I NaI + C2H5 – O – C2H5

Reactions:

Action on strong acids:

1. Ethyl ether dissolves in concentrated HCl or H2SO4 on shaking in the
cold forming an oxonium salt.
2. They heated with concentrated H2SO4 under reflux ether slowly forms
ethyl hydrogen sulphate.

C2H5 – O – C2H5 + HCl Cold Shaking C2H5 – Ö+ – C2H5

Ḧ

C2H5 – O – C2H5 H2SO4 2C2H5HSO4 + H2O

Formation of peroxide:
In contact with light and air, ether forms ether peroxide a pungent oily liquid of
high boiling point. It is unstable and may exploit on heating.

CH3CH2 – O – CH(CH3) – O – O – H

Dimethyl ether:
Dimethyl ether may be prepared by heating methyl alcohol with H2SO4 or passing
methanol vapour under 15 atmospheric pressure over alumina at 350 C.

Aldehydes and ketones:

A primary alcohol on mild oxidation (or dehydrogenation) forms an aldehyde.

Cu
CH3 – CH2 - OH CH3CHO + H2
400 C

A secondary alcohol on oxidation (or dehydrogenation) yields ketones.

CH3 – CH – CH3 Cu / 300 C CH3 – C – CH3 + H2

| ‖
OH O

IUPAC names of aldehydes are obtained by substituting the terminal –e in the

name of the parent alkane by –al. The longer unbranched chain containing the
–CHO group is chosen as the parent alkane.

For ketone, IUPAC names of ketones are derived from the parent alkane by
putting –ONE for the ending –e in the name of alkane.
Example:

CH3CHO - Ethanal
CH3COCH2CH3 - 2 butan one

Formaldehyde (HCHO):
Formaldehyde is commercially most important aldehyde. It occurs in traces in
plant cells containing chlorophyll.

Preparation from methanol – Formaldehyde is mostly manufactured by passing a

mixture of methyl alcohol vapour and air (1:1 ratio) over a silver or copper gauze
at 450 – 600 C.

CU
CH3OH + ½O2 HCHO
450 – 600 C

Properties:
Formaldehyde is a very pungent, colourless gas highly soluble in water. It kills
bacteria probably by coagulating their proteins. Formaldehyde is an antiseptic
and disinfectant used for preserving biological and anatomical specimens.
Acetaldehyde:
It occurs in green fruits having a tart taste, in traces, in human breath and
occasionally in urine.

Manufacturing:
1. From ethanol: Ethanol (50 – 95%) vapour and air are passed through a
reactor containing silver gauze at 375 – 550 C.
Ag
CH3 CH2OH + ½O2 CH3CHO
375 – 550 C

2. From ethylene: Ethylene (from petroleum cracking) and oxygen (both

very pure form) are passed under 7 atmospheric pressure over Cuprus
chloride and Vanadium chloride catalyst.
CH2 = CH2 + ½O2 CH3CHO
Reactions:

Addition reaction:
Addition of ammonia: An aldehyde in ether solution reacts with dry ammonia in
the cold and form aldehyde ammonia, which is usually crystalline and soluble in
water.

CH3 Ō
CH3 –C =O + NH3
C
|
H H (+)NH3

OH
|
CH3 – C –NH2
|
H
Formaldehyde is an exception. It forms no aldehyde ammonia but yields a
polycyclic compound, hexa Methylene tetramine or hexamine when treated with
concentrated ammonia solution.

Hexamine is good for gout, an accelerator for vulcanisation of rubber and a

urinary antiseptic.

CH2

N N

CH2 CH2
Evaporate
4NH4OH + 6HCHO
- 10 H2O N
|
CH2 CH2 CH2

N
Acetaldehyde and aqueous hydroxylamine hydrochloric acid react at room
temperature in presence of excess sodium carbonate to yield acetaldoxime.

CH3 CH3

C =O + H2NOH C =NOH

H H

Aldol condensation: In presence of dilute alkali, 2 molecule of an aldehyde having

an alpha hydrogen atom combines to form a  - hydroxy aldehyde known as
Aldol.

CH3CHO + HCH2CHO OH¯ CH3-CH(OH)CH2-CHO

Cannizzaro reaction:

Aldehydes with no alpha hydrogen atom cannot undergo Aldol type condensation
in presence of alkali. They undergo Cannizzaro reaction in which 1 molecule of
the aldehyde oxidises another molecule to a carboxylic acid and itself gets
reduced to a primary alcohol. Thus formaldehyde and concentrated aqueous
KOH on shaking in the cold form methyl alcohol and potassium formate.

2HCHO KOH CH3OH + H– C –OK

‖
O

Acids:
Fatty acids
On oxidation, an aldehyde takes one more oxygen atom and forms a carboxylic
acid.

Nomenclature:
Fatty acids are generally known by their common names. These names usually
associated with their original sources. For example, formic acid, acetic acid etc

Greek letters , ,  etc. are used to indicate the position of a subsistent on other
functional group, if any in the molecule. IUPAC names are derived from the
parent alkanes. i.e., alkanes having the same number and arrangement of
carbon atoms as the acid by replacing the –e with –oic acid.

