Chemistry s5 Full Note

CHEMISTRY FOR S5 MCB, PCM& PCB
Key competences by the end of Senior Five
Key competences by the end of Senior Five
 Apply IUPAC rules to name the organic compounds and explain the types of isomers for
organic compounds.
 Relate the physical and chemical properties of alkanes for the preparation methods, uses
and isomerism in organic compounds.
 Relate the physical and chemical properties of alkenes and alkynes to their reactivity and
uses.
 Relate the physical and chemical properties of halogenoalkanes to their reactivity and uses.
 Compare the physical and chemical properties of alcohols and ethers to their preparation
methods, reactivity and uses.
 Compare the chemical nature of carbonyl compounds to their reactivity and uses, the
chemical nature of carboxylic acids and acid halides to their reactivity.
 Relate the functional groups of esters, acid anhydrides, amides and nitriles to their
reactivity, preparation methods and uses.
 Relate the chemical nature of amines and amino acids to their properties, uses and
reactivity.
 Interpret phase diagrams for different compounds.
 Prepare standard solutions and use them to determine concentration of other solutions by
titration.
 Explain the effect of different factors on the molar conductivity of different electrolytes
and the applications of conductivity measurements.
 Predict the products of given electrolytes during electrolysis and work out quantitatively
to determine how much is liberated at a given electrode using Faraday’s law.
 Design an experimental procedure to verify the enthalpy changes of chemical reactions.
 Deduce how Hess’s law is applied to Born-Haber cycle.
 Predict the feasibility of chemical reactions.
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TOPIC AREA: ORGANIC CHEMISTRY
SUB-TOPIC AREA: ALIPHATIC COMPOUNDS
Unit 1: Introduction to organic chemistry
1. Brief history
At the very beginning of the nineteenth century chemists generally thought that compounds from
living organisms were too complicated in structure to be artificially synthesized from non-living
things, and that a 'vital force' or vitalism conferred the characteristics of living beings on this form
of matter. They named these compounds 'organic', and preferred to direct their investigations
toward inorganic materials that seemed more promising.
Organic chemistry received an advance when it was realized that these compounds could be treated
in ways similar to inorganic compounds and could be created in the laboratory by means other than
'vital force'. Around 1816 Michel Chevreul started a study of soaps made from various fats and
alkali. He separated the different acids that, in combination with the alkali, produced the soap. Since
these were all individual compounds, he demonstrated that it was possible to make a chemical
change in various fats (which traditionally come from organic sources), producing new compounds,
without 'vital force'.
In 1828 Friedrich Wöhler first manufactured the organic chemical urea (carbamide), a constituent
of urine, from the inorganic ammonium cyanate NH4OCN by heating, in what is now called the
Wöhler synthesis.
Although Wöhler was, at this time as well as afterwards, cautious about claiming that he had thereby
destroyed the theory of vital force, most have looked to this event as the turning point.
Wöhler’s ideas were further strengthened by Kolbe (1845) who obtained ethanoic acid (purely
organic compound) from its constituent elements (carbon, hydrogen and oxygen).
The original definition of "organic" chemistry came from the misconception that organic
compounds were always related to life processes. However, organic molecules can be produced by
processes not involving life.
Organic chemistry is a branch of chemistry in which carbon compounds and their reactions are
studied. Apart from elemental carbon, only certain classes of carbon compounds (such as oxides,
carbonates, hydrogencarbonates and carbides) are conventionally considered as inorganic.
The basic structures of any organic compound consist of a skeleton of carbon atoms joined together
in chains or rings.
Hence, Organic chemistry is a branch of chemistry which involves the scientific study of the
structure, properties, composition, reactions, and preparation (by synthesis or by other means) of
chemical compounds consisting primarily of carbon and hydrogen, which may contain any number
of other elements, including nitrogen, oxygen, halogens( chlorine, fluorine, bromine, iodine) and
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other chemical elements as well as phosphorus, silicon and sulfur and further more metals like tin,
Na, K, Lead, Ca, Cu, Zn, Li, Al, Hg, … .
2. General properties of organic compounds

The following major properties that characterize organic compounds can distinguish organic
compounds from inorganic compounds:
 Most organic compounds are liquid, others are gas and a few are solid.
 Lower density(less than 1.00 or closed to 1.00, the one of water) characterizes organic
compounds.
 Organic compounds frequently exhibit isomerism while inorganic almost do not except
complex molecules (see the course of senior 6).
 Organic compounds are characterized by lower boiling and melting point within reference
to inorganic compounds since some are ionic compounds.
 Are usually insoluble in water but soluble in organic solvents like CCl 4, CS2, benzene, ether,
acetone, etc
 Organic compounds frequently have covalent bonding while inorganic can have ionic and
or covalent bonding reason they do not allow the electricity to pass easily compared to
mineral compounds.
 Organic compounds have complex but slower reaction compared to inorganic compounds.
 Organic compounds are more volatile than inorganic, and can be easily broken down by the
effect of heat (lower thermal stability) reason why they can be used by source of energy
(fuels, oil for combustion).
3. Application of organic chemistry
Organic chemistry is applied in many field of our everyday life such as:
 Petroleum industry in refinery of petroleum oil and its treatment to get quality fuels,
kerosene, mazout, gasoline and other derivatives resulting from petroleum,….
 Pharmaceutical industry: drug synthesis and medicines, additives, antibiotics…
 Agriculture domain by synthesis of pesticides like DDT, herbicides, fungicides, …
 Plastic industry: polymer synthesis like rubber, polyethylene, PVC pipes …
 Paints, dyes, varnish industry and solvents synthesis.
 Cosmetic synthesis like soaps, detergents, perfume, glycerin…
 Explosive synthesis like TNT: Trinitrotoluene (grenade powder), TNG: Trinitro glycerine
(dynamite)…
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4. Classification of organic compounds
A. Classification of Organic Compounds Based on Structure
(1) Acyclic or open-chain or aliphatic compounds: Organic compounds in which all the carbon
atoms are linked to one another to form open chains (straight or branched) are called acyclic or
open chain compounds. These may be either saturated or unsaturated. For example,
(2) Cyclic or closed-chain compounds: Cyclic compounds contain at least one ring or closed
chain of atoms. The compounds with only one ring of atoms in the molecule are known as
monocyclic but those with more than one ring of atoms are termed as polycyclic. These are further
divided into two subgroups.
A) Homocyclic or carbocyclic : These are the compounds having a ring or rings of carbon atoms
only in the molecule. The carbocyclic or homocyclic compounds may again be divided into two
types:
1. Alicyclic compounds: These are the compounds which contain rings of three or more carbon
atoms. These resemble with aliphatic compounds than aromatic compounds in many respects. That
is why these are named alicyclic, i.e., aliphatic cyclic. These are also termed as polymethylenes.
Some of the examples are,
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2. Aromatic compounds: These compounds have a cyclic system containing delocalised –
electron(ring having alternate single and double bonds). Generally, these compounds have some
fragrant odour and hence, named as aromatic (Greek word aroma meaning sweet smell).
B) Heterocyclic compounds: Cyclic compounds containing one or more hetero atoms (e.g. O,
N, S etc.) in the ring are called heterocyclic compounds. These are of two types:
1. Alicyclic heterocyclic compounds: Heterocyclic compounds which resemble aliphatic
compounds in their properties are called Alicyclic heterocyclic compounds. For example,
2. Aromatic heterocyclic compounds: Heterocyclic compounds which resemble benzene and

other aromatic compounds in most of their properties are called Aromatic heterocyclic compounds.
For example,
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B. Classification of Organic Compounds Based on Functional Groups
A functional group is an atom or group of atoms or an unsaturation (Double and triple bonds) in a
molecule that gives the molecule its characteristic chemical properties.
All compounds with the same functional group belong to the same class. Various classes of
compounds having some of the common functional groups are listed in the table.
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Homologous series: a series of compounds in which each successive compound differs from the
previous one by a CH2 unit. e.g: Homologous series of n-alkanes.
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5. Types of formulae for organic compounds (Empirical, Molecular and structural
formulae)
A. Empirical formula
This is the simplest formula which expresses the ratio of number of atoms of elements present in a
molecule. For example CH2, CHO2
Empirical formula is calculated from the mass or percentage composition.The steps are :
i. The percentage of each element is divided by its atomic mass.

ii. The result in i. above is now then divided by the smallest one among them to give the atomic
ratio.
iii. If the atomic ratio obtained in ii. is not a whole number, then they should be multiplied by a
suitable common factor to convert each of them to a whole numbers. Minor fractions are to be
ignored.
Example: A certain organic compound has 39.13% by mass carbon, 52.23% oxygen and the rest
of hydrogen. Calculate the empirical formula of the compound.
Answer:
Elements C H O
% composition 39.13 8.64 52.23
Relative Ratio of 39.13

12  3.26 8.64
1  8.64 52.23
16  3.26
atoms,molecules
Atomic ratio 3.26

3.26 1 8.64
3.26  2.65 3.26
3.26 1
Empirical formula 3 7.95=8 3

:C3H8O3
Note: 2.65 can not be corrected to 3 so we multiply those atomic ratios with 3 .
B. Molecular formula
This is a formula expressing the true number of atoms of various elements present in a molecule.
For example: CH4, C5H10, and C6H6
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molecularweight
Molecular formula = Empirical formula x n, where n= Empiricalweight
when n=1, then the molecular formula is the same as the empirical formulae
Example: An organic compound that contains 31.9% by mass carbon, 6.8% hydrogen and 18.51%
nitrogen the rest being oxygen has a vapour density of 37.5. Calculate the molecular formula of the
compound. Note that Vapour density =½molecular weight.
Answer:
Elements C H O N
% composition 31.9 6.8 42.79 18.51

12  2.568 6.8
1  6.8 42.79
16  2.674 18.51
14 =1.322
atoms,molecules
Atomic ratio 2.658

1.322  2.01  2 6.8
1.322  5.14  5 1.322
1 =2.02=2 1.322
1.322 1
Empirical formula C2H5NO2

:
 molecular weight = 2 x vapour density= 2x37.5= 75gr/mol
n=
molecularweight
Empiricalweight = 75
75 1
hence molecular formule=empirical formula= C2H5NO2
Example2: 0.45g of organic acid on combustion gave 0.44g of carbon dioxide and 0.09g of water.If
the molecular weight of the acid is 90, deduce the molecular formula.
45 x100  26.66 %
x 00..44
12
Answer: Percentage of carbon in CO2 : 44
 45 x100  2.22 %
x 00..09
2
Percentage of hydrogen in H2 O: 18
 Percentage of oxygen = 100-26.66-2.22=71.12%
Elements C H O
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% composition 26.66 2.22 71.12

12  2.22 2.22
1  2.22 71.12
16  4.44
atoms,molecules
Atomic ratio 2.22

2.22 1 2.22
2.22 1 4.44
2.22 2
Empirical formula CHO2
Molecular formula n= 90/45=2 C 2H 2O4 Acide oxalique
Note: From the above calculation, we can extend our generalized expression:
12 mco2
% of carbon in CO2   100
44 msample
2 mH 2O
% of hydrogen in H2O   100
18 msample
% of Oxygen  100  (% of H 2  % of carbone)
https://preparatorychemistry.com/Bishop_Combustion_Analysis.htm
https://bit.ly/2YZ62sM
Activity: The laboratory analyses of an organic compounds A containing carbon, hydrogen,

nitrogen and oxygen provide the following information in terms of percentage 58.45% for C; 4.95%
for H; 17% for N and the rest is the one of oxygen.
(i) Determine its empirical formula

(ii) Deduce from (i) the molecular formula of A if its molar mass is 170g.mol-1.
Note : For gaseous hydrocarbon:
A gaseous hydrocarbon exploded in air by the reaction
y
Cx H y  (x  )O2  xCO2  2y H 2O
4
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When this is cooled, contraction in volume occurs due to the condensation of water vapour to liquid.
The resultant volume after contraction is due to excess O 2 and CO2. The volume of CO2 is
determined by adding aqueous NaOH or KOH, which absorbs all the CO2.
Example 3: 15cm3 of a gaseous hydrocarbon were exploded with 105cm3 of oxygen, after cooling;
the residual gas occupied 75cm3. On addition of caustic potash, there was a fall in volume to 30cm 3.
What is the molecular formula of the hydrocarbon?
Answer:
Volume of hydrocarbon reacting: 15cm3

The volume of 75cm3= volume of unreacted O2 and of CO2 produced
Volume of O2 reacted = (105-30)cm3=75cm3
y
By the reaction Cx H y  (x  )O2  xCO2  2y H 2O
4
V CO2 = X .VCxHy
45= x.15 → x=3
y
V O2 = (x  ) VCxHy
4
y
75 = (x  ) .15
4
y
5 = (3  )
4
y=8
The molecular formula is C3H8 (propane) CH3CH2CH3
C. Structural formula
Structural formula shows how the different atoms in a molecule are bonded (i.e. linked).The main
types of structural formulae of organic molecules are:
 Displayed Formulae (also called developed Formulae)
 Semi- Displayed Formulae (also called "Semi-Developed Formulae" or "condensed

Formulae" )
 Skeletal Formulae(also called stick Formulae)

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Descriptions and examples of each of these types of structural formulae of organic molecules
1. Displayed Formulae
Displayed Formulae of organic molecules include every atom and every bond between atoms
drawn in full so that it is possible to see which atoms are connected to which other atoms and by
which type of covalent bond.
Examples of Displayed Formulae
Propanoic Acid Hexanenitrile Propyl Pentanoate
2.Semi-Displayed Formulae
Displayed formulae can be simplified by grouping together the hydrogen atoms attached to each
carbon atom in the chain(s), resulting in semi-displayed formulae.
Depending on the level of "simplification", single covalent bonds between adjacent carbon atoms
in a chain or branch may, or may not, be shown.
Examples:
The examples of molecules shown below are the same as those represented by displayed
formulae (above).
OR, even shorter OR, even shorter OR, even shorter
3. Skeletal Formulae
Skeletal formulae are the least detailed structural diagrams of organic molecules.
A skeletal formula shows just the carbon skeleton (or carbon backbone) and functional groups.
A skeletal formula does not explicitly show:
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 carbon atoms
 hydrogen atoms attached directly to carbon atoms
 bonds between carbon atoms and hydrogen atoms
A skeletal formula does explicitly show:
 bonds between carbon atoms

 bonds to functional groups
 functional groups
A skeletal formula is a 2-dimensional structural formula in which the following have been
removed:
 carbon atoms
 hydrogen atoms attached directly to carbon atoms
 bonds between carbon atoms and hydrogen atoms
Drawing and Interpreting Skeletal Formula
To draw a skeletal formula:
a. Draw the 2-dimensional structural formula

b. Identify the carbon skeleton (backbone) and any functional groups present.
c. Remove all the hydrogen atoms (and their bonds) bonded directly to carbon atoms that
form the skeleton
(Do not remove hydrogen atoms that form part of a functional group)
d. Remove all the carbon atoms (but not their bonds)
e. You may need to neaten up your skeletal formula by joining the lines up to meet at a
point
To draw a 2-dimensional structural formula given the skeletal formula:
a. Place a carbon atom at the end of each line

(and/or at the place where two or more lines meet)
b. Add bonds so that each carbon atom makes 4 bonds
c. Add hydrogen atoms to the end of each of these bonds
Examples of Skeletal Formulae
The molecules represented below are the same as those whose displayed formulae appear in
Section (1.) and whose semi-displayed formulae appear in Section (2.).
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6. Isomerism in organic compounds (structural isomers, stereoisomers).
From the molecular formula it is possible to suggest different possible structure, by calculating the
deficiency index i for any organic compound whose general formula is CnHmNzOy which allow us
to know whether double or triple bonds; or a ring are possible.
 zm
i  n 1   , with
 2 
n representing all tetravalent atoms,m for all monovalent atom,
z for all trivalent atoms like N and finall y for divalent atoms.
Note: If i=0 means that there is no double or triple bonds and even the ring.
If i=1 means that there is only one double bond or one ring but no triple bond
If i=2 means that there are two double bonds or two rings or one double bond and one ring
or one triple bond
This means that a double bond and a ring contribute one to the value of deficiency index and the
tripe bond contribute two to the value of deficiency index.
Example: C3H6O has the deficiency number which is 1, therefore represent structure with one
double bond let C=C, C=O and a ring or cyclic compounds.
H H O H O H
H2C CH
H C C C
H C C C H
H O CH3
H H
H H
cyclic
Aldehyde
ketone ether ,
OH
H2C CH2
CH
O CH2 H2C
HO-CH2-CH=CH2 CH2
ether
Prop-2-en-1-ol , Alcohol
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By contrast C2H6O has deficiency number which is zero, hence there is no double, triple bond and
a ring. Hence, we can suggest CH3-CH2OH and CH3-O-CH3.
From the above observation, we conclude that for one molecular formula, it is possible to obtain
different structures i.e. molecules. These structures are called isomers.
Briefly, isomers are defined as molecules of identical atomic compositions (molecular formulas),
but with different bonding arrangements of atoms or orientation of their atoms in space. Based on
this definition, several types of isomerism are possible including structural isomerism, and
stereoisomerism.
A. Structural isomerism
This type of isomerism arises from the differences in the arrangement of atoms within the molecule
resulting in two or more different structural formulae. Thus structural isomers have same molecular
formula but different structures.
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Tautomerism: It is a special type of functional isomerism in which the isomers differ in the
arrangement of atoms but they exist in dynamic equilibrium with each other and this phenomenon
is termed ad tautomerism. Example: Acetaldehyde and vinyl alcohol are tautomers which exist in
equilibrium as shown.
B. Stereoisomerism
Stereoisomerism occurs when two or many compounds have the same molecular formula and same
structural formula but differ in the spatial arrangement of atoms.
1. Geometrical isomerism ( cis-trans isomerism)
This arise when there is a prevention of rotation around at least one bond in a compound, for
example the presence of double bond in a molecule prevent rotation and this gives rise to two
isomers; the isomer with similar groups on the same side of the double bond is called Cis isomer
while that with the same group on the opposite is called a trans isomer.
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Example:
H3C CH3 H3C H

C C
C C
H H CH3
H
cis - 2 - butène trans - 2 - butène
Ph COOH Ph H
H H H COOH
cis trans
Note: 1. For a compound to be a geometrical isomer, the 2 similar groups should not be on the same
carbon atom.
2. Geometrical isomers do not have the same physical and chemical properties
Exemple. 1,4 butenedioic acid C4H4O4
HOOC COOH HOOC H

C C C C
H H and H COOH
Table: Properties of maleic and fumaric acid
Cis but-2-enedioic FOCUSED Trans1,4 but-2-enedioic

acid (maleic acid) PARAMETER acid( fumaric acid)
135°C Melting points 287°C
79 Solubility(g/100g H2O) 0,7
1000 Ka1 96
Maleic acid forms an anhydride on gentle heating but fumaric acid does not. On strong heating
fumaric acid forms an anhydride as maleic acid showing that rotation about the double bond is
possible at high temperature.
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2. Optical isomerism
Optical isomerism arises when two compounds have same molecular and structural formulae but
one is not superimposable upon the other and are mirror images.
Just as the right hand and left hand are different, optical isomers (known as enantiomers) are
different from each other and differ in the way they rotate plane-polarized light. This property
where a compound rotates plane-polarized light is called optical activity.
Whereas geometrical isomers may show marked difference in their physical and chemical
properties, optical isomers have similar physical and chemical properties except that they show
pronounced difference towards plane-polarized light and how they react with optically active
reagents.
Note: For a compound to show optical isomerism, the molecule should be asymmetric i.e. the
carbon atom at the middle should be attached to 4 different groups. A carbon atom with four
different group attached on it is said to be chiral.
a a
C* d d C*
b b
c c
Examples:
* H3C
*
CH CH2OH
H3C CH2 CH CH3
OH NH2
If a molecule has a chiral center in its structure, then two mirror image arrangements are possible
in space. There are only ever two optical isomers formed for each chiral carbon. If there are two
chiral carbons, then there will be two pairs of optical isomers.
These molecules are optical isomers, because the molecules of one isomer will rotate the direction
of plane-polarized light (light that is traveling in the same plane, not in all directions) in the opposite
direction that the other isomer will.
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Enantiomers that rotate polarized light in a clockwise direction are known as dextrorotatory(+)
(right-handed) molecules, and enantiomers that rotate polarized light in a counterclockwise
direction are known as levorotatory(-) (left-handed) molecules.
A solution containing equal amounts of both enantiomers (50% levorotatory and 50%
dextrorotatory is known as a racemic mixture that will not rotate polarized light, because the
rotations of the two enantiomers cancel each other out.
Optical activity is measured using an instrument called polarimeter.
How a polarimeter works
7. General rules of nomenclature of organic compounds according to IUPAC system.

How to name organic compounds using the IUPAC rules
In order to name organic compounds you must first memorize a few basic names. These names
are listed within the discussion of naming alkanes. In general, the base part of the name reflects
the number of carbons in what you have assigned to be the parent chain. The suffix of the name
reflects the type(s) of functional group(s) present on (or within) the parent chain. Other groups
which are attached to the parent chain are called substituents and are used as prefix for the name.
1. Alkanes (saturated hydrocarbon)
The saturated hydrocarbon form homologous series (series in which members have similar
chemical properties and each differs from the preceding by a methylene group –CH2 ).
The first four members are known by their common names, from C5 and above the Greek prefixes
indicating the number of carbon atoms is written followed by the suffix “ane” of the alkanes.
Alkyl groups are obtained when one hydrogen atom is removed from alkanes; therefore their names
are deduced from the corresponding alkanes by replacing “ane” desinence with “yl” desinence. The
names of the straight chain saturated hydrocarbons for up to a 100 carbon chain are shown below.
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n= number of C Name of influx R-H Alkane alkyl R group
1 Meth ane CH4 -yl CH3-
2 eth ane CH3CH3 -yl CH3CH2-
3 Prop ane CH3CH2CH3 -yl CH3CH2CH2-
4 But ane CH3(CH2)2CH3 -yl CH3(CH2)2CH2-
5 Pent ane CH3(CH2)3CH3 -yl CH3(CH2)3CH2-
6 Hex ane CH3(CH2)4CH3 yl CH3(CH2)4CH2-
7 Hept ane CH3(CH2)5CH3 yl CH3(CH2)5CH2-
8 Oct ane CH3(CH2)6CH3 yl CH3(CH2)6CH2-
9 Non ane CH3(CH2)7CH3 yl CH3(CH2)7CH2-
10 Dec ane CH3(CH2)8CH3 yl CH3(CH2)8CH2-
11 undec ane CH3(CH2)9CH3 yl CH3(CH2)9CH2-
12 Dodec ane CH3(CH2)10CH3 yl CH3(CH2)10CH2-
13 Tridec ane CH3(CH2)11CH3 yl CH3(CH2)11CH2-
14 Tetradec ane CH3(CH2)12CH3 yl CH3(CH2)12CH2-
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15 Pentadec ane CH3(CH2)13CH3 yl CH3(CH2)13CH2-
16 Hexadec ane CH3(CH2)14CH3 yl CH3(CH2)14CH2-
17 Heptadec ane CH3(CH2)15CH3 yl CH3(CH2)15CH2-
18 Octadec ane CH3(CH2)16CH3 yl CH3(CH2)16CH2-
19 Nonadec ane CH3(CH2)17CH3 yl CH3(CH2)17CH2-
20 Eicos ane CH3(CH2)18CH3 yl CH3(CH2)18CH2-
30 Triacont ane CH3 (CH2)28CH3 yl CH3 (CH2)28CH2-
40 Tetracont ane CH3(CH2)38CH3 yl CH3 (CH2)38CH2-
50 Pentacont ane CH3(CH2)48CH3 yl ……………….
60 Hexacont ane CH3(CH2)58CH3 yl ……………….
70 Heptacont ane CH3(CH2)68CH3 yl ……………….
80 Octacont ane CH3(CH2)78CH3 yl ……………….
90 Nonacont ane CH3(CH2)88CH3 yl …………………
100 hect ane CH3(CH2)98CH3 yl CH3(CH2)98CH2-
There are a few common branched substituents which you should memorize. These are shown
below.
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Rules of naming branched alkanes
Here is a simple list of rules to follow. Some examples are given at the end of the list.
1. Identify and name the longest carbon chain. This chain is called the parent chain.
2. Identify and name all of the substituents (groups appending from the parent chain).
3. Number the carbons of the parent chain from the end that gives the substituents the lowest
position numbers. When comparing a series of numbers, the series that is the "lowest" is the
one which contains the lowest number at the occasion of the first difference. If two or more
side chains are in equivalent positions, assign the lowest number to the one which will come
first in the name (alphabetically).
4. If the same substituent occurs more than once, the location of each point on which the
substituent occurs is given and those location numbers are written together separated by a
comma. In addition, the number of times the substituent group occurs is indicated by a prefix
(di, tri, tetra, etc.).
5. If there are two or more different substituents they are listed in alphabetical order using the
base name (ignore the prefixes). The only prefix which is used when putting the substituents
in alphabetical order is iso as in isopropyl or isobutyl. The prefixes sec- and tert- are not used
in determining alphabetical order except when compared with each other.
6. If chains of equal length are competing for selection as the parent chain, then choose the chain
which has the greatest number of side chains.
7. For cyclanes (cyclic alkanes), the prefix “cyclo" is recommended and then after the name of the
alkanes of the same carbon number. But in case of ramified cyclanes, the priority is for the ring.
In summary, the name of the compound is written out with the substituents (with their location
numbers as prefix) in alphabetical order followed by the base name (derived from the number of
carbons in the parent chain). Commas are used between numbers and dashes are used between
letters and numbers. There are no spaces in the name.
Here are some examples:
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3 CH3 CH3
1 5 4 3 2 1
2
CH3 CH CH3 CH CH2 C CH3
3 CH3 CH3 CH3

2-Metyl propane or isobutane
2, 2, 4-Trimethyl pentane
CH3 CH3 CH3
1 2 3 4 5 6 7 8
CH3 C CH3
CH3 C CH2 CH CH2 CH2 CH2 3C CH3
10 9 8 7 4 2 1
6 5
CH3 CH3 CH2CH3 9 CH2CH3
2,2-Dimethyl propane or neopentane 10
4-Ethyl 2,2,8,8 tetramethyl decane
not 7-Ethyl 2,2,9,9-tetramethyl decane
5 CH3 CH3
7 6 4
H H
3 2 1
CH3 CH2 C C C C CH3
H H
cyclobutane cyclopentane
CH3 CH2CH2CH3 Cyclopropane
:2,3,5 Trimethyl-4-propyl heptane
Isomerism in alkanes
Alkanes show structural isomerism. The easiest way to find isomers is to draw the longest chain of
carbon atoms first and then reduce it by one carbon first until repetition begins to occur.
E.g. C6H14
(a) CH3-CH2-CH2-CH2-CH2-CH3 hexane (straight chain isomers)
(b) Then reduce the length by one gives 5 carbon atoms

23 | P a g e
Note: The 6th carbon atom cannot be attached to carbon atom number 1 or 5, as this will make the
longest chain of carbon atoms still with 6carbons. It should be attached to a carbon atom in the
middle.
CH 3  CH  CH 2  CH 2  CH 3
| : 2 - methyl pentane
CH3
CH 3  CH 2  CH  CH 2  CH 3
| : 3 - methyl pentane
CH3
(c) Longest chain reduced further to 4 carbon atoms
CH
CH 3  CH  CH  CH 3 3
| | : 2,3 - dimethyl butane
and | : 2,2-dimethyl butane
CH  C  CH  CH
CH3 CH3 3 2 3
|
CH
3
Thus C6H14 has 5 isomers.
Notice: When the number of carbon increase, so closely the number of isomers increase as much
as possible.
Activity: Give possible structure and provide their names according to IUPAC whose general
formula is, C3H8, C4H10, C5H12, C7H16 and C8H18 . Among these isomers, state the molecules
with one asymmetric carbon or chiral carbon atom
2. Alkyl halides
The halogen is treated as a substituent on an alkane chain. The halo- substituent is considered of
equal rank with an alkyl substituent in the numbering of the parent chain. The halogens are
represented as follows: F fluoro-; Cl chloro-; Br bromo-; I iodo-; If several of the same halogen
atoms are present, use the prefixes di-, tri-, tetra-, etc.
 The longest continuous chain of carbon atoms containing the halogen atom is the parent.
 Number the parent chain from the end nearest the halogen atom. If the parent chain has
branched alkyl groups, number the chain from the end nearest the first substituent, regardless
if it is an alkyl group or halogen. If the chain can be numbered from either end based on the
position of the substituents, number from the end near the substitutent that comes first
alphabetically.
 For cycloalkanes containing halogen as the only substituents, begin numbering from the
halogen atom.
 List all substituents in alphabetical order followed by the base name (derived from the number
of carbons in the parent chain)
24 | P a g e
Common Names
Common names are often used for simple alkyl halides.To assign a common name:
 Name all the carbon atoms of the molecule as a single alkyl group.
 Name the halogen bonded to the alkyl group.
 Combine the names of the alkyl group and halide, separating the words with a space.
Examples:
Isomerism in Alkyl halides
Alkyl halides exhibit both chain and position isomerism:
 Position isomerism: This arises due to the different positions taken by the halogen atom on the same
carbon chain. Ex. Molecular formula C4H9Br.
CH3-CH2-CH2-CH2Br: 1-Bromo butane CH3CH2-CHBr-CH3: 2-bromo butane
25 | P a g e
 Chain isomerism that arises due to different arrangement of carbon atoms in chains.
H
CH3
H3C C CH2Br
H3C C Br
CH3
CH3
1-bromo-2-methyl propane
2-Bromo-2-methyl propane
Activity: Give all possible structure whose molecular formula is C5H11Cl and identify:
(a) Chain isomers

(b) Position isomers
(c) A structure which represent stereoisomers
3. ALKENES
 In the IUPAC system of nomenclature, alkenes are named by replacing, the”ane” suffix of
the corresponding alkanes with “ene”. If there is more than one double bond, the suffix is
expanded to include a prefix that indicates the number of double bonds present (-adiene, -
atriene, etc.).
 The longest chain containing the double (C = C) bond is usually taken as the parent chain.
 The parent chain is numbered so that the carbon atoms with the multiple bonds have the
lowest numbers.
 The position of the double bond has to be stated and precede the “ene” suffix. This applies
to alkenes with 4 or more carbons atoms in the longest chain.
 The position of double bond prime on the position of an alkyl and halo substituents (if
present) when numbering carbon chain.
 For a branched unsaturated acyclic hydrocarbon, the parent chain is the longest carbon chain
that contains the maximum number of double bonds.
 If there is a choice in numbering not previously covered, the parent chain is numbered to
give the substituents the lowest number at the first point of difference.
Examples:
 CH3-CH=CH2: Propene,
 CH3-CH2-CH=CH2: but-1-ene,
 CH3-CH=CH-CH3:But-2-ene
 CH2=C(CH3)-CH=CH2: 2-methyl buta-1,3-diene (isoprene)
 CH2= CH-CH(CH2CH3)-CH2-CH2-CH(CH3)-CH2-CH(CH3)-CH2-CH3:
3-Ethyl 5,7-dimethyl oct-1-ene
Isomerism in alkenes
26 | P a g e
Alkenes exhibit four types of isomerism.
 Chain isomerism: Chain isomerism arises due to differences in the nature of the carbon
chain. Note: in chain Isomerism, the position of double bond does not change.
CH 3 CH 2 CH  CH 2 1 - butene ( straight chain isomer)
Example: C4H8 has
CH 3 C  CH 2 2 - methyl - 1 - propene (Branched chain isomer)
|
CH 3
 Position isomerism: this isomerism arises as a result of different position taken by the
double bond in the same chain:
Example: CH 3 CH 2 CH 2 CH  CH 2 pent - 1 - ene and CH 3CH 2CH  CH - CH3 pent - 2 - ene
Note: The positions of the double bond change but not the structure of the carbon chain.
 Function group isomerism: Both alkenes and cycloalkanes (hydrocarbons where the
carbon atoms are arranged in a ring) are functional group isomeric.
Examples: C3H6
CH 3CH  CH 2 Propene and
H2C
CH2
H2C
cyclopropane
 Geometrical Isomerism: This type of Isomerism arises because of the inability of the
double bond to allow free rotation around it , therefore cis and trans isomers are possible.
Example:
H
CH3
H H
C C
H3C H
CH3
CH3
Trans But-2-ene and Cis but-2-ene
4. Alkynes
 In the IUPAC system of nomenclature, alkynes are named by replacing, the”ane” suffix of
the corresponding alkanes with “yne”. If there is more than one triple bond, the suffix is
expanded to include a prefix that indicates the number of triple bonds present (-adiyne, -
atriyne, etc.).
 The longest chain containing the triple bond (or multiple bonds) bond is usually taken as
the parent chain.
 The parent chain is numbered so that the carbon atoms with the multiple bonds have the
lowest numbers.
 The position of the triple bond has to be stated and precede the “yne” suffix. This applies
to alkynes with 4 or more carbons atoms in the longest chain.
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 The position of triple bond prime on the position of an alkyl and halo substituents (if present)
when numbering carbon chain.
 For a branched unsaturated acyclic hydrocarbon, the parent chain is the longest carbon chain
that contains the maximum number of multiple bonds (double or triple).
 If the triple bond is equidistance from the two ends, begin at the end nearer the first branch
point.
 When both double and triple bonds are present, the -en suffix follows the base name directly
and the -yne suffix follows the -en suffix (notice that the e is left off, -en instead of -ene),
i.e. the name end in the suffix enyne. The location of the double bond(s) is(are) indicated
before the “en”suffix as before, and the location of the triple bond(s) is(are) indicated
between the -en and -yne suffixes.
 When both double and triple bonds are present number the chain from the end nearer the
first multiple bond, whether double or triple. When there is a choice in numbering, double
bond receives a low number.
Examples:
 C2H2: Ethyne or acetylene

 CH 3  C  C  C (CH 3 ) 2  CH 3 : 4,4-dimethyl pent-2-yne
CH  C  C  C  C  CH  CH
 3 2 3 : Hept-2,4- di yne
 CHCCH2CH=CHCH3: Hex-4-en-1-yne
 CH2=CHCH2CCCH3: Hex-1-en-4-yne
 CH2=CHCH2CCH: pent-1-en-4-yne
Isomerism in alkynes
Alkynes exhibit three types of isomerism such as:
 Chain isomerism: This arises due to different chain structure while the triple bond position
doesn’t change.
Example: Molecular formula C5H8 represents
CH3CH2CH2C  CH: pent-1-yne straight chain isomer) and
CH3CH(CH3)CCH: 3-methylbut-1-yne
 Position isomerism: This arises due to different position of the triple bond in the same chain.
Example: C4H6 represents CH 3  CH 2  C  C  H and CH3  C  C  CH3
 Function isomerism: Alkynes shows functional isomerism with dienes (alkenes with two
double bonds) or cycloalkanes with double ring or cycloalkanes with one double bond.
Example: C4H6 represents
CH 3  CH 2  C  C  H ; CH2  CH  CH  CH2 (buta-1,3- diene)
28 | P a g e
: cyclobutene CH3 3-methy
cyclopropene
Note: Unlike alkenes, alkynes do not show geometrical isomerism because the molecule around
the triple bond is linear.
Activity: Give and name according to IUPAC all possible structural whose molecular formula
is C4H6. Define also their relationships in terms of isomerism.
5. Alcohols
 Alcohols are named by replacing the suffix –ane of the corresponding alkane with -anol. If
there is more than one hydroxyl group (-OH), the suffix is expanded to include a prefix
that indicates the number of hydroxyl groups present (-anediol, -anetriol, etc.).
 The longest carbon chain containing the OH group is the parent chain
 The position of the hydroxyl group(s) on the parent chain is (are) indicated by placing the
number(s) corresponding to the location(s) between the -an and -ol suffixes.
Here is an important list of rules to follow:
1. The hydroxyl group takes precedence over alkyl groups and halogen substituents, as well as
double bonds, in the numbering of the parent chain.
2. When both multiple (double or triple) bonds and hydroxyl groups are present, the –en (or –
yn) suffix follows the parent chain directly and the -ol suffix follows the –en (or –yn) suffix
(notice that the e is left off, -en instead of –ene or yn instead of –yne ). The location of the
double bond(s) is(are) indicated before the -en suffix as before, and the location of the
hydroxyl group(s) is(are) indicated between the -en and -ol suffixes.
3. If there is a choice in numbering not previously covered, the parent chain is numbered to
Examples:
 CH3OH: Methanol;
 CH3-CH2-OH: ethanol
 CH3-CH2-CH2-OH: Propan-1-ol ;
 CH3-CHOH-CH3: Propan-2-ol
 CH3-CH2-CH2-CH2OH: Butan-1-ol ;
 HOCH2-CH2OH: Ethane-1, 2-diol
 HOCH2-CHOH-CH2OH: propane-1, 2, 3-triol commonly known as glycerin or glycerol.
 CH3-CH=CH-CHOH-CH2-CHCl-CH3: 6-Chloro hept-2-en-3-ol
 (CH3)2 CH-CHOH-CCH: 4-Methyl pent-1-yn-3-ol
Note: Common names are often used for simple alcohols.

29 | P a g e
To assign a common name:
 Name all the carbon atoms of the molecule as a single alkyl group.
 Add the word alcohol, separating the words with a space. For example:
Isomerism in alcohols
Regarding the issue of isomerism, we have:
 Chain isomers: this is due to the difference in the structure of the chain. Example:
butan-1-ol and 2-methyl propan-1-ol
 Position isomers: this is due to different positions taken by the –OH in the same carbon
chain. Example: for C3H8O: there exist propan-1-ol and propan-2-ol
 Functional isomers: Except methanol which has one carbon, other alcohols are
functional group isomeric with ethers. Example: C2H6O has 2 functional isomers: CH3-
CH2-OH (Alcohol) and CH3-O-CH3 (ether).
6. Ethers
In the IUPAC system of naming, ethers are considered as alkoxy derivatives of alkanes reason
why the general naming consist of alkoxyalkane ; in case of unsymmetrical ethers ( i.e where
R≠R’) the larger of the two alkyl group is taken as the parent hydrocarbon.
Examples:
 CH3-O-CH3: methoxymethane
 CH3-CH2-CH2-O-CH3:1- methoxypropane
 CH3CH2CH2CH2-O-CH3: 1-methoxybutane
Note: Ethers may also be named by the common system by prefixing the names of the alkyl groups
attached to oxygen before the word “ether”, but in case of symmetric ethers, they are taken as
dialkyl ether.
If other functional groups are present then the group is considered to be an alkoxy substituent
Alkoxy Group Name: CH3O–Methoxy, CH3CH2O– Ethoxy, (CH3)2CHO– Isopropoxy,

(CH3)3CO– tert-Butoxy, C6H5O– Phenoxy
30 | P a g e
Isomerism in Ethers
 Chain isomers: this is due to the difference in the structure of the chain. Example:
C5H12 ; 1-Methoxy-2-methylpropane and 1-Methoxybutane
 Position isomers: this is due to different positions taken by an alkoxy group in the same
carbon chain. Example: for C4H10O; 1-Methoxypropane and 2-Methoxypropane
 Functional isomers: Ethers are functional isomeric with saturated monohydric alcohols.
Example: C2H6O has 2 functional isomers: CH3-CH2-OH (Alcohol) and CH3-O-CH3
(ether).
Epoxides
Epoxides are ethers having the oxygen atom in a three membered ring. Epoxides are also called
oxiranes.
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Nomenclature of Epoxides
• Epoxides bonded to a chain of carbon atoms are named as derivatives of oxirane.
• When an epoxide is bonded to a ring, the O atom is considered a substituent, called an epoxy
group, bonded to a cycloalkane, and two numbers are used to designate the atoms to which the O
atoms are bonded.
Epoxides are also named as alkene oxides, because they are often prepared by adding an O atom
to an alkene. To name an epoxide in this way:
 Mentally replace the epoxide oxygen by a double bond.

 Name the alkene.
 Add the word oxide.
7. Aldehydes
Here is an important list of rules to follow:
The longest continuous chain having the aldehydes group is taken as the parent chain.
Aldehydes are named by replacing the suffix “e” of the corresponding hydrocarbon by
“al”. If there is more than one -CHO group, the suffix is expanded to include a prefix that
indicates the number of -CHO groups present (-dial for the presence of 2 of these groups
on the parent).
 If other functional groups are present, the chain is numbered such that the aldehyde carbon
is in the "1" position and the position number is not indicated unless functional groups
of higher precedence are present.
 If a prefix form is required, "oxo-" is used (as for ketones), with the position number
indicating the end Carbone of a chain: e.g: CHOCH2COOH is 3-oxopropanoic acid. If
32 | P a g e
the carbon in the carbonyl group cannot be included in the parent chain as in the example
given above the prefix "formyl-" is used.
 The carbonyl group takes precedence over alkyl groups, an alkoxy groups and halogen
substituents, as well as double bonds, and any other functional group seen previously in the
numbering of the parent chain.
 When both multiple bonds and carbonyl groups are present, the –en (–yn) suffix follows the
parent chain directly and the -al suffix follows the -en(–yn) suffix (notice that the e is left
off, -en(–yn) instead of -ene(–yne)). The location of the multiple bond(s) is(are) indicated
as before, and the -al suffix follows the -en(–yn) suffix directly.
 Cyclic aldehydes (containing an aldehyde group directly attached to a cycle) are named by
adding the word <carbaldehyde> to the name of the cycle. (The carbon to which the
aldehyde group is attached is carbon “1”).
 Aromatic aldehydes (containing an aldehyde group directly attached to a benzene ring) are
named after the parent compound benzaldehyde. (The carbon to which the aldehyde group
is attached is carbon “1”).
H2C=O: Methanal; CH3-CHO: Ethanal; OCHCH2C(CH3)=CHCHO: 3-Methylpent-2-ene-1,5-

dial.
Common names are used for the simplest aldehydes
Common names of aldehydes are delivered from common names of corresponding carboxyilic
acids where the ending ic or oic acid is replaced by aldehyde
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8. Ketones
In the IUPAC nomenclature system,
 The longest continuous chain having the ketone group is taken as the parent chain.
 The terminal “e” of the corresponding hydrocarbon is replaced by “one”
 Molecules with more than one ketone group are named by preceding the suffix with a
counting prefix (dione, trione, etc.); position numbers must be used for each ketone
group.
 Number the chain starting with the end closest to the ketone group (i.e., the carbonyl
carbon should have the lowest possible number).
 If a prefix form is required, "oxo-" is used with the position number indicating it location
in the carbone a chain: e.g: CH3COCH2COOH is 3-oxobutanoic acid.
 The ketone group takes precedence over alkyl groups, an alkoxy groups and halogen
substituents, as well as double bonds, and any other functional group seen previously
except aldehyde group in the numbering of the parent chain.
 When both multiple bonds and carbonyl groups are present, the –en (–yn) suffix follows
the parent chain directly and the –one suffix follows the -en(–yn) suffix (notice that the e
is left off, -en(–yn) instead of -ene(–yne)). The location of the multiple bond(s) is(are)
indicated as before, and the -one suffix follows the -en(–yn) suffix directly.
 For cyclic ketones, the carbonyl group is always numbered “1”; this does not need to be
included in the name. The numbering continues clockwise or counterclockwise to give
the lowest number for the next substituent.
Common names for simple ketones
34 | P a g e
The names shown above are still considered to be acceptable IUPAC names
Common names for simple ketones can be derived by naming the two alkyl or aryl groups
bonded to the carbonyl group in alphabetical order as separate words followed by the word
ketone.
CH3CH2COCH(CH3)2: Ethyl isopropyl ketone
CH3CH2CO CH2CH3: Diethyl ketone
CH3CH2COCH3: Ethyl methyl ketone
Activity: Draw structural formulas for the following molecules:
a. 3-ethyl-2-pentanone
b. 2,4,6-trimethylheptanal
c. 3-ethylcyclopentanone
d. 4-chloro-2-phenylpentanal
e. 3-methylcyclopentanecarbaldehyde
f. 3,7-dimethylocta-2,6-dienal
Isomerism in carbonyl compounds
 Chain isomers: exist for both aldehydes and ketones

Example:
 Butanal and 2-methylpropanal
 Pentan-2-one and 3-methylbutan-2-one
 Position isomers: exist for only ketones because carbonyl group of aldehydes is always
on position 1.
Example: Pentan-2-one and Pentan-3-one
 Functional isomers: Aldehydes and ketones show functional isomerism with each other,
cyclic (and insaturated) ether, unsaturated alcohols (enol) that may provide geometric
isomers( cis and trans or of E-Z convention)and cyclic alcohol.
Example: C3H6O has the deficiency number which is 1, therefore represent structures with
double bond let C=C, or C=O or cyclic compounds. Some of those compounds are:
propanal, propanone,1-methoxyethene, 1-methyloxirane and prop-2-en-1-ol
35 | P a g e
 Tautomerism: carbonyl compounds are tautomers with enol.
Example:
 propanone and prop-1-en-2-ol
 Propanal and prop-1-en-1-ol
9. Amines
 The IUPAC nomenclature is analogous to that for alcohols, except the -e ending of the
parent alkane is replaced with -amine.
 Other substituents on the carbon chain are given names and numbers indicating their
position in the usual way.
 Molecules with more than one amine group are named by preceding the suffix with a
counting prefix (diamine, triamine, etc.); position numbers must be used for each amine
group. e.g: H2NCH2CH2CH2NH2: Propane-1,3-diamine
 For secondary amines (of the form R-NH-R), the longest carbon chain attached to the
nitrogen atom becomes the base name of the amine; the other chain is prefixed as an alkyl
group with location prefix given as N: CH3NHCH2CH3 is N-methylethanamine. Tertiary
amines (R-NR-R) are treated similarly: CH3CH2N(CH3)CH2CH2CH3 is N-ethyl-N-
methylpropanamine. Again, the substituent groups are ordered alphabetically.
 If a prefix form is required, "amino-" is used with the position number indicating it
location in the carbone a chain: e.g: H2NCH2CH2CH2CH2OH: 4- Aminobutan-1-ol the
alcohol group has priority over an amino group, meaning that the compounds are named
as alcohols rather than as amines. The amino group is a substituent on the alcohol.
 Aromatic amines are called by their historical/trivial names, with phenylamine being called
aniline.
Primary amine:
3-methylcyclohexanamine
 Secondary
N-methyl-1-butanamine
36 | P a g e
N-methyl-2-butanamine
 Tertiary
N,N-diethyl-4-octanamine
N,N,2-trimethyl-3-pentanamine
Common names are used for the simplest amines
As is common in organic chemistry, the simplest members have trivial names derived by adding
the suffix amine to the alkyl part.
Thus:
Activity: draw the structure of N-ethyl-N-metylpropan-1-amine
Isomerism in amines
About isomerism, amines exhibit the following isomerism:
 Chain isomerism that arises due to the difference in structure of the carbon chain
Example: 2-methylpropan-1-amine and butan-1-amine.
 Positional isomerism that arises because of the different positions taken by –NH2 in the
same carbon chain.
Example: propan-1-amine and propan-2-amine
 Particular chain isomerism (metamerism), resulting from different substitution on
nitrogen; which result to primary, secondary and tertiary amines.
Example: propylamine, ethylmethylamine and trimethylamine
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Activity: Work out to find different isomers whose molecular formula C 3H9N and C4H11N and
name them according to IUPAC nomenclature.
10. Carboxylic acids

 Carboxylic acids are named by counting the number of carbons in the longest continuous
chain including the carboxyl group and by replacing the ending -e of the corresponding
alkane with -oic acid.
 If there are two -COOH groups, the ending is expanded to include a prefix that indicates
the number of -COOH groups present (-dioic acid)
 It is not necessary to indicate the position of the -COOH group because this group will be
at the end of the parent chain and its carbon is automatically assigned as C-1 and is not
included in the name.
 Name the substituents attached to the principal chain in the usual way.
 The carboxyl group takes priority over any other functional groups previously discussed.
 Unsaturated acids are named by changing the influx from -an- to –en- or -yn- with a number
designates the location of the multiple bonds.
 Cycloalkanes with carboxyl substituents are named as cycloalkanecarboxylic acids.
 For compounds with more than two carboxylic acid groups the suffix carboxylic acid is
used including the prefix that indicates the number of –COOH groups present. In this case
carbon of the –COOH group are not considered in the parent chain.
E.g: HOOC-CH2-CH(COOH)-CH2-COOH: propane-1,2,3-tricarboxylic acid
(E)-4-methylhex-3-enoic acid
3,3-dimethylcyclohexanecarboxylicacid
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Aromatic acids of the form Ar-CO2H are named as derivatives of benzoic acids, with ortho, meta
and para indicating the location relative to the carboxyl group.
Common names (or trivial names) for several important aliphatic acids
For common carboxylic acids some traditional names such as acetic acid are in such widespread
use they are considered retained IUPAC names, although "systematic" names such as ethanoic
acid are also acceptable.
• Acids with formula RCOOH
Number of Prefix as in Common name Common name Common name

carbons new system for alcohol for aldehyde for acid
Methyl alcohol
1 Meth- Formaldehyde Formic acid
(wood alcohol)
Ethyl alcohol
2 Eth- Acetaldehyde Acetic acid
(grain alcohol)
3 Prop- Propyl alcohol Propionaldehyde Propionic acid
4 But- Butyl alcohol Butyraldehyde Butyric acid
5 Pent- Amyl alcohol Valeraldehyde Valeric acid
6 Hex- Caproyl alcohol Caproaldehyde Caproic acid
7 Hept- Enanthyl alcohol Enanthaldehyde Enanthoic acid
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8 Oct- Capryl alcohol Caprylaldehyde Caprylic acid
9 Non- Pelargonic alcohol Pelargonaldehyde Pelargonic acid
10 Dec- Capric alcohol Capraldehyde Capric acid
11 Undec- - - -
12 Dodec- Lauryl alcohol Lauraldehyde Lauric acid
13 Tridec- - - -
14 Tetradec- Myristyl alcohol Myristaldehyde Myristic acid
15 pentadec-
Cetyl alcohol
16 Hexadec- Palmitaldehyde Palmitic acid
Palmityl alcohol
17 Heptadec- - - Margaric acid
18 Octadec- Stearyl alcohol Stearaldehyde Stearic acid
20 Eicos- Arachidyl alcohol - Arachidic acid
 Acids with formula HOOC-CnH2n-COOH
 HOOC -COOH: oxalic acid.

 HOOC-CH2-COOH: malonic acid.
 HOOC – CH2-CH2-COOH: Succinic acid
 HOOC-(CH2)4-COOH: caproic acid or adipic acid
 HOOC-(CH2)8-COOH: sebacic acid
40 | P a g e
 Alkenoic acids:
 CH2=CH-COOH : acrylic acid

 CH3-CH=CH-COOH: crotonic acid
 CH2=C (CH3)-COOH: metacrylic acid
 CH3 -(CH2)7- CH=CH-(CH2)7- COOH: Oleic acid
 Hydroxy-acids
 CH2OH-CH2-COOH : IUPAC : β –lactic acid

 CH3-CHOH-COOH : α –lactic acid
 CH2OH-CHOH-COOH : glyceric acid
 HOOC-CHOH-COOH: malic acid
 HOOC-CHOH-CHOH-COOH: tartaric acid
Isomerism in carboxylic acids
Regarding the issue of isomerism, we have for Mono carboxylic acids chain and functional
isomerism:
 Chain isomers: this is due to the difference in the structure of the chain.
Example: 2-methylpropanoic acid and Butanoic acid.
 Functional isomers: Functional isomers of acid can be ester, aldehydes and ketones with
hydroxyl substitution, alkenes with 2 hydroxyl groups (unsaturated alcohol: diol) that may leads
to geometric isomerism, and finally ring that can be cyclic alcohols or cyclic ether, organic
peroxides.
Example: for C3H8O2 we have: propanoic acid, Methyl ethanoate, etc.
Functional group derivative of carboxylic acids
11. Acid Chlorides
Acid Chlorides names are derived from the corresponding carboxylic acid name by replacing the
-ic acid ending with -yl choride or replacing the –carboxylic acid ending with -carbonyl chloride
Examples:
ClOC-CH=C(CH3)-CH2-COCl: 3-Methylpent-2-ene-1,5-dioyl chloride.
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Activity: Let A be an organic compound which is an acid chloride with formula C 3H5ClO.Suggest
all possible isomers of A and name them.
12. Acid Anhydrides
Acid anhydrides may be symmetric (ROC-O-COR) or unsymmetric (ROC-O-COR’)
According to IUPAC nomenclature,
 Name symmetrical anhydrides as the carboxylic acid except the word acid is replaced with
anhydride
O O
ethanoic anhydride
e.g.: H3C O CH3
O O
O O
O
H O H
Methanoic or formic ahydride Benzoic anhydride

H
H
(CH3CH2CH2 CO)2O
O O Butanoic anhydride
O
maleic anhydride
 Name unsymmetrical anhydrides as the parent carboxylic acids arranged in alphabetical

order without the word acid followed by the word anhydride
e.g.: ethanoic methanoic anhydride
O O
H3C
Activity: Give all possible structures whose formula is C 4H6O3 and define their relationships in
terms of isomerism and give their names according to IUPAC.
13. Esters
Esters (R-CO-O-R') are named as alkyl derivatives of carboxylic acids. The alkyl (R') group is
named first. The R-CO-O part is then named as a separate word based on the carboxylic acid name,
with the ending changed from –oic acid to -oate.
For examples:
 CH3CH2CH2CH2COOCH3 is methyl pentanoate

 (CH3)2CHCH2CH2COOCH2CH3 is ethyl 4-methylpentanoate.
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For esters such as ethyl acetate (CH3COOCH2CH3), ethyl formate (HCOOCH2CH3) or dimethyl
phthalate that are based on common names of acids, IUPAC recommends use of these established
names, called retained names. The -oate changes to -ate. Some simple examples, named both
ways, are shown below.
CH3
H3C O
Methyl ethanoate
O O CH3
O
CH2CH3 CH
CH2CH3
H3CH2C O O CH3
H3C O
Ethyl propanoate Ethyl ethanoate
Isopropyl benzoate
If the alkyl group is not attached at the end of the chain, the bond position to the ester group is
infixed before "-yl": CH3CH2CH(CH3)OOCCH2CH3 may be called but-2-yl propanoate or but-2-
yl propionate.
Activity 1: Give all possible molecular (isomers in their varieties) whose molecular formula
C2H4O2 .The same as but for C4H8O2.
14. Salts of carboxylic acids
Salts of carboxylic acids (R-CO-O-M) are named as esters where the name of alkyl (R') group is
replaced by the name of the salt cation (M).
For examples:
 CH3CH2CH2CH2COONa is Sodium pentanoate

 (CH3)2CHCH2CH2COONH4 is Ammonium 4-methylpentanoate.
 CH3COOK is Potassium ethanoate (or Potassium acetate)
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 HCOONa is Sodium methanoate (or Sodium formate)
15. Amides
Amides (R-CO-NH2) are named as the carboxylic acid except the –ic(or -oic) acid ending is
replaced with -amide or the -carboxylic acid ending is replaced with –carboxamide ( if the carbon
in the amide group cannot be included in the main chain).
Amides that have additional substituents on the nitrogen are treated similarly to the case of amines:
they are ordered alphabetically with the location prefix N for example: HCON(CH3)2 is N,N-
dimethylmethanamide.
H3C NH2
Ethanamide or
O
H3C NH-CH3
N-Methyl ethanamide (N-methylacetamide)
H2N NH2
Amino methanamide
amino formamide or urea
Note: Amides form tautomers with iminol. For example: CH3CONH2 and CH3C(OH)=NH
Activity: Give all possible structure whose formula is C3H7NO and give their names according to
IUPAC.
16. Nitriles
According to IUPAC, nitriles, so called organic cyanide are named by adding nitrile to name of
hydrocarbon chain which includes the nitrile C atom.
And common names are obtained by replace -ic acid with –onitrile and -carboxylic acid with
carbonitrile or name as alkyl cyanide (in these cases the C of the CN group is not included in the
alkyl part).
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Example:
 H3C-CN Ethanenitrile or Acetonitrile

 CH3CH(CH3)CN: 2-methylpropane nitrile or isopropyl cyanide
 CH3CH2-CN: propanenitrile
 CH2=CH-CN: Prop-2-enenitrile
N
C
N
C
benzonitrile
Cyclopentane carbonitrile
If a prefix form is required, "cyano-" is used with the position number indicating it location in
the carbone a chain:
O
3
NC
: 4-Cyano butanoic acid
1 OH
e.g: 4 2
Note: -CN functional group is taken as substituent in case it is in a molecule containing functional
groups that take priority on it, such as carboxylic acid, esters, acid anhydrides, and amide.
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ORDER OF PRECEDENCE OF GROUPS
When compounds contain more than one functional group, the order of precedence determines
which groups are named with prefix or suffix forms. The highest-precedence group takes the
suffix, with all others taking the prefix form. However, double and triple bonds only take suffix
form (-en and -yn) and are used with other suffixes.
Prefixed substituents are ordered alphabetically (excluding any modifiers such as di-, tri-, etc.),
e.g. chlorofluoromethane, not fluorochloromethane. If there are multiple functional groups of the
same type, either prefixed or suffixed, the position numbers are ordered numerically (thus ethane-
1,2-diol, not ethane-2,1-diol.) The N position indicator for amines and amides comes before "1",
e.g. CH3CH(CH3)CH2NH(CH3) is N,2-dimethylpropanamine.
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ORGANIC REACTIONS
Types of Organic Reactions
1. Addition Reactions: A + B → C
C2H4 + Br2 → C2H4Br2
2. Elimination Reactions: D → E + F
CH 3  CH 2 Br  CH 2  CH 2  HBr
3. Substitution Reactions:
CH4 + Cl2 → CH3Cl + HCl
4. Rearrangements: J → K
O O
CH3 C CH3 CH3 CH2 CH
(Ketone) (Aldehyde)
In organic reaction we consider two types of reactant
 Substrate: In an organic reaction, reactant which supplies carbon to the new bond.
 Attacking reagent: In an organic reaction, chemical substance that attacks the organic
molecule (substrate) and leads to the formation of product.
Different types of attacking reagent:
Nucleophiles (electron rich sites, seek nucleus) are synonymous with Lewis bases and
Electrophiles (electron poor sites, seek electrons) are synonymous with Lewis Acids, Polar
reactions are Lewis Acid-Base reactions.
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How do these reactions occur? Mechanism
 In an organic reaction, we see the transformation that has occurred. The mechanism
describes the steps behind the changes that we can observe
 Reactions occur in defined steps that lead from reactant to product
Steps in Mechanisms
 A step involves either the formation or breaking of a covalent bond

 Steps can occur in individually or in combination with other steps
 When several steps occur at the same time they are said to be concerted
Chemical reactions are concerned with the breaking and making of bonds.
We must explain how electrons are exchanged during the formation of new bonds and breaking of
old bonds.
Breaking bonds is sometimes called bond fission. The ways bond break has an important influence
on reactions. In a covalent bond, a pair of electrons is shared between the two atoms.
When the bond breaks, these electrons get redistributed between the two atoms. There are two
ways this redistribution can happen.
•Symmetrical -homolytic
•Unsymmetrical –heterolytic
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In symmetrical bond breakage the dot beside each atom represents the unpaired electron that the
atom has gained from the shared pair in the bond. The atoms have no overall electric charge,
because each has equal numbers of protons and electrons. But the atoms are highly reactive,
because the unpaired electron has a strong tendency to pair up with another electron from another
substance. These highly reactive atoms or group of atoms with unpaired electrons are called free
radicals.
Free radicals are most commonly formed when the bond being broken has electrons that are fairly
equally shared. When the electrons are unequally shared, the bond is polar and the heterolytic
fission is more likely.
Indicating Electron Movement in Reaction Mechanisms
 Curved arrows indicate breaking and forming of bonds

 Arrowheads with a “half” head (“fish-hook”) indicate homolytic and homogenic steps
(Called ‘radical processes’)
 Arrowheads with a complete head indicate heterolytic and heterogenic steps (called ‘polar
processes’)
For example:
(a) Polar Reactions (Opposite charges attract)
Polar reactions occur between regions of high electron density and regions of low electron density
(known as reactive site).
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(b) Radical Reactions
 Not as common as polar reactions
 Radicals react to complete electron octet of valence shell
 A radical can break a bond in another molecule and abstract a partner with an electron,
giving substitution in the original molecule
 A radical can add to an alkene to give a new radical, causing an addition reaction
Describing Reaction Intermediates
If a reaction occurs in more than one step, it must involve species that are neither the reactant nor
the final product. These are called reaction intermediates or simply “intermediates”
 What are they? Carbocation, Carbanion, Carbon radical

 How are they formed? Species produced during cleavage of bonds
 How do they look like? Crf table below
 Are they stable? They are highly reactive species with variable stability.
General principles of stability:
 Increase charge Unstable

 Decrease charge Stable
 Localise charge Unstable
 Disperse, delocalise change Stable
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Reaction Intermediates:
Name of the Oder of stability of the Reason for stability order

species species
Factors that influence organic reactions (Electronic structures)
1. Inductive Effect
The process of electron displacement along the chain of carbon atoms due to the presence of a polar
covalent bond at one end of the chain is called inductive effect (or I-effect). It is a permanent effect.
NOTE: Inductive effect decreases on moving away from the atoms involved in the initial polar
bond and becomes negligible from the fourth atom onwards.
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For comparing the relative effects, hydrogen is taken as standard and the atoms or groups can be
classified into two categories:
(i) Atoms or groups of atoms having electron-attracting more than hydrogen are referred to
as having -I (electron withdrawing or attracting) effect.
Example:
(ii) Atoms or groups of atoms having smaller electron attracting power than hydrogen are
referred to as having + I (electron donating or repelling) effect.
Example:
Application of inductive effect
Acidity and basicity:
An acid is a substance that donates a proton (Bronsted-Lowry). Acidic compounds have low
pKa-values and are good proton donors, as the anions (or conjugate bases), formed on the
deprotonation, are relatively stable.
In water:
The more stable the conjugate base the stronger the acid and vice-versa. The conjugate base
can be stabilised by –I groups which can minimize the negative charge. Predictably, this effect is
going to be related to three major factors:
1) the electronegativity of the element (the more electronegative, the more stable the
conjugate base (weak base), the more acidic)
2) The distance between the electronegative element and the negative charge(the shorter the
distance, the more stable the conjugate base, the more acidic)
3) The number of electronegative element (the more electronegative element a compound
possess, the more stable the conjugate base, the more acidic)
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CH3NHCH3 is more basic than CH3NH2 and methylamine more basic than NH3. This is because
in dimethylamine there are two methyl group with (+I) in methylamine there is one methyl group
and for ammonia there is no group to affect the electron density on nitrogen.
Stability of carbocation and carbanion
The order of stability of carbocation is: Tertiary > secondary > primary. For example:
The tertiary carbocation has three alkyl groups around the carbon with the positive charge. These
groups through their collective Inductive effect (+I) neutralize the positive charge to a certain extent
thus stabilising it. The secondary has two alkyl groups, the primary one alkyl group and methyl
none, this is responsible for their decreasing stability.
The order of stability of Carbanion is: Primary> secondary > Tertiary. For example:
(CH3)3C- < CH3CH2- <(CH3)2CH- <CH3-
The tertiary carbocation has three alkyl groups around the carbon with the negative charge. These
groups through their collective Inductive effect (+I) increase the negative charge to a certain extent
thus destabilizing it. The secondary has two alkyl groups, the primary one alkyl group and methyl
none, this is responsible for their increasing stability.
In contrast negative charge is stabilized by adjacent electron withdrawing groups
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2. Resonance or Mesomeric Effect (A way to indicate delocalization of electron)
If a molecule can be assigned two or more Lewis structures, none of which is capable of describing
all the known properties of the compound, then the actual structure is intermediate or resonance
hybrid of these structures. This phenomenon is called resonance. The various structures written are
called resonating structures or canonical forms.
An example is CH2=CH-CH=CH2, which from the Lewis structure shown consists of two double
bonds and a single bond. So C1-C2and C3-C4 bond lengths should be substantially shorter than
that between C2 and C3, but all bonds are found to be of the same length in reality. So the above
representation of bonds and electrons is not entirely accurate.
In reality this inadequacy of accurate representation of covalent molecule is inherent in the Lewis
model. So we use multiple structures to represent the actual molecule which exists in nature and
these structures represent one or more properties of the actual molecule.
To extend the example above CH2=CH-CH=CH2 can be written as CH2+-CH=CH-CH2– by moving

the electrons in the following manner:
These structures are called resonance structures of the main molecule; now we can understand why
all the bonds have equal length as structure 2 has a double bond character on C2-C3. So overall all
C-C bonds have some double bond character so the actual representation of the molecule found in
nature would be something like:
This structure now would be called a resonance hybrid of all the resonance structures.
A few points about Resonance hybrids would summarize the concept:
 A resonance hybrid is the actual representation of the molecule.

 It has properties from all the resonance structures.
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 It has the least energy of all the resonance structures (that is why it exists in nature) and the
structures which have energy close to it contribute the most towards it. This means if X is
the hybrid of A, B and C, and that C has the lowest energy (or is the most stable) X will
look the most like C.
 This extra stabilization of the resonance hybrid is denoted by Resonance energy.
Resonance occur in conjugated system
Element of conjugation are: Atoms with lone pairs, π bonds, radicals, and carbocations. Atoms
that lack any of these features cannot participate in resonance.
“Conjugation” is the name we give for the phenomenon where π electrons (that is, “electrons in
p orbitals”) can be shared over more than two atoms. In conjugated system the above element of
conjugation are separated by only one single bond.
Here’s an example of a conjugated diene and a non-conjugated dienes.
In each of these we can draw resonance forms where the middle atom participates in a π system.
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Examples:
1. resonance positive
2. resonance positive
Application of resonance effect
The more resonance structures an anion, cation or neutral a  system can have the more stable it is.
Acidity and basicity:
The conjugate base can also be stabilized by –M groups which can delocalise the negative
charge. (The more spread out the negative charge, the more stable it is)
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Example1: Ethanonic acid is a stronger acid than ethanol because its conjugate base is more
stable due to Delocalization of charge (by spreading the charge across several atoms)
Example2: Phenol is a stronger acid than hexanol because its conjugate base is more stable due
to Delocalization of charge (by spreading the charge across several atoms)
Activity: which protons in red would you expect to be more acidic? Explain. Remember, any
structural feature that increases the stability of the conjugate base will increase acidity.
The resonance effect also nicely explains why a nitrogen atom is basic when it is in an amine,
but not basic when it is part of an amide group.
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Here’s another way to think about it: the lone pair on amide nitrogen is not available for bonding
with a proton being part of the delocalized pi bonding system. The lone pair on amine nitrogen,
by contrast is not part of a delocalized pi system, and is available to form a bond with any acidic
proton that might be nearby. If an amide group is protonated, it will be at the oxygen rather than
the nitrogen.
Stability of carbocation, Carbanion and carbon free radicals

1. Resonance effect stabilize Carbocations
A positive charge that is adjacent to one or more Pi bonds or adjacent to atom with a lone paire
can disperse its positive charge over multiple atoms.
Examples:
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2. Resonance effect stabilize Carbanions
Along the same lines, a negative charge that is adjacent to one or more Pi bonds can disperse its
negative charge over multiple atoms. For example:
3. Resonance effect stabilize free radicals

Radicals prefer a greater degree of alkyl substitution. Even more so, radicals prefer to be in
the allylic position (means adjacent to one or more Pi bonds).
Therefore here is the order of radical intermediate stability:
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Electromeric Effect
It is a temporary effect which takes place between two atoms joined by a multiple bond, i.e., a
double or a triple bond. This occurs at the requirements of the attacking reagent and involves
instantaneous transfer of a shared pair of electrons of the multiple bonds to one of the linked atoms.
The electromeric effect is classified as +E effect and-E effect:
(i) When the π-electrons of the multiple bond are transferred to that atom to which the reagent gets
attached, it is called +E (positive electromeric) effect.
Example:
(ii) When the π- electrons of the multiple bond are transferred to that atom to which the attacking
reagent does not get attached, it is called-E (negative electromeric) effect.
Example:
Inductomeric effect
Inductomeric effect is the temporary effect that takes place in sigma bonded system and it accounts
only in the presence of an attacking reagent. This is a molecular polarizability effect occurring by
the inductive mechanism of electron displacement.
Example:
In methyl chloride the -I effect is further increased temporarily by the approach of hydroxyl ion.
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Polarizability: The relative tendency of a molecule to become polarized in the presence of an
external electric field (solvent or other polar molecules). It is like making something magnetic by
pass a magnet over it.
Polarization: change in electron distribution as a response to change in electronic nature of the

surroundings. Polarizability is the tendency to undergo polarization.
Structure and Reactivity: Acidity and Basicity
In this section we will analyze how structure affects acidity and basicity. Acids and bases are vital
to many chemical reactions and we need to understand what properties contribute to their strength.
Electronic factors involved are:
1. Atom: Look at what atom the charge is on for the conjugate base.
For atoms in the same row, we consider electronegativity. The further to the right on the
periodic table an atom is, the more electronegative it is. If a conjugate base's negative charge
is on a more electronegative atom, it is more stable, and thus the parent acid is stronger.
Example: Which is the strongest acid H2O, NH3, or CH4?
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 For atoms in the same column, we consider an atom's ability to stabilize a charge. The
further down on the periodic table an atom is, the better it is at stabilizing a charge. If a
conjugate base's negative charge is more stabilized on an atom further down a group, it is
a more stable molecule, and thus the parent acid is stronger.
Resonance Stabilization: Look at resonance structures. The more distributed the charge of the
conjugate base is, the stronger the parent acid is.
Inductive Effect: Look for inductive effect. If there are many electronegative atoms near the
conjugate base's negative charge, electron density is pulled toward these atoms. This creates more
stable anions and thus more acidic parent molecules. However, if there are many alkyl groups,
electron density is pushed by these groups and increase the negative charge ; this creates less stable
anions and thus less acidic the parent acid.
Orbital: Look at the orbital where the negative charge for the conjugate base is.
Another important aspect to consider when determining acidity is the hybridization of the atom.
We know that s orbitals are closer to the nucleus than p orbitals.
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This tells us that the more s character a hybrid orbital has the closer are the electrons to the nucleus.
Such atoms are less willing to share their electron density. This creates more stable anions and
thus more acidic parent molecules.
Stability of conjugate bases in increasing order:
Charge: In general, a base with a negative formal charge has a greater driving force to share
electron density than a neutral base. This relates to the principle introduced regarding charge
density and basicity.
The greater the electron density (in this case due to negative charge), the stronger the base and the
weaker the conjugate acid For example, in comparing the acidities of H3O+ and acetic acid we
must first analyze the structure of their conjugate bases H2O and acetate ion. At first it may seem
that due to resonance, the basicity of acetate is below that of H 2O. However, the acetate ion also
has a negative charge which H2O lacks.
In this case, charge has a greater influence on pKa than resonance. As a result, H2O is the weaker
of the two bases and H3O+ is the stronger of the two acids.
The high charge densities an atom possess the more unstable will be. For example:
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UNIT 2: ALKANES
Key unit competency Relate the physical and chemical properties of the alkanes to the
preparation methods, uses and isomerism.
Learning objectives
- Name straight chain alkanes up to carbon-20
- Define homologous series
- Use IUPAC system to name straight and branched alkanes
- Describe the preparation methods of the alkanes
- Prepare and collect methane gas
- Respect of procedure in experiment to carry out preparation of methane or propane
- Describe and explain the trend in physical properties of homologous series of alkanes
- Be aware of the dangers associated with combustion reactions of the alkanes
- Write reaction for free radical mechanism for a photochemical reaction
- State the chemical properties of the alkanes
- Develop practical skills and interpreting results in making appropriate deductions.
- Appreciate the importance of the alkanes in daily life
- Appreciate the dangers caused by the alkanes to the environment as major sources of air
contaminants
- State the uses of the alkanes
Alkanes are the simplest class of organic compounds. They are made of carbon and hydrogen
atoms only and contain two types of bonds, carbon-hydrogen (C-H)and carbon-carbon (C-C)
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single covalent bonds. They do not have functional groups. Alkanes form a homologous series
with the general formula CnH2n+2 where n is the number of carbon atoms in the molecule. The
first member of the family has the molecular formula CH4(n=1) and is commonly known as
methane and the second member with molecular formula is C2H6(n=2) is called ethane. These
compounds are also known as the saturated hydrocarbons.This name is more descriptive than the
present-day term ―alkane‘‘ because both their composition(carbon and hydrogen) and the fact
that the four single covalent bonds of each carbon in their molecules are fully satisfied or
‗‘saturated‘‘. The name alkane is the generic name for this class of compounds in the IUPAC
system of nomenclature. These hydrocarbons are relatively unreactive under ordinary laboratory
conditions, but they can be forced to undergo reactions by drastic treatment. It is for this reason
that they were named paraffins(Latin parum affinis=little activity).
Occurrence of Alkanes
1) The alkanes exist in nature in form of natural gases and petroleum. Natural gas and
petroleum existence are the results of decomposition of died bodies after many years ago.
2) The most natural gas is found in lake Kivu as methane gas but in form of traces like ethane,
propane and butane
3) Petroleum is the most world energy, it is formed by decomposition by bacteria for millions
of years died marine living things and as the last product is petroleum and natural gases
which are separated in fractional distillation of their crude oil and the results are obtained
according to their boiling point.
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Figure 2.1 Fractional distillation of petroleum
Source:www.bbc.uk/schools/gcse/fractionaldistillationofcrudeoil
The fractional distillation and the different fractions are summarized in the table and figure
below:
Table 2.1 Fractions of petroleum
Fraction Number of Catoms B.P range 0oC
Natural gas C1- C4 Below 40
Petrol C5- C10 40-175
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Kerosene/paraffin C10- C14 175-275
Diesel oil C14- C18 275-300
Lubricating oil, waxes Above 18 300-350

( heavy gas oil)
Bitumen, asphalt, Above 40 Above 350

(residues)
Preparation of alkanes
 From sodium salt of carboxylic acids
When sodium salts, of carboxylic acids, are heated with soda lime, they eliminate a molecule of
carbon dioxide gas to form alkanes according to the general equation.
For example Methane can be prepared by the reaction between sodium acetate and sodium
hydroxide solid according to the equation:
It is collected by the
downward displacement of water.
Note: The reaction is practically used to reduce one the length of carbon chain. It is referred as
decarboxylation of sodium carboxylates.
 Reduction by addition of hydrogen (hydrogenation) to alkenes and alkynes in the

presence of catalyst like Nickel, Palladium or platinum produces alkanes. (Sabatier and
Senderen’s reaction).
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Ni CH3-CH2-CH3
CH3-CH=CH2
0C
150
Propene propane
Ni
+ H2
Note: Reduction with Platinum and Polladium, as catalyst occurs at room temperature while that
with Nickel requires a temperature of about 1500C.
This reaction is called hydrogenation reaction of alkenes and alkynes; it is also called a
reduction reaction of alkenes and alkynes.
N.B: In organic chemistry, reduction reaction is the reaction that results in increasing of hydrogen
content in the new product. [Hydrogen content in the product (C6H12) is higher than the hydrogen
content in the reactant (C6H10)].
 From halogeno alkanes or Alkyl halides
Reduction of alkyl halides to alkanes may be done in different ways:
 Using H2 in the presence of palladium as a catalyst,
R  X  H 2 
Pd
RH  HX
Ex : CH 3  Cl  H 2 
Pd
CH 4  HCl
 Using Grignard reagent as intermediate, this one is done in two steps; the first one is the
formation of Grignard reagent(organomagnesium) the second is its hydrolysis.
MgXOH 
 
RX  Mg 
 RMgX  RH  MgNH2 X
ether H 2O / NH 3 / CH 3OH

Mg (CH O) X  , R is a alkyl group.
 3 
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 Corey-House Alkane synthesis: This method is superior to Wurtz synthesis. It involves
first conversion of alkyl halide to lithium dialkyl cuperate, LiR 2Cu and then coupling
between lithium alkyl cuperate and an alkyl halide.
e.g:
 On reduction of alkyl halides with Zn and concentrated hydrochloric acid, alkyl halides are
converted to alkanes.
 Wurtz reaction is used to synthesize an alkane from two molecules of alkyl halides when
heated with sodium metal in ether solution.
e.g.: 2CH3CH 2 Br  2 Na ether

  CH3  CH 2  CH 2  CH3  2 NaBr
/ heat
Note: (i)This reaction is practically useful in organic synthesis to increase the length of
carbon chain.
(ii) This reaction conduct to a mixture of products when the two molecules of halogeno
alkane are different. (i.e R-R, R-R’, R’-R’):Rand R’are different.
To prevent this mixture of products we can use an organomagnesium compound as an

intermediate.
EX: CH3CH2 Br  Mg  CH3CH2 MgBr CH

3Br
 CH3  CH2  CH3  MgBr2
Note: the yield of this reaction using saturated alkyl halide is low but is good using allylic
alkyl halide (R-CH=CH-CH2X)
 When Alkyl halides are treated with Zn-Cu couple, in the presence of ethanol, alkanes are
formed.
Note: Zn-Cu couple is obtained by adding Zinc granules in aqueous copper (II) sulphate
solution where copper is deposited on the Zn pieces.
Example:
 From carbonyl compounds(From aldehydes or ketones)
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Reduction of carbonyl compounds, with amalgamated Zinc and HCl (Clemmensen reaction)
O
Zn(Hg)/conc. HCl
CH3CH2 C CH3 CH3CH2CH2CH3+H2O
Ex :
Note: Under special conditions, reduction also is effected by use of H2 and Ranley Nickel or using
hydrazine and KOH through Wolf Kishner reduction.
Properties of Alkanes
Physical Properties
The values of the melting, boiling points, density and physical state of some alkanes are
summarized in the table below
Table 2.2 Physical chemistry parameters about alkanes and their trends
From the above table, it is noticed that:
1) First four members (methane to butane) are colourless, odourles gases , next thirteen
(C5 to C17)are colourless, odourles liquids while higher alkanes are colourless wax
like solids.
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2) In case of normal alkanes boiling points increase with rise in molecular weights.
As a rule the boiling points of alkanes having branched carbon chain are lower than
those of isomeric normal alkanes.
4) Variation in the melting point of alkanes is not regular. Alkanes with odd number of
carbon atoms have lower melting point than the next lower and next higher alkanes
having even number of carbon atoms. This is due to the greater inter molecular
attraction in even numbered alkanes having end carbon on the opposite sides of the
molecules.
Explanation: The boiling point and melting depends on the magnitude of the Van Der Waal‘s
forces between the molecules. These forces increase in magnitude with molecular weight.
Note: Branched chain isomers have lower boiling and melting pointsthan their straight chain
isomers, because straight chain isomers are moreclose packed than branched chain isomers.
Boiling points decrease with increase in branching because increased branching gives the molecule
a more nearly spherical shape and this reduces the extent of contact between neighboring
molecules, in other words the branched isomers are less packed than strait chain isomers, and
hence the attractive force between the molecules are reduced hence decrease in the boiling points.
Solubility: Alkanes are not soluble in water, because of their low polarity and also because of their
inability to form hydrogen bonds. They are, however soluble in non polar solvents, like CCl4, CS2,
benzene, and are miscible with one another.
Chemical properties.
Generally, alkanes are quite inert towards common reagents because:
- The C-C bond and C-H bonds are strong and do not break easily.
- Carbon and hydrogen have nearly the same electronegativity value hence C-H bond is only
slightly polarized; generally C-H bond is considered as non polar.
-The C-C bond is completely non polar.