Formic acid thus becomes methanoic acid and acetic acid becomes ethanoic
acid.
Manufacturing of formic acid:

From oxalic acid: Formic acid may be prepared in the laboratory by heating
oxalic acid with glycol at about 100 C.

From carbon monoxide: Most of the formic acid is made by passing carbon
monoxide under pressure (14 – 18 atmosphere) into aqueous NaOH solution
(30%) at 160 – 250 C. Into a slurry of dried sodium formate in 85 – 90 % formic
acid, concentrated sulphuric acid is added slowly with cooling for acidification.

H2SO4
CO + NaOH 2HCOONa 2HCOOH + Na2SO4

Reactions:
Dehydration: The acid and its salt are decomposed into monoxide by warm
concentrated sulphuric acid.
HCOOH H2SO4 CO + H2O

Reducing action: Formic acid and formats reduce Ammonical silver nitrate to
silver and decolourise acetified potassium permanganate (KmnO4) solution. A
soluble formate with silver nitrate gives silver formate which on heating splits into
silver.

Formation of sodium oxalate:

Sodium formate yields sodium oxalate and hydrogen at about 400 C.

2HCOONa 400 C NaOOC – C00Na + H2

Acetic acid
Preparation / Manufacturing:
1. In the laboratory acetic acid may be prepared by oxidising ethanol with
sodium dichromate and moderately strong sulphuric acid.

CH3CH2OH 20 CH3COOH + H2O

2. From acetaldehyde: Most of the acetic acid is manufactured from

acetaldehyde. A concentrated solution of acetaldehyde is led into a reactor
at about 60 C containing manganese acetate. Air under 5 atmosphere
pressure is introduced into it.
CH3CH0 + ½O2 CH3COOH

3. From ethanol by fermentation: Dilute acetic acid or vinegar is made by

aerobic oxidation of aqueous alcohol (about 10%) with aceto bacta acetic.

Properties:
Acetic acid gives acetyl chloride with phosphorous penta chloride (PCl5).

CH3COOH PCl5 CH3COCl + POCl3 + HCl

Pyrolysis of acetic acid: In presence of phosphoric acid under reduced
pressure at 700 C yields ketene.

CH3COOH CH3 =CO + HCl

Ester
If an alcohol reacts with an acid organic or inorganic, an ester and water are
formed. Reaction is reversible. Forward reaction is called esterification and
backward one is hydrolysis.
CH3COOH + C2H5OH ⇌ CH3 – C – O – C2H5 + H2O
‖
O

Nomenclature: In both, IUPAC and common systems, esters are named by

mentioning the alkyl group of the alcohol portion first followed by the name of the
acid part –ic acid being replaced by –ate.

CH3 – CO – O – C2H5 - Ethyl propionate

Preparation:
From acid alcohol: By heating an alcohol and acid in presence of concentrated
sulphuric acid or dry HCl gas, esters commonly prepared. The order of reactivity
in esterification which involves the breaking of the O–H bond is
primary>secondary>tertiary. Excess of alcohol or acids shifts the equilibrium
towards the right. For a high yield of ester, water must be removed from the site
of reaction.

Reactions:

Ammonolysis: with ammonia gas or concentrated ammonia, organic esters yield

simple amides at room temperature.
CH3COOH + NH3 ⇌ CH3CONH2 + C2H5OH

Reaction with phosphorous penta chloride (PCl5): Organic esters form acid
chlorides and alkyl chlorides with phosphorous penta chloride (PCl5) on heating.

CH3COOH + PCl5 CH3COCl + C2H5Cl + POCl3

Thio alcohols (Thiols or Mercaptons):
R – SH may be regarded as alcohols of which oxygen has been replaced by
sulphur or as H2S, in which one atom of hydrogen has been replaced by an alkyl
group. Their functional group is –SH is called mercapto or sulph – hydryl.
Thioalcohols are commonly called alkyl Mercaptons. In the IUPAC system they
are named alkane thiols.

Example
CH3 – CH2 – SH - Ethyl Mercaptan or ethane thiol.

Preparation: A Mercaptan is usually prepared by refluxing an alkyl halide with

potassium hydro sulphide in alcohol.

CH3I + KSH CH3SH + KI

On heating an alcohol with phosphorous penta sulphide a Mercaptan is obtained

in low yield.

5C2H5OH + P2S5 5C2H5SH + P2O5

Properties:
Salt formation: As weak acid, thiols react vigorously with strongly electro
positive metals to form mercaptines.
2 C2H5SH + 2Na 2 C2H5SNa + H2

Formation of ester: Thiols form thio ester with carboxylic acid in presence of
mineral acid.

H+
CH3COOH + C2H5SH ⇌ CH3C– S– C2H5 + H2O
‖
O

Oxidation: The action of oxidising agents on thiols is very much different from
that of alcohol. On mild oxidation, e.g. with H2O2 or ferric chloride thiols form
disulphides.

2 C4H9SH + [O] C4H9S – S – C4H9

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