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- alkanes have no unshared electrons to offer.
Therefore electrophillc or nucleophillic reagent find no site for attack on alkane molecules.
They, however, undergo the following reactions.
1) Reaction with oxygen (Oxidation or Combustion):
Combustion of alkanes breaks down to carbon dioxide and water if oxygen is enough to burn all
quantity of hydrocarbons. In general:
3n+1 O2(g) n CO2(g) + (n+1)H2O(l) + heat released

CnH2n+2 +
2
The evolution of heat in this reaction forms the basis of the use of these hydrocarbons as source of
heat and power.
If oxygen is not present in sufficiently large quantities, carbon monoxide or carbon is produced
instead of carbon dioxide. This is called incomplete combustion.
Examples of incomplete combustion reactions are:
C4H10 + 4½O2 4CO + 5H2O Incomplete combustion
C4H10 + 2½O2  4C + 5H2O Incomplete combustion
Carbon dioxide(CO2) ,produced from the burning of alkanes or fossil fuels for heating ,transport
and electricity generation, is the major atmospheric pollutant that increases the greenhouse
potential of the atmosphere. Carbon dioxide is the major Green House Effect (GHE) Gas. Burning
wood and Forests produce also carbon dioxide and participate in increasing of that gas in the
atmosphere. Some other GHE gases such as, methane, are produced by human activities,
Agriculture (Rice), Cattle-rearing.
There are many natural ways of reducing atmosphere carbon dioxide:
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(i) Water in seas dissolves millions of tonnes (but less now than it didin the past, since the average
ocean temperature has increased by 0.5oC in the last 100 years, and gases are less soluble in hot
than in cold water).
(ii) Plankton can fix the dissolved carbon dioxide into their body mass by photosynthesis
(iii) Trees fix more atmospheric carbon dioxide than do grass and other vegetation through
photosynthesis according to the equation below.
6CO2 + 6H2O C6H12O6 +6O2 There are other ways than natural ways of reducing GHE gases
and among them there are the use of technologies that reduce the green house gas emissions, the
recycling of the GHE.
2) Reaction with halogens (halogenations) X2 with X =F, Cl, Br, I
Halogens do not react in the same way with alkanes;
 Fluorine is extremely reactive, and his reaction is destructive. The reaction is:
Light(hv)
CnH2n+2 + (n+1)F2 nC(S) +(2n+2) HF
 Reaction with other halogens give:
R-H + X2 → RX+ HX It is a substitution reaction.
This reaction take place in the presence of high temperature or UV light
Mecanism: This reaction is a chain reaction.
A chain reaction is a series of reactions in which the products of one reaction are reactant of next
reaction in the chain.
i. step 1 : Chain Initiation (radical formation)
h
Br2  2 Br 
ii. step 2 : Chain propagation
CH 4  Br  CH 3  HBr

 CH 3  Br2  CH 3 Br  Br 
iii. step 3 : chain termination (Radical combinations)
CH3  CH 3   CH 3  CH 3
CH 3   Br  CH 3 Br
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Br  +  Br  Br2
Hence, the generalized reactions product is like
Light(hv)
CnH2n+2 + X2 CnH2n+1X + HX
R-X
X2 : Can be Cl2, Br2 and in some case I2 but not F2
Notice: (i) Br2 reacts as Cl2 but slowly while iodine react hardly or do not while fluorine, the most
electronegative element of the periodic table reacts in order to give coke.
The reaction of alkanes react with these halogens in presence U.V light or diffused sunlight or at
o
temperature 300-400 C form a mixture of corresponding substituted products.
For example: Methane reacts with chlorine to give mixture of different substituted products.
It is difficult to stop this reaction at first step. However, the yield of CH3x can be improved by
taking excess of methane. Ethane and higher alkanes react with chlorine and bromine in a similar
way and all possible substitution products are obtained.
(ii) Due to radical formation involved, the main products of reaction is the one from the
most stable radical starting with tertiary, secondary, primary and methyl in decreasing order of
stability.
H
Cl2/sunlight CH3CH2CH2Cl + CH3 C CH3
CH3CH2CH3
30% Cl
70%
(iii) Iodination: It is reversible. The hydrogen iodide formed during iodination reduces the
product back to reactant hence it must be carried out in the presence of strong oxidizing
agent like iodic acid or nitric acid which destroys the hydroiodic acid (HI) as it is formed.
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3) Nitration: This involves replacement of hydrogen atom by –NO2 group. Nitration is carried out
o
by heating mixture of alkanes and nitric acid vapours at 400-500 C. The process is known as
Vapour Phase Nitration.
Since the reaction is carried out at high temperature, chain fusion also takes place during the
reaction and mixture of all possible mono nitro derivatives are obtained.
For example,
4) Dehydrogenation of alkanes gives alkenes under heat and a catalyst like V2O5.
5) Action of heat
Alkanes are stable on heat but around 7000c and in the presence of catalyst alkanes decompose in
different products by the breakage of different bonds. . In other words the larger alkanes can be
broken up into smaller alkanes. The process by which this is carried out is called cracking.
Cracking has the added advantage of producing other useful hydrocarbons not naturally present in
crude oil, such as alkenes (widely used as petrochemicals), cycloalkanes and branched alkanes
(widely used in motor fuels) and aromatic hydrocarbons (used as petrochemicals and as motor
fuels).
Thus cracking is important for two reasons:
i) It converts low-demand fractions into higher demand fractions
ii) It makes useful hydrocarbons not naturally found in crude oil
There are two types of cracking: thermal cracking and catalytic cracking. Both involve the
breaking of C-C bonds to form smaller molecules. C-C bonds are weaker than C-H bonds and so
break more easily when heated.
a) Thermal cracking
In thermal cracking, the bonds are broken using a high temperature (400 – 900oC) and a high
pressure (70 atmospheres).
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The high temperatures mean that the molecule breaks near the end of the chain, giving a high
percentage of small alkenes such as ethene.
Most thermal cracking reactions involve the formation of one of smaller alkane molecules and one
alkene molecule. Naphtha (C7 – C14) is usually used as the starting material.
Eg C8H18  C6H14 + C2H4
H H H H H H H H H H H H H H
H H
H C C C C C C C C H H C C C C C C H + H
C C
H
H H H H H H H H H H H H H H
Eg C6H14  C3H8 + C3H6
H H H H H H H H
H H
H C C C C C H H C C C H + C C C H
H H H H H H H
H H H H
b) Catalytic cracking
In catalytic cracking, the bonds are broken using a high temperature (450 oC, which is generally
lower than in thermal cracking), a slight pressure (slightly greater than 1 atmosphere), and a
zeolite catalyst.
Catalytic cracking is cheaper and more efficient than thermal cracking as it uses a lower
temperature and pressure.
The zeolite catalyst favours the formation of branched alkanes and cycloalkanes, which are widely
used in motor fuels. The most important product of catalytic cracking is 2-methylheptane, which
is the major component of petrol. It also produces aromatic hydrocarbons such as benzene, which
have a variety of uses.
H H
H H H H H C C
H C C C C C H H C C H + 3H2
H H H H H C C
H H
Eg
Uses of alkanes
(1) Methane (CH4)
-It is used as a fuel for homes, ovens, water heaters, kilns and automobiles as it combusts with
oxygen to produce heat.
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-Highly refined liquid methane is used as rocket fuel.
-Also used as fuel for electricity generation.
-As a vehicle fuel in the form of liquefied natural gas (LNG). It is more environment friendly than
gasoline/petrol and diesel.
-Methane can be used as raw material in the production of urea, a fertilizer.
(2) Butane (C4H10)
- Butane is a key ingredient of synthetic rubber.
- It is used as fuel in cigarette lighters.
- When blended with propane and other hydrocarbons, it may be referred to commercially as LPG,
for liquefied petroleum gas.
- Butane gas cylinders are used in cooking.
- Also used in aerosol spray cans.
(3) Propane (C3H8)
- Propane is used as a propellant for aerosol sprays such as shaving creams and air fresheners.
- Used as fuel for home heat and backup electrical generation in sparsely populated areas that do
not have natural gas pipelines.
- Propane is commonly used in theme parks and in movies for explosions and special effects.
(4) Ethane (C2H6)
- Ethane is used in the preparation of ethene and certain heavier hydrocarbons.
- Ethane can be used as a refrigerant in cryogenic refrigeration systems.
(5) Pentane (C5H12)
- Pentane is used in the production of polystyrene foams and other foams.
- Used in laboratories as solvents.
- It is also active ingredients of pesticides.
- Used as solvent in liquid chromatography.
(6) Hexane (C6H14)

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- It is used in the formulation of glues for shoes, leather products, and roofing.
- It is also used to extract cooking oils ( such as canola oil or soy oil) from seeds.
- Hexane is used in extraction of pyrethrine from pyrethrum; e.g. pyrethrum factory in Musanze
District.
- Also for cleansing and degreasing a variety of items, and in textile manufacturing.
(7) Heptane (C7H16)
- Heptane is used as solventin paints and coatings.
- Pure n-heptane is used for research and development and pharmaceutical manufacturing.
- Also as a minor component of gasoline.
- It is usedin laboratories as a non-polar solvent.
UNIT 3: ALKENES AND ALKYNES

Key unit competency Relate the physical and chemical properties of alkenes and alkynes to
their reactivity and uses
Learning objectives
- Explain the reactivity of alkenes in comparison to alkanes
- Explain the existence of geometrical isomerism in alkenes
- Describe the industrial process of preparing alkenes and alkynes
- Apply IUPAC rules to name alkenes and alkynes
- Carry out an experiment to prepare and test ethene gas
- Outline the mechanisms for electrophilic addition reactions for alkenes and alkynes
- Write the structural formulae of straight chain alkenes and alkynes
- Apply Markovnikov’s rule to predict the product of hydrohalogenation of alkenes
- Classify alkynes as terminal and non-terminal alkynes using their different structures
- Appreciate the combustion reaction as source of fuels.
- Appreciate the uses and dangers of addition polymers (polythene used for polythene bags,
polypropene for plastic bottles etc.)
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Alkenes or Olefins
Alkenes are unsaturated hydrocarbons containing carbon-carbon double bond (C=C) in their
molecules. General formula of alkene is C nH2n. They are commonly known as olefins because
lower members form oil products with chlorine or bromine (Latin Oleum=Oil; ficane = to make).
Ethylene and propylene are the first and second members of this series respectively.
2
Double bonded carbon in alkenes is sp hybridised. The Carbon-Carbon double bond in alkene
2
consists of one sigma (σ) and one pi (π) bond. Sigma bond is formed by overlapping of sp hybrid
orbital of each carbon and π bond is formed by overlapping of unhybridised p-orbitals. The two
carbon atoms which are double bonded in alkanes are held more tightly together than in alkane
o
with the result C=C bond length in alkene is less (1.34A ) than C-C bond length in alkanes.
For example;
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Orbital Structure of Ethane
Alkenes are more reactive than alkanes this is due to the availability of more exposed π-electrons.
Alkenes are abundant in the nature. Alkenes play many important roles in biology. Ethene, for
example, is a plant hormone—a compound that controls the plant‘s growth and other changes in
its tissues.
Ethene affects seed germination, flower maturation, and fruit ripening. They are described as
unsaturated hydrocarbons because they can undergo addition reactions.
Preparation of alkenes
Different methods are used for the preparation of alkenes. Alkenes are generally synthesized by
elimination or addition reactions from saturated and unsaturated compounds respectively through
the following scheme:
Elimination(-AB)
H2/Pd*
C C C C C C
Addition(+AB) -H2/heat
A B CH2- Alkynes
alkenes
1) Dehydration of alcohols
An alkene may be obtained by dehydration of an alcohol.
By the reaction between alcohols and hot dehydrating agent(e.g. H2SO4 , H3PO4, Al2O3 or P2O5 )
o
When an alcohol is heated with concentrated sulphuric acid at 100 C or with phosphoric acid at
o o
200 C or by passing alcohol vapour over alumina, P2O5 or anhydrous zinc chloride at 350-400 C
a molecule of water is eliminated and alkene is formed.
RCH2CH2OH →R-CH=CH2 + H2O
CH 3CH 2CH 2  OH 

Al2O3 , heat
 CH 3CH  CH 2  H 2O
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The ease of dehydration follows the following order.
o o o
3 alcohol >2 alcohol >1 alcohol
o o
Dehydration of unsymmetrical 2 or 3 alcohol can proceed in two ways and mixture of alkene is
formed for example dehydration of 2-butanol yields mixture of 2-butene. (major product) and 1-
butene (minor product).
In such cases major products can be predicted by Saytzeff’s rule. Which states that “Hydrogen is
preferentially eliminated from the carbon atom with fewer number of hydrogen atoms.” Thus 2-
butene is the major product in above example. In other words Saytzeff’s rule states that “Greater
the number of alkyl groups attached to the double bonded carbon atoms, the more stable is the
Alkene.” Hence more substituted alkene is preferentially formed. The ease of formation of alkene
is ,
R C=CR > R C=CHR > R C=CH > RCH=CHR > RCH=CH
2 2 2 2 2 2
This can be explained on the basis of more stability of more substituted carbonium ion formed.
2) By dehydrogenation of Alkyl halides: when an alkyl halide is heated with alcoholic NaOH or
KOH, one molecule of hydrogen halide (HX) is eliminated to give alkene.
The ease of dehydrogenation of alkyl halide is

o o o
3 alkyl halide>2 alkyl halide >1 alkyl halide
o o
In case of dehydrogenation of 2 and 3 alkyl halides the major product can be predicted according
to Saytzeff’s rule. E.g.
3) By Dehydro Halogenation of Vicinal Dihalide: when vicinal dihalides (containing two

halogen atoms at adjacent carbon) are heated with zinc dust in alcohol or with magnesium alkenes
are produced.
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When the two halogen atoms are attached to non-adjacent carbon atoms, a cyclic alkane is formed.
Examples:
4) By controlled Hydrogenation of Alkyne: Alkyne is presence of Lindlar Catalyst react with

Hydrogen in controlled manners to give alkene.
A Lindlar catalyst is a heterogeneous catalyst that consists of palladium deposited on calcium

carbonate and poisoned with different lead derivatives such as lead oxide or lead acetate and
quinoline. A heterogeneous catalyst is the one which is in the phase different from that of the
reactants.
5) Cracking of Alkanes: Paraffins on heating at 500-800°C in absence of air get decomposed to
lower molecular weight alkene, alkanes and hydrogen.
Properties of Alkenes:
Physical properties:
1) The first three members are gases at ordinary temperature, next 14 are liquids and the higher
ones are solids. Except ethylene all members are colorless and odorless. Ethylene is pleasant
smelling gas.
2) Alkenes are insoluble in water but soluble in non polar solvents.
3) Generally, their boiling points and melting points of alkenes are less than those of alkanes
but also rise with increase of molecular weights. Further like alkanes, the branched chain
alkenes have lower boiling points than the corresponding n-alkenes.
4) Like alkanes, alkenes are generally non polar, but certain alkenes due to their
unsymmetrical structure are weakly polar. Trans alkene has a smaller dipole moment than
cis-isomer because trans isomer is relatively more symmetrical than cis-alkene. Due to
poorer symmetry molecules of cis-alkenes do not fit into the crystal lattice so well as in the
trans-isomer with the result cis alkenes have generally lower melting points than the trans.
Chemical properties:
Alkenes are more reactive than alkanes due to the presence of π-bond. The π electrons constituting
π bond are located much farther the carbon nuclei and are easily available for reaction when
needed. The overlap of atomic orbital forming π-bond is not as effective as that in σ bonds. Thus
π bond is weaker than σ bond and can be easily broken.
Addition reactions are the most important reactions of the carbon-carbon double bond. π electrons
of double bond are easily available to the reagent. Thus carbon-carbon double bond acts as a source
of electrons for electrophilic reagents and undergoes electrophilic addition reaction.
General equation of electrophillic addition
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Mechanism of electrophillic addition to Carbon-Carbon double bond:
Electrophilic addition reactions take place in two steps:
(i) Attack of electrophile (E+) to Carbon- Carbon double bond. Formation of a carbocation
(ii) The nuclephile attack the carbonium ion to give the addition product.
Because the addition reactions are initiated by electrophiles, they are referred to as electrophilic
addition reactions.
Some of the important reactions of alkenes are following:
1) Addition of hydrogen halides
Hydrogen halides (HCl, HBr, HI) react with alkenes to yield halogenoalkanes. The reaction is
carried either with reagents in the gaseous state or in inert solvent like tetrachloromathane.
In case of symmetrical alkene only one alkyl halide is formed but when the olefin is unsymmetrical
two products are possible.
For Example:
It has been found that isopropyl bromide is the major product. In such cases addition is governed
by Markonikov’s rule which states that,
“When an unsymmetrical reagent(such as HX, H2SO4,HOCl etc) adds to an unsymmetrical alkene,
then the negative part of the reagent is added to that carbon atom of the double bond which bears
the least number of hydrogen atoms i.e which bears more substituents and positive part of the
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reagent is added to that carbon atoms which bears greatest number of hydrogen atoms i.e. which
bears less substituents.”
The reaction take place through ionic mechanism. Markonikov’s rule can be explained with the
help of mechanism.
Step I: Attack of electrophile (H+) to double bond to form more stable carbocation.
More stable carbocation is preferentially formed.

Step II. Attack of nucleophile (Br-) to carbonium ion (more stable) to give major product.
Peroxide Effect - Anti markovnikov addition: Kharasch and Mayo 1933) discovered that
addition of HBr to propane or other unsymmertrical alkene in presence of organic peroxide (R-O-
OR) yields mainly n-alkyl bromide(anti markonikov’s product). This effect is known as peroxide
effect or Kharasch effect. But it does not apply to addition involving HCl, HI or HF
In presence of peroxide the addition takes place via a free radical mechanism rather than the ionic
mechanism. This addition of free radical to double bond involves the intermediate formation of
more stable free radical.
Example:
/
CH3-CH2-CH=CH2 +HBr Peroxyde
  CH 3  CH 2 CH 2 CH 2 Br
Mechanism
Free Radical Initiation
Peroxide O-O bond breaks easily to form free radicals.
Propagation Steps
Hydrogen is abstracted from HBr.
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Bromine adds to the double bond.
H
CH3CH2 C CH2Br secondary

. . radical: more
CH3CH2 CH CH2 + Br H stable
CH3CH2 C CH2 primary

radical
unstable
Br
HBr
H H
CH3CH2 C CH2Br CH3CH2 C CH3
H Br
90% 10%
2) Addition of water
The hydration of alkenes catalysed by an acid is an electrophilic addition. In the laboratory ethene
can be transformed into ethanol. The first step consists of adding concentrated sulphuric acid. The
second step consists of the hydrolysis of the product of the first step. In industry the reaction is
carried out at approximately 300 oC in the presence of phosphoric acid as a catalyst.
Example: Hydration of 2-methylbut-2-ene
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3) Addition with cold concentrated sulphuric acid
When cold concentrated sulphuric acid react with alkene, an alkyl hydrogen sulphate is obtained.
If the starting alkene is unsymmetrical, two different alkyl hydrogen sulphates are obtained. If the
alkyl hydrogen sulphate is warmed in the presence of water, an alcohol is obtained.
Example: Reaction of propene with H2SO4
Mechanism:
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4) Addition of Diborane [Hydroboration]: Diborane (B2H6) adds to the double bond as BH3 to
form trialkyl borane. The positive part of BH3 is the boron, the negative part is hydrogen.
Try alkyl borane on treatment with alkaline aqueous solution of hydrogen peroxide are converted
to alcohols.
o
USE: They are used for the synthesis of 1 alcohol.
5) Addition of halogens
The addition of halogens (halogenation) on alkenes yields vicinal dihalogenoalkanes. The reaction
takes place with pure reagents or by mixing reagents in an inert solvent. When a chlorine or
bromine molecule approaches an alkene, the pi electrons cloud interact with the halogen molecule
causing its polarisation.
Example: Reaction of ethene with bromine
Ex: H2C==CH2 + Br2 → BrH2C-CH2Br
Mechanism:
The reaction with bromine is a useful test for alkenes. The brown red colour of bromine is
discharged in alkenes, With bromine water, the reaction gives a mixture of organic products.
Example: H2C=CH2 + H2O + Br2 → HOCH2CH2Br + BrCH2CH2Br + HBr
Bromine water containing sodium chloride gives a mixture of three organic products.
Example: H2C=CH2 +Br2+H2O+NaCl→HOCH2CH2Br(major product)+ClCH2CH2Br(smaller
amount) + BrCH2CH2Br (traces) + NaBr
6)Addition of Hydrogen
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Addition of hydrogen to alkenes takes place under pressure and in the presence of catalyst like Ni,
Pt or Pd to produce saturated hydrocarbons. This is called catalytic hydrogenation.
This reaction is very useful when transforming vegetable oils into fats such as margarine by
hydrogenation. The process is referred as hardening.
Oxidation reactions
Alkane undergo oxidation reaction readily to form different compounds under different conditions.
(i) Transformation to epoxides
Alkene reacts with a peroxyacid (sometimes called peracids) , a carboxilic acid that has an extra
O atom in –O-O-(peroxy) linkage to form an epoxide (also called oxirane).
Catalytic oxidation: Alkenes react with oxygen under pressure in presence of silver catalyst at
o
250-400 C to form Epoxides.
Ethene react with oxygen in the presence of silver as a catalyst to yield epoxyethane.
Opening the Epoxide Ring
Most epoxides are easily isolated as stable products if the solution is not too acidic. any moderately
strong acid protonates the epoxide. Water attacks the protonated epoxide (back-side attack),
opening the ring. diol is formed. To synthesize the glycol without isolating the epoxide, use aqueous
peroxyacetic acid or peroxyformic acid.
Epoxides Vs Glycol
Epoxidation reagents can be chosen to favour either epoxide or glycol.
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Peroxyacetic acid is used in strongly acidic water solutions to yield glycols.(through the
protonation of epoxide)
Peroxybenzoic acids are weak acids that can be used in non nucleophlic solvents such as CCl4 to
yield epoxides.
ii) Hydroxylation of alkenes
Two reagents are used:

 Osmium tetroxide (expensive, highly toxic & volatile), followed by hydrogen peroxide or
 Cold, dilute aqueous potassium permanganate, followed by hydrolysis with base
On oxidation with Osmium tetroxide (expensive, highly toxic & volatile), followed by hydrogen
peroxide alkenes give glycols.
Oxidation with dilute Cold KMnO4: On oxidation with cold alkaline KMnO4 (Bayers’s Reagent)
alkenes give glycols.
Since the bright purple colour of KMnO4 disappears during the reaction, Bayers’s reagent is used
as a test for detecting the presence of Olefinic double bond. colour changes from deep purple to
dark brown colour of MnO2.
iii) Oxidative Cleavage

Both the pi and sigma bonds break. C=C becomes C=O.
Two methods:
 Warm concentrated or acidic KMnO4, or acidic KCr2O7 .
 Ozonolysis.
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Products of oxidation depend on the structure of alkenes. Disubstituted carbons become
ketones. Monosubstituted carbons become carboxylic acids (from aldehydes). Terminal
=CH2 - becomes CO2.
Examples
Used to determine the position of a double bond in an unknown alkene.
 Oxidation with Hot KMnO4: Alkene on treatment with hot potassium permanganate
solution split at the double bond to form ketone and /or acids.
 Oxidation with acidic KMnO4 or K2Cr2O7: Alkenes when oxidized with these strong
oxidizing agents they are converted to ketones and /or carboxylic acid e.g.
 Oxidation with ozone: Ozone adds to an alkene molecule to form an ozonide. The reaction
is carried out at low temperature (below 20oC) in non-aquous medium.
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Ozonide on warming with zinc and water hydrolysed to yield smaller carbonyl fragments.
(the by-product of the hydrolysis of ozonide is hydrogen peroxide reason why it is carried
out in the presence of a reducing agent).
The process of preparing the Ozonide and then decomposing it to get the carbonyl
compound is called Ozonolysis.
USE: This is the best method for location the position of the double bonds in unknown alkene with
the help of products formed.
 Combustion: Alkene are completely burnt in air to give carbon dioxide, water and energy.
Example:
iv) Hydroformylation
The hydroformylation is a process by which alkenes react with carbon monoxide and hydrogen in
the presence of rhodium catalyst to give aldehydes.
Example:
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Substitution of Alkenes by Halogens: Alkenes having alkyl group undergo substitution, when
treated Cl2 or Br2 at high temperature. One of the allylic hydrogen is replaced by halogen atom. For
example
Polymerization
Compounds having double bonds can combine repeatedly two or more times to form long chain
molecules. The reaction is called polymerization.
Alkenes undergo addition polymerisation reaction to form long chain polymers.i.e a polymer is a
large molecule containing a repeating unit derived from small unit called monomers. A
polymerisation reaction involves joining together a large number of small molecules to form a large
molecule.
nZ Z-Z-Z--Z-Z-Z-Z-Z-Z-Z-Z-...........Z
monomer
unit polymer chain
For example.
These reactions are catalyzed by HF, H SO or organic peroxide and conditions of high temperature
2 4
and pressure are generally required.
Mechanism for the polymerisation of ethene.
(1) Initiation
It is a free radical initiation.
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(2) Propagation
(3) Termination
where the part between brackets indicates a unit of the formula of the polymer that repeats itself in
the formula; n indicates the number of the units in a formula of a polymer and is a very large
number.
Summary of most alkene polymers obtained from alkenes as monomers and their uses
93 | P a g e
Alkynes
Alkynes are also unsaturated hydrocarbons but they are more unsaturated than alkenes. Alkynes are
characterized by the presence of carbon-carbon triple bond (C≡C) in hydrocarbon molecule. The
triple bond of alkynes consists of a strong sigma (σ) two weak pi(π) bonds. In alkynes triple bonded
carbon atom are sp hybridized. The σ – bond is formed by the overlap of sp- hybrid orbitals and the
π bonds are formed by the separated overlap of the two P-orbitals. Carbon- Carbon distance in
o o
acetylene is 1.20A and C-H bond length is 1.06A . As acetylene molecule is linear, the H-C-C
o
bond angle is 180 .
94 | P a g e
There are two types of alkynes: terminal alkynes and non-terminal (internal)alkynes
A terminal alkyne has a triple bond at the end of the chain.
terminal alkyne has a triple bond in the middle of the chain.
Examples:
Methods of Preparation:
Preparation of ethyne
Ethyne (acetylene) can be prepared from calcium carbide which is obtained by reduction of
calcium oxide by coke at high temperature. Here calcium oxide oxide obtained by heating calcium
carbonate is heated together with coke to a temperature of about 2000 0C in an electric furnace.
3C  CaO   CaC2  CO  112kCal

0
2000 C
The calcium dicarbide is then hydrolyzed

2CaC 2 (s) + 2H O → C2H2(g) + Ca (OH)
2 (l) 2 (aq)
A more quick industrial production consists of heating methane alone at high temperature for 0.01-
0.05second.
General methods of preparation

A) Preparation of alkynes by substitution
(Alkylation of acetylene)
The hydrogen atom of ethyne as that of other terminal alkynes is slightly acidic and therefore it
can be removed by a strong base like NaNH2 or KNH2.The products of the reaction are acetylides.
Acetylides react with halogenoalkanes to yield higher alkynes.
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H  C  C  H  R  C  C  H  R  C  C  R'
Acetylene Terminal alkyne internal alkyne
Other strong base like an organomagnesium ( RMgX) can be used
H  C  C  H   H  C  C  MgX  RH
RMgX
H  C  C  MgX 
RX
H  C  C  R  MgX 2
H  C  C  R   XMg  C  C  R  R' H
R ' MgX
MgX  C  C  R 
 R'C  C  R  MgX 2
R'X
Preparation of Alkynes by Elimination
i) Dehydrogenation of Tetra halides: When Vic –tetra halides are heated with zinc dust in alcohol,
alkynes are produced.
ii) Dehydrohalogneation of Vicinal (or germinal) Dihalides: When these dihalides are heated
with alcoholic KOH or (NaNH2), alkynes are formed.
Properties of Alkynes:
Physical Properties:
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Alkynes are non-polar compounds with physical properties similar to those of alkenes with the
same number of carbon atoms. Their linear structure gives them greater intermolecular forces than
alkenes
i) The First three members are gases, next eight are liquids, and the higher members are solids.
ii) Alkynes are colourless and odourless except acetylene which has garlic colour.
iii) They are only slighty soluble in water but dissolve in organic solvents.
iv) Their boiling points, melting points and specific gravities show a regular increase with the
increase in molecular weights.
Chemical Properties:
Due to the presence of pi-electrones alkynes give the same kind of addition reactions as do alkenes.
Even though they have a higher electron density than alkenes, they are in general less reactive
because the triple bond is shorter and therefore the electron cloud is less accessible.
In addition to electrophyllic additions, alkynes also undergo nucleophillic additions with

electron rich regents.
Other reactions of alkynes result from acidic hydrogen atoms in acetylene and 1-alkynes, which
can be easily removed by means of a strong base and hence acetylenes or 1-alkynes are considered
as weak acids.
Following are some important general chemical reactions of alkynes,
1) Addition of Hydrogen: In presence of catalyst like finely divided Ni, Pt, or Pd, alkynes add two
molecule of hydrogen to give corresponding alkanes.
The reaction can be stopped at alkene stage using Lindlar’s Catalyst (Pd deposited on
CaCO3 or Pd on BaSO4 deactivated by lead acetate (Pb(OAc)2) and quinolone)
2) Addition of Halogen: Halogens add to alkyne to form first dihalide and then tetra halide.
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3) Addition of Halogen Acids: Two molecule of halogen acids can be added to symmetrical
alkynes in two stages. After addition of one molecule alkyne become unsymmetrical derivative of
alkene so that the addition of a second molecule takes place according to Markonikov’s rule .
Thus both the halogens become attached to the same carbon atom. In case of unsymmetrical
alkynes addition takes place in accordance with Markonikov’s rule.
4) Addition of Hypo Halous acids: Addition of two molecules of hypohalous acids to alkynes
takes place according to Markonikov’s rule. Haloaldehyde or Haloketones are the final products.
OH X O X
HOX HOX -H2O
RC CH R C CH X R C CH R C CH
HO OH X X
For example, Acetylene with HOBr give dibromo acetaldehyde
6) Addition of Water( hydration): Alkyne react with water in presence of sulphuric acid
and mercuric sulphate at 60oC to form aldehyde or ketones.
Example:
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7) Hydroboration-oxidation (indirect hydration): Overall result is addition of water to a triple
bond.
 Internal alkynes lead to ketones.

 Terminal alkynes add BH2 to the less substituted, terminal carbon. After oxidation to the
enol, tautomerization yields an aldehyde.
Examples:
8) Addition of Hydrogen Cyanide (this is a nucleophilic addition reaction): Alkynes react with
hydrogen cyanide in presence of barium cyanide to give addition product alkenyl cyanide. For
example, on addition of HCN acetylene gives vinyl cyanide or acrylonitrile.
USE: Acrylonirile is used for the manufacture of synthetic rubber and synthetic fiber,
Orlon.
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Acidity of terminal alkynes
Before we leave these unsaturated functional groups, one unusual feature of terminal
alkynes needs to be understood. A terminal alkyne is acidic, although very weakly so, it can
be deprotonated by treatment with a strong base to yield a carbanion (a negatively
charged organic ion).
The strong base that is often used is sodium amide in liquid ammonia. It is the amide anion
that affects the deprotonation:
Example:
We should note that anhydrous conditions are essential otherwise, the anion itself will
immediately react with any water present:
The alkyne is regenerated and hydroxide ion is formed; in other words, water is a stronger
(much stronger) acid than a terminal alkyne.
Why can we form an alkynide ion apparently so readily?
The carbon is sp hybridised and as such has a greater percentage of s character than the
sp2 or sp3 hybridised carbon. The electrons in the sp hybrids are therefore closer to the
positively-charged nucleus, resulting in a carbon that can better tolerate a negative charge
(i.e make a stable anion).
Conjugate Base Hybridization "s Character" pKa
CH3CH2- sp3 25% 50
CH2CH- sp2 33% 44
HCC- sp 50% 25
A base to deprotonate a terminal alkyne it must be stronger base than alkynide, that is why
other strong bases such as organo metallic compound and metal hydride can also be used
to produce salt of terminal alkynes.
Examples:
R  C  C  H  R' MgX (  R  C  C  MgX  R' H

C2 H 5 ) 2 O
R  C  C  H  NaH  R  C  C  Na  H 2 
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Nucleophilic Substitution Reactions of Alkynides
Alkynide anions are strong bases and strong nucleophiles. Therefore, they are able to displace halides and
other leaving groups in substitution reactions. The product is a substituted alkyne.
Because the ion is a very strong base, the substitution reaction is most efficient with methyl or primary
halides without substitution near the reaction center,
Secondary, tertiary or even bulky primary substrates will give elimination by the E2 mechanism.
Nucleophilic Addition of Alkynides to Carbonyl compounds
Alkynide anions will add to aldehydes and ketones to form alkoxides, which, upon protonation, give
alcohols.
SALT FORMATION
As hydrogen in 1-alkyne and acetylene are acidic, they can form salts with metals by replacement
of acidic hydrogen. These salts are known as Acetylides or alkynides in general.
1. Reaction with metals
Terminal alkynes react with active metals to yield alkynides and hydrogen gas. Internal alkynes do not
react as they do not have an acidic hydrogen atom.
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2. Reaction with metal salts
When a terminal alkyne is passed through a solution of ammoniacal silver nitrate, a white
precipitate of silver alkynide is formed.
Examples:
H  C  C  H  2 AgNO3 
NH3
 Ag  C  C  Ag  2 NH 4 NO3
When a terminal alkyne is passed through a solution of ammoniacal copper(I) chloride, a red
precipitate of copper(I) alkynide is formed.
H  C  C  H  2CuCl 
NH3
 Cu  C  C  Cu  2NH 4Cl
The reactions above are used to:
 Differentiate between terminal and non-terminal alkynes.

 Differentiate terminal alkyne and alkene
Oxidation of Alkynes
Alkynes, similar to alkenes, can be oxidized gently or strongly depending on the reaction
environment.
 Alkynes form vicinal dicarbonyls in neutral permanganate solution.

 During strong oxidation with ozone or basic potassium permanganate, the alkyne is cleaved
into two products.
Because at least one of the reaction products is a carboxylic acid, it is important to consider the
acid-base chemistry of the product in the reaction solution. Carboxylic acids are deprotonated in
basic solutions to carboxylates. A second reaction step is required to protonate the carboxylate
to the neutral form of the carboxylic acid.
The generic reactions are summarized below for the different oxidative conditions gentle or
strong.
Gentle Alkyne Oxidation
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Strong Alkyne Oxidation - Oxidative Cleavage
o Alkynes undergo oxidative cleavage of the σ and both π bonds.

o Internal alkynes are oxidized to carboxylic acids (RCO2H).
o Terminal alkynes afford a carboxylic acid and CO2 from the sp hybridized C—H bond.
USE: These reaction are useful in determination of structure of alkynes.
The combustion of alkynes produces carbon dioxide and water with given off a greater amount of
energy in terms of heat. Particular to acetylene, the flame of acetylene in UV-spectrometer can have
temperature raising between 20000C and 30000C.
3n  1
CnH2n-2 + O2  nCO2  (n  1) H 2O  heat
2
Polymerization
Alkynes, when passed through a red hot iron tube, undergo cyclic polymerization to form aromatic
hydrocarbons. For example, three molecules of acetylene combine to give benzene under these
conditions.
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Under similar condition three molecules of propylene polymerizes to give mesitylene.
11) Isomerisation: Alkynes when treated with traces of alkali like alc.KOH and NaNH2 undergo
isomerisation, for example 1-alkynes on treatment with alkali isomerises to 2-alkyne.
On the other hand 2-alkyne with NaNH2 in inert solvent gives 1-alkyne.
Uses of alkenes and alkynes
 Alkenes are extremely important in the manufacture of plastics which have many
applications such as: packaging, wrapping, clothing, making clothes, artificial flowers,
pipes, cups, windows, ...
 Ethene is a plant hormone involved in the ripening of fruits, seed germination, bud
opening;
 Ethene derivatives are also used in the making of polymers such as polyvinylchloride
(PVC), Teflon,...
 Alkenes are used as raw materials in industry for the manufacture of alcohols, aldehydes,
...
 Alkynes are used in the preparation of many other compounds. For example ethyne is
used in the making of ethanal, ethanoic acid, vinyl chloride, trichloroethane, ...
 Ethyne (acetylene) is used as a fuel in welding and cutting metals.
 Propyne is used as substitute for acetylene as fuel for welding.
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UNIT 4: HALOGENOALKANES (ALKYL HALIDES)
Key unit competency
The learner should be able to relate the physical and chemical properties of halogenoalkanes to
their reactivity and their uses
Learning objectives
 Define halogenoalkanes and homologous series.
 Explain the reactivity of halogenoalkanes.
 Explain the physical properties of halogenoalkanes.
 Describe preparation methods for halogenoalkanes.
 Explain different mechanisms in halogenoalkanes.
 Explain the uses and dangers associated with halogenoalkanes.
 Draw displayed structural formulae of halogenoalkanes and give names using IUPAC
system.
 Classify halogenoalkanes according to developed formula as primary, secondary and

tertiary.
 Write reaction mechanisms of halogenoalkanes as SN1, SN2, E1 and E2.
 Test for the presence of halogenoalkanes in a given sample organic compound.
 Appreciate the uses and dangers of halogenoalkanes in everyday life.
 Develop the awareness in protecting the environment.
 Develop team work approach and confidence in group activities and presentation sessions.
DEFINITION AND CLASSIFICATION
Alkyl halides or halogenoalkane or haloalkane are the compounds derived from the saturated
hydrocarbons by replacement of one of the hydrogen atom by halogen atom.
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Halogen atom(s) in haloalkanes is attached to the sp3hybridised carbon atom of an alkyl group.
Thus they can be represented by general formula R-X where R= alkyl group; X= Cl, Br, I or F.
o o
Halogen atom may be attached to a methyl, 1 , 2o or 3 Carbon atom of alkyl group. Thus alkyl
o o o
halide can be classified as primary (1 ), secondary(2 ) or tertiary (3 ) depending upon whether the
halogen is attached to primary, secondary of tertiary carbon atom.
Examples:
Preparation methods of halogenoalkanes
1) By direct Halogenation of Alkanes: Alkanes when treated with chlorine or bromine in the
o
presence of U.V light or at high temperature (400 C) gives alkyl chloride or alkyl bromide along
with poly halogen derivatives. For example,
2) By addition of Hydrogen Halide to Alkene: When alkenes are treated with hydrogen halides,
addition of hydrogen halide takes place in accordance with Markonikov’s rule except the addition
of HBr in presence of organic peroxide [R-O-O-R].
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3) By treatment of Alcohol with Halogen Acid: Alcohols react with HBr or HI to give alkyl
bromide or alkyl iodide. They react with HCl in presence of zinc chloride catalyst.
1. Conversion of alcohol to alkyl bromide by reaction with HBr (or KBr, H2SO4)
The reactions that took place are the following.

KBr + H2SO4 →HBr + KHSO4
2. Conversion of alcohol to alkyl chloride by reaction with Lucas reagent (HCl, ZnCl2)
4) By treatment of Alcohol with Phosphorous Halides: Alcohols react with phosphorous halides (PX5
or PX3) to give alkyl halides.
PBr3 or PI3 are produced in situ by the reaction of bromine or iodine with red phosphorus
5) By treatment of Alcohol with Thionyl Chloride: Alcohols when treated with thionyl chloride
in the presence of pyridine give alkyl chloride. Pyridine acts as scavenger for HCl formed.
(Note: For the synthesis of alkyl chloride, thionyl chloride generally gives better yields than PCl3 or PCl5.)
Preparation of alkyl dihalide

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I. From aldehydes or ketones
Cl
O
PCl5 + O=PCl3
R C R'
R R'
Cl
II. From alkynes:

R  C  C  R'2HX  R  CH 2  CX 2  R'
III. From alkenes:
CH3CH=CHCH3 + Br2 → CH3CHBrCHBrCH3
Preparation of alkyl tetrahalide from alkynes
CH3CCH + 2Cl2 →CH3CCl2CHCl2
Physical properties of halogenoalkanes
 Methyl chloride, Methyl bromide, Methyl fluoride and Ethyl chloride are gases at room
temperature. Other alkyl halides up to C18 are colorless liquids with a sweet pleasant smell
and beyond C18 are solids.
 Although alkyl halides are polar in nature, they are insoluble in water but soluble in organic
solvents. Insolubility in water is due to the inability to form hydrogen bonding with water
and to break already existing hydrogen bonding in water molecule.
 Their densities decrease in the following order; Iodide> bromide>Chloride > fluoride.
Iodo, bromo and polychloro derivatives are denser than water but chloro derivatives are
less dense than water.
 For a given alkyl group boiling points of alkyl halides follow the following order.
Alkyl iodide> Alkyl bromide> Alkyl Chloride> Alkyl fluoride.
For a given halogen atom, the boiling points of alkyl halides increase with the increase in
the size of the alkyl group.
This is because with the increase in size and mass of halogen atom the magnitude of Van
der Waal forces increase.
Comparison of the boiling point(°C) of a few examples reveals the expected trend of
increasing boiling point with increasing molecular weight.
CH3Cl: -24° CH3Cl: -24° C2H5Cl: 13° CH3CH2CH2Cl: 46°
CH2Cl2: 40° CH3Br: 5° C2H5Br: 38° CH3CH2CH2Br: 71°
CHCl3: 61° CH3I: 42° C2H5I: 72° CH3CH2CH2I: 102°
CCl4: 77°
For isomers, as we observed with the alkanes, chain branching results in a lower boiling
point,
e.g.:
CH3CH2CH2CH2Cl: 77° CH3CH2CHClCH3: 69°
108 | P a g e
(CH3)2CHCH2Cl: 69° (CH3)3CCl: 51°
 Alkyl halides have higher bp and mp than alkanes having the same number of carbons.
Chemical properties of halogenoalkanes
In alkyl halides (C-X) bond is highly polar because of the high electronegativity of the halogen
atom. Thus alkyl halides are very reactive compounds alkyl halides can be used to prepare
nearly all types of organic compounds and thus synthetically they are very important. They
undergo substitution, elimination, and reduction reactions.
Substitution Reaction
The (C-X) bond is strongly polarized covalent bond due to the high electronegativity of
halogen atom.
Thus carbon atom of C-X bond is therefore a good site for the attack of nucleophiles (electron
rich species) and the nucleophilic substitution reactions are most common reactions of the
alkyl halides.
The common nucleophile are –OH, -CN, -SH, NO2-, -NH2 and OR-.
Nucleophilic substitution in alkyl halides takes place in two pathways.
1) SN1 Mechanism( unimolecular nucleophilic substitution ):
SN1 is characterized by:
 First order kinetics; the expression of the rate is given by R=k[Substrate],
 Racemization
 Rearrangement may occur
 Reactivity sequence: CH3 halide < 1° alkyl halide < 2° alkyl halide < 3° alkyl halide
 In this mechanism substitution takes place in two steps.
109 | P a g e
Let us consider the hydrolysis of bromide by aqueous NaOH.
Step-I: This involves the ionization of alkyl halide to give a planar carbonim ion in which
central positively charged carbonium ion is SP2 hybridised.
Step-II: This involves the attack of nucleophile on carbonium ion from either side to give the
substitution product.
Remember that if alkyl halide is optically active then we will get the recemic mixture of two
enatiomers
Primary alkyl halides do not proceed in this way because of the unstable nature of the
intermediate (the primary carbonium ion)
Example of SN1 reaction: hydrolysis of tertiary alkyl halides with sodium hydroxide
The hydrolysis can also take place when water alone is added to tertiary alkyl halides. In this
case water molecules act as nucleophiles.
The potential energy (P.E ) against reaction co-ordinate for hydrolysis of tertiary alkyl halides
is as below (Potential energy is the energy stored in chemical bonds of a substance, or the
energy of an object due to its position).
The diagram below shows that the products formed have lower energy than the reactants, this
indicates a favorable situation for the reaction to occur spontaneously.
110 | P a g e
Carbocation
intermediate
Potential Transition state 1
Energy [ R3C …... X ] Transition state 2
[ R3C …... OH ]
Ea2
+ -
Ea1 R3C + X
Reactants
-
R3CX + OH ΔHrx
Products
-
R3COH + X
Progress of the reaction
The potential energy of the system initially increases because the energy is required to break
C-X bond; but when the stable carbocation is formed, energy is released and the potential
energy decreases a bit. As the carbocation and the nucleophile (OH-) require a minimum
energy (activation energy) to collide efficiently, the P.E rises again until the transition state is
reached, where the carbon-oxygen is being formed. When this bond is completely formed,
energy is released and the potential energy decreases.
2) SN2 Mechanism [Bimolecular nucleophilic substitution]
SN2 is characterized by:
 Second order kinetics; the expression of the rate is given by R=k[Substrate][Nu -]
 complete stereochemical inversion (All S N2 reactions proceed with backside attack of

the nucleophile, resulting in inversion of configuration at the stereogenic center).
 Absence of rearrangement
 Reactivity sequence: CH3 halide > 1°alkyl halide > 2° alkyl halide > 3° alkyl halide
 In this mechanism substitution takes place in one step.
1o alkyl halide halides undergo substitution by SN2 mechanism. This is one step process in which
the attack of the nucleophile and the ejection of the halide ion takes place simultaneously. 1 o alkyl
halide undergoes substitution by SN2 mechanism via formation of transition state as shown below:
111 | P a g e
Example: Let us consider the hydrolysis of methylbromide by aqueous NaOH.
Bulkier the alkyl group, more is the steric hindrance in the formation of transition state that is why
30 alkyl halide do not proceed in this way.
The potential energy (P.E ) against reaction co-ordinate for hydrolysis of primary alkyl halides is
as below.
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The P.E of the system initially increases along AB curve because energy is required to break
C-I bond; but when C-O is formed, energy is released and this is shown by the curve BC. Since
energy released by the formation of C-O bond is greater than the energy required to break C-
I, the products end up with a lower energy compared to the reactant and this is favourable for
the reaction to occur. At B a maximum P.E is reached when C-I bond is partially broken and
C-O bond is partially formed. This state is called the transition state or activated complex.
The energy barrier, Ea, which must be overcome in order that the transition state is reached,
is called the activation energy of the reaction. The P.E of the system then falls along BC
releasing energy due to the formation of C-O bond.
Secondary alkyl halides however react by either SN1 or SN2mechanism depending on the
solvent.
Use of the SN Reaction in Organic Synthesis
The conversion of one compound into another through a chemical reaction is called synthesis.
The SN reaction is often used to convert alkyl halides into other functional groups
113 | P a g e
Some important substitution reactions of alkyl halides are given below:
i) Reaction with aqueous KOH: When alkyl halides are refluxed with aq.KOH, halogen is
substituted by –OH group to give alcohols.
For example:
ii) Reaction with moist Silver Oxide: Alkyl halides on treatment with moist silver oxide also
gives alcohols.
Example:
114 | P a g e
iii) Reaction with sodium Alkoxide: Alkyl halides on treatment with sodium alkoxide give
ethers. This reaction is known as Williamson ether Synthesis.
Example:
iv) Reaction with Dry Silver Oxide: Alkyl halides on heating with dry silver oxide give
ethers.
E.g. 2CH3I +Ag2O → CH3-O-CH3
v) Reaction with Sodium or Potassium Cyanide: Alkyl halides are refluxed with sodium or
potassium cyanide to give alkyl.
Example:
Alkyl cyanides are very important synthetic intermediates. They can be easily converted to
carboxylic acids and primary amines.
Alkyl halides when react with AgCN, isocyanides are formed.
vi) Reaction with AgNO2: Alkyl halides are refluxed with silver nitrite form nitro alkane.
Some Alkyl nitrites are also formed.
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Example:
vii) Reaction with R-COOAg: When alkyl halide are refluxed with alcoholic solution of
silver salt of carboxylic acid an ester is formed.
Example:
viii) Reaction with Alkynides: Alkyl halides react with sodium alkynides to give higher
alkyne.
ix) Reaction with Ammonia: Heating of alkyl halides with alcoholic solution of ammonia in
a sealed tube results a mixture of different classes of amines.
Example:
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Elimination reactions
An elimination reaction is reaction in which a saturated organic compound loses an atom or

group of atoms to form an unsaturated organic compound.
Elimination reactions most commonly occur when a hydrogen atom on one carbon atom and
a leaving group on an adjacent carbon are removed forming a double bond.
Alkyl halides when boiled with alcoholic potassium hydroxide form alkenes by elimination
reaction. Hence the alkyl halide loses a molecule of the hydrogen halide.
Example:
In alcohol, there is an equilibrium between the solvent and KOH
Note: Elimination reaction usually occurs in competition with substitution reaction, the nature
of the product formed depends on the solvent, temperature, and structure of the halide.
Elimination is favoured by use of high temperature and a strong base e.g alcohol instead of
water.
So when chloroethane is treated with a solution of potassium hydroxide two organic products
are formed depending on the conditions of the reaction.
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Sodium ethoxide is a strong base. It favours elimination more than substitution. The rate of
elimination to substitution product depends on the structure of the alkyl halide and experiment
condition.
For example, in case of 1o alkyl halide substitution product is also formed (Ether is formed by
SN2 mechanism in which CH3CH2O- is acting as nucleophile. while Ethene is formed by
elimination reaction in which CH3CH2O- is acting as base) but in case of 2o and 3o alkyl halide
elimination product predominates.
Elimination reactions, like nucleophilic substitution reactions, can be either unimolecular

(E1) or bimolecular (E2) processes.
The E1 process competes with the SN1 reaction through a common carbocation intermediate.
The E1 process is favored with alkyl halides that form stable carbocations (resonance
stabilized carbocations or tertiary halides).
The E2 process involves both the alkyl halide and a base in the rate determining step and is
favored when strong bases are present.
E2 is characterized by:
 Second order kinetics, the expression of the rate is given by R=k[Substrate][base]
 Anti periplanar conformation for elimination
 Absence of rearrangement
 Reactivity sequence: CH3 halide< 1° alkyl halide< 2° alkyl halide < 3° alkyl halide
Mechanism for the E2 Reaction
The mechanism proposed for the E2 reaction is based on the observed second order rate expression,
as well as the stereochemical outcome observed in alkyl halides with multiple stereocenters. The
E2 like the SN2 is a single step mechanism.
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Example: mechanism of the reaction between alcoholic KOH and 2-Bromo-2-methylbutane to
give 2-Methylbut-2-ene.
E1 is characterized by:
 First order kinetics, the expression of the rate is given by R=k[Substrate]
 Rearrangement may occur.
 Reactivity sequence: CH3 halide < 1° alkyl halide < 2° alkyl halide < 3° alkyl halide
Mechanism for E1 Reactions
The E1 like the SN1 is a two steps mechanism.
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1o ,2oand 3o alkyl halides undergo dehydrohalogenation by E 2 mechanism with strong bases
and 3o alkyl halides do so by E1 mechanism with weak bases.
Saytzeff’s Rule: In case of unsymmetrical alkyl halide dehydro halogenation yield more than
one alkene. One of them, the most highly substituted alkene, is the major product. In such cases
elimination of HX is governed by Saytzeff’s rule. According to which the main product is the
most highly substituted alkene. Or in other words Hydrogen is eliminated from the Carbon
atom of alkyl halide which bears the least number of hydrogen atoms.
For example, when 2-bromobutane undergo elimination with alc. KOH, two alkenes are
possible and major one is more substituted alkene. (In accordance with Saytzeff’s rule).
Reduction: Alkyl halides are reduced to alkanes by different reducing agents like LiAlH4,
Zn/HCl and H2/Ni or Pd etc.(see preparation of alkanes)
Wurtz Reaction: When alkyl halides react with metallic sodium in dry ether two molecules
join together to give alkane with double number of carbon atoms.
Reaction with Mg and Li: Alkyl halides react with Magnesium in dry ether to give alkyl
magnesium halide, the Grignard reagent.
But with Lithium in dry ether alkyl halides give alkyl Lithium.
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Grignard reagent is an important group of organometallic complex which has the great
synthetic utility in organic chemistry. Alkyl Lithium behaves in the same way as Grignard
reagent but with increase reactivity.
Reaction of polyhalides
These are compounds in which more than one halogen atom is present. There are two main
types of dihalides.
Gem dihalides: This is where two halogen atoms are attached to the same carbon atom.
Example: CH3CCl2CH3
Vicinal dihalides: Here the two halogen atoms are on adjacent carbon atoms
Example: CH3-CH2-CHCl-CH2Cl
The reactions of dihalogenoalkanes are similar to those of monohalogenoalkanes but require

more reagents.
Examples:
Elimination reaction with excess hot alkali produces alkynes
Testing for halogenoalkanes
Silver nitrate solution can be used to find out which halogen is present in a suspected
halogenoalkane. The most effective way is to do a substitution reaction which turns the halogen
into a halide ion, and then to test for that ion with silver nitrate solution.
The halogenoalkane is warmed with some sodium hydroxide solution in a mixture of ethanol and
water. Everything will dissolve in this mixture and so you can get a good reaction. The halogen
atom is displaced as a halide ion:
The mixture is acidified by adding dilute nitric acid. This prevents unreacted hydroxide ions
reacting with the silver ions. Then silver nitrate solution is added. Various precipitates may be
formed from the reaction between the silver and halide ions:
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Table 1:
ion present observation
Cl- white precipitate
Br- very pale cream precipitate
I- very pale yellow precipitate
Confirming the precipitates
It is actually quite difficult to distinguish between these colors, especially if there isn't much
precipitate. You can sort out which precipitate you have by adding ammonia solution.
Table 2:
original precipitate observation
AgCl precipitate dissolves to give a colorless solution
precipitate is almost unchanged using dilute ammonia solution,

AgBr but dissolves in concentrated ammonia solution to give a
colorless solution
precipitate is insoluble in ammonia solution of any

AgI
concentration
Comparing halogenoalkane reactivities
(i) Reactivity of Alkyl Halides Towards Sodium Iodide: Test for SN2
In this part of the experiment, you will test the reactivity of several alkyl halides in an SN2 reaction.
Iodide ion (I-) is an effective nucleophile in SN2 displacements. In acetone solution, other alkyl
halides (alkyl chlorides or bromides) can be converted to alkyl iodides easily by this method.
Although one might expect such a reaction to be reversible, it can be driven to formation of R-I by
using anhydrous acetone as the solvent. Sodium iodide (NaI) is soluble in this solvent, but sodium
chloride and sodium bromide are not. If a reaction occurs, a precipitate of sodium chloride or
sodium bromide forms and thus the ion is not available in solution for the reverse reaction.
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The displacement mechanism involves a one-step, concerted, SN2 reaction. Therefore, the reaction
occurs most quickly when attack at the carbon that bears the halogen (X) is least hindered
sterically.
For alkyl halides, the order of reactivity is primary > secondary > tertiary.
(ii) Silver Nitrate Test: Test for SN1
Theory
In the presence of ethanolic silver nitrate, alkyl halides that can form “stable” carbocations react,
through an SN1 mechanism to provide a substitution product, in this case, an ether derived from
the alkyl halide and the ethanol nucleophile. The silver of the silver nitrate reagent acts as a Lewis
acid to promote formation of the carbocation. An insoluble silver halide is formed as a by-product,
along with the carbocation. The observed precipitate (the silver halide) indicates a carbocation has
formed. Once the carbocation is generated, it reacts with the oxygen atom of ethanol, to first
generate an oxonium ion, which rapidly is converted to the ether product.
The Silver Nitrate Test allows for the identification of alkyl halides by observing them in an
alcoholic silver nitrate environment. The rate at which the silver halide salt precipitate forms is
characteristic of different types of alkyl halides. You will test the reactivity of several alkyl halides
in a SN1 reaction.
In this case, the reaction mechanism is SN1, the slow step being the breaking of the carbon-halogen
bond. The carbocation then reacts rapidly with alcohol to form the ether.
Organic halide reactivity parallels the stability of the corresponding carbocations. For saturated
alkyl groups, this order is tertiary > secondary> primary.
Tertiary, allylic, and benzylic alcohols react very quickly, while secondary alkyl halides react
fairly quickly. Primary as well as aryl, alkenyl (vinyl), and alkynyl halides do not react at all.
In addition, alkyl iodides react faster than alkyl bromides which in turn react faster than chlorides,
which sometimes require heating.
Uses of halogenoalkanes and dangers associated with CFCs
Halogenoalkanes have many uses in our everyday life such as in agriculture, at home, industry as
solvents, plastics, medicine and in pharmacy and other.
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Solvents:
 CH2Cl2 Dichloromethane (or methylene chloride) is an important solvent, once used to

decaffeinate coffee. CH2Cl2 is olso used in varnish and paints manufacturing.
 CCl4 is used as the most organic solvent for fats and oils and can be used as fire extinguisher
 CH3CCl3: is used in cleaning of most ink.
 CHCl=CCl2: is used in dry cleaning and in caffeine extraction
 Polyvinyl chloride (PVC): PVC is the most widely used of the amorphous plastics.
Other industrial uses
 PVC is lightweight, durable, and waterproof. it is used to make pipes, insulating material on
electrical wires, bottles that have applications in a wide range of industries, it is also used
for a number of domestic purposes. It can be used in the production of raincoats, rubber
boots, shower curtains or other goods ...
 Generally alkyl fluorides are very inert (this is very useful in the case of teflon, the polymer
of tetrafluoroethene (–CF2–CF2–)n, whose chemical inertness makes it useful not only for
lining frying pans but also in the construction of apparatus used in corrosive chemical
reactions.
Medicine:
 CHCl3 (chloroform): is used in anesthesia
 The general anesthetic halothane, CF3CHClBr is used instead of toxic agents like
chloroform or flammable compounds like ether.
 CF2CF2 again form polymers that are used in orthopedic and prosthetic appliances, hearing aids,
corrosion resistant and mechanical parts, upholstery, electric insulation.
Agriculture:
DDT: Dichloro diphenyl trichloroethane is used as insecticide- DDT. Colorless chemical pesticide,
dichlorodiphenyltrichloroethane, used to eradicate disease-carrying and crop-eating insects. It was
first isolated in Germany in 1874, but not until 1939 did the Swiss Nobel Prize-winning chemist
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Paul Müller recognize it as a potent nerve poison on insects. The product is banned in Rwanda.
Below is the structure of DDT.
Cl CH Cl
CCl3
Home: Refrigeration, perfumes, etc…
Halogenoalkanes which have boiling temperatures just below room temperature can easily be
liquefied by a slight increase in pressure. Halogenoalkanes containing chlorine and fluorine and
no hydrogen are Chlorofluorohydrocarbons. Examples are CFCl3, CCl2F2 and C2Cl2F4. They
are usually called chlorofluorocarbons or CFCs. In addition to having low boiling temperatures,
they are non-flammable, odourless, stable, non-toxic and solvents.
CFCs appeared to be ideal for use as fluids in refrigerators and as solvents in aerosol sprays,
they were developed in the 1920s as what appeared to be ideal replacements for liquid ammonia
and liquid sulphur dioxide, which were formerly used as fluids in refrigerators and air-conditioning
units. Being good solvents, they were also ideal as the solvents in aerosol sprays. Aerosols were
used to dispense insecticides, hairsprays, perfumes and deodorants, window-cleaning, polishes,
waxes and laundry products. As more and more uses were found for these remarkable compounds,
CFCs became big business, with hundreds of thousands of tones being produced yearly. Now they
are being phased out. These stable, non-toxic compounds are dangerous!
Their high stability has turned out to be a problem, during all the time that the use of CFCs
was increasing, no-one thought about what would happen to the gases in the atmosphere. Because
of their lack of reactivity and insolubility in water, there is no natural process for removing CFCs.
In fact they drift up into the stratosphere where ultraviolet light causes photolysis, i.e. a reaction
cause by light. The chlorine radicals formed in photolysis take part in a chain reaction which
converts ozone into oxygen.
Cl. + O3 → ClO. + O2
ClO. + O→ Cl. + O2
ClO. + O3→ ClO2 + O2
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As you can notice, the chain of reaction above results in the decomposition of ozone ,which does
have the capacity to absorb, and stop dangerous UV from reaching the Earth into ordinary oxygen.
This can be avoided if and only if human activities send no CFCs in the atmosphere.
This reduce the thickness of the ozone layer. Reactions (a) to (c) form a chain. This is why one
chlorine radical from one CFC molecule can destroy thousands of ozone molecules.
And what can be done?
Replacements for CFCs have been found, because of concern over the decrease in the ozone
layer, many nations have agreed to cut down the use of CFCs. Alternative compounds are already
in production. Hydrohalocarbons contain at least one hydrogen atom per molecule. The C-H bond
can be attacked by HO• radicals in the lower atmosphere and the compounds do not reach the
upper atmosphere. Hydrohalocarbons include Hydrochlorofluorocarbons, HCFCs, e.g.
CHCl2CF3, used in blowing plastics foam and CHClF2, used in air-conditioners
Hydrofluorocarbons, HFCs, e.g. CH2FCF3, used in air-conditioners and refrigerators. HCFs cause
no damage to the ozone layer, although they are greenhouse gases.
UNIT 5: ALCOHOLS AND ETHERS
Key unit competency:
To be able to compare the physical and chemical properties of alcohols and ethers to their
preparation methods, reactivity and uses.
Learning objectives:
 Distinguish between alcohols from other organic compounds by representing the functional
group of alcohols
 Classify primary, secondary and tertiary alcohols by carrying out the method of
identification
 Write the name of alcohols by using IUPAC system
 Describe the physical properties of alcohols to other series of organic compounds
 Carry out the method of preparation of alcohols

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 Describe the local process of making alcohol by fermentation.
 Explain the effect of oxidation on urwagwa when it overstays
 Compare the physical, chemical and the method of preparation of alcohols to ethers
 State the use of ethers
1. ALCOHOLS
Alcohols are the hydroxy derivatives of saturated hydrocarbon in which hydroxy(-OH) group is
attached to saturated carbon atom.
All the chemical properties of alcohols are due to the presence of –OH group thus hydroxyl group
is the functional group of alcohols.
Alcohols can be represented by the general of C H OH or ROH where R is an alkyl group.
n 2n+1
Alcohols can be classified as mono, di, tri and polyhydric alcohols depending on the number of
hydroxyl groups (1, 2, 3 or more) present in a molecule. For example
Monohydric alcohols [R-OH] are further subdivided into 1o, 2o and 3o alcohols depending upon
the nature of carbon atom to which –OH group is attached.
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General Methods of preparation of alcohol
1) By the Hydrolysis of alkyl halides: Alkyl halides when refluxed with aqueous alkali (NaOH
or KOH) or moist silver oxide (AgOH) produce alcohols. The hydrolysis occurs by a nucleophilic
substitution reaction.
2) By hydration of olefins: Alkenes react with Sulphuric acid (98%) to give first addition product,
alkyl hydrogen sulphates which on hydrolysis give alcohols.
In case of unsymmetrical alkenes for addition, Markonikov’s rule is followed.
Except ethyl alcohols primary alcohols cannot be prepared by this method. Overall reaction is the
Markonikov’s addition of water to a double bond.
Alkenes in the presence of aluminium oxide reacts with water to form alcohols in vapor phase then
condense to give liquid alcohols.
OH
CH3
H2O
CH3 C CH2 CH3 C CH3
Al2 O3
CH3
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3)Hydroboration-Oxidation of Alkenes: When alkenes are treated with diborane, trialkyl
boranes are formed. In this reaction diborane adds as borane (BH3). The positive part of BH3 is
boron and negative part is hydrogen. e.g.
Trialkyl borane on treatment with alkaline aqueous solution of hydrogen peroxide gives
1oalcohols.
The overall reaction of hydroboration-oxidation results anti- Markonikov’s addition of water to

double bond. e.g.
4) Hydrolysis of Esters: The hydrolysis of esters can be catalyzed by either an acid or a base, with
somewhat different results.
Esters on hydrolysis in the presence of mineral acid produce alcohols and carboxylic acids. Acidic
hydrolysis is simply the reverse of esterification. The ester is heated with a large excess of water
containing an acid catalyst. Like esterification, the reaction is reversible and does not go to
completion.
As a specific example, butyl acetate and water react to form acetic acid and 1-butanol.
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When a base (such as sodium hydroxide [NaOH] or potassium hydroxide [KOH]) is used to
hydrolyze an ester, the products are a carboxylate salt and an alcohol.
Alkaline hydrolysis of esters is called saponification; In a saponification reaction, the base is a

reactant, not simply a catalyst. The reaction goes to completion:
As a specific example, ethyl acetate and NaOH react to form sodium acetate and ethanol:
5)By catalytic Reduction of Carbonyl Compounds: Aldehydes on reduction give 1o alcohols

and ketones give 2o alcohols. 3o Alcohols can’t be prepared by this method.
i) Reduction by using alcoholic sodium [Bouveoult-Blanc reduction]:
ii) Reduction by using LiAlH4 or NaBH4 : Sodium borohydride, NaBH4, is usually chosen
because of its safety and ease of handling
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iii)Reduction with H2:
When aldehydes and ketones are reduced by hydrogen in the presence of a suitable catalyst like
Pt, Ni or Pd, they form primary and secondary alcohols respectively.
Lithiun aluminum hydride, LiAlH4, is more reactive reducing agent than NaBH4.
LiAlH4 does not reduce C=C but reduce all compound containing carbonyl groups, including acids,
esters, ketones, and aldehydes. Sodium borohydride, NaBH4 is more selective and does not reduce
carbonyl groups of acids and derivatives; it also may be used in aqueous and alcoholic solution,
whereas LiAIH4 may not.
Lithium tetrahydridoaluminate is more selective than catalytic hydrogenation which can reduce
both the double bond and the carbonyl group.
6)By catalytic Reduction of carboxylic acid, Acid chlorides, acid anhydride, and esters:
Acids, esters, anhydrides and acyl chlorides are all reduced to 1º-alcohols, by lithium aluminum
hydride(LiAlH4).
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7) From Grignard Reagent:
i)Reaction of organometallic compounds with carbonyl compounds
Grignard Reagent (RMgX) first react with carbonyl compound to give the addition product which
on acid-hydrolysis gives corresponding alcohol.
Grignard reagent with formaldehyde, aldehydes other than formaldehyde and ketones leads to the
formation of 1o, 2o and 3o alcohols respectively. For example,
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ii) Reaction of Grignard reagents with cyclic ethers
1)
O
R MgX R OH
2)H2O
primary alcohol
with increament
of 2 carbon to R
R,
1) R,
O
R MgX R OH
2)H2O
Secondary alcohol
with increament
of 2 carbon to R
R,,
R,
R,,,
1) R,
O
R MgX R OH
2)H2O
Tertiary alcohol
with increament
of 2 carbon to R
iii) Reaction of Grignard reagents with esters, acid halides, and anhydrides
Reaction of an excess of Grignard reagents with acyl chlorides, anhydrides and esters leads to
alcohol products, this occurs by sequential addition-elimination-addition reactions, and finishes
with hydrolysis of the resulting alkoxide salt.
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The organometallic reagent is a source of a nucleophilic alkyl or aryl group which bonds to the
electrophilic carbon of the carbonyl group Substituent Y (Cl or OR or RCOO) . The aldehyde or
ketone product of this elimination then adds a second equivalent of the reagent.
Example:
8) By the reaction of aliphatic primary amine with nitrous acid: Primary aliphatic amines
react with nitrous acid to give alcohols.
Nitrous acid is prepared in situ by the reaction between sodium nitrite and hydrochloric acid
therefore the reaction can be represented as below:
Synthesis of methyl alcohol (methanol)
The industrial synthesis of methyl alcohol involves hydrogenation of carbon monoxide. Although
this reaction has the favorable ∆H° value of —28.4 kcal mole-1, it requires high pressures and high
temperatures and a suitable catalyst; excellent conversions are achieved using zinc oxide-chromic
oxide as a catalyst:
Preparation of ethanol
By fermentation of carbohydrates
This method is mainly used to prepare ethanol industrially. Ethanol is prepared from starch (e.g:
maize, cassava, millet, sorghum) and sugar (molasses) by fermentation process.
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Fermentation can be defined as a sequence of chemical changes in organic substances produced
by the action of enzymes produced by microorganism.
Alcoholic fermentation being the process in which enzymes act on carbohydrates to give simpler
compounds like ethanol (alcohol) and CO2.
(a) From starch:
malt obtained either from maize grain, millet, or cassava contains an enzyme called diastase which
catalyses the hydrolysis of starch to maltose
At room temperature, yeast is added and one of its enzymes called maltase catalyses the hydrolysis
of maltose to simple sugar so called glucose.
C12H22O11 maltase
+ H2O 2 C6H12O6
maltose Glucose
Finally, another enzyme of yeast called zymase catalyses the decomposition of glucose to ethanol.
Zymase
C6H12O6 2 CH3CH2OH + 2CO2
(b) From sugar
Molasses containing sugars is mixed with water and yeast and then allowed to ferment for several
days after which ethanol are obtained during fermentation process.
One enzyme of the yeast called sucrase catalyses the hydrolyses of sucrose present in the molasses
to glucose and fructose.
Sucrase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose glucose fructose
Thus, another enzyme of yeast called zymase catalyses the decomposition of glucose to ethanol.
Zymase
C6H12O6 2 CH3CH2OH + 2CO2
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The ethanol obtained by fermentation process is only about 11%. This is made concentrated by
distillation which converts it to about 95% ethanol.
This on further distillation yields a constant boiling mixture whose composition does not change
(an azeotropic mixture). Therefore, 100% ethanol is obtained by either: Adding quick lime which
removes water or distilling with of benzene as a third component.
Physical properties
 Lower alcohols are colorless, toxic liquids while higher having more than 12 carbons are
solids. They have characteristic sweet alcoholic odor and burning taste.
 Lower alcohols are easily soluble in water but solubility decreases with increase in
molecular weight. Solubility of lower alcohols in water is due to the Hydrogen bonding
between highly polarized –OH groups present both in water and alcohols.
Hydrogen bonding between alcohol and water molecules.
But Higher alcohols have less tendency to form hydrogen bonds with water molecule
because of the presence of non-polar long hydrocarbon chain and hence the solubility in
water decreases.
 Boiling points of alcohol increase with the increase in number of carbon atoms but their
boiling points are much higher than those of the corresponding alkanes. This is again
because of intermolecular hydrogen bonding. Highly polar –OH groups of different alcohol
molecule and partially negative oxygen in another alcohol molecule.
Hydrogen bonding between alcohol molecules.
 Among isomeric alcohols boiling and melting points decreases with branching.
 Primary> Secondary>Tertiary.
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 Alcohols are less volatiles than alkyl halides and hydrocarbon with comparable mass
and some can have the considerable viscosity as their OH group increase such case of
glycerin, this is due to the presence of many OH groups in glycerin which increase
intermolecular forces that enhance the cohesion and hence the viscosity increase.
Chemical Properties
Alcohols are chemically reactive compounds this is due to the presence of reactive functional
group, -OH group, which is polar in nature. Because of the high electronegativity of oxygen atom
both C-O and O-H bonds in alcohols are polar bonds.
Alcohols undergo following reactions.
1) Reactions involving only the hydrogen atom of the –OH group:
These reactions involve cleavage of oxygen and hydrogen bond.
i) Reaction with alkali metals: Alcohols react with sodium or potassium to form alkoxides with
the liberation of hydrogen gas.
This reaction shows the acidic nature of alcohols. Primary alcohols are more acidic than secondary,
which in turn is more acidic than tertiary thus order of acidic nature is as follows.
1oalcohols>2oalohols>3oalcohols
This is because of the +I effect of the alkyl groups attached. It would be maximum in tertiary
alcohols.
2)Reaction with carboxylic Acids: Alcohols react with organic acids in the presence of mineral
acids such as sulphuric acid (catalyst) with elimination of water under 100 °C to produce an ester
with given off a perfume smell. This reaction is called “esterification”. The reaction is reversible.
Example:
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The mechanism
Step 1
In the first step, the ethanoic acid takes a proton (a hydrogen ion) from the concentrated
sulphuric acid. The proton becomes attached to one of the lone pairs on the oxygen which is
double-bonded to the carbon.
The transfer of the proton to the oxygen gives it a positive charge. The positive charge is
delocalised.
The various structures are known as resonance structures or canonical forms.
Step 2
The positive charge on the carbon atom is attacked by one of the lone pairs on the oxygen of
the ethanol molecule.
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Step 3
A proton (a hydrogen ion) gets transferred from the bottom oxygen atom to one of the others.
Step 4
Now a molecule of water is lost from the ion.
The structure for the latest ion is just like the one we discussed in step 1. The positive charge
is actually delocalised and there will also be contributions from structures where the charge
is on the either of the oxygens:
Step 5
The hydrogen is removed from the oxygen by reaction with the hydrogensulphate ion which
was formed way back in the first step.
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3) Reaction with Acid halides and Acid anhydrides: Alcohols can more easily esterified
by the action of acid Chloride or acid anhydride.
4) Reaction with Grignard Reagent: Alcohols react with Grignard reagent to give alkanes.
(B) Reaction involving –OH group: These reactions involve cleavage of Carbon-oxygen bond
[-C-/-OH]
5) Reaction with phosphorous Halides: When alcohols react with phosphorous penta
halide[PX5] or phosphorous tri halide [PX3], replacement of –OH group by halogen atom take
place and alkyl halides are formed.
PBr3 and PI3 are usually prepared in situ (see alkyl halide preparation).
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6) Reaction with thionyl chloride: This involves replacement of –OH group by chlorine atom.
7) Reaction with halogen acids: Alcohols react with halogen acid to give corresponding alkyl
halides.
The reactivity of halogen acids are in the order,
HI >HBr >HCl
No catalyst is required in case of HI and HBr but HCl reacts only in presence of anhydrous ZnCl 2
catalyst.
Mechanism: Primary alcohols follow SN2 mechanism for the substitution of –OH group by
halogen atom.
Step 1: Protonation of Alcohol
Step 2: Attach of nucleophile [X-]
2o and 3o alcohols follow SN1 mechanism.
Note:
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This reaction is called LUCAS test and is used to distinguish between simple primary, secondary
or tertiary alcohols. In this reaction, the alcohol is shaken with a solution of zinc chloride in
concentrated hydrochloric acid.
Observations: Immediate cloudiness indicates presence of a tertiary alcohol. If the solution

becomes cloudy within 5 minutes, then the alcohol is a secondary one. Primary alcohol would
show no cloudiness at room temperature since the reaction is very slow.
For example, all alcohols which are isomers of C4H10O can be distinguished by the LUCAS test.
8) Reaction with sulphuric acid: The action of concentrated sulphuric acid is of great interest as
it gives different products under different conditions.
i) At room temperature, ethyl alcohol reacts with concentrated sulphuric acid to give ethyl
hydrogen sulphate.
ii) When alcohols are heated with concentrated H2SO4, phosphoric acid or other dehydrating agent
dehydration takes place to give alkenes. For example
Mechanism: Mechanism involve formation of carbocation.
Step 1: Protonation of alcohol.
Step 2: Elimination of water molecule to give carbocation.
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Step 3: Removal of proton from carbocation:
The ease of dehydration of alcohols follow the following order 3 o>2o>1o. This is also the order of
stability of carbocation. this reaction is the intramolecular dehydration of water.
This imply that the temperature and concentration of acid required to dehydrate an alcohol depend
on the structure of the alcohol substrate:
Primary alcohols are the most difficult to dehydrate and generally require heating in concentrated
sulphuric acid at a high temperature. Secondary alcohols acid catalyzed dehydration requires
lower temperature and tertiary alcohol acid catalyzed dehydration requires temperatures slightly
above room temperature. Examples:
Primary alcohol
Secondary alcohol
Tertiary alcohol
With secondary and tertiary alcohols, dehydration may occur in two ways, e.g.:
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According to Saytzeff’s rule more substituted alkene is the major product.
Some primary and secondary alcohols also undergo rearrangements of their carbon skeletons
during dehydration.
iii) When excess of primary alcohol is heated with concentrated sulphuric acid at 140oC, an ether
is formed. This reaction is an intermolecular dehydration. Example:
Mechanism: Mechanism involves the following steps.
Step 1: Protonation of one Molecule.
Step 2: Attack of another alcohol molecule on the electrodeficient carbon and elimination of water
molecule:
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Step 3: Removal of proton from Oxonium ion leads to the formation of ether.
Alcohols can also be dehydrated by passing the vapours of alcohol over heated aluminia to give
ethers or alkenes e.g.
9) Oxidation: Nature of oxidation products of alcohols depend upon the nature of alcohols,
oxidizing agent used and reaction conditions. Most commonly used oxidizing agents are:
– Potassium permanganate (KMnO4). Deep purple in color, such a solution is a strong oxidant. In
the course of reaction, the purple Mn(VII) is reduced to Mn(IV), which precipitates as brown
manganese dioxide (MnO2). When used in acidic medium it is reduced to Mn(II) with a pale pink
color (practically colorless)
– Chromic acid (H2CrO4). A strong oxidant usually used with alcohols, chromic acid can be
produced in solution by two methods:
 From sodium (or potassium) dichromate (Na2Cr2O7) and aqueous sulfuric acid, or
 By dissolving chromic anhydride (CrO3) in concentrated sulfuric acid and water (this
version is called Jones'reagent). During an oxidation reaction, the orange-colored Cr(VI)
in this reagent forms greenish-blue Cr(III), which remains in solution.
Primary alcohols are easily oxidized to aldehydes and then to carboxylic acids both with the same
number of carbon atoms as the parent alcohol. E.g.:
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Secondary alcohols oxidized to ketone with same number of carbon atoms, but these ketones can’t
be easily oxidized, these undergo oxidation under very drastic conditions to give mixture of
carboxylic acid with lesser number of carbon atoms than parent alcohol. Eg:
Tertiary alcohols are resistant to oxidation.
These reaction allows us to distinguish primary, secondary alcohols with tertiary alcohols because
a primary and secondary alcohol turn colorless the solution of KMnO4 from violet; while the
acidified potassium dichromate is turned from orange to green. This is the general principle of
breath analyzer the degree of the color change is related to the level of alcohol expelled from the
suspect’s breath.
Alcohol can also be oxidized by passing a mixture of alcohol vapour and air over a silver catalyst
at 500°C. Primary alcohol produce aldehyde and secondary alcohol produce ketone. Example:
Another industrial process for the oxidation of alcohol is by passing alcohol vapor alone over a
heated copper catalyst at 3000C.
Iodoform test
Secondary alcohols having the following structure R-CHOH-CH3 only undergo oxidation, on
treatment with iodine solution in the presence of sodium hydroxide to give yellow precipitate of
tri-iodomethane.
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Note: This is a reaction which is characteristic of methyl ketones, CH 3-CO-R’; but iodine here
acting as an oxidizing agent first oxidizes the CH3-CHOH-R’toCH3-CO-R’; then the methyl
ketone formed then gives the yellow precipitate of CHI3 (Iodoform). From the reaction involved
we have the Iodoform test.
Example: Ethanol when reacted with (I2 and NaOH) or NaOI gives yellow ppt of iodoform since
it has the presence of CH3-CH (OH)- group.
Uses of alcohols
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In medicine: In more modern times, ethyl alcohol can be used for its antiseptic properties, and it's
often found in antibacterial wipes and hand sanitizers. It is effective at killing most bacteria, fungi,
and many viruses on the hands and skin, and it is a useful alternative to hand soaps. Medical
professionals often use gel sanitizers before treating patients to prevent the spread of harmful
bacteria.
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Ethyl alcohol can also be used as an antidote to help reverse or lessen the effects of certain
chemicals, primarily other alcohols like methanol. Once ethanol is added to the system, it competes
with the other alcohols to be broken down by the body, and slows down the metabolism of other
chemicals in the bloodstream where they typically become toxic.
Side effects of ethanol include irritation to the eyes and skin. When ingested, it can cause stomach
irritation resulting in nausea and vomiting. Since it is an intoxicating agent, those who consume
alcohol may experience dizziness, feelings of euphoria or an alcohol induced “high,” and loss of
consciousness if ingested in large enough amounts. Long-term consumption may cause serious
liver damage and depression, as well as leading to alcohol dependency.
Methanol is much toxic than ethanol. Drinking methanol leads to blindness and then to death.
2. ETHERS
Ethers are the organic compounds in which an oxygen atom is connected to two alkyl (or aryl
groups). The general formula for ether is R−O−R'. The functional group is [C-O-C].
From their general structure formula, we can classify them into 3 classes:
If same alkyl groups are attached to central oxygen atom ethers are classified as simple or
symmetrical ethers (R-O-R). Examples:
CH 3  O  CH 3
CH 3CH 2  O  CH 2CH 3
While ethers containing different alkyl groups attached with central oxygen atom are classified
as mixed or unsymmetrical ethers (R-O-R’). Examples:
CH 3  O  CH 2  CH 3
CH 3  CH 2  O  CH 2  CH 2  CH 3
The fact that functional group is –O-, we can have cyclic ethers e.g: epoxide:
O
Methods of preparation:
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i) Dehydration of alcohols: By heating excess of alcohol with concentrated sulphuric acid at
140oC
ii) By passing alcohol vapors over Al2O3 at 250oC:
2) By heating alkyl halides with silver oxide: Ethers are obtained by heating alkyl halides with
dry silver oxide.
This method is useful for the preparation of simple ethers only.
3) Williamson Ether Synthesis: This is the most important industrial and laboratory method of
preparation of ethers. It involves the treatment of sodium alkoxide with an alkyl halide. Both
symmetrical unsymmetrical ethers can be prepared by this method.
Tertiary and Secondary alkyl halides undergo elimination reaction with sodium alkoxide (strong
base). For example
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Thus to introduce a tertiary group it will be better to take this group as a base, not as a tertiary
halide. For example
for preparing (CH3)3C-O-C2H5 , we should start with (CH3)3C-ONa and C2H5Br.
Mechanism: It follows SN2 mechanism. Displacement of halide ion by alkoxide ion.
5)Action of Diazomethane on Alcohols: Ethers can be prepared by treatment of primary or

secondary alcohols with diazomethane in presence of fluoroboric acid as a catalyst.
But this method is only useful for the preparation of methyl ethers.
6) Reaction of lower halogenated ether with Grignard reagent
Higher members can be prepared by the action of grignard reagent on lower halogenated ethers.
Physical properties
 Ethers are highly volatile and flammable substances.

 Except dimethyl ether and ethyl methyl ether, which are gases all are pleasant smelling
colorless liquids.
 Their boiling points gradually increase with the increase in molecular weight because of
increasing magnitude of Van der Waal’s forces with size. But ethers have lower boiling
points than isomeric alcohols because they are incapable of forming intermolecular
hydrogen bonds due to the absence of –OH groups.
 Ethers are sparingly soluble in water since their oxygen atom is not capable of forming H-
bond with hydrogen with hydrogen atom of water molecule but are soluble in organic
solvents.
Chemical Properties:
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Ethers are much less reactive compounds because they are quite stable. They do not react with
active metals, strong bases like NaOH, reducing and oxidizing agents.
1) Halogenations: The alkyl group undergoes substitution reaction with chlorine or bromine. The
resultant product is halogenated ether in absence of sunlight. However, in presence of sunlight, it
substitutes all the hydrogen atoms of ethers.
For example:
The extent of substitution depends on reaction conditions.
2) Basic Nature: Ethers behave as Lewis bases because of the presence of two lone pairs of
electrons on the oxygen atom. Therefore, they form salts with strong acids.
For example, they react with cold concentrated sulphuric acid or HCl to give oxonium salt. The
oxonium salts are soluble in acid solution. We can facilitate the regeneration of ether by hydrolysis
of these salts.
This property is used to separate ethers from alkanes. Since alkanes do not react with acids.
Ethers also form coordination complexes with Lewis acids like BF3, AICI3, RMgX etc. Therefore,
we can derive the fact that ethers are very good solvents for Grignard reagents.
R"
R
R
O Mg O
R' R'
X
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3) Hydrolysis: Ethers on heating with dilute sulphuric acid under pressure, they hydrolyse to give
alcohols.
But if concentrated sulfuric acid is used, then the products are alcohol and alkyl hydrogen sulphate.
Ethers containing secondary and tertiary alkyl groups form alkenes with conc. sulphuric acid.
For example
Mechanism:
4) Reaction with Phosphorus Penta-chloride: With PCl5 ether cleave to give alkyl chlorides
5) Reaction with HI and HBr: Ethers react with hot concentrated HI or HBr to give an alcohol
and alkyl halide.
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In case of mixed ethers the halogen atom attacks to the smaller alkyl groups, due to the sterric
effect. e.g.
The order of reactivity of halogen acid is
HI>HBr>HCl
This is because Strong conditions are usually necessary for ether cleavage. Strong acid and good
nucleophile. Concentrated HCl is far less effective in cleaving ethers, because Cl - is a weaker
nucleophile in water than either I- or Br-.
With the excess of acid, the alcohol initially produced is also converted to alkyl halide. e.g.
6) Combustion of ethers gives carbon dioxide and water:

3(n+m)
CnH2n+1-O-Cm H2m+1 + O2 (n+m) CO2 + (n+m+1) H2O
2
Example: C2H5O C2H5 + 6O2 → 4CO2 + 5H2O
7) Formation of peroxides (Auto oxidation): On standing in contact with air ethers combine with
oxygen to form peroxide (less volatile than the parent ether) which is highly explosive.
These peroxides decompose violently at high temperature. Thus ethers should be purified before
distillation. When ethers that contains peroxide is distilled, at the end of distillation residual
peroxide may explode. Because of this ether should never be evaporated to dryness. This type of
contamination can be purified by treatment with a reducing agent such as alkaline ferrous
sulphate.
Besides this, we must also check the purity of ether before its use as an anaesthetic agent. An
impure ether (having peroxide linkage) gives red colour when shaken with ferrous ammonium
154 | P a g e
sulphate and potassium thiocyanate. This could prove to be lethal for the patients on whom we try
anaesthesia.
On mixing with KI solution, it liberates I2 which turns starch paper blue.
We can make these ethers free from peroxide linkages by distilling them with highly concentrated
sulphuric acid, H2SO4.
Epoxide
Epoxides are the cyclic ethers in which ethereal oxygen is linked with two adjacent carbons to
form three membered ring. Means epoxy compound contain oxiran ring. The C—O—C bond angle
for an epoxide is 600, a considerable deviation from the tetrahedral bond angle of 109.5 0. Thus,
epoxides have angle strain, making them more reactive than other ethers.
Epoxy ethane or ethylene oxide (oxiran) is the most important member of this group.
Method of preparation
Epoxides may, in general, be prepared by epoxidation of alkenes with peroxy acids.
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Ethylene oxide may be obtained:
i) By Reaction of Chlorohydrin with base:
Possibly the mechanism is:
ii) By oxidation of ethylene with oxygen in the presence of silver catalyst.
Properties
Ethylene oxide is toxic, flammable gas having b.p 10.7 oC. Generally, epoxides are reactive
compound, this is because to release their strain they have the tendency to open their ring. These
oxygen atoms combine with the reactive hydrogen atom of various compounds to form hydroxyl
group.
Reaction with HOH: hydrolysis of epoxide can be catalyzed by an acid or by a base.
Reaction with alcohols
Reaction with Ammonia
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Reaction with hydrogen halide, e,g HBr
Reaction with LiAlH4
Unsymmetrical epoxides give the more highly substituted alcohol with main product.
Reaction with HCN:
Reaction with Grignard Reagent:
Ethylene oxide reacts with Grignard Reagent to give addition product which on hydrolysis yield
primary alcohol.
Uses of ethers
We commonly use ethers as:
 General anaesthetic agent.
 As a refrigerant. This is because it produces cooling on evaporation.

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 A solvent for oils, fats, resins, Grignard reagent etc.
 For providing inert & moisture free medium for reactions e.g. Wurtz reaction.
UNIT 6: CARBONYL COMPOUNDS: ALDEHYDES AND KETONES
Key unit competency
To be able to compare the chemical nature of carbonyl compounds to their reactivity and uses.
Learning objectives
 Describe the reactivity of carbonyl compounds
 State the physical properties of aldehydes and ketones
 Describe the preparation reactions of ketones and aldehydes
 Explain the mechanism of nucleophilic addition reactions of carbonyl compounds
 Prepare ketones from secondary alcohols by oxidation reactions
 Compare aldehydes and ketones by using Fehling’s solution and Tollens’ reagent
 Write and name carbonyl compounds and isomers of ketones and aldehydes
 Write equations for the reactions of carbonyl compounds with other substances
 Compare the physical properties of carbonyl compounds to those of alcohols and alkenes
 Differentiate the methyl ketones from other ketones by using the iodoform test
 Carry out an experiment to distinguish between carbonyl compounds and other organic
compounds
 Carry out an experiment to distinguish between ketones and aldehydes
 Carry out an experiment to prepare ethanal and propan-2-one.
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Aldehydes and Ketones
Introduction and definitions
Aldehydes and Ketones compounds belong to a class of reactive organic compounds resulting
O
from a simple replacement of methylene (-CH2-) group by carbonyl group( ) so called

carbonyl compounds.
The carbonyl group ( ) is found in aldehydes, ketones, and many other organic functional
groups.
The carbon and oxygen in the carbonyl group are sp2-hybridized, with bond angles of 120°.
In aldehydes carbonyl carbon on one side attached to hydrogen atom and to carbon atom (or an
hydrogen atom in formaldehyde) on other side, thus functional group of aldehydes is –CHO. This
group occurs at the end of a chain.
In ketones carbonyl carbon, on both sides attach to carbon atoms, thus the functional group in
ketones occurs within a chain.
R and Rʹ can be alkyl or aryl groups for ketones, even they can be the same or different, but for
aldehydes R can be an hydrogen atom(formaldehyde) or an alkyl (or aryl groups).
Methods of Preparation
Both Aldehydes and ketones may be prepared by the following methods.
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1) From alcohols
Primary and secondary alcohols in liquid phase can be oxidized by use of acidified K2Cr2O7 to
Aldehydes and ketones respectively.
Note: one major disadvantage of this method for preparing Aldehydes is that the Aldehydes
produced are further oxidized to carboxylic acids.
In order to prevent this further oxidation of aldehyde to carboxylic the following technique are
used:
 Use an excess of the alcohol than potassium dichromate (VI). Potassium dichromate (VI)
is limiting reactant hence there isn’t enough oxidising agent present to carry out the second stage
of oxidizing the aldehyde formed to a carboxylic acid.
 Carry out the reaction under heat (at a temperature in between the bp of aldehyde and that
of the corresponding alcohol) so that Aldehydes which have lower boiling points than
corresponding alcohol are removed from the reaction mixture as soon as they are formed.
Therefore, the alcohol must be added to the hot oxidizing agent. distil off the aldehyde as soon as
it forms. Removing the aldehyde as soon as it is formed this means that aldehyde is removed from
solution where oxidizing agent is, to prevent further oxidation.
The solution of dichromate (VI) ions, Cr 2O72-, is orange, during chemical reaction dichromate
(VI) ions is reduced to chromium (III) ions, Cr3+ which is green.
To simplify the writing of the reaction, [O] represents oxygen from an oxidising agent. Then the
reaction is written as follows:
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In vapor phase both the primary and secondary alcohols can be dehydrogenated by passing their
vapour over heated copper at 3000C to give Aldehydes and ketones respectively.
CH 3CHOH Cu
/ 300
  CH 3  C  CH 3  H 2
0
C
CH 3CH 2OH Cu
/ 300
  CH 3  C  H  H 2
0
C
| || ||
CH3 O O
Also by passing the vapors of alcohols together with air over heated silver catalyst, Aldehydes or
ketones are produced.
2) From alkenes
Oxidative cleavage of alkenes using ozone forms an ozonide. Ozonides are not isolated, but are
treated with a mild reducing agent like Zn or dimethyl sulfide (CH3)2S to produce aldehydes and
ketones.
In case of a mixture of Ketone and Aldehydes are produced, here can be separated by fractional
distillation even though it is not easy to achieve it except retaking again several times.
3) From alkynes
When alkynes are passed through hot dilute sulphuric acid in the presence of mercuric sulfate,
carbonyl compounds are produced.
2
CH 3  CH 2  C  CH  H 2 O H   CH 3  CH 2  CH (OH )  CH 2
2 SO4 / Hg

Tautomerism
 CH3  CH 2  CO  CH3
Note: Terminal alkynes yield methyl ketone, and only acetylene give an aldehyde (acetaldehyde)
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Aldehydes and ketones can also be prepared using hydroboration of alkynes.
4) Hydrolysis of gem-Dihalides: Aldehydes are prepared by the hydrolysis of gem dihalides

containing both halogen atom on terminal carbon atom.
Ketones are prepared by the hydolysis of gem-dihalides containing both halogen atoms on non
terminal carbon atom.
For example:
5) From carboxylic acid
In the vapor phase, the contact of an acid with MnO at 300oC produce ketones but when one of the
acids is formic acid aldehydes are formed.
 If only one acid is used symmetric ketone is obtained but
 If a mixture of two acids is used a mixture of three ketones is obtained.
 If a diacid is used a cyclic ketone is formed.
Schemes of these reactions are:
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MnO,3000C
R-CO-OH + HO-CO-R R-CO-R + CO2 + H2O
MnO,3000C
R-CO-OH + HO-CO-H R-CO-H + CO2 + H2O
COOH MnO,3000C
O + CO2 + H2O
COOH
6) Dry distillation of calcium salts of Acids
Aldehydes are prepared by pyrolysis of calcium salt of carboxylic acid with calcium methanoate.
( HCOO) 2 Ca  ( RCOO) 2 Ca heat


 2CaCO3  2 RCHO
( HCOO) 2 Ca  (CH 3CH 2COO) 2 Ca heat


 2CaCO3  2CH 3CH 2CHO
While calcium formate alone on heating gives formaldehyde.
( HCOO) 2 Ca heat

 CaCO3  H 2 CO
Ketones are obtained by heating calcium salt of carboxylic acid other than calcium formate.
(CH 3CH 2COO)2 Ca  

heat
 CaCO3  CH 3CH 2  CO  CH 2CH 3
The scheme for these reactions can be represented as follow:
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7) Reduction of Acid Chlorides: [Rosenmund Reduction]: Aldehydes can be prepared by the
reduction of acid chloride in the presence of palladium supported over barium sulphate.
Aldehydes can also be easily reduced to primary alcohol but the catalyst is poisoned by the Sulphur
or quinoline and thus aldehydes are the final product.
Ketones cannot be prepared by this method.
8) Reaction of Acid Chlorides and an organocadmium
This reaction produce a ketone.

O
O
R' Cd R' +
2 2 + CdCl2
R Cl R R'
9) From acid anhydrides
Passing the vapor of acid anhydride on hot manganese dioxide MnO2 (that acts as a catalyst of
decarboxylation) produce a ketone with the evolution of Carbone dioxide. This process is specific
to ketones only.
O O
O MnO2
+ CO2
Heat R R'
R O R'
Ketone
Acid Anhydride
10) From Grignard Reagent: Aldehydes can be prepared from Grignard Reagent (RMgX) in three
ways.
i) From hydrogen cyanide:
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ii) From alkyl formates
example:
iii) From ethyl orthoformiate and Grignard reagent
Only aldehydes can be obtained from ethyl orthoformiate once treated with Grignard reagent.
H OCH2CH3 H OCH2CH3
R MgX H2O/H+
C OCH2CH3 C OCH2CH3
2 CH3CH2OH + R-CHO
OCH2CH3 R
Ketones can also be prepared from Grignard reagent in two ways,
i) From alkyl cyanide:
ii) From acid Chlorides:
Aldehyde or ketones so formed, may further react with excess of the Grignard reagents to give
alcohols.
11) Oxo process: This method is industrially important for the preparation of aldehydes. It
involves the treatment of an alkene with carbon monoxide and hydrogen in the presence of cobalt
carbonyl catalyst at high temperature and pressure.
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Ketones cannot be prepared by this method.
12) Wacker process: This method involves the treatment of alkene with acidified aqueous
solution of palladium chloride, PdCl2 and cupric chloride, CuCl2.
Physical Properties of Aldehydes and Ketones
 Formaldehyde is gas at room temperature and other aldehydes and ketones are colourless
liquids.
 Lower aldehydes and ketones are soluble in water due to capability of forming hydrogen
bonds with water molecules. But higher members containing more than five carbon atoms
are insoluble in water and soluble in organic solvent.
 Since aldehydes and ketones are polar compounds.
Their boiling points are higher

than corresponding non polar compounds (such as hydrocarbons). But these molecules
are not capable of forming intermolecular hydrogen bonds. Their boiling points are lower
than corresponding alcohols.
 Density of aldehydes and ketones are lesser than that of water.
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Chemical properties
Both aldehydes and ketones contain carbonyl group, therefore they undergo same reactions like
nucleophilic addition reactions, condensation, oxidation, reduction, halogenation etc.
A. Nucleophilic Addition Reactions
Both aldehydes and ketones contain highly polar carbonyl group.
Carbonyl carbon is electron deficient and carbonyl oxygen is electron rich. The electron deficient
carbon is readily attacked by electron rich nucleophiles and electron rich oxygen is attacked by
electron deficient electrophiles. The typical reaction of aldehydes and ketones is nucleophilic
addition. They undergo nucleophilic addition reaction by following general reaction.
These addition reactions occur by two different mechanisms:
– Base-catalyzed addition (under basic or neutral conditions)
– Acid-catalyzed addition (under acidic conditions)
a. Base Catalysed Addition:
Step 1: Attack of nucleophile at carbonyl carbon to form new σ-bond.
Step 2: Attack of electrophile ( e.g., -H+) at negatively charged oxygen to give addition product.
b. Acid Catalysed Addition:
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Step 1: Protonation of carbonyl group.
Step 2: Attack of nucleophile on protonated carbonyl carbon to give addition product.
Addition products remains same in both acid and base catalysed reaction.
Aldehydes are more susceptible to nucleophilic attack than ketones as described below:
1. Inductive effect: Alkyl groups are electron donating in nature (i.e., show +I-Effect).
Hence, the presence of alkyl groups attached to the carbonyl group increases the electron
density on the carbonyl carbon. this reduce the positive charge on carbonyl carbon thereby
decreases its reactivity towards nucleophilic addition reactions. Therefore, the order of
reactivity is:
2. Steric hindrance: The more the number and the bigger the size of the alkyl group, the
more difficult for a nucleophile to attack due to steric hindrance (crowding). Hence, the
order of reactivity is:
Some important examples of nucleophilic addition and nucleophilic addition-elimination

reactions:
(1) Addition of Grignard reagent: Aldehydes and Ketones react with Grignard reagent to give
the addition product which can be hydrolysed with dilute acid to yield alcohol. Only formaldehyde
gives 10 alcohols, other aldehydes give 20 alcohol and ketones give 3 o alcohols.
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Formation of alcohols via addition of Grignard reagents to aldehydes and ketones is carried out in
two steps:
Step 1: Addition of the nucleophilic alkyl group to the carbonyl carbon, the product of this step is
a halomagnesium alkoxide.
Step 2: Protonation of the alkoxide oxygen. The product of this step is an alcohol.
For example
(2) Addition of salts of terminal alkynes
The anion of a terminal alkyne is a nucleophile and adds to the carbonyl group of an aldehyde or
ketone to give an addition product.
Examples:
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(3) Addition of hydrogen cyanide
Hydrogen cyanide adds across the carbon-oxygen double bond in aldehydes and ketones to
produce compounds known as hydroxynitriles or cyanohydrins.
For example, with ethanal (an aldehyde) you get 2-hydroxypropanenitrile:
With propanone (a ketone) you get 2-hydroxy-2-methylpropanenitrile:
The reaction isn't normally done using hydrogen cyanide itself, because this is an extremely
poisonous gas. Instead, the aldehyde or ketone is mixed with a solution of sodium or potassium
cyanide in water to which a little sulphuric acid has been added.
The solution will contain hydrogen cyanide (from the reaction between the sodium or potassium
cyanide and the sulphuric acid), but still contains some free cyanide ions to act as nucleophile.
This is important for the mechanism.
H2SO4 +KCN→KHSO4+HCN
The pH of the solution is maintained in range 4 - 5, because this gives the fastest reaction. The
reaction takes place at room temperature.
The mechanism for the addition of HCN to propanone
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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 from somewhere - for example, from a
hydrogen cyanide molecule.
The hydrogen ion could also come from the water or the H3O+ (often written as H+(aq)) present in
the slightly acidic solution.
The product of the reaction above has two functional groups:
The -OH group which behaves like ordinary alcohol and can be replaced by other substituent like
chlorine, which can in turn be replaced to give other functional group, for example, an -NH2 group;
The -CN group which can be hydrolysed into a carboxylic acid functional group -COOH.
(4) Reaction of NaHSO3 with aldehydes or ketones
Aldehydes and ketones when treated with saturated aqueous solution of sodium bisulphite, a white
solid addition compound is formed. This Hydrogen sulphite with negative charge act as
nucleophile, where the product formed is separated as white crystals. For example, Propanone
react with hydrogen sulphite, as below:
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These bisulphites can be decomposed with dilute acids or bases to regenerate the carbonyl
compound, therefore this process of formation and decomposition of bisulphite is used for the
purification and separation of carbonyl compounds from mixtures.
(5) Addition of water
Addition of water to an aldehyde or ketone gives a product called a hydrate or a gem-diol (two -
OH groups on the same carbon).
The reaction is both acid-catalyzed and base-catalyzed.
Addition under Acidic Conditions
Addition under Basic Conditions
NOTE: this reaction is reversible. The equilibrium favors the product only with an unhindered
aldehyde like formaldehyde, and less stable carbonyl compound like aldehydes containing nearby
electron withdrawing groups
(6) Addition of alcohols
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Formation of Hemiacetals (or hemiketal) and Acetals (or ketal)
When an alcohol adds reversibly to an aldehyde (or ketone), the product is called a hemiacetal (or
hemiketal), these one are unstable and can’t be isolated in most cases.
Hemiacetals (or hemiketal) undergo further reversible reactions under acidic conditions. It reacts
further with alcohols to form acetals (or ketals)
Aldehydes react with alcohols first to form hemiacetals, which then react with excess alcohol to
produce acetals.
• Ketones react with alcohols first to form hemiketals, which then react with excess alcohol to
produce ketals.
Note: Hemiacetals are formed in both acid- and base-catalyzed reactions. But Hemiacetals undergo
further reversible reactions under acidic conditions only.
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Mechanism of acetal formation
Hydrolysis of Acetals and Ketals
Under acidic conditions, water can be used to reverse the previous reaction, and regenerate the
original aldehyde or ketone from the acetal or ketal.
This is an example of a hydrolysis reaction, in which water causes a compound to be split into its
component substances.
Reactions Involving addition followed by removal of water (condensation reactions)
(7) Reaction with Ammonia Derivatives

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Nucleophiles, such as ammonia and its derivatives (H2N-Y) add to the carbonyl group of aldehydes
and ketones. The reaction is reversible and catalysed by acid. The equilibrium favours the product
formation due to rapid dehydration of the intermediate to form >C=N-Y.
Y = Alkyl, aryl, OH, NH2, C6H5NH, NHCONH2, etc.
These reactions are very important and characteristic reactions of carbonyl compounds. The
products of these condensation reactions are brightly colored (yellow or orange) crystalline
solids with sharp melting points which is used for identifying them.
General mechanism of the reaction involves following steps.
Step 1: Attack of nucleophile on carbonyl carbon to give unstable addition product.
Step 2: Removal of water to give the final product.
All the ammonia derivatives follow the same mechanism. The ammonia derivatives are amine,
hydrazine, phenyl hydrazine, 2,4-dinitrophenyl hydrazine, hydroxylamine, and semicarbazide.
a) Reaction with 1o amine: Aldehydes and ketones react with primary amines in the presence of
an acid to form imines, or Schiff bases
b) Reaction with Hydrazine: Aldehydes and ketones form hydrazones with hydrazine (NH2NH2)
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c) Reaction with phenyl hydrazine: Aldehydes and ketones form phenyl hydrazone with phenyl
hydrazine.
d) Reaction with 2,4-Dinitro phenyl hydrazine (2,4-DNP or 2,4-DNPH or Brady's Reagent)
Aldehydes and ketones react with 2,4-dinitrophenyl hydrazine to form 2,4-dinitrophenyl

hydrazone.
This reaction is used to test carbonyl group i.e. aldehydes and ketones, with a positive test if a
yellow or orange precipitate is formed.
e) Reaction with Hydroxylamine: Aldehydes and ketones form oxime with

hydroxylamine(NH2OH).
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f) Reaction with Semicarbazide: Aldehydes and ketones give Semicarbazone with semicarbazide
B. Reduction
(i) Reduction to alcohols: Aldehydes and ketones are reduced to primary and secondary alcohols
respectively by catalytic hydrogenation (H2/ Ni or Pt), nascent hydrogen (Na-Hg or Na/C2H2OH),
as well as by sodium borohydride (NaBH4) or lithium aluminium hydride (LiAlH4 ) (see unit 5)
(ii) Reduction to hydrocarbons: The carbonyl group of aldehydes and ketones is reduced to CH2-
group on treatment with zinc amalgam and concentrated hydrochloric acid [Clemmensen
reduction] or with hydrazine followed by heating with sodium or potassium hydroxide in high
boiling solvent such as ethylene glycol (Wolff-Kishner reduction).
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C. Oxidation
Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxidised to
carboxylic acids on treatment with common oxidising agents like nitric acid, by acidic potassium
permanganate, acidic potassium dichromate, etc. Even mild oxidising agents, mainly Tollens’
reagent, Fehling’s solution and Benedicts solution and thus act as a strong reducing agents.
Example:
Ketones are generally oxidised under vigorous conditions, i.e., strong oxidising agents such as
acidic dichromate, KMnO4 and con. HNO3 and at elevated temperatures. Their oxidation involves
carbon-carbon bond cleavage to afford a mixture of carboxylic acids having lesser number of
carbon atoms than the parent ketone.
Ketones are not oxidized by milder oxidizing agents thus they do not reduce Tollen’s reagent,
Fehling solution and Benedicts solution.
The mild oxidising agents given below are used to distinguish aldehydes from ketones:
(i) Tollens’ test
On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution (Tollens’
reagent), a bright silver mirror is produced due to the formation of silver metal. The aldehydes are
oxidised to corresponding carboxylate anion. The reaction occurs in alkaline medium.
(ii) Fehling’s test
Fehling reagent comprises of two solutions, Fehling solution A and Fehling solution B. Fehling
solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium potassium tartrate
(Rochelle salt). These two solutions are mixed in equal amounts before test. On heating an
aldehyde with Fehling’s reagent, a reddish brown precipitate is obtained. Aldehydes are oxidised
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to corresponding carboxylate anion. Benedict solution (alkaline solution of cupric ion complexed
with citrate ions) reacts in the same way as Fehling Solution.
(iii) Oxidation of methyl ketones by haloform reaction
Acetaldehyde and methyl ketones (ketones having at least one methyl group linked to the carbonyl
carbon atom) react rapidly with halogen (Cl 2,Br2 or I2) in the presence of alkali to give haloform
and salts of carboxylic acids having one carbon atom less than that of carbonyl compound. This
reaction is known as Haloform reaction.
The general equation is:
Example: Iodoform reaction. this reaction is used for detection of CH3CO- group (or
CH3CH(OH)-group which produces CH3CO- group on oxidation). The positive result is pale
yellow precipitate of CHI3.
R = H, alkyl, aryl
The reagents of iodoform test are I2 and OH-solution. The reaction takes place into two main
steps:
 Three hydroxides, OH-, remove three hydrogens from methyl group and the place of
hydrogen is taken by iodide.
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 CI3- group is a good leaving group; CI3- is replaced by OH- to form carboxylic acid, because
CI3- is a base according to Bronsted-Lowry, it reacts with acid to form the following product:
The overall equation for reaction of iodoform test:
D. Reactions due to Acidity of α-hydrogens of aldehydes and ketones
The aldehydes and ketones undergo a number of reactions due to the acidic nature of α-hydrogen.
The acidity of α-hydrogen atoms of carbonyl compounds is due to the strong electron withdrawing
effect of the carbonyl group and resonance stabilization of the conjugate base.
1. Condensation Reactions: These reactions involve formation of enolate ion which attack on
carbonyl carbon of another molecule to give condensation product.
(i)Aldol condensation: Aldehydes containing at least one α- hydrogen atom. When treated with
dilute base like NaOH undergo condensation reaction to give products called Aldols. The reaction
is known as aldol condensation. Aldols are the compounds containing both aldehydic and
Alcoholic functional groups. For example, two molecules of acetaldehyde combine in presence of
dilute NaOH to form 3-hydroxy butanal.
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Mechanism:
Following steps are involved in the mechanism of aldol condensation reaction.
Step 1: Formation of enolate ion
Step 2: Attack of enolate ion (nucleophile) on carbonyl carbon of another molecule of

acetaldehyde.
Step 3: Abstraction of proton from water molecule to give final product Aldol.
Aldol when heated easily loses a molecule of water to form α,β-unsaturated compound. For
example
Overall reaction:
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Ketones containing α-hydrogens also undergo condensation to give ketols. For examples, two
molecule of acetone condense together in the presence of barium hydroxide to form diacetone
alcohol ( Ketol)
Diacetone alcohol on heating loses one molecule of water to form mesityl oxide.
Overall reaction:
(ii) Cross aldol condensation
When aldol condensation is carried out between two different aldehydes and / or ketones, it is
called cross aldol condensation. If both of them contain α-hydrogen atoms, it gives a mixture of
four products. This is illustrated below by aldol reaction of a mixture of ethanal and propanal.
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Ketones can also be used as one component in the cross aldol reactions.
2. Halogenation
Both aldehydes and ketones react with halogens in which the hydrogen atoms on the carbon next
to the carbonyl group (α-hydrogen) are replaced by the halogen atoms. This reaction is catalyzed
by any stronger base that can remove the hydrogen in α-position of carbonyl group. Examples:
O
O
Br Br
4 Br2 /excess Br Br
NaOH + 4HBr
3. Alkylation
Alkylation consists of addition of alkyl group in α-position of carbonyl group of an aldehydes or

a ketone released by alkyl halides in concentrated NaNH2.
O
O
NaNH2 + HX
+ R"-X R
R
CH R'
CH R' heat 1000C
R"
H
Other reactions
(i) Cannizzaro reaction:
Aldehydes which do not have an α-hydrogen atom, undergo self-oxidation and reduction
(disproportionation) reaction on heating with concentrated alkali. In this reaction, one molecule of
the aldehyde is reduced to alcohol while another is oxidised to salt of carboxylic acid. One half of
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the aldehydes are oxidized to carboxylic acid and other half are reduced to alcohol. This reaction
is known as Cannizzaro reaction.
Mechanism: Following steps are involved
Step 1: Attack of the –OH on the carbonyl group.
Step 2: Hydride transfer:
(ii) Reaction with PCl5: Aldehydes and ketones react with PCl5 to give gem-dihalides.e.g.
Uses of aldehydes and ketones
Aldehydes and ketones have many uses for example in industries such as pharmaceutical industry
and in medicine.
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a. Formaldehyde:
 Formalin is a trade name for a solution containing 40 percent formaldehyde and 60 percent
water or water and methyl alcohol; it is employed as a disinfectant, insecticide, fungicide,
and deodorant. Formaldehyde is used extensively in the chemical industry in the synthesis
of organic compounds.
 Its most important use is in the manufacture of synthetic resins, Bakelite (a strong
thermosetting polymer whose monomers are phenol and formaldehyde catalyzed by strong
mineral acid), fertilizers and preservation of some organic specimens (anatomic specimen).
Recent tests have indicated that it is a carcinogen.
b. Acetone as solvent:
Acetone is soluble in water at all proportions and also dissolves in many organic compounds.
Boiling point of acetone is low, 56 °C, which makes it easier to be removed by evaporation.
Acetone is an industrial solvent that is used in products such as paints, varnishes, resins, coatings,
and nail polish removers.
c. Aldehydes and ketones
Organic molecules that contain ketones or aldehydes functional group are found in different foods
such as irish potatoes, yellow bananas.
Aldehydes and ketones perform essential functions in humans and other living organisms. For
examples sugars, starch, and cellulose, which are formed from simple molecules that have
aldehyde or ketone functional group
d. Aldehydes and ketones in human’s body
Aldehydes and ketones functional group are found in humans hormones like progesterone,
testosterone.
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UNIT 7: CARBOXYLIC ACIDS AND ACYL CHLORIDES
The learner should be able to compare the chemical nature of the carboxylic acids and acid halides
to their reactivity.
Learning objectives
 Explain the physical properties and uses of carboxylic acids and acyl chlorides
 Describe the inductive effect on the acidity of carboxylic acid
 Explain the reactions of carboxylic acids and acyl chlorides
 Apply the IUPAC rules to name different carboxylic acids acyl chlorides
 Write the structural formula and isomers of carboxylic acids
 Distinguish between carboxylic acids from other organic compounds using appropriate
chemical test
 Prepare carboxylic acids from oxidation of aldehydes or primary alcohols
 Compare the physical properties of carboxylic acids to those of alcohols
 Outline the mechanisms of esterification and those of reaction of acyl chlorides with
ammonia, amines and alcohols
 Develop a culture of working as a team group activities and self-confidence in presentation
 Appreciate the uses of carboxylic acids as the intermediate compounds in industrial

processes such as aspirin, vinegar and perfumes
I. Carboxylic Acids
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Organic compounds containing carboxyl group (-COOH) are known as carboxylic acids. They can
be represented by the general formula: RCOOH
They are further classified as mono, di, tri etc., carboxylic acids, according to the number of
carboxylic groups present in their molecules. The long chain monocarboxylic acids are also called
fatty acids because many of them are obtained from fats.
Methods of Preparation
Some important methods of preparation of carboxylic acids are as follows.
1) By the oxidation of primary alcohols or Aldehydes: Primary alcohols or aldehydes are

oxidized by oxidizing agent such acidified potassium permanganate or potassium dichromate to
carboxylic acid. In this process, the mixture is heated under reflux. Primary alcohols are first
oxidized to aldehydes then further oxidation of aldehydes produces carboxylic acid.
Example:
2) By the hydrolysis of amides and nitriles: Nitriles are hydrolysed to amides and then to
carboxylic acids in the presence of H+ or OH- as catalyst. Mild reaction conditions are used to stop
the reaction at the amide stage.
3) By the Hydrolysis of Ester: Acidic hydrolysis of esters gives directly carboxylic acids while
basic hydrolysis gives carboxylates, which on acidification give corresponding carboxylic acids.
Example of acid catalyzed hydrolysis of esters
Example of base catalyzed hydrolysis of esters
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4) By the Reaction of Grignard Reagents with CO2: Grignard reagent react with CO2 to give
first addition product which on hydrolysis yield carboxylic acid.
As we know, the Grignard reagents and nitriles can be prepared from alkyl halides (refer Unit4).
The above methods (2 and 4) are useful for converting alkyl halides into corresponding carboxylic
acids having one carbon atom more than that present in alkyl halides (ascending the series).
Example:
5) From acyl halides and anhydrides
Acid chlorides when hydrolysed with water give carboxylic acids or more readily hydrolysed with
aqueous base to give carboxylate ions which on acidification provide corresponding carboxylic
acids. Anhydrides on the other hand are hydrolysed to corresponding acid(s) with water.
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6) From dicarboxylic acid: Monocarboxylic acids can be prepared by heating carboxylic acids
which have two carboxylic functional groups attached to the same carbon atom.
Note that the reaction is used to reduce length of the carbon chain. The mono carboxylic acid
prepared has one carbon atom less than the starting dicarboxylic acid.
7) From alkenes (Oxidation of alkenes)
Carboxylic acids are also obtained by heating alkenes with concentrated acidified potassium
permanganate. The reaction unfortunately forms a mixture of compounds that must be later
separated.
8) By Carboxylation of Alkenes: This is a recent industrial method of preparation of carboxylic

acids and is called Koch Reaction. This involves treatment of alkene with carbon monoxide and
steam under pressure with phosphoric acid, H3PO3 at 400oC.
Physical properties of carboxylic acids

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 Aliphatic carboxylic acids up to ten carbon atoms are colorless liquids at room temperature
with unpleasant odors. The higher acids are wax like solids and are practically odorless due
to their low volatility.
Anhydrous acetic acid freezes at (17oC) slightly below ordinary room temperature, reason
why it is called glacial acetic acid. But a mixture of acetic acid with water solidifies at
much lower temperature.
 Carboxylic acids have higher boiling point than aldehydes, ketones and even alcohols of
comparable molecular masses. This is due to more extensive association of carboxylic acid
molecules through intermolecular hydrogen bonding. The hydrogen bonds are not broken
completely even in the vapors phase. In fact, most carboxylic acids exist as dimer in the
vapor phase or in the aprotic solvents.
 Simple aliphatic carboxylic acids having up to four carbon atoms are miscible in water due
to the formation of hydrogen bonds with water. The solubility decreases with increasing
number of carbon atoms. Higher carboxylic acids are practically insoluble in water due to
the increased hydrophobic interaction of hydrocarbon part.
Carboxylic acids are generally soluble in organic solvents such as ethanol, toluene, and
diethyl ether.
 Like most acids, carboxylic acids tend to have a sour taste (e.g., vinegar, citric acid, etc.)
Ethanoic acid/acetic acid is the main ingredient in vinegar.
Chemical Properties of Carboxylic Acids
Acidity of Carboxylic Acids:
Solutions of carboxylic acid turn blue litmus paper red therefore; they are acidic in nature but they
are weak acids as compared to inorganic acids (e.g. HCl or H2SO4). They can donate a proton and
form salts with strong bases but they are only partially ionized in aqueous solution.
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The acidic character of carboxylic acid is due to the resonance stabilization of the carboxylate ion
formed by ionization.
Effect of substituents on the acidity of carboxylic acids:
Substituents may affect the stability of the conjugate base (here carboxylate) and thus, also affect
the acidity of the carboxylic acids. Electron withdrawing groups increase the acidity of carboxylic
acids by stabilizing the conjugate base through delocalization of the negative charge by inductive
and/or resonance effects. Conversely, electron donating groups such as alkyl group decrease the
acidity by destabilizing the conjugate base.
The conjugate base can be stabilised by –I groups which can minimize the negative charge.
Predictably, this effect is going to be related to three major factors:
4) The electronegativity of the element (the more electronegative, the more stable the
conjugate base (weak base), the more acidic the corresponding acid)
5) The distance between the electronegative element and the negative charge (the shorter the
distance, the more stable the conjugate base, the more acidic the corresponding acid)
6) The number of electronegative element (the more electronegative element a compound
possesses, the more stable the conjugate base, the more acidic the corresponding acid)
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For example, chloroethanoic acid is a stronger acid than ethanoic acid. This is because chlorine
being electronegative, will withdraw electron towards itself thus reducing the electron density
around the O-H bond thus weakening it. It causes O-H bond to easily break, and the concentration
of hydrogen ions will be high in the solution.
The effect of the following groups in increasing acidity order is: Ph < I < Br < Cl < F < CN < NO2
< CF3
Thus, the following acids are arranged in order of increasing acidity (based on pKa values):
On the other hand, the conjugate base can be destabilized by +I groups which can increase the
negative charge. Since formic acid has no alkyl group, it is the strongest of all carboxylic acids. It
is ten times stronger than acetic acid.
HCOOH>> CH3COOH >CH3CH2COOH
This shows that the acidity strength decreases as the alkyl chain increases.
Reactions of carboxylic acids
Carboxylic acids are reactive, and their reactions are classified into:
Reaction involving –H of hydroxyl group O-H (i.e. reaction as acids)
Reaction involving -O-H group of carboxylic acid (i.e.nucleophilic substitution reactions).
Reaction involving carbonyl group (reduction reaction to alcohols)
Reactions Involving Cleavage of O–H Bond
1) Reaction with metals
Carboxylic acids react with strongly electropositive metals with the liberation of hydrogen and
form salt.
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2) Reaction with alkali solutions
Strong alkalis such as sodium hydroxide react with carboxylic acids by the process of
neutralization that forms salts of carboxylic acids and water.
3) Reaction with sodium carbonate and sodium hydrogencarbonate
Like other mineral acids, carboxylic acids react with carbonates and bicarbonates to form salts,
water and carbon dioxide.
The reaction of acids with carbonates is the basis for the chemical test of carboxylic acid functional
group and it can be used to distinguish carboxylic acids from other functional groups in qualitative
analysis. Carbon dioxide produced is also tested by lime water and it turns lime water milky
4) Reaction with ammonia and amines: Carboxylic acid react with ammonia and amines to form
ammonium salt which on strong heating give acid amides with the elimination of water.
Reaction involving the whole group –O-H
5) Esterification
i. Fischer esterification
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Carboxylic acid reacts with alcohols in the presence of concentrated H 2SO4 to form esters
(Esterification reaction). The reaction requires heating under reflux.
O O
H2SO4
+ H-O-R' + H2O
R'
Heat at 1000C
R OH R O
O O
H2SO4
+ H-O-CH2CH3 + H2O
Heat at 1000C CH2CH3
H3C OH H3C O
Following mechanism is suggested for the esterification
It is noted that the oxygen atom in the ester formed comes from the alcohol and the one in water
is from the acid. In the mechanism of esterification, the acid loses -OH group while the alcohol
loses H-atom.
ii. Formation of methyl ethers using diazomethane
Carboxylic acid react with diazomethane (CH2N2) to give product with perfume smell i.e. ester of
the class methyl esters within given off N2.
O O
+ CH2N2 ether + N2
diazomethane
R OH
heat
R OCH3
carboxylic methyl ester
acid
6) With phosphorus halides, thionyl chloride
Due to the presence of -OH group in carboxylic acids, like alcohols, they react with PCl 5, PCl3 and
SOCl2 and the organic product is acyl chloride. This is the basis reaction of the synthesis of acyl
chlorides from carboxylic acids. Thionyl chloride (SOCl2) is preferred because the other two
products are gaseous and escape the reaction mixture making the purification of the products
easier.
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7) Dehydration: Carboxylic acid on dehydration with P2O5 (dehydrating agents) give acid
anhydride.
8) Reduction of carboxylic acids
Carboxylic acids are reduced to primary alcohols on treatment with reducing agent such as LiAlH4
in dry ether or by use of hydrogen in the presence of Ni catalyst. The reduction does not form
aldehyde as an intermediate product, like in oxidation of primary alcohols.
O OH
1. LiAlH4 /ether
H
+LiOH + Al(OH)3
2. H2O
R OH R H
9) Halogenation
Carboxylic acids having an α-hydrogen are halogenated at the α-position on treatment with
chlorine or bromine in the presence of small amount of red phosphorus to give α-halocarboxylic
acids. The reaction is known as Hell-Volhard-Zelinsky reaction.
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10) Decarboxylation
When carboxylic acids are heated at high temperature, alkanes are produced with a shift of one
carbon to acid chain.
heat
R-CO2H RH +CO2
Carbone dioxide given off is also observed for β-keto acids in order to give ketones even at mild
heating than above.
O O O
warm + CO2
OH
3-oxobutanoic acid
11) Oxidation: All the acids, are extremely resistant to oxidation, except formic acid which is
oxidized by different oxidizing agents to produce carbon dioxide and water.
Reactions of salts of carboxylic acids:
i. Heating of Sodium salt: When sodium salts of carboxylic acid are heated with soda lime
[NaOH + CaO] alkanes are formed.
ii. Heating of Ammonium salt: When ammonium salts are heated, amides are formed.
When ammonium salts are heated with P2O5, alkyl nitriles are formed.
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iii. Heating of Calcium salt: Calcium salts of carboxylic acids on heating give aldehydes and
ketones.
a) Calcium formate gives formaldehyde.
b) Calcium salt of any carboxylic acid other than formic acid gives ketones.
c) Calcium salt of any carboxylic acid. when heated with calcium formate gives
aldehyde.
Uses of carboxylic acids
Carboxylic acids occur naturally in fats and oils, acidic dairy and citrus fruits. Following are some
of their most important uses:
Food industry and nutrition
 Food additives: Sorbic acid, benzoic acid, etc.
 Main ingredient of common vinegar (acetic acid).
 Elaboration of cheese and other milk products (lactic acid).
Pharmaceutical industry
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 Antipyretic and analgesic (acetylsalicylic acid or aspirin).
 Active in the process of synthesis of aromas, in some drugs (butyric or butanoic acid).
 Antimycotic and fungicide (Caprylic acid and benzoic acid combined with salicylic acid).
 Active for the manufacture of medicines based on vitamin C (ascorbic acid).
 Manufacture of some laxatives (Hydroxybutanedioic acid).
Other industries
 Manufacture of varnishes, resins and transparent adhesives (acrylic acid).
 Manufacture of paints and varnishes (Linoleic acid).
 Manufacture of soaps, detergents, shampoos, cosmetics and metal cleaning products (Oleic
acid).
 Manufacture of toothpaste (Salicylic acid).
 Production of dyes and tanned leather (Methanoic acid).
 Manufacture of rubber (Acetic acid).
 Preparation of paraffin candles (Stearic acid)
Carboxylic Acid Derivatives (Acid Derivatives):
Introduction
All compounds that generate the parent carboxylic acid on hydrolysis are called derivatives of
acids.
The carboxylic derivatives can be classified as shown in the following table:
CLASS GENERAL EXAMPLE

FORMULA
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1.Ester O O
R' CH3
R O H3C O
Methyl ethanoate
2.Acid chlorides O O
: Ethanoyle chlorides
R Cl H3C Cl
3.AMIDES O O
(Primary)
R NH2 H3C NH2

Ethanamide
(a)Monosubstitut O O
es
(Secondary) R NHR' H3C NH-CH3

N-Methyl ethanamide
(b)Disubstituted O O
(Tertiary) R' CH3

R N H3C N
-CH3
N,N-Dimethyl Ethanamide
R''
4.Acid O O O O
anhydrides
ethanoic anhydride
R O R H3C O CH3
5.Nitriles R C N H3C C N : Ethanonitrile
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6.Carboxylic salts O O
: Sodium acetate
Sodium ethanoate
R OM H3C ONa
From the above table, it is obvious that esters, acid chlorides, acid anhydrides, amides and
carboxylic salts have similarity (presence of carbonyl group) but nitriles can be taken apart from
the set even though are acid derivatives.
Carboxylic Acid Derivatives such as esters, acid chlorides, acid anhydrides and amides undergo
Nucleophilic Acyl Substitution Reactions
General mechanism:
Their reactivity order toward nucleophilic substitution is as follow:
ACID CHLORIDES
Acid halides are the derivatives of carboxylic acids in which the –OH function of carboxyl group
is replaced by a halogen atom. Acid halides are also known as acyl halides. Acid chlorides are
most important of all the acid halides.
They are represented as:
Methods of Preparation:
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Acid chlorides are prepared by heating carboxylic acids with PCl3, PCl5 and SOCl2.
SOCl2 is the most used since it produces gases that can be easily separated to the mixture but it
has a negative impact because it gives SO 2 which a greenhouse gas.
Physical properties
a. Appearance
Acyl chlorides are colourless fuming liquids. Their characteristic strong smell is caused by
hydrogen chloride gas that is produced when they get in contact with moisture. For example, the
strong smell of ethanoyl chloride is a mixture of vinegar odour and the acrid smell of hydrogen
chloride gas. They also have tear producing property. i.e lachrymators.
b. Solubility
Acyl chlorides are slightly soluble in water due to their small dipole that can interact with the
polarity of water molecule. They cannot be said to be soluble in water because they readily react
with water. It is impossible to have a simple aqueous solution of acyl chlorides, rather we have the
products of their reaction with water, but most soluble in organic solvents and their density is
closed to the one of water.
c. Boiling and melting points
Acyl chloride molecules interact by Van der Waals forces (dipole-dipole interaction) whose
strength increases with the increase in molecular masses of the compounds. Their boiling points
are lower than those of corresponding acids due to absence of hydrogen bonding.
Chemical properties
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Acid chlorides are very reactive compounds as they are more readily attacked by nucleophile
because of the electron withdrawing effect of highly electronegative, chlorine atom attached to
carbonyl carbon. This further diminishes the electron density on the carbonyl carbon. Cl atom is
replaced by the nucleophile.
Some important reactions of acid chloride are following.
1) Reaction with water (Hydrolysis): Acyl chlorides violently react with water to form
corresponding carboxylic acids with an evolution of white acidic fumes of hydrogen chlorides.
O
O
H2O
+HCl
R OH
R Cl
Mechanism:
2) Reaction with alcohols (Alcoholysis): They react with alcohol to produce esters with high
yields than esterification of an alcohol and carboxylic acid, since Cl-atom in acyl chloride is a
better leaving group than O-H for the case of carboxylic acid.
Mechanism:
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3) Reaction with Ammonia and amine (Aminolysis): Acyl chlorides react with ammonia and
amines to yield amides. Ammonia, primary amines and secondary amines form primary amides,
secondary amides and tertiary amides respectively.
O
+HCl
NH3
R NH2
O
O
+
R'-NH2 +HCl
R Cl
R NHR'
O
R'-NHR''
R'
+HCl
R N
R"
Mechanism:
4) Reaction with salt of carboxylic acids: Anhydrides are formed.
5) Reaction of acid chlorides with organometallic reagents
Acid chlorides react with two equivalents of a Grignard reagent to give a 3° alcohols.
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Reduction
a) Acid chlorides are reduced to primary alcohols with lithium aluminium hydride LiAlH 4
b) Acyl chlorides may be reduced catalytically to aldehydes or to alcohols.
i. The hydrogenation of acid chloride in the presence of Ni or Pd gives alcohols.
ii. When reduced in presence of poisoned Palladium Catalyst, they form aldehyde. This
reaction is called Rosenmund Reduction.
Uses
Acid chlorides have not many applications in our everyday life, but industrially they are used in
synthesis of perfumes and nylons, which are polymers of high importance in textile industry. They
can also be used in pharmaceutical industries to synthesize drugs with aromatic ester or amide
functional groups like aspirin or paracetamol.
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UNIT 8: ESTERS, ACID ANHYDRIDES, AMIDES AND NITRILES.
To be able to relate the functional groups of esters, acid anhydrides, amides and nitriles to their
reactivity, preparation methods and uses.
I. ACID ANHYDRIDES
Carboxylic acid anhydrides are organic compounds that are derivatives of carboxylic acid where the –OH
group is replaced by –OC(O)R. The general formula is represented as: (RC(O)) 2O or
When the two R groups are identical, the acid anhydride is symmetric and when the two R groups are
different, the acid anhydride is asymmetric. The general molecular formula of acid anhydride is CnH2n-2O3
Preparations of acid anhydrides
1) By dehydration of Carboxylic acids in presence of P2O5.
O O O
P2O5
2
heat
R OH R O R
2) By reaction of acid halide with sodium salt of carboxylic acid.
Mechanisn: addition-elimination
Physical properties
 The lower acid anhydrides are colourless liquids with an irritating smell and density close to unity.
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 They have high boiling point compared with generating acids due to the high molecular weight
but low for acid of the same molecular masse due to absence of hydrogen bonding in acid
anhydrides.
 They are insoluble in water but dissolve slowly because of the slow hydrolysis. They are most
soluble in organic solvents such as ether and benzene.
Chemical properties
They undergo nucleophilic substitution reactions more easily than alkyl halides and esters; and the attack
is one the positive carbonyl carbon by the nucleophile. In anhydrides –OCOR group is replaced by
nucleophile like acid chlorides but they are less reactive than acid chlorides because –OCOR group is not
as electronegative as Cl atom.
The anhydrides give all the nucleophilic substitution reaction given by acid chlorides but with less vigour.
1) Hydrolysis: Acids anhydride are hydrolyzed in water to form the parent acid.
O O
O
H2O 2
R O R
R OH
2) Reaction with alcohols: They react with alcohol to produce esters with high yields than esterification
of an alcohol and carboxylic acid since -O-COR in acid anhydrides is a good leaving group than O-H for
the case carboxylic acid
O
O O
R'-OH +R-COOH
R
R O R O-R'
Ester acid
This reaction is very important in pharmaceutical industries and it indicates the main use of acid
anhydrides as it is the basis of aspirin manufacture as shown below.
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3) Reaction with ammonia and amine to produce amides.
+ R-COOH
NH3
O R NH2
O
O
+ R-COOH
R'-NH2
R
R O
R NHR'
O
R'-NHR'' + R-COOH
R'
R N
R"
Note: Carboxylic acid obtained in the above reaction can react with ammonia if it is in excess to produce
amides reason why the main product of the reaction is an amide not a mixture of an acid and an amide.
4) Decarboxylation: Passing the vapor of acid anhydride on manganese dioxide MnO2 that act as a catalyst
of decarboxylation a ketone is formed with the evolution of Carbone dioxide.
O O
O MnO2
+ CO2
Heat R R'
R O R'
Ketone
Acid Anhydride
5) Reduction of acid anhydrides
Anhydrides are reduced by Lithium tetrahydridoaluminate, LiAlH4, to yield two primary alcohols.
Summary of acid anhydrides reaction:
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Uses
 It is primarily employed as an intermediate in the manufacture of industrial chemicals,

pharmaceuticals, perfumes, plastics, synthetic fibers, explosives, weed killers, and other chemical
products.
 Acetic anhydride is used for the manufacture of cellulose acetate, and for the manufacture of aspirin.
II. ESTERS
Esters are carboxylic acid derivatives in which the –OH group has been replaced by alkoxy (-OR)
group. The general formula of esters is CnH2nO2 and they can be represented as,
A large number of esters occur in flowers, fruits of the plants and provide the fragrance to flowers and
fruits.
Method of Preparation
Generally, esters are prepared by carboxylic acids and their other derivatives.
i) By the reaction of carboxylic acid with alcohols in presence of acid (Fischer’sEsterification method).
ii) By the reaction of Acid Chlorides with Alcohols.
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iii) By the reaction of acid anhydrides with alcohols
O
O O
R'-OH +R-COOH
R
R O R O-R'
Ester acid
iv) By the reaction of Carboxylic salts with alkyl halide.
v) By the reaction of carboxylic acid with Diazomethane.
But only methyl esters are formed by this method.
vi) By the reaction of an ester with alcohols (Trans-esterification or Transformation).
Alcohols react with esters to undergo an exchange of the alkoxide segment. The reaction is acid catalyzed
and the used alcohol must be in excess. This is a very common technique of producing new esters from
available esters.
vi) By the reaction of alkyl halide with silver salt of carboxylic acid.
Physical Properties of esters:

209 | P a g e
 They are colorless liquids or solids with sweet fruity smells therefore, the fruity smell is used as
test for esters in qualitative analysis.
 Their boiling points are less than acids and alcohols of the closed molar mass because they lack
hydrogen bonds.
 Melting and boiling points of esters increase as the molecular mass increases.
 Small esters are fairly soluble in water but the solubility decreases as the length of the chain
increases. They are generally insoluble in water and soluble in most organic solvents such as
ethanol.
Chemical properties of esters:
Esters give nucleophilic substitution reaction similar to acids halides because of the electron withdrawing
effect of the –OR group.
In esters –OR group is replaced by nucleophile like acid chlorides and acid anhydride but they are less
reactive than these ones because –OR group is not a good leaving group as -Cl and RC(O)O.
General reactions of esters are given below.
1) Hydrolysis
a) Acid hydrolysis: Esters are hydrolyzed in presence of acid catalyst (H2SO4) or HCl) to give parent
carboxylic acid and alcohol.
b) Alkaline hydrolysis: The alkaline hydrolysis of ester to form sodium or potassium salt of carboxylic acid
and alcohol is referred to as Saponification.
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Mechanism of base catalyzed reaction:
2)Trans-esterification
Alcohols react with esters to undergo an exchange of the alkoxide segment. The reaction is acid catalyzed
and the used alcohol must be in excess. This is a very common way of producing new esters from readily
available esters.
3) Reaction with Ammonia
Esters can be converted into primary, secondary and tertiary amides by an aminolysis reaction with
ammonia, primary amine and a secondary amine respectively.
4) Reduction
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Compared to ketones and aldehydes, esters are relatively resistant to reduction. Esters are reduced by
Lithium tetrahydridoaluminate (LiAlH4) giving two alcohols, one from the acyl segment (RC=O) and one
from the alkoxide segment (RO-) as shown by the reaction below.
When a less reactive reducing agent such as diisobutylaluminium hydride (DIBAH) is used the acyl segment
is converted into an aldehyde and the alkoxide group is still converted into an alcohol. Exactly one
equivalent of the hydride must be used, and the reaction must be carried out at -78 °C
5) Reaction with Grignard Reagent: Esters with Grignard reagent first gives ketone which on further
reacting with another molecule of the Grignard Reagent gives tertiary alcohol.
Uses of Esters
Esters find various uses:
 They are used as organic solvent

 Due to their aroma, they are used as constituent of fragrance, essential oils, food flavoring
and cosmetics.
 They are used to manufacture soaps, detergents and glycerol.
 They are used to provide energy in the body
 Polyesters are used to produce plastics etc.
Saponification and Detergents
Surfactants like soaps and detergents are important cleaning products which play an essential role in our
daily life. By safely and effectively removing soils, germs and other contaminants, they help us to stay
healthy, care for our homes and possessions, and make our surroundings more pleasant.
212 | P a g e
Soaps
Soaps are water-soluble sodium or potassium salts of fatty acids. Soaps are made from fats and oils, or
their fatty acids, by reacting them with a strong alkali. The process is known as “saponification”.
Fats and oils
Fats and oils are lipid esters known as triglycerides. The fats (solid lipids at room temperature and
pressure) and oils (liquid lipids at room temperature and pressure) used to produce soaps find their
sources from animal or plant. Each fat or oil is made up of a distinctive mixture of several different
triglycerides.
In the formation of a triglyceride molecule, three fatty acid molecules reacted with one molecule of
propane-1,2,3-triol or glycerol as shown below:
Examples of fatty acids found in triglycerides:
Saponification reaction
The reaction of saponification involves the collision between triglycerides in fat/oil and aqueous NaOH or
KOH. The result is the formation of soap and glycerol
213 | P a g e
Example:
The reaction of saponification is exothermic because there is liberation of heat and the soap formed
remains in suspension form in the mixture. Soap is precipitated as a solid from the suspension by
adding common salt to the suspension.
The other soap making process is with the neutralization of fatty acids with an alkali. Oils and fats are
hydrolyzed with high-pressure steam to yield glycerine and crude fatty acids.
The fatty acids are later purified using distillation method and then react with an alkali to produce water
and soap.
Alkali like sodium hydroxide produces sodium soap which is hard. Potassium soaps are soft.
Scum:
In hard water soap don't give lather .Hard water contains calcium and magnesium salts, which combine
with soap molecules to form insoluble precipitates known as scum.
DETERGENTS
A detergent is a surfactant or mixture of surfactants that has cleaning properties in dilute solution with
water. Like soaps, detergents are amphiphilic, meaning they have both hydrophobic and hydrophilic
regions.
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Synthetic detergents have similar molecular structures and properties as soap. Although the cleansing
action is similar, the charged ends of detergent do not form insoluble precipitates with the calcium and
magnesium ions in hard water; making them more efficient than soap, However, they are less
environmental friendly because of a reduced biodegradability.
There are over a thousand synthetic detergents available. Detergent molecular structures consist of a long
hydrocarbon chain and a water soluble ionic group. Their general structure is R-SO4- Na+, where R is a long-
chain alkyl group. The majority are alky sulfates. Others are "surfactants" (from surface active agents)
which are generally known as alkyl benzene sulfonates. examples:
Detergents may be used for household cleaning, laundry or for body and hand washing. They exist in the
powder or liquid form.
Difference between Soap and Detergent
The key differences between soaps and detergents are tabulated below.
Difference Between Soap and Detergent
Soaps Detergents
Consist of a ‘-COONa’ group attached to a fatty acid Consist of a ‘-SO3Na’ group attached to a long alkyl
having a long alkyl chain. chain.
They do not lose their effectiveness in hard water and

They are not effective in hard water and saline water
saline water.
Detergents containing a branched hydrocarbon chain

Soaps are completely biodegradable
are non-biodegradable
215 | P a g e
They have a tendency to form sum in a hard water
These compounds do not form scum.
environment.
They are derived from natural sources such as

Detergents are synthetic derivatives.
vegetable oils and animal fats.
Soaps are environment-friendly products since they These compounds can form a thick foam that causes
are biodegradable. the death of aquatic life.
Examples of soaps: sodium palmitate and sodium Examples of detergents: deoxycholic acid and sodium
stearate. lauryl sulfate.
How do soaps and detergents work?
The cleaning property of both soaps and detergents results from their capacity to emulsify water-insoluble
materials (dirt, oil, grease, etc.) and hold them in suspension in water. This ability originates from the
molecular structure of soaps and detergents. Examples:
When a soap or detergent adds on to water that contains oil or other water-insoluble materials, the soap
or detergent molecules surround the oil droplets and form clusters, known as micelles, in which the polar
ends of the molecules are on the outside of the cluster and the non-polar ends are in the middle.
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The carboxylate end of the soap molecule is attracted to water; it is called the hydrophilic (water-loving)
end. The hydrocarbon chain is attracted to oil and grease and is repelled by water it is known as the
hydrophobic (water-hating) end. This is represented in the figure below:
The oil or grease is “dissolved” in the alkyl groups of the soap molecules while the ionic end allows the
micelle to dissolve in water. As a result, the oil droplets are dispersed throughout the water (this is
referred to as emulsification) and can be rinsed away.
III. AMIDES
Amides are acid derivatives in which the –OH group is replaced by -NH2, -NHR or –N(R)2. The functional
group comprises nitrogen atom which is attached to the carbonyl carbon atom. The carbonyl group linked
to nitrogen atom is called an amide linkage. The general structure of amides is:
Where R on nitrogen can be hydrogen atoms (for primary amides), alkyl groups (for tertiary amides). For
secondary amides only one R is a hydrogen atom. Their general molecular formula is CnH 2n+1ON. Examples
of some amides are given in the table below:
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Preparation of amides
Amides can be prepared from all of the other acid derivatives when they react with ammonia and primary
or secondary amines. Their production of amides involves the following reactions.
i) By the action of Ammonia on Acid Chlorides:
NH3 +HCl
R NH2
O
O
R'-NH2 +HCl
R Cl
R NHR'
O
R'-NHR''
R'
+HCl
R N
R"
ii) By heating of Ammonium salts of Carboxylic acid:
218 | P a g e
iii) By the action of ammonia on Anhydrides
O O
NH3 O
O
+
warm H
R O R
R O
acid anhydride R NH2
acid amide
iv) By the action of Ammonia on esters
v) By the action of water on nitriles
The hydrolysis of nitriles also produces amides
Physical Properties:
i) All amides except methanamide which is a colorless liquid are white, odourless, crystalline solids.
ii) Among the other derivatives of acids, only acid amides are capable of forming intermolecular hydrogen
bonds due to which they have sharp melting points that are higher than those of corresponding acids.
Intermolecular hydrogen bonding in amides
219 | P a g e
iii) Simple amides (up to C ) are soluble in water but solubility in water decreases as we ascend the series.
6
All the amides are soluble in organic solvents.
iv) N-substituted amides(2o) often have lower melting points and boiling points than N,N-unsubstituted
amides(1o) because fewer hydrogen bonds can form and N,N-disubstituted amides(3o) cannot form
hydrogen bonds, and have even lower melting points and boiling points.
Chemical properties
Amides are stabilized by resonance.
Since the electron pair on N-atom is not readily available to an acid, amides are less basic than amines.
Amides are least reactive of the acid derivatives. Important reactions of amides are given below.
i) Hydrolysis: Amides are hydrolyzed by acid or alkali on prolonged heating to carboxylic acid.
ii) Reaction with Nitrous Acid (HONO): Amides when heated with Nitrous acid (NaNO 2 + HCl) give
carboxylic acids.
iii) Reduction: Amides can be reduced by LiAlH4 or BH3 to give amines.
H
O H
LiAlH4
Ether R NH2
R NH2
220 | P a g e
O
R
H
R' LiAlH4 N
R N
R''
Ethanol
R H
R''
Disubstituted amides Tertiary amine
iv) Dehydration: When heated with strong dehydrating agent such as phosphorous pentoxide or thionyl
chloride, they form nitriles.
v) Hofmann’s Degradation:
Amides react with a mixture of sodium hydroxide and bromine or sodium hypobromite to produce
amines. The reaction is called degradation as the carbon chain is reduced by one carbon.
RCONH2 + 4NaOH + Br2 → RNH2 + Na2CO3 + 2NaBr + 2H2O
Example: CH3CONH2 + 2NaOH + Br2 → CH3NH2 + Na2CO3 + 2NaBr + 2H2O
This equation can be simplified as follows:
CH3CONH2 + NaOBr→CH3NH2 + NaBr + CO2
Note: Hoffman degradation reaction is used to test the presence of the amide functional group. When an
amide is treated with sodium hypobromite, a colorless gas which turns milky lime water is evolved, CO 2
This reaction is also called Hoffmann’s rearrangement.
Uses of Amides
Amides have many applications as well as in industry and in medicine with focus in pharmacy.
 In medicine: Some amides are used as drug and vitamin like Penicellin and nicotinamide (vit B 5).
221 | P a g e
O
CH3
O
CH
NH2 C N
CH3
O C
CH CH CH3
N CH2 S
C NH
Vitamin B5 Penicillin
A part from these drugs, others are known like diazepam (valium), which acts as a mind-altering by fitting
specific receptors.
Urea containing creams are used in skin treatment to promote its rehydration. It softens the skin.
 In industry as polymers for example nylon-66 which is a polyamide. Nylon-6,6 is a synthetic textile
produced when hexane-1,6-dioic acid (adipic acid) reacts with hexane-1,6-diamine. Materials and
clothes are made from nylo-6,6.
amide bond
O O
n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2 (CH2)4 C NH (CH2)6 NH

HN
nylon-6,6
+ 2n H2O
n
 In agriculture, they are used as fertilizers like urea:
Because of its high nitrogen content, commercially prepared urea is used in the manufacture of
agricultural fertilizers.
Urea is also employed as a stabilizer in nitrocellulose explosives and is a basic constituent of

synthetically prepared resins for example in polyurethane synthesis.
Study of Urea
Urea is a white crystal substance. Its melting point is 132°C and decomposes before boiling. It is more
soluble in water and in ethanol but is insoluble in ether.
Structure
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Urea is an amide derivative of carbamic acid (NH2COOH). Hence it is also called Carbamide. Its IUPAC name
is Amino Methanamide. Its formula is H2NCONH2. Urea has important uses as a fertilizer and feed
supplement, as well as a starting material for the manufacture of plastics and drugs.
Preparation of urea
From Urine
After evaporating the urine, the concentrated nitric acid is added to it, causing the nitrate to separate into
crystals. On filtering it, urea is produced by reaction with barium carbonate. It is separated by
crystallization.
2NH2CONH2.HNO3 + BaCO3 → 2NH2CONH2 + Ba(NO3)2 + H2O + CO2
Laboratory
In the laboratory urea is produced by the action of ammonia on carbonyl chloride
(phosgene) or ethyl carbonate.
Wöhler Synthesis
Ammonium Cyanate
Urea is the first organic compound made in the laboratory. It was first created in the laboratory
by Friedrich Wöhler in 1828 by heating a mixture of Potassium cyanate and ammonium sulfate.
Ammonium cyanate is formed due to the ionic reaction of potassium cyanate and ammonium sulfate. In
which urea is formed by reorganization of atoms.
2KCNO + (NH4)2SO4 → 2NH4CNO + K2SO4
NH4CNO → NH2CONH2
Industrial Manufacture
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From Ammonia
Ammonium carbamate is formed by heating a mixture of liquid ammonia and liquid carbon dioxide in
autoclave at high temperature. Which is obtained by heating to 150°C at 50 atmospheric pressure.
2NH3 + CO2 → NH2COONH4
NH2COONH4 → NH2CONH2 + H2O
From Cyanide
In this method, firstly, the mixture of calcium carbide and nitrogen react to give calcium cyanamide
and carbon is obtained according to the following reaction. This mixture is called nitrolime and is used as
fertilizer.
CaC2 + N2 → CaCN2 + C
This mixture is reacted with dilute sulfuric acid. Dilute sulfuric acid converts calcium cyanamide into
cyanamide. This is followed by urea from partial water decomposition of Cyanamide.
CaCN2 + H2SO4 → H2N-C≡N + CaSO4
H2N-C≡N + H2O → H2N-CO-NH2

or The produced CaCN2 is then treated with a mixture of water and carbon dioxide to produce
urea.
IV. NITRILES
Nitriles are organic compounds with the general structure R-CN where -C N is its functional group.
The nitrile compounds include a nitrogen atom attached to a carbon atom by a triple covalent bond.
Their general molecular formula is CnH2n-1N. Unlike other acid derivatives they do not contain an
acyl group. The smallest organic nitrile is ethanenitrile, CH3CN. Hydrogen cyanide, HCN, doesn't
usually count as organic, even though it contains a carbon atom.
Preparations of nitriles
Primary alkyl nitriles are generally prepared by the reaction of potassium or sodium cyanide with a primary
alkyl halide. Secondary and tertiary nitriles cannot be formed by this route, and are thus made by the
dehydration of an amide (usually with SOCl2, but occasionally also with P2O5):
1) From amide and ammonium carboxylate salts, by dehydration
O
P2O5
NH4+ R C N + 2 H2O
heat: 7000C
R O
-
224 | P a g e
O
P2O5
heat R C N + H2O
R NH2
2) From alkyl halides (cyanidation process)
The halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol.
The halogen is replaced by a -CN group and a nitrile is produced.
R X + KCN R CN + KX
Nitrile
Physical properties
 The nitrile compounds exist as colorless solids and liquids having a characteristic odor.
 Boiling points increase as the length of the carbon chain increases. They have boiling points
ranging between 82 and 118 °C. The high boiling points are due to strong dipole-dipole
moments caused by the polarity of the C N bond. They are just very polar molecules. The
nitrogen is very electronegative and the electrons in the triple bond are very easily pulled
towards the nitrogen end of the bond. Nitriles therefore have strong permanent dipole-
dipole attractions as well as van der Waals dispersion forces between their molecules.
 Lower nitriles are highly soluble in water but this solubility decreases with the increase in
molecular mass as the non-polar part becomes lager. The reason for the solubility is that
although nitriles cannot hydrogen bond with themselves, they can hydrogen bond with
water molecules. One of the slightly positive hydrogen atoms in a water molecule is
attracted to the lone pair on the nitrogen atom in a nitrile and a hydrogen bond is formed.
There will also, of course, be dispersion forces and dipole-dipole attractions between the
nitrile and water molecules. Forming these attractions releases energy. This helps to supply
the energy needed to separate water molecule from water molecule and nitrile molecule
from nitrile molecule before they can mix together.
 They are more volatile than corresponding acid of the same molar weight since they have no
hydrogen bonding.
 Their boiling points and melting points are low comparing to their corresponding acid.
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 Their density is almost close to the one of water.
Chemical properties
Chemical reactions of nitriles are so very few since they are divided into addition (nucleophilic addition),
reduction of triple bonds and late on they can undergo substitution in alpha position
1) Addition of Water: Amides can be hydrolyzed to carboxylic acids in acidic aqueous solutions, and to
carboxylate salts with base-catalyzed hydrolysis:
R-C≡N + 2H2O + H+ → R-COOH + NH4+
R-C≡N + H2O + OH- → R-COO- + NH3
In both cases, the transformation consists of two main parts; conversion of the nitrile to an amide
and hydrolysis of the amide to the corresponding carboxylic acid.
226 | P a g e
227 | P a g e
These reactions indicate why nitriles is considered as a derivative of carboxylic acid.
We can isolate amides as reaction products by hydrolyzing the nitrile with concentrated sulfuric acid; This
is an often-used method. Aqueous H2SO4 (75%), aqueous H2SO4 (70%) in acetic acid or 96% H2SO4 at
228 | P a g e
temperatures of 60 -150 oC can be used to hydrolyze nitriles to amides effectively without significant
further hydrolysis to the acids.
However, in more dilute aqueous acid, the intermediate amide is further hydrolyzed to the carboxylic
acid.
2) Addition of Organometallic Reagents: Reaction of nitriles with organometallic reagents such as

Grignard reagents or organolithium followed by hydrolysis leads to the formation of ketones as shown
Both Grignard and organolithium reagents can be used to convert nitriles to ketones.
229 | P a g e
3) Reduction of nitriles
a) Reduction by metal hydride: Nitriles can be reduced to primary amines when treated
with LiAlH4 or to aldehydes when a milder reducing agent such as DIBAL is used.
Just like any other reduction reaction, an acidic or aqueous workup is needed to get rid of the ionic
intermediates. If the final product of the reaction is an amine, then usually it is treated with a hydroxide to
deprotonate and isolate it in a neutral amine form.
230 | P a g e
The Mechanism of Nitrile Reduction by DIBAL
DIBAL is a milder reducing agent than LiAlH4 and it can be used for selective reduction of esters and
nitriles to aldehydes.
The reaction again starts with a hydride addition to the C-N triple bond forming an iminium anion. The
difference between DIBAL and LiAlH4 is that DIBAL is not powerful enough to perform another
hydride addition to the negatively charged intermediate.
b) The reduction by hydrogen and a metal catalyst
231 | P a g e
The carbon-nitrogen triple bond in a nitrile can also be reduced by reaction with hydrogen gas in the
presence of a variety of metal catalysts.
Commonly quoted catalysts are palladium, platinum or nickel.
The reaction will take place at a raised temperature and pressure. It is impossible to give exact details
because it will vary from catalyst to catalyst.
For example, ethanenitrile can be reduced to ethylamine by reaction with hydrogen in the presence of a
palladium catalyst.
Hence, reaction of nitrile can be summarized as follow:
Nitriles find many uses:
 Nitriles are used in the manufacture of nitrile gloves, seals, and pipes or tubes as they
exhibit resistance to chemicals.
 They are used as an antidiabetic drug which is used in the treatment of breast cancers.
 They are utilized in the applications of oil resistant substances and also for low-temperature
uses
 They are also employed in automotive systems, hydraulic tubes and also in aircraft systems.
 Nitriles can be used as organic solvents and also in chromatography.
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UNIT 9: AMINES AND AMINO ACIDS
The learner should be able to relate the chemical nature of the amines and aminoacids to their
properties, uses and reactivity.
Learning objectives
At the end of this unit, the students will be able to:
 Explain the amino acid forms in the solution of different pH.
 Explain the isoelectric point in amino acids.
 Describe the physical properties and uses of amines.
 Describe the preparation methods of the amines.
 Describe the reactions of amino acids and amines with other substances.
 Classify amines as primary, secondary and tertiary amines.
 Compare and contrast the physical properties of the amino acids to those of carboxylic
acids and amines.
 Test the presence of amines and amino acids in the solution.
AMINES
Introduction and definition
Amines are one of the organic compounds containing nitrogen. They are one of the most important classes
of organic compounds which are considered to be derived from ammonia by replacement of the hydrogen
atoms of the ammonia with one or more alkyl or aryl groups.
They are present in vitamins, proteins, hormones, etc. They are extensively used in the manufacturing of
many drugs and detergents.
Classification of amines
We classify amines in a different way to alcohols or alkyl halides. The classification is based on how many
of the hydrogens of ammonia are replaced by alkyl (and/or aryl) groups.
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Thus:
 Primary amine(R-NH2) resulting from one replacement of only one hydrogen of NH3
 Secondary amine resulting from a replacement of two hydrogen of ammonia by alkyl group (R and
R’ ) or aryl group(Aryl) group let be R-NH-R’
 Tertiary amine if all the hydrogen have been replaced by alkyls or aryl groups let be NR3 e.g.
H3C H3C H2CH2CH3C
N CH3 N CH3 N CH2CH3
CH2CH3 , CH3 CH3
Note: If the alkyl groups are the same, we have symmetric amine and else are unsymmetrical amine.
A part from the three classes of amines above discussed, we have quaternary ammonium salts considered
as derivatives of ammonium salts but with replacement of all four hydrogen by alky groups:
R"'
"R R
_
N X
+
R'
Natural occurrences
Amines are a very common functional group in organic chemistry, and especially so for naturally occurring
compounds. Natural amines occur in proteins, vitamins, hormones, etc. amine exist as natural product in
plants concentrated in leaves as alkaloids like nicotine, morphine, cocaine and also in animals like:
Seretonin a derivative of ethylamine, which performs a vital role in the transmission of nerve impulses.
Suppression of levels of this chemical in the brain is believed to be responsible for a very common ailment,
mental depression. An elevation above normal levels is thought to cause anxiety.
Histamine and adrenalin are two other examples of ethylamine derivatives that are biologically important;
histidine is believed to be responsible for allergic symptoms while adrenalin is also a neurotransmitter.
Preparation of amines
1. Reductive Amination
The most general method for synthesizing amines involves the reduction of an imine or oxime derivative
of an aldehyde or ketone.
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The reduction is most commonly achieved via LiAlH4 or by catalytic hydrogenation. The overall effect is to
add another alkyl group to the original nitrogen. This works to make primary, secondary or tertiary amines.
Primary Amines are made from condensation of hydroxylamine (zero alkyl groups bound to N) with a
ketone or aldehyde, followed by reduction of the oxime produced.
The reduction is achieved by use of LiAlH4, NaBH3CN (sodium cyanoborohydride - mild reducing agent) or
catalytic hydrogenation.
e.g:
Secondary Amines are made via condensation of a primary amine (one alkyl group) with a ketone
(aldehyde), followed by reduction of the imine produced.
E.g.
Tertiary Amines are made via the condensation of a secondary amine (two alkyl groups) with an aldehyde
or ketone, generating an iminium salt.
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The iminium salts are usually unstable, and so are reduced as they are formed by a reducing agent already
in the reaction mixture.
This reducing agent therefore cannot be so reactive to react with the ketone or aldehyde starting material,
and thus sodium cyanoborohydride (NaBH3CN) is most commonly used.
e.g:
2. Acylation - Reduction to Amines
Again this method adds one alkyl group to the nitrogen of an amine. The ammonia (or a 1° amine or a 2°
amine) is acylated with an acid chloride, and the amide produced thus is reduced with LiAlH 4 to produce
the desired amine. The C=O of the amide is reduced to CH2
Ammonia yields a 1° amine., A 1° amine yields a 2° amine., A 2° amine yields a 3° amine.
E.g.
3. Reduction of Nitriles
Cyanide ion (-CN) is also a good nucleophile, and the products it produces are called nitriles.
236 | P a g e
Nitriles are reduced with LiAlH4 or catalytic hydrogenation to primary amines.
e.g:
In this reaction acidic or alkaline conditions should not be used to avoid the possible hydrolysis of the -CN
group.
4. Reduction of Nitro Compounds
Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely divided nickel,
palladium or platinum and also by reduction with metals in acidic medium. Nitroalkanes can also be
similarly reduced to the corresponding alkanamines.
Aromatic nitro compounds are reduced to anilines.
Reduction with iron scrap and hydrochloric acid is preferred because FeCl 2 formed gets hydrolysed to
release hydrochloric acid during the reaction. Thus, only a small amount of hydrochloric acid is required
to initiate the reaction.
237 | P a g e
5. Reaction alkyl halides
As seen before, these reactions have a tendency to over alkylate, which gives mixture of products.
A situation where this is a viable synthetic route is using a large excess (10:1) of ammonia with a primary
alkyl halide to produce a primary amine. The reaction is carried out in a sealed tube at 100 °C
6. Gabriel Synthesis
In 1887, Gabriel developed a new method for the synthesis of primary amines, which eliminated the
danger of over alkylation.
His strategy of using the phthalimide anion as a protected form of ammonia that cannot be alkylated more
than once.
This procedure is used for the preparation of primary amines. Phthalimide on treatment with ethanolic
potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl halide followed by
alkaline hydrolysis produces the corresponding primary amine. However, primary aromatic amines cannot
be prepared by Gabriel phthalimide synthesis because aryl halides do not undergo nucleophilic
substitution with the anion formed by phthalimide.
The Gabriel synthesis is a three-stage procedure used to prepare primary aliphatic amines from the
corresponding organic halides.
eg:
238 | P a g e
Stage 1:
mechanism:
Stage 2:
mechanism:
Stage 3:
mechanism:
239 | P a g e
7. From alcohol
In this method, alcohol is heated with ammonia at temperature of about 3000C in the presence of a small
amount of the powder of Al2O3 as a catalyst.
R R R
Al2O3/ 3000C R-OH R-OH
NH3 + R-OH NH N
R-NH2 Al2O3/3000C Al2O3/3000C
-H2O
R R
240 | P a g e
8. From primary amide (The Hoffman Rearrangement)
Hoffmann developed a method for the preparation of primary amines by treating an amide with bromine
in an aqueous or ethanolic solution of potassium hydroxide. This is a degradation reaction with migration
of an alkyl or aryl group taking place from carbonyl carbon of the amide to the nitrogen atom. The reaction
is valid for the preparation of primary amines only, and it yields uncontaminated compound with other
amines.
+ Br2 + 2KOH R NH2 +2KBr +CO2 +H2O

R C Heat
NH2 Amine
e.g.
O
H3CH2CH2C C
+ Br2 + 2KOH CH3CH2CH2 NH2 +2KBr +CO2 +H2O
Heat
NH2 Propylamine
Note: The amine prepared has one carbon atom less than amide
Mechanism
The reaction starts with the deprotonation of the amide to give a resonance stabilized anion that becomes
brominated.
Isocyanate reacts with water to form carbamic acid, which loses CO2.
241 | P a g e
Physical properties
The physical properties of amines parallel those of alcohols, since amines can also form intermolecular
hydrogen bonds:
Because of hydrogen bonding, they have higher boiling points than alkanes of closed molecular mass. Let
us discuss the data assigned in the following table:
Compounds Molecular mass(in g.mol-1) Boiling points( in 0C)
CH3-NH2 31 -7.0
CH3-CH3 30 -89.0
CH3-CH2CH2-NH2 59 49.0
CH3-NH-CH2CH3 59 35.0
(CH3)3N 59 3.5
CH3-(CH2)2-CH2-OH 74 118.0
242 | P a g e
CH3CH2-NH-CH2CH3 73 55.6
CH3-(CH2)3-CH3 72 36.0
(i) Because nitrogen is less electronegative than oxygen atom, the hydrogen bonding formed
by amines are weaker than those in alcohols of corresponding molecular mass.
(ii) Also because primary amines have more hydrogen atom on nitrogen atom, they form
many hydrogen bonds hence owing to higher boiling points than those of secondary
amine of the same closed molecular weight.
(iii) Because tertiary amine has no hydrogen atom on the nitrogen atom, it exhibits no
hydrogen bonding so it has lower boiling points than secondary or primary amine of
corresponding molecular mass and not quite similar to those of hydrocarbon of similar
mass.
 Briefly, the greater the number of hydrogen an amine has, the many hydrogen
bonds it can form hence the higher is its boiling point.
 The less number of hydrogen bonding an amine can form, the most trend to
volatile is reason why most amines are more volatile than corresponding
alcohols, therefore become more poisonous and toxic than alcohol.
Lower members are completely soluble in water, as amines can readily hydrogen bond to water. Solubility
decreases with increasing hydrophobic alkyl content which do not easily interact with water molecule.
The lower molecularweight amines with up to about five carbon atoms are soluble in water. The higher-
molecular-weight amines that are insoluble in water will dissolve in acid to form ionic amine salts.
Amines tend to be gases at low molecular weight. In fact, methyl, dimethyl, trimethyl, and ethyl -amines
are gases under standard conditions. Most common alkyl amines are liquids, and high molecular weight
amines are, quite naturally, solids at standard temperatures.
243 | P a g e
Additionally, gaseous amines possess a characteristic ammonia smell, while liquid amines have a
distinctive “fishy” smell: higher molecular-weight amines often smell like rotting fish, and are often found
in decaying animal tissues. Cadaverine [H2N(CH2)5NH2] and putrescine [H2N(CH2)4NH2] are some of
the examples.
Chemical properties
1. Basicity of Amines
The nitrogen atom of amines has a lone pair of electrons, and this gives rise to characteristics of
nucleophilicity and basicity (a Lewis base).
Amine as a nucleophile:
Amine as a base:
Amines are basic, and therefore their aqueous solutions are basic (pH>7), and the base strength is talked
of it terms of base-dissociation constant (K ).
b
Amines dissolve in water to give weakly alkaline solution like ammonia. The solution turns red blue litmus
paper.
_
R-NH2 + H2O R-N+H3 + HO
Base ACID base
Conjugated
acid-base acid
couple
By the law of mass action of Peter Wage, we can write the expression of K b and late the one of pKb defined
as cologarithm of Kb which express the basic strength because the greater the value of of K b (i.e the
smallest pKb), the more basic is the solution and the molecule fix more easily the released proton.
 

 R  NH 3   HO 

Kb  and pK b   log K b
 R  NH 2 
Effects on Amine Basicity
244 | P a g e
As we saw the basic character of amines is due to the presence of non-bonded electron pair on nitrogen
atom which donate electrons. Therefore, the strength of the base will depend on the availability of the
non-bonded electron pair.
(a) Alkyl group substitution
For example, methylamine CH3-NH2 is therefore a stronger base than ammonia because of the presence
of the methyl group with a positive inductive effect (electron pushing).
The methyl group pushes electrons towards the nitrogen atom. This increases the electron density on the
nitrogen; the non-bonded electrons are therefore easily available for proton attraction.
However the above logic implies that secondary amines should be stronger bases than primary amines,
and that tertiary amines the strongest bases of all.
This is not true, and the real situation is more complicated involving solvation effects and steric hindrance.
The overall net result of the combination of these effects is that
Secondary amine >primary amine>tertiary amine>ammonia.
The anomalous behavior of tertiary amines is due to steric hindrance i.e. the alkyl groups tend to prevent
the approaching proton while a secondary amine are more basic than primary.
(b) Resonance Effects
Amino benzene or phenylamine or aniline C6H5-NH2 is weaker base than aliphatic primary amines because
the non-bonded pairs of electrons on the nitrogen atom become involved with the delocalization in the
benzene ring and hence is less available for proton attraction.
Briefly, the order of basicity is predicted to be in order:
NH2
CH3
H H CH3
N H CH3
N N NH3
CH3
CH3
CH3
(c) Hybridization Effects
We have already observed that electrons held in orbitals that have more s character are held more tightly.
Therefore a lone pair held in an sp orbital will be more strongly held (i.e. less basic) than a lone pair held
in an sp3 orbital.
2. SALTS OF AMINES
Weakly basic amines can be fully protonated by strong acids and this reaction is quite general. It results
in the formation of salts, which are named as alkyl ammonium salts.
245 | P a g e
triethylammonium hydrogensulphate
The amine salt consists of two parts: the cationic ammonium ion, and the anionic counter ion. Amines are
generally volatile, smelly liquids, whereas the ammonium salts are crystalline, high melting solids.
These ionic solids are soluble in water, but insoluble in organic solvents. The free amines are generally
insoluble in water, but soluble in organic solvents. This provides an excellent method for the separation
and isolation of amine compounds.
Free amines are insoluble in water, but when dilute acid is added, the ammonium salt is produced, which
dissolves. (Formation of a soluble salt is a simple chemical analytical test for amine functionalities).
246 | P a g e
When the solution is made alkaline (by adding NaOH), the now purified free amine is regenerated, which
is insoluble in the aqueous solution and therefore precipitates, or can be extracted into an organic solvent.
This procedure is typical/useful for the purification of all amine containing compounds
Note: These salts formed with mineral acids are regarded as strong electrolytes and therefore their
solutions conduct electricity and their solutions in water are acidic.
3. Reactions of Amines
1. Reactions of amines diluted with acids
Amines, like ammonia, are bases. Being basic in nature, they react with acids to form salts.
Amine salts on treatment with a base like NaOH, regenerate the parent amine.
2. With Carbonyl Groups
The reaction of amines with ketones and aldehydes generate imines.
The mechanism for imine formation proceeds through the following steps:
1. An unshared pair of electrons on the nitrogen of the amine is attracted to the partial-positive
carbon of the carbonyl group.
2. A proton is transferred from the nitrogen to the oxygen anion.
247 | P a g e
3. The hydroxy group is protonated to yield an oxonium ion, which easily liberates a water
molecule.
4. An unshared pair of electrons on the nitrogen migrate toward the positive oxygen, causing
the loss of a water molecule.
5. A proton from the positively charged nitrogen is transferred to water, leading to the imine's
formation.
Example: Show how to synthesize the following amines from the indicated starting materials. N-
cyclopentylaniline from aniline
Solution
This synthesis requires adding a cyclopentyl group to aniline (primary) to make a secondary amine.
Cyclopentanone is the carbonyl compound
3. Alkylation of Amines
Amines react with primary alkyl halides to give alkylated ammonium halides.
248 | P a g e
(This direct alkylation usually proceeds via the SN2 mechanism, so does not work with tertiary halides
which are too hindered).
Since amines are bases, this creates a problem:
The ammonium salt formed initially can be deprotonated by the remaining amine.
This produces a secondary amine, which can react with the alkylhalide.
Direct alkylation can not be easily stopped at the desired level. Complex mixtures of products are
observed.
They are two cases where the alkylation of amines is reasonable synthetic route:
(1) Exhaustive alkylation to give tetra-alkylammonium salts. If enough alkyl halide is used to alkylate the
amines all the way to the tetraalkylammonium cations, then we get a single (exhaustively) alkylated
product.
e.g:
(2) Reaction with a large excess of ammonia.
Since ammonia is so inexpensive, it can (acceptably) be used in large excess. The primary alkyl halide is
added slowly to the large excess of ammonia, and so the probability of dialkylation is as low as possible.
249 | P a g e
4. Acylation of Amines using Acid Chlorides
Primary and secondary amines react with acid chlorides, acid anhydrides and ester to form amides.
Tertiary amines can not be acylated due to the absence of a replaceable hydrogen atom.
O O
C
+ HCl
R
R' NH2 +R C NHR'
acide Cl heat
amine amide
chlorides
O
O
O
C C + R-COOH
Heat R
R' NH2 +R C R NHR'
O
Amide
O
O
R C + R"-OH
R' NH2 +R Heat
C NHR' alcohol
OR''
Ester Amide
5. Reaction with carboxylic acid
Because amines are basic, they neutralize carboxylic acids to form the corresponding ammonium
carboxylate salts. Upon heating at 200°C, the primary and secondary amine salts dehydrate to form the
corresponding amides.
6. Reaction of Amines with Sulfonyl Chlorides (Sulfonamides)
Sulfonyl chlorides are the acid chlorides of sulfonic acids.

250 | P a g e
Just like before, amines react with displacement of the chlorine. The amides derived from sulfonic acids
are called sulfonamides.
7. Amines as Leaving Groups (Hoffman Elimination)
The amino group (-NH2 or -NHR) is a poor leaving group. However, the amino group can be
converted into a very good group via exhaustive methylation (usually using CH 3-I).
The quaternary ammonium salt is a very good leaving group since when it leaves, it produces a neutral
amine.
The elimination of the quaternary ammonium salt usually takes place via the E2 mechanism, a strong base
is required.
The ammonium iodide salt is converted to the corresponding hydroxide salt (strong base) by reaction with
silver oxide.
Heating the quaternary ammonium hydroxide salt an alkene is produced.
This is called the Hoffman elimination.
251 | P a g e
E.g. 2-butanamine is exhaustively methylated, converted to the hydroxide salt and heated, thus
generating a mixture of 1-butene (major) and 2-butene (minor).
Activity: Predict the major product(s) formed when the following amine is treated with excess
iodomethane, followed by heating with silver oxide.
Solution
Solving this type of problem requires finding every possible elimination of the methylated salt. In this case,
the salt has the following structure:
8. Reaction with nitrous acid
The reaction of amines with nitrous acid (HNO2) is a very useful synthetic reaction. Nitrous acid is unstable
and must be prepared in the reaction solution by mixing sodium nitrite with acid.
Na+ -O-N=O + HCl → H-O-N=O + Na+Cl-
In very acidic media, nitrous acid can become protonated and lose water (acid catalyzed dehydration) and
generate the nitrosonium ion, NO+.
252 | P a g e
Reaction with Primary Amines (Diazonium Salts)
Primary amines react with nitrous acid (actually nitrosonium ion) to produce compounds of the type R-
N2+.these are called diazonium cation.
The diazotization procedure starts with the nucleophilic attack of the primary amine on the nitrosonium
ion.
Deprotonation of the intermediate generates an N-nitrosoamine.
Tautomerism (proton transfer from nitrogen to oxygen) generates a compound which undergoes an acid
catalyzed elimination of water, thus generating the diazonium cation.
The overall balanced reaction is:
Alkyl(alphatic)diazonium salts are unstable even at 00C, and immediately lose nitrogen to give carbocation
and N2 gas. This carbocation R+ is capable of reaction with any nucleophile in solution. Therefore, reacting
primary amines with nitrous acid leads to a mixture of alcohol, alkenes, and alkyl halides.
253 | P a g e
But Primary aromatic amines form stable diazonium salts in solution at 0°–10°C and widely used for
synthesis. E.g:
e.g: When aniline(aromatic amine) is treated with 2-naphtol and then the hydrochloric acid and sodium
nitrite are added, a bright red solid results. The bright red solid is due to the reaction of diazonium salt
formed by the reaction between the phenylamine and hydrochloric acid and sodium nitrite with 2-
naphtol. This reaction is used to test aromatic amine (See organic chemistry of S6)
N N+Cl-
2-Naphtol OH
NH2
NaNO2+HCl N N
0
<10 C OH
Phenyldiazonium
bright red solid
Warming these salts initiates decomposition into highly reactive cations. These cations can react with any
anion present in solution to form a variety of compounds.
The +N≡N group is easily replaced by many different groups, Nitrogen gas, N 2, is a by-product.
254 | P a g e
Secondary aliphatic and aromatic amines form nitrosoamine with nitrous acid.
This time there isn't any gas produced. Instead, you get a yellow oil called a nitrosamine. These
compounds are powerful carcinogens - avoid them!
For example:
255 | P a g e
Tertiary amines and nitrous acid
Again, a quite different result. This time, nothing visually interesting happens - you are left with a
colourless solution.
All that has happened is that the amine has formed an ion by reacting with the acid present. With
trimethylamine, for example, you would get a trimethylammonium ion, (CH 3)3NH+.
Acidity of Amines
We normally think of amines as bases, but it must be remembered that 1º and 2º-amines are also very
weak acids (ammonia has a pKa = 34).
The same factors that decreased the basicity of amines increase their acidity. Strong base can substrate
a proton of the amine.
(C2H5)2NH + C4H9MgX(Li ) (C2H5)2N(–)(+)MgX(Li(+)) + C4H10
As alkynes and alcohol, primary or secondary amines react with alkalis metals to give no isolable metallic
derivative.
e.g: (CH3)2NH +Na→ (CH3)2Na +1/2 H2
Uses
Amines are prepared synthetically to make polymers, drugs and dyes. Amines can be used as dyes
(colorants) or as drugs:
Primary aromatic amines are used as a starting material for the manufacture of azo dyes. They react with
nitrous (II) acid to form diazonium salt which can undergo a coupling reaction in order to form an azo
compound. The azo group absorbs light and gives diverse colors to compounds. Many of them are
important dyes or are used in the preparation of dyes used in photography, as litmus and in tissues.
Amines are useful in biochemistry field like nicotine(extracted from the leaves of nicotiana tabacum)
which is a powerful excitant of central nervous system, caffeine and cocaine(extracted from leaves of a
shrub and chew coca) that acts seriously on CNS as local anesthesia used in medicine as drug.
256 | P a g e
CH3 O
O CH3 N
C OCH3
N
H3C N Cccaine
N
CH3 Caffeine O
N C
O N
Nicotine O
In medicine, amines can be used as drugs.
Chlorpheniramine is an antihistamine that helps to relief allergic disorders due to cold, hay fever,
itchy skin, insect bites and stings.
Diphenhydramine is the common antihistamine.
Chlorpromazine is a tranquillizer that anaesthetizes without inducing sleep. It is used to relieve

anxiety, excitement, restlessness or even mental disorder.
Acetaminophen is also known as paracetamol or p-acetaminophenol, it is an analgesic that

relieves pains such as headaches. It is believed to be less corrosive to the stomach and is an
alternative to aspirin.
Amines are widely encountered in biological and pharmacological studies. Some important examples are
the 2-phenylethylamines, some vitamins, antihistamines, tranquilizers, and neurotransmitters
(noradrenaline, dopamine and serotonin) which act at neuromuscular synapses.
AMINO ACIDS
Amino acids are organic molecules that contain an amino group and a carboxyl group. The key elements
of an amino acid are carbon (C), hydrogen (H), oxygen (O), and nitrogen (N). About 500 naturally occurring
amino acids are known.
The amino acids in proteins are called alpha (α)-amino acids because the amino group is attached to the
α-carbon. A carbon connected to any carboxylic acid carbon is termed an α-carbon.
Amino acids as are generally represented using the following formula:
257 | P a g e
All amino acids in proteins (except proline) contain –H, -NH2, and –COOH bound to the α-carbon. They
are differentiated by the side chains (called R-groups) also bound to the α-carbon.
Classification of Amino Acids
The difference between amino acids depends on their side-chain R groups because this is the only point
of difference (all amino acids contain a carboxyl group, an amino group, and an H). The most important
characteristic of R groups is polarity. As a result, amino acids are classified into four groups: nonpolar,
polar acidic, polar basic and polar-neutral amino acids.
Amino acids are known by common names and each is abbreviated using a three-letter code.
There are 20 common natural amino acids used to make proteins, 10 amino acids of them are essential
to human nutrition (we can biosynthesize the others).
The following table shows the 20 common naturally amino acids:
258 | P a g e
259 | P a g e
The 10 essential amino acids are: valine, leucine, isoleucine, threonine, methioninie, lysine, phenylamine,
and tryptophan. Arginine and histidine are essential for children.
260 | P a g e
Physical properties
 Melting points
The amino acids are crystalline solids with surprisingly high melting points. It is difficult to pin the melting
points down exactly because the amino acids tend to decompose before they melt. Decomposition and
melting tend to be in the 200 - 300°C range.
For the size of the molecules, this is very high. Something unusual must be happening.
If you look again at the general structure of an amino acid, you will see that it has both a basic amine
group and an acidic carboxylic acid group.
There is an internal transfer of a hydrogen ion from the -COOH group to the -NH2 group to leave an ion
with both a negative charge and a positive charge.
This is called a zwitterion.
A zwitterion is a compound with no overall electrical charge, but which contains separate parts which are
positively and negatively charged.
This is the form that amino acids exist in even in the solid state. Instead of the weaker hydrogen bonds
and other intermolecular forces that you might have expected, you actually have much stronger ionic
attractions between one ion and its neighbours.
These ionic attractions take more energy to break and so the amino acids have high melting points for the
size of the molecules.
 Solubility
Amino acids are generally soluble in water and insoluble in non-polar organic solvents such as
hydrocarbons.
261 | P a g e
This again reflects the presence of the zwitterions. In water, the ionic attractions between the ions in the
solid amino acid are replaced by strong attractions between polar water molecules and the zwitterions.
This is much the same as any other ionic substance dissolving in water.
The extent of the solubility in water varies depending on the size and nature of the "R" group.
The lack of solubility in non-polar organic solvents such as hydrocarbons is because of the lack of attraction
between the solvent molecules and the zwitterions. Without strong attractions between solvent and
amino acid, there won't be enough energy released to pull the ionic lattice apart.
 Optical activity
Amino Acid Stereoisomers
All α-amino acids, except glycine, are chiral because the α-carbon is bound to four different groups.
Glycine is exempt because it has two hydrogen atoms attached to the α- carbon (recall chiral carbons
must have four different groups attached).
As chiral molecules, amino acids can exist as D or L isomers.
When writing Fischer projections for amino acids, the -COOH group is always written at the top and the R
group at the bottom. If the NH2 is on the Left we have the L- isomer, if it is on the right, we have the D-
isomer.
In biological systems, only ′′L′′ isomers are found in proteins.
An example: L-Alanine, and D-Alanine
You can't tell by looking at a structure whether that isomer will rotate the plane of polarization of plane
polarized light clockwise or anticlockwise. All the naturally occurring amino acids have the same L-
configuration, but they include examples which rotate the plane clockwise (+) and those which do the
opposite (-).
For example: (+)alanine, (-)cysteine, (-)tyrosine; (+)valine
It is quite common for natural systems to only work with one of the optical isomers (enantiomers) of an
optically active substance like the amino acids. It isn't too difficult to see why that might be. Because the
molecules have different spatial arrangements of their various groups, only one of them is likely to fit
properly into the active sites on the enzymes they work with.
262 | P a g e
COMPARISON OF PHYSICAL PROPERTIES OF AMINO ACIDS TO THOSE OF CARBOXYLIC
ACIDS AND AMINES
The amino acids, carboxylic acids and amines have different functional groups; this is the base of their
different physical properties as shown in the following table
Amines Carboxylic acids Amino acids
General
structure
Carboxylic acids are

Hydroge Primary and secondary able to form a hydrogen
n bond amines can form bond. Amino acids exist as zwitterion
hydrogen bond one to even in the solid state. Instead of
other. Carboxylic acids have the weaker hydrogen bonds and
high boiling points due other intermolecular forces that
As a result of hydrogen to their ability to form you might have expected, you
bonding, primary and hydrogen bond one actually have much stronger ionic
secondary amines have another. attractions between one ion and its
higher boiling points neighbours.
than alkanes of similar The ability to form
size. hydrogen bonds, in These ionic attractions take more
addition to the energy to break and so the force
Lone pairs on amines presence of polar C=O, that exist between amino acids is
imply their hydrogen C-O, and O-H bonds, ionic bonds.
bond to water. (water gives small carboxylic
solubility better than acids a significant water
alkanes) solubility.
An increasing number
of carbon atoms leads
to a reduction in water
solubility.
Their hydrogen bonds

enhance the possibility
of bringing two acid
molecules together by
forming a dimer
263 | P a g e
The amino acids are crystalline
Physical Low molecular Many carboxylic acids solids with surprisingly high
state weight Amines tend are colorless liquids melting points.
to be gases and many with disagreeable
heavier ones are odors.
liquids or solids at
normal standard Aliphatic carboxylic
temperatures. acids with 5 to 10
carbon atoms are all
Gaseous amines liquids which have
possess a “goaty” odors.
characteristic
ammonia smell, The acids with more
while liquid amines than 10 carbon atoms
have a distinctive are wax-like solids, and
“fishy” smell. their odour diminishes
with increasing of
Volatile amines have molar mass and these
strong odors. - results in the
Amines smell like decreasing degree of
rotten fish. volatility.
Many amines are

physiologically
active.
-Smaller amines are

irritating to the skin,
eyes, and mucous
membrane and are
toxic by ingestion.
The α-amino acids crystallize as the

Melting Primary and Carboxylic acids have dipolar forms, H3N+−CHR−CO2–,
and secondary amines high melting and and the strong intermolecular
boiling boil at higher boiling points electrical forces in the crystals lead
point temperatures than compared to most to higher melting points than those
alkanes but at lower organic compounds of simple amines or
temperatures than of the same mass or monocarboxylic acids.
alcohols of number of carbon
comparable molar atoms. The melting points are so high that
mass. decomposition often occurs on
melting and tend to be in the 200 –
The boiling points of 300°C range.
tertiary amines is low
264 | P a g e
because they do not
form a hydrogen
bond.
All three classes of

Solubility amines can engage in The carboxyl group Amino acids are generally
hydrogen bonding with readily engages in soluble in water and insoluble in
water. hydrogen bonding non-polar organic solvents such
with water as hydrocarbons. The extent of
Amines of low molar molecules. the solubility in water varies
mass are quite soluble depending on the size and
in water; the borderline The acids with one to nature of the “R” group.
of solubility in water is four carbon atoms
at five or five carbon are completely The dipolar structures of amino
atoms. miscible with water. acids greatly reduce their
solubility in nonpolar organic
Solubility decreases solvents compared to simple
The higher molecular
as the carbon chain amines and carboxylic acids.
weight amines that are
length increases
insoluble in water will
because dipole
dissolve in acid to form
forces become less
ionic amine salts.
important and
dispersion forces
become more
predominant.
The carboxylic acids

generally are soluble
in such organic
solvents as ethanol,
toluene, and diethyl
ether.
CHEMICAL PROPERTIES OF AMINO ACIDS
a) The acid-base behavior of amino acids
Amino acids contain an acidic group (-COOH) and a basic group (NH2).
265 | P a g e
The reactivity of amino acids involves the reactions of both amines and carboxylic acids. The carboxylic
acid (COOH) has a tendency to donate H+ and the amine group (NH2) has a tendency to accept H+.
The product of this “internal” acid-base reaction is a dipolar ion (two poles) called a zwitterion (from the
German meaning “double ion”).
Zwitterions are simultaneously electrically charged and electrically neutral. They contain positive and
negative charges that cancel resulting in a net charge of zero. Zwitterions are the neutral form of the
amino acid despite the presence of “ion” in the name.
Zwitterions gain H+ in acidic solutions and lose H+ in basic solutions.
Example:
 Reaction with hydrochloric acid;
266 | P a g e
 Reaction with sodium hydroxide:
Isoelectric point in aminoacids (pI)
At a certain pH the positive and negative charges of an amino acid are equal resulting in an overall net
charge of zero. This pH is called the isoelectric point (pI), only the neutral form of the amino acid
(zwitterion) exists at the pI. This pH varies from amino acid to amino acid.
Worked example: The pI value for an amino acid is 6.0. Draw the general form of the amino acid that
predominates in solution at each of the following pH values:
a) pH < 1 b) pH = 6.0 c) pH > 12
Solution
At low pH ( pH<1) both amino and carboxyl groups are protonated giving an overall charge of 1+. At high
pH (pH>12) both groups have lost their protons giving an overall charge of 1-. Zwitterion present at pH =
pI.
The pI is given by the average of the pKa that involve the zwitterion, i.e. that give the boundaries to its
existence.
The table below shows the pKa values and the isoelectronic point, pI, are given below for the 20 α-amino
acids
pKa1= α-carboxyl group, pKa2 = α-ammonium ion, and pKa3 = side chain group
pKa and pI values for the 20 α-amino acids
267 | P a g e
There are 3 cases to consider:
1. Neutral side chains
These amino acids are characterised by two pKa values: pKa1 and pKa2 for the carboxylic acid and the
amine respectively. The isoelectronic point will be halfway between, or the average of, these two pKa
values . This is most readily appreciated when you realise that at very acidic pH (below pKa1) the amino
acid will have an overall positive charge and at very basic pH (above pKa2 ) the amino acid will have an
overall negative charge.
Example: For the simplest amino acid, glycine, pKa1= 2.34 and pKa2 = 9.6, pI = 5.97.
268 | P a g e
The other two cases introduce other ionisable groups in the side chain “R” described by a third acid
dissociation constant, pKa3
2. Acidic side chains
The pI will be at a lower pH because the acidic side chain introduces an “extra” negative charge. So the
neutral form exists under more acidic conditions when the extra -ve has been neutralised. For example,
for aspartic acid shown below, the neutral form is dominant between pH 1.88 and 3.65, pI is halfway
between these two values, i.e. pI = 1/2 (pKa1 + pKa3), so pI = 2.77.
3. Basic side chains
The pI will be at a higher pH because the basic side chain introduces an “extra” positive charge. So the
neutral form exists under more basic conditions when the extra positive has been neutralised. For
example, for histidine, which has three acidic groups of pKa’s 1.82 (carboxylic acid), 6.04 (pyrrole NH) and
9.17 (ammonium NH), the neutral form is dominant between pH 6.04 and 9.17; pI is halfway between
these two values, i.e. , so pI = 7.60.
b) Condensation and polycondensation reaction (Peptides and polypeptides formation)
Amino acids can join together through an amide linkage by eliminating molecule of water. This
process is known as condensation. In biochemistry, the amide linkage is known as a peptide
linkage and the short chains of amino acid units are called peptides. A dipeptide has two amino
acids, tripeptide has three and so on; with a large number of amino acid units, the molecule is
called polypeptide. For example:
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Alanine glycine serine
O O O
H
H2N CH C OH + N CH C OH + H2N CH C OH
CH3 H H CH2
OH
Alanyl Glycyl Seryl
O O O
H2N CH C HN CH C HN CH C OH + 2 H2O
CH3 H amide CH2

amide linkage
linkage OH
Tripeptide: Ala-Gly-Ser
Note: As amino acids contain both acid and amine groups some properties are similar as those of these
functional groups
Acid group give salts in the presence of bases, esters by the reaction with alcohol, and can be transformed
in the habitual way in acid chlorides
Primary amines react with acid chlorides to form amides and with nitrous acid to form α-
hydroxyacid and nitrogen is liberated.
O
H2O CH C OH + HNO 2 RCH(OH)COOH + N2 + H2O
This reaction is the basis for the quantitative estimation of amino in the protein. By Van Slyke method.
(The measurement of the volume of N2 evolved).
Other properties result from the presence of the two groups.
Individual amino acids can be separated by electrophoresis and/or chromatography
Electrophoresis
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Amino acids can be separated based on their charge in solution at a given pH
e.g., at pH 7, alanine is aprox. neutral, arginine is mainly +, glutamic acid is mainly -; depending on their
charge, the molecules migrate towards either a positive or negative electrode (moving through wet gel or
paper)
PREPARATION OF AMINO ACIDS
Most plants and microorganisms are able to use inorganic compounds to make all the amino acids
they require for normal growth. Animals, however, must obtain some of the standard amino acids
from their diet in order to survive; these particular amino acids are called essential. Essential amino
acids for humans include lysine, tryptophan, valine, histidine, leucine, isoleucine, phenylalanine,
threonine, methionine, and arginine. They are found in adequate amounts in protein-rich foods
from animal sources or in carefully chosen combinations of plant proteins.
In addition to the amino acids that form proteins, more than 150 other amino acids have been found
in nature, including some that have the carboxyl and amino groups attached to separate carbon
atoms. These unusually structured amino acids are most often found in fungi and higher plants.
On the other hand the laboratory synthesis of amino acid can be affected.
By Gabriel synthesis
An ester of α haloacid is treated with potassium phtalimide to form corresponding substituted

phtalimide. This on hydrolysis with dilute HCl gives phtalic and an α amino acid.
O O
NCH2COOC2H5
NK + ClCH2COOC2H5 -KCl
Chloroethylacetate
O
O
Potassium phthalimide +
-C2H5OH H2O/H
COOH
+ H2NCH2COOH
COOH Glyceline
Phthalic acid
By Strecker synthesis
This method assembles an alpha-amino acid from ammonia (the amine precursor), cyanide (the
carboxyl precursor), and an aldehyde. This reaction (shown below) is essentially an imino analog
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of cyanohydrin formation. The alpha-amino nitrile formed in this way can then be hydrolyzed to
an amino acid by either acid or base catalysis.
PEPTIDES AND POLYPEPTIDES
Structure
It is worth noting that once amino acids are connected, we no longer call them “amino acids”, instead, we
refer to the bonded units as “residues.”
All peptide chains will have an amino group at one end (a free, unbound -NH3+) and a carboxylate at the
other (a free –COO-).
By convention, we draw peptides and polypeptides with the N-terminal (unreacted or free amino group)
on the left end of the peptide chain and the C-terminal (the carboxylate group) on the right end of the
polypeptide.
Peptides are named by listing the amino acid residues in order from the N- to C-terminal.
For example, a dipeptide could be written as (Ala-Gly), a tripeptide as (Thr-Gly-Ala), and a pentapeptide
as (Lys-His-Ala-Thr-Gly).
Example: Explain why the notation Gly-Ala and Ala-Gly represent two different molecules.
Solution:Gly is the N-terminal end of Gly-Ala and Ala is the N-terminal end of Ala-Gly as represented
below:
Structure of Gly-Ala
Structure of Ala-Gly
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Thus, in the pentapeptide Tyr- Gly-Gly-Phe-Leu (YGGFL), tyrosine is the amino-terminal (N-terminal)
residue and leucine is the carboxyl-terminal (C-terminal) residue Leu-Phe-Gly-Gly-Tyr (LFGGY) is a
different pentapeptide, with different chemical properties.
This above illustration of the pentapeptide Tyr-Gly-Gly-Phe-Leu (YGGFL) shows the sequence from the
amino terminus to the carboxyl terminus. This pentapeptide, Leu-enkephalin, is an opioid peptide that
modulates the perception of pain. The reverse pentapeptide, Leu-Phe-Gly-Gly-Tyr (LFGGY), is a different
molecule and shows no such effects.
A polypeptide chain consists of a regularly repeating part, called the main chain or backbone (in blue
color), and a variable part, comprising the distinctive side chains ( in green color).
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The polypeptide backbone is rich in hydrogen-bonding potential. Each residue contains a carbonyl group,
which is a good hydrogen-bond acceptor and, with the exception of proline, and NH group, which is a
good hydrogen-bond donor. These groups interact with each other and with functional groups from side
chains to stabilize particular structures, as will be discussed later.
Complete hydrolysis of polypeptides (extended heating in aqueous HCl) breaks all amide bonds and
releases all the individual amino acids.
Studied the hydrolysis of amides under acidic conditions, you will find that this is basically the same
reaction. That's not surprising because what biologists and biochemists call a peptide link (in proteins, for
example) is what chemists call an amide link.
PROTEINS NATURAL POLYPEPTIDES
Uses of amino acids as building blocks of proteins
Like carbohydrates and lipids, proteins contain the elements carbon (C), hydrogen (H) and oxygen (O),
but in addition they also always contain nitrogen (N), sulphur(S) as well as iron (Fe) and phosphorus (P).
The process of construction of proteins begins by amino acids bonding together, as seen earlier, through
peptide bonds. When many amino acids join together a long-chain polypeptide is produced. The linking
of amino acids in this way takes place during protein synthesis.
Protein Structure
In general, proteins are defined as polypeptide chains having 50 or more amino acids.
Protein structure is described using four levels of organization: primary, secondary, tertiary, and
quaternary structure.
The Primary Structure of Proteins
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The simplest level of protein structure, primary structure, is simply the sequence of amino acids in a
polypeptide chain. The primary structure of a protein refers to its linear sequence of amino acide.
One of those sequences is: –Gly–Ile–Val–Cyst–Glu–Gln–Ala–Ser–Leu–Asp–Arg–Asp–Arg–Cys–Val–Pro–
The primary structure is held together by peptide bonds that are made during the process of protein
biosynthesis. The two ends of the polypeptide chain are referred to as the carboxyl terminus (C-terminus)
and the amino terminus (N-terminus) based on the nature of the free group on each extremity.
The Secondary Structure of Proteins
Proteins fold or align in a consistent manner which generates specific repeating patterns. These patterns
are referred to as secondary structures.
There are two common types of protein secondary structures: the alpha helix (α-helix) and the beta
pleated sheet (β-pleated sheet). Hydrogen bonding is responsible for the secondary structure of
proteins.
α-helix: An α-helix is basically a spring-like structure stabilized by hydrogen bonds formed between a
carbonyl oxygen and an amino hydrogen separated by 4 amino acid residues. This bonding holds the
polypeptide chain in the helical shape.
β-pleated sheet: A less common type of secondary structure is called a β-pleated sheet. β-pleated sheets
form when portions of the polypeptide chain align side by side in a sheet-like array held together by
hydrogen bonds. The hydrogen bonds are again formed between carbonyl oxygens and amino hydrogens,
but unlike α-helices, the residues may be separated by great distances on the polypeptide chain. The
direction of the polypeptide chain is always determined from the amino terminal and follows the
repeating pattern of N-Cα-C(carbonyl)-N- Cα-C(carbonyl)-N-Cα-C(carbonyl). The sheets may be parallel or
antiparallel depending on the direction of the chains involved.
A parallel β-pleated sheet. Note the chains involved run in the same direction.
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The Tertiary Structure of Proteins
The overall three-dimensional shape that results from attractive forces between amino acid side chains is
referred to as a tertiary structure of proteins. Tertiary structures are the first form of functional proteins
and are formed by interacting secondary structures.
This is often simplified into models like the following one for the enzyme dihydrofolate reductase.
Enzymes are, of course, based on proteins.
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The tertiary structure of a protein is held together by interactions between the the side chains - the "R"
groups. There are several ways this can happen.
Ionic interactions
Some amino acids (such as aspartic acid and glutamic acid) contain an extra -COOH group. Some amino
acids (such as lysine) contain an extra -NH2 group.
You can get a transfer of a hydrogen ion from the -COOH to the -NH2 group to form zwitterions just as in
simple amino acids.
You could obviously get an ionic bond between the negative and the positive group if the chains folded in
such a way that they were close to each other.
Hydrogen bonds
Notice that we are now talking about hydrogen bonds between side groups - not between groups actually
in the backbone of the chain.
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For example, the amino acid serine contains an -OH group in the side chain. You could have a hydrogen
bond set up between two serine residues in different parts of a folded chain.
You could easily imagine similar hydrogen bonding involving -OH groups, or -COOH groups, or -CONH2
groups, or -NH2 groups in various combinations - although you would have to be careful to remember that
a -COOH group and an -NH2 group would form a zwitterion and produce stronger ionic bonding instead of
hydrogen bonds.
Van der Waals dispersion forces
Several amino acids have quite large hydrocarbon groups in their side chains. A few examples are shown
below. Temporary fluctuating dipoles in one of these groups could induce opposite dipoles in another
group on a nearby folded chain.
The dispersion forces set up would be enough to hold the folded structure together.
Sulphur bridges
An additional feature in proteins which is covalent bound. It involves the amino acid cysteine.
If two cysteine side chains end up next to each other because of folding in the peptide chain, they can
react to form a sulphur bridge. This is another covalent link and so some people count it as a part of the
primary structure of the protein.
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Because of the way sulphur bridges affect the way the protein folds, other people count this as a part of
the tertiary structure. This is obviously a potential source of confusion!
The Quaternary Structure of Proteins
The highest level of protein organization is called the quaternary structure. It is formed by interacting
tertiary structures and it represents some of the most complex proteins known. Quaternary structures
are typically composed of two or more protein subunits (tertiary structures). Nonprotein components may
also be present. Hemoglobin is a tetramer (four subunits) containing two copies of one polypeptide and
two copies of another: two identical chains of 141 amino acid residues each (alpha) and two identical
chains of 146 residues each (beta).
PROTEIN HYDROLYSIS
Our body’s digestive system must break down proteins into amino acid units for them to be absorbed
from the intestine into the blood. Once absorbed, amino acids can be used to synthesize the human
proteins. The process of protein digestion involves hydrolysis reactions that are catalyzed by enzymes.
DENATURATION OF PROTEINS
Denaturation is the partial or complete disorganization of a protein’s characteristic three-dimensional

shape as a result of disruption of its secondary, tertiary, and quaternary structural interactions.
Denaturation renders the protein nonfunctional and can be caused by a variety of factors, ie; heat, acids,
bases, organic compounds, heavy metal ion, and mechanical agita
UNIT 10. PHASE DIAGRAMS
Key unit competency: To be able to interpret the phase diagrams for different compounds.
 Define a phase
 Explain the term phase equilibrium
 Explain the effect of change of state on changing pressure and temperature
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 Define heterogeneous and homogeneous equilibria
 Define triple point, critical point, normal boiling and melting points of substances
 Relate the physical properties of compounds to their phase diagrams.
 Locate triple point, critical point, normal boiling and melting points on the phase
 diagrams
 Compare the phase diagrams for water with that carbon dioxide
 Develop analysis skills, team work, and attentiveness in interpreting the phase
 diagrams and in practical activities
1. Phase equilibrium
Definition of key terms

A phase is a homogeneous portion of a system which has uniform physical characteristics.
A phase can be separated from other parts of the system by a clear boundary (limit). A phase can
be a solid, liquid, vapor (gas) or aqueous solution which is uniform in both chemical composition
and physical state.
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Examples:
i. A mixture of gases (air) consists of one phase only

ii. A mixture of oil and water consists of two different liquid phases
iii. A mixture of solids, each solid is regarded as having one phase
A component: it is a chemical species which may be used to specify the composition of a system.
Example:
i. A three-phase system of water (i.e. water, ice, and vapor) is a one component system. The
constituent substance of the three phases is water only.
ii. A mixture of water and ethanol is a one phase, two components system because there are
two different chemical compositions.
An equilibrium: it is the state of a reaction or physical change in which the rates of the forward
and reverse processes are the same and there is no net change on the amount of the equilibrium
components
A phase equilibrium: it is a balance between phases, that is, the coexistence of two or more phases
in a state of dynamic equilibrium. The forward process is taking place at the same rate as the
backward process and therefore the relative quantity of each phase remains unchanged unless the
external condition is altered.
Properties of a system at equilibrium.
 Macroscopic properties (e.g. colour, pressure, concentration, pH) are constant i.e. It
appears as if nothing is changing
 Can only be reached in a closed system
 Forward rate = Reverse rate
 Can be established from either direction at equilibrium, the concentrations of all reactants
and products will remain constant
2. Homogeneous and heterogeneous equilibria
a) Homogeneous equilibrium
A system with one phase only is described as a homogeneous system and when this system is at
equilibrium, it is said to be in homogenous equilibrium.
In general, a homogeneous equilibrium is one in which all components are present in a single
phase. In a case of a chemical reaction, both reactants and products exist in one phase (gaseous
phase, liquid phase or aqueous solution and solid phase).
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For example, in the esterification of acetic acid and ethanol the equilibrium is homogeneous
because all involved substances are in the same liquid phase. All the reactants and products are
liquids
b) Heterogeneous equilibrium
A system consisting of more than one distinct phases is described as heterogeneous system. when
this system is at equilibrium, it is said to be in heterogeneous equilibrium. The phases may be
any combination of solid, liquid, gas, or solutions.
For example, in the manufacture of quick lime from lime stone the following equilibrium is
involved:
3. Phase diagrams
A phase diagram is a graph illustrating the conditions of temperature and pressure under which the
various phases (solid, liquid, and gaseous) of a system are stable and the conditions under which
equilibrium exists between the distinct phases of a substance.
The general form of a phase diagram for a substance that exhibits three phases is shown below:
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Phase diagram for a one component system
Phase diagrams are divided into three single phase regions that cover the pressure-temperature
space over which the matter being evaluated exists: liquid, gaseous, and solid states. The lines that
separate these single-phase regions are known as phase boundaries. Along the phase boundaries,
the matter being evaluated exists simultaneously in equilibrium between the two states that border
the phase boundary.
Any point on the diagram that does not fall on a line corresponds to conditions under which one
phase is present. Any other point on the three curves represents equilibrium between two phases.
The gas phase is stable phase at low pressures and elevated temperatures. The conditions under
which the solid phase is stable extend to low temperatures and high pressures. The stability ranges
for liquids lie between the other two regions. That is between solid and liquid regions.
i. Boiling curve
The line TC is the vapor pressure curve of the liquid. It represents the equilibrium between the
liquid and the gas phases. The temperature on this curve where the vapor pressure is equal to 1atm
and it is the normal boiling point of the substance. The vapor pressure curve ends at the critical
point (C) which is the critical temperature corresponding to the critical pressure of the substance
which is the pressure required to bring about liquefaction at critical temperature.
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ii. Critical point
Critical point consists of the temperature and pressure beyond which the liquid and gas phases
cannot be distinguished. Every substance has a critical temperature above which the gas cannot
be liquefied, regardless the applied pressure.
iii. Sublimation curve
The line AT is the sublimation curve which represent the variation in the vapor pressure of the
solid as it sublimes into gas at different temperatures. The reverse process is deposition of the gas
as a solid. Sublimation point is the temperature at which the solid turns to gas at a constant pressure.
iv. Melting curve
The line TB is the melting curve which represent the change in melting point of the solid with
increasing pressure. The line usually slopes slightly to the right as pressure increases. For most
substances, the solid is denser than the liquid, therefore, an increase in pressure favors the more
compact solid. Thus, higher temperatures are required to melt the solid at higher pressures. The
temperature at which the solid melts at a pressure of 1atm is the “normal melting point”.
v. Triple point
The triple point T is a point where the three curves intersect. All the three phases exist at
equilibrium at this temperature and pressure. The triple point is unique for each substance.
vi. Supercritical fluid
A supercritical fluid is any substance above its own thermodynamic critical point where distinct
liquid and gas phases do not exist.
Supercritical fluid show properties in between liquids and gases. They can diffuse through solids
like a gas and dissolved materials like a liquid.
3. 1. Phase diagram of water

Water is a unique substance in many ways due to its properties. One of these special properties is
the fact that solid water (ice) is less dense than liquid water just above the freezing point. The
phase diagram for water is shown below:
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Phase diagram of water
Water can turn into vapor at any temperature that falls on the vapor pressure curve depending on
the conditions of pressure, but the temperature at which water liquid turns into vapor at normal
pressure (1atm) is called the normal boiling point of water, 100 °C
Point E on the above Figure is the critical point of water where the pressure is equal to 217.75
atm and the temperature is about 374 °C. At 374°C, particles of water in the gas phase are moving
rapidly.
At any other temperature above the critical point of water, the physical nature of water liquid and
steam cannot be distinguished; the gas phase cannot be made to liquefy, no matter how much
pressure is applied to the gas.
The phase diagram of water is not a typical example of a one component system because the line
AD (melting point curve) slopes upward from right to left. It has a negative slope and its melting
point decreases as the pressure increases. This occurs only for substances that expand on freezing.
Therefore, liquid water is denser than solid water (ice), the reason why ice floats on water.
3.2. Phase diagram of carbon dioxide

Compared to the phase diagram of water, in the phase diagram of carbon dioxide the solid-liquid
curve exhibits a positive slope, indicating that the melting point for CO 2 increases with pressure
as it does for most substances. The increase of pressure causes the equilibrium between dry ice
and carbon dioxide liquid to shift in the direction of formation of dry ice that is freezing. Carbon
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dioxide contracts on freezing and this implies that dry ice has higher density than that of liquid
carbon dioxide. The Figure below shows the phase diagram of carbon dioxide.
Phase diagram of carbon dioxide
The triple point is observed at the pressure above 1atm, indicating that carbon dioxide cannot exist
as a liquid under normal conditions of pressure. Instead, cooling gaseous carbon dioxide at 1atm
results in its deposition into the solid state. Likewise, solid carbon dioxide does not melt at 1atm
pressure but instead sublimes to yield gaseous CO2.
4. Comparison of phase diagrams of substances that expand and those that contract on
freezing
For the phase diagrams, some materials contract on freezing while others expand on freezing. The
main differences between substances that expand and those that contract on freezing can be
highlighted by comparing the phase diagrams of carbon dioxide and that of water. The phase
diagram of carbon dioxide as the substance that contracts on freezing and that of water as the
substance that expands on freezing.
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Both phase diagrams for water and carbon dioxide have the same general Y-shape, just shifted
relative to one another. This shift occurs because the liquid phase in the dry ice can only occur at
higher temperatures and pressures, whereas, in ice the liquid phase occurs at lower temperatures
and pressures. There are two more significant differences between the phase diagram of carbon
dioxide and that of water:
4.1. Melting curve

The melting curve of carbon dioxide slopes upwards to right whereas that of water slopes upward
to left.
This means that for carbon dioxide the melting point increases as the pressure increases, a
characteristic behavior of substances that contract on freezing. For water the melting point
decreases as the pressure increases, a characteristic behavior of substances that expend on freezing.
Expansion of water on freezing
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Ice floats on liquid water, this unusual behavior is caused by the open structure of the regular
packing of water molecules in ice due to the network of hydrogen bonding in ice which is more
extensive than in liquid. The ice is less dense than water reason why it floats in water.
Water reaches its maximum density at 4°C (40°F). As it cools down further and freezes into ice, it
actually becomes less dense. The reason for this is found in the molecular structure of water and
because of its hydrogen bonding.
As water is cooled below 4°C, the hydrogen bonds adjust to hold the negatively charged oxygen
atoms apart with space in between. This produces a crystal lattice, which is commonly known as
'ice'.
In this configuration, ice water is about 9% less dense than liquid water. In other words, ice takes
up about 9% more space than water, so a liter of ice weighs less than a liter of water. Thus, ice
water is less dense than liquid water.
One fortunate consequence of this physical phenomenon is that lakes and rivers freeze from top to
bottom, allowing fish to survive even when the surface of a lake has frozen over. If ice sank, the
water would be displaced to the top and exposed to the colder temperature, forcing rivers and lakes
to fill with ice and freeze solid.
The most energetically favorable configuration of water molecules is one in which each molecule
is hydrogen-bonded to four neighboring molecules. Because of the thermal motion of the
molecules above the freezing point, this ideal configuration is never achieved in the liquid phase.
But when water freezes to ice and thermal energy is removed, the water molecules settle into
exactly this kind of an arrangement in the ice crystal.
4.2. Triple point

The triple point of carbon dioxide is above atmospheric pressure. This means that the state of liquid
carbon dioxide does not exist at ordinary atmospheric pressure. Dry ice remains as a solid below
-78ºC and changes to fog (gas) above -78ºC. It sublimes without forming liquid at normal
atmospheric pressure. The sublimation of carbon dioxide results in a low temperature which causes
water vapors in the air to form moist.
Ice is stable below 0 ºC and water is stable between 0ºC and 100 ºC while water vapor is stable
above 100 ºC. At normal atmospheric pressure, ice can first melt and ultimately boils as the
temperature increases.
5. Applied aspect of phase diagrams
The phase diagram is used to:
 Indicate the condition of temperature and pressure under which single phase of matter
exist or state of equilibrium can happen.
 Indicate the physical state of matter that exists under specific conditions.
 Provide the pressure dependence of phase transition temperatures (M.P, B.P and S.P).
The applications of phase diagrams are useful for engineer’s materials and material applications.
The scientists and engineers understand the behavior of a system which may contain more than
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one component. Multicomponent phase’s diagrams show the conditions for the formation of
solutions and new compounds. The phase diagrams are applied in solidification and casting
problems. Many materials and alloy system exist in more than one phase depending on the
conditions of temperature, pressure and compositions. In the area of alloy development, phase
diagrams have proved invaluable for tailoring existing alloys to avoid over design in current
applications, each phase has different microstructure which is related to mechanical properties.
The development of microstructure is related to the characteristics of phase diagrams. Proper
knowledge and understanding of phase diagrams lead to the design and control of heating
procedures for developing the required microstructure and properties.
Phase diagrams are consulted when materials are attacked by corrosion. They predict the
temperature at which freezing or melting begins or ends. Phase diagrams differentiate the critical
point, triple point, normal boiling point, etc of some substances.
Examples • Zn-Fe based high-order phase diagrams have found a wide range of applications in
continuous galvanizing. • The Zn-rich corner of the Zn-Fe-Al phase diagram is being used daily
for scientific interpretation of bath assays.
In general the industrial applications of phase diagrams include alloy design, processing, and
performance.s
UNIT 11: SOLUTIONS AND TITRATION
Be able to prepare standard solutions and use them to determine concentration of other solutions
by titration.
Learning objectives:
 Define the terms standard solution and primary standard solution.
 Explain the properties of a standard primary solution.
 Explain the titration process, emphasizing the need for precise measurements.
 Prepare solutions with different concentrations.
 Properly use the burettes, pipettes during titration.
 Interpret the experimental data obtained by titration and report.
 Carry out acid-base, redox titrations and do calculations involved.
 Develop a team approach and a sense of responsibility in performing the experiments of

titration.
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 Respect of procedure in practical experiment.
 Develop a culture of orderliness in performing practical experiments.
 Appreciate the use of appropriate measurements in daily life.
SOLUTIONS AND CONCENTRATIONS
Introduction
Solutions are homogeneous mixtures of two or more substances in which the substance present in largest
quantity is called the solvent, and the substance present in smallest quantity is called the solute.
Although a solvent can be a gas, liquid, or solid, the most common solvent is liquid water since it is
cheapest and the most available and has specific chemical properties of dissolving ionic compounds, polar
and compounds that can form hydrogen bonding.A solution with water as the solvent is called an aqueous
solution.
The amount of dissolved material (solute) in a solution is called the concentration and can be expressed
in different units
The concentration of a given solution can be determined through experiment by titration of that solution
using the solution whose concentration is known (standard solution) exploiting chemical reactions as well
as acid-basic reaction, redox reaction, precipitation reaction and electrochemical reactions.
CONCENTRATION UNITS
Several quantitative expressions of concentration are used in chemistry.
 Molarity, M = moles solute/liter of solution
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 Percentage (weight(w/W); Volume (v/V) affected by100 as a multiplicative factor. =
(mass (or volume) of solute/mass(or volume) of solution) x 100%
Mass percent solutions are defined based on the grams of solute per 100 grams of
solution. Example: 20 g of sodium chloride in 100 g of solution is a 20% by mass solution.
Volume percent solutions are defined as milliliters of solute per 100 mL of solution.
Example: 10 mL of ethyl alcohol plus 90 mL of H2O (making approx. 100 mL of solution)
is a 10% by volume solution.
Mass-volume percent solutions are also very common. These solutions are indicated by
w/v% and are defined as the grams of solute per 100 milliliters of solution.
Example: 1 g of phenolphthalein in 100 mL of ethyl alcohol is a 1 w/v% solution.
Note: Mass of solution = mass of solute + mass of solvent
 Parts per million, ppm = (mass of solute/mass of solution) x 106

 Mass per volume,Tm, g/L = mass of solute/liter of solution
 Molality, η= moles of solute/mass of solvent
Thus, a 0.1 molal solution of sodium chloride in water has 5.8443 grams of NaCl in 1000 grams (or 1kg of
water) of H2O.
Example: Calculate the molality of a solution of NaCl obtained by dissolving 50g of NaCl in 500g of water.
Answer: By definition, the molality is given by
 Mole fraction, χ = moles of solute/total moles
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 Normality: Normality is defined as the number of equivalents of solute per liter of
solution, and as such, is similar to Molarity. Normality, N = equivalents of solute/liter of
solution
Number of equivalents of solute = mass of solute/equiv. weight
nf is an integer constant ≥ 1
Hence, N(normality) = nf x M(molarity)
Function number, nf depends on substance, chemical species and chemical reaction that can be calculate
using the following simple definitions;
1. For, an acid, HnX, the function number nf is given by the number of the protons (H+) that
can be released into solution or that can be neutralized by a base.
2. For a base of Arrhenius, of generalized formulation, M(OH)m, the function number is

equal to the number of HO- that is released in solution or neutralized by an acid or more
general number of protons fixed or gained by a base.
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3. For any salts, of generalized formula, MxAy, the function number is equal to the number
of total positive charge as well as total negative charge from the dissolution of the salt in
solution.
4. In case of redox reaction involving reducing and oxidizing agent, the function number or
number of function is equal to the number of electrons that are exchanged.
Relation between different expressions of concentrations
a) Conversion between Percent Solutions
You may wish to convert mass percent to volume percent or vice versa. If so, follow this procedure:
A 10% by mass solution of ethyl alcohol in water contains 10 g of ethyl alcohol and 90 g of water.
1. The formula for determining the volume of the component (ethyl alcohol in our example) is:Volume
mass of ethyl alcohol
=
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑒𝑡ℎ𝑦𝑙 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
2. Determine the volume of the total solution by dividing the mass of the solution by the density of the
solution.
3. Determine the percent by volume by dividing the volume of the component by the volume of the
solution.
Let’s solve 1, 2, and 3 above as follows:
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1. Mass of ethyl alcohol = 10 g (given)
Density of ethyl alcohol = 0.794 g/mL (from handbook)
Volume of ethyl alcohol =10 g/0.794 gmL-1= 12.6 mL
2. Mass of solution = 100 g (given)
Density of solution (10% ethyl alcohol) = 0.983 g/ml (from handbook)
Volume of solution =100 g/0.983 g/mL = 101.8 mL
3. Volume percent of solution
Percent = volume of ethyl alcohol/ total volume of solution
=12.6/101.8= 12.4%
Reverse the procedure to convert volume percent to mass percent.
Note: The volume percent statement generally is accurate but the volume percent is not always calculated
directly from the volumes of the mixed ingredients because the final volume may not equal the sum of
the separate volumes. In our solution above note that if the alcohol volume (12.6 mL) is added to the
water volume (90 mL), the final volume is less than 102.6 mL.
b) Calculating Molarity from Percent Solutions
To determine the molarity of a mass percent solution, the density of the solution is required. Use the
following procedure:
1. Determine the mass of solution by multiplying the volume of the solution by the density of the solution.
Mass = volume x density
2. Determine concentration in percent by mass of the solute in solution. Change to the decimal equivalent.
3. Calculate the molar mass of the compound, MM.
4. Multiply mass (step 1) by mass % (step 2) and divide by molecular mass (step 3) to find the number of
moles present in the whole solution.
5. Divide the number of moles (step 4) by the volume in liters of the solution to find the molarity of the
solution.
Example: Determine molarity of 37.2% hydrochloric acid (density 1.19 g/mL).
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1. Mass of solution = 1,000 mL x 1.19 g/mL = 1,190 g
2. Mass % = 37.2 % = 0.372
3. Molar mass of hydrochloric acid = 36.4 g/mol
4. mass x mass %/ MmHCl
= 1,190 g x 0.372/36.4 g/mol= 12.1 moles
5. Molarity = moles/liters = 12.1 moles/1 liter = 12.1 M
𝐝∗%∗𝟏𝟎
Note: from the above calculation M=
𝐌𝐌𝐬
c) Relationship between molarity, normality and Tm
Examples:
1. A solution of sodium hydroxide has been prepared by dissolving 10 g in a beaker of 250Cm 3.
(a) Calculate its concentration in g/L, mol/L and normality.
Answer:
By definition, the concentration in g/L, mol/L and normality are given by
2. The stock solution available in your reagent chemical store has the following indication:
dangerous, corrosive, toxic, harmful, 1.84kg/L; 98%; 98g/mol ; H2SO4.
(i) Calculate its molarity
(ii) Deduce from (i) its normality, and its concentration in g/L
(iii) Calculate the mass of pure sulfuric acid contained in 1 Litre.

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Answer:(i) Let us consider d=1.84 since
EXERCISES
1. Determine the molarity of a solution prepared by dissolving 141.6 g of citric acid, C 3H5O(COOH)3, in
water and then diluting the resulting solution to 3500.0 mL. ans: 0.2106 M
2. What is the molarity of a salt solution made by dissolving 280.0 mg of NaCl in 2.00 mL of water? Assume
the final volume is the same as the volume of the water. ans: 2.40 M
3. What is the molarity of a solution that contains 390.0 g of acetic acid, CH3COOH, dissolved in enough
acetone to make 1000.0 mL of solution? ans: 6.494 M
4. Determine the molality of a solution of 560 g of acetone, CH3COCH3, in 620 g of water. ans: 16 m
5. What is the molality of a solution of 12.9 g of fructose, C6H12O6, in 31.0 g of water? ans: 2.31 m
6. How many moles of 2-butanol, CH3CHOHCH2CH3, must be dissolved in 125 g of ethanol in order to
produce a 12.0 m 2-butanol solution? ans: 1.50 mol 2-butanol
7. What is the percentage concentration of 75.0 g of ethanol dissolved in 500.0 g of water? ans: 13.0%
ethanol
8. A chemist dissolves 3.50 g of potassium iodate and 6.23 g of potassium hydroxide in 805.05 g of water.
What is the percentage concentration of each solute in the solution?
ans: 0.430% KIO3 0.765% KOH
9. A student wants to make a 5.00% solution of rubidium chloride using 0.377 g of the substance. What
mass of water will be needed to make the solution? ans: 7.16 g H2O
10. What mass of lithium nitrate would have to be dissolved in 30.0 g of water in order to make an 18.0%
solution? ans: 6.59 g LiNO3
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11. A solution is prepared by dissolving 13.5 g of sugar in 0.100 kg of water. What is the mass % of this
solution?
12. A solution of hydrochloric acid contains 36% HCl by mass. Calculate the mole fraction of HCl in this
solution.
13. A solution containing equal masses of glycerol, C3H8O3, and water has a density of 1.10 g/mL. Calculate
the molarity and molality of this solution.
14. A solution of H2O2 is 30.0% by mass with a density of 1.11 g/mL. Calculate the molarity, molality and
mole fraction of this solution.
Preparation of Standard solution
Introduction
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Many of the reagents used in science are in the form of solutions which need to be purchased or prepared.
For many purposes, the exact value of concentration is not critical; in other cases, the concentration of
the solution and its method of preparation must be as accurate as possible.
Professional quality solutions are possible when high quality and fresh chemicals and solvents are used,
and careful procedures are followed. These solution containing a precisely known concentration of an
element or a substance are called standard solution
Primary and Secondary Standards
We divide analytical standards into two categories: primary standards and secondary
standards.
A primary standard is a substance of high purity and stability which can be directly and accurately weighed
and dissolved in a known volume of solvent to give a primary standard solution.
A primary standard is a reference chemical used to measure an unknown concentration of another known
chemical. It can be used directly when performing titrations or used to calibrate standard solutions.
Primary standards exhibit distinctive characteristics that ideally suit them for making accurate and reliable
assessments of concentration without the need for specialized equipment. These characteristics
(properties) include:
 A primary standard must be a solid compound.
 have a known formula
 high level of purity (analytical reagent grade >99.8% pure)
 low reactivity (high stability)
 high molar weight (to reduce error from mass measurements)
 not hygroscopic (absorbing moisture) nor efflorescent (losing water) or affected by atmospheric
carbon dioxide or surrounding environment
 non-toxic
 inexpensive
 It is anhydrous
 Can be weighed easily
 Should be ready to use and available
 High solubility (if used in titration)
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Some important examples of primary standard are;
Primary Standards for Acid-Base Titrations
 Na2CO3, anhydrous sodium carbonate, for the titration of acids

 Na2B4O7(Sodium tetraborate),
 KH(C8H404) (Potassium hydrogen phthalate), for the titration of bases
 KH(I03)2 (Potassium hydrogen iodate),
 C6H5COOH (Benzoic acid)
Most alkali hydroxides, such as sodium hydroxide, NaOH, are not suitable for use as a primary standard
because they readily absorb moisture, H2O and carbon dioxide, CO2, from the atmosphere
Hydrochloric acid, HCl, and sulfuric acid, H2SO4, are not suitable for use as a primary standard because
although they are both commercially available as concentrated solutions that are easily diluted, the
concentration of the "concentrated" solution is not accurately known.
Nitric acid, HNO3, is not suitable for use as a primary standard because it always contains a little nitrous
acid, HNO2, which has a destructive action on many acid-base indicators.
Primary Standards for Redox Titrations
 potassium dichromate, K2Cr2O7, for redox titrations

 Potassium bromate (KBrO3) for standardization of sodium thiosulfate solutions
 Pure iron
 KBrO3 (potassium bromate),
 KIO3 (potassium iodate) and KH(IO3)2 (potassium hydrogen iodate).
 Sodium Oxalate (Na2C2O4),
 Arsenic (‫ )׀׀׀‬oxide(As2O3)
Potassium permanganate, KMnO4, is not suitable for use as a primary standard because it
 cannot be obtained pure enough

 Readily reacts with traces of organic material or other reducing substances in water
 decomposes in sunlight
A secondary standard this is a substance which gives solutions of approximately known concentrations.
This makes it essential that the secondary standard must first be standardized against the primary
standard.
A secondary standard is a chemical or reagent which has certain properties such as:
 It has less purity than primary standard

 Less stable and more reactive than primary standard
 But its solution remains stable for a long time
 Titrated against primary standard
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Examples of secondary standards
As noted above, substances like hydrochloric acid and sulfuric acid are not suitable for use as
primary standards because the concentration of the commercially available concentrated acids is
not known accurately.
However, you can prepare a dilute solution of these acids with an approximate concentration, and
then determine the concentration accurately by titration with a primary standard solution of a base
such as sodium carbonate.
Because the accurate concentration of acid has been derived using a primary standard, the acid is
referred to as a secondary standard.
Similarly, alkali hydroxides such as sodium hydroxide are unsuitable for use as primary standards
because they absorb moisture and carbon dioxide from the atmosphere.
However, you can prepare a sodium hydroxide solution with an approximate concentration by
weighing out some NaOH pellets and dissolving them in distilled water in a volumetric flask.
This solution can then be titrated with an acidic primary standard solution, such as potassium
hydrogen phthalate, KH(C8H4O4), in order to determine the concentration of the basic solution
more accurately.
Because the accurate concentration of the base has been derived using a primary standard, the base
is referred to as a secondary standard.
Therefore, substances which easily react with the components of air (O2, CO2 etc.), react when they are
weighting are called Secondary Standard Substance. e.g. HCL, H2SO4, NaOH, KOH, KMnO4, etc. are the
Secondary Standard Substance
Standard solution
In analytical chemistry, a standard solution is a solution containing a precisely known concentration of an

element or a substance. A known mass of solute is dissolved to make a specific volume and the resulting
solution has a known concentration. It is prepared by using a primary standard. It is often used to determine
the concentrations of other substances by titration. For example, you might prepare a standard solution of
KHP to determine the concentration of a solution of NaOH.
Properties of a primary standard solution
Standard solutions are carefully prepared solutions that are:
 Very stable.
 Of precisely known concentration
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 Its concentration must remain constant all the time.
 Its reaction with the analyte must be rapid in order to minimize the waiting period after
addition of each reagent.
 Its reaction must be reasonably complete.
 It should be possible to describe the reaction by a balanced chemical reaction.
 It contains greater percentage of purity.
Preparing Standard Solutions
We can prepare standard solutions in two ways depending on the state of the substance to be used:
Starting from Solids (dissolution): this can be done by weighing a known mass of the solid and dissolving
it in a specific volume of distilled water
Starting from concentrated solution (dilution): this consist of diluting a known volume of the
concentrated solution with diluted water to make a specified volume of a solution
To prepare laboratory solutions, usually a given volume and concentration are required. The following
examples illustrate the calculations for preparing solutions.
Preparation of standard solutions
The most common unit of solution concentration is molarity (M). The molarity of a solution is defined as
the number of moles of solute per one liter of solution. Note that the unit of volume for molarity is liters,
not milliliters or some other unit.
Also note that one liter of solution contains both the solute and the solvent. Molarity, therefore, is
a ratio between moles of solute and liters of solution.
In the preparation of solution, glasses, volumetric flask, pipette, glass rod, measuring cylinder, analytical
balance, spatula, beakers, magnetic stirrer and other laboratory devices are used.
Preparation of solution by dissolution of solids
If starting with a solid, use the following procedure:
• Determine the mass in grams of one mole of solute, the molar mass, Mm.
• Decide volume of solution required, in liters, V.
• Decide molarity of solution required, M.
• Calculate the mass in grams of solute (m) required using equation 1.
eq. 1. m = Mm x M x V
Example: Prepare 800 mL of 2 M sodium chloride.
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(MmNaCl = 58.45 g/mol)
mNaCl = 58.45 g/mol x 2 mol/L x 0.8 L
mNaCl = 93.52 g NaCl
Dissolve 93.52 g of NaCl in about 400 mL of distilled water, and then add more water until final volume is
800 mL.
Procedure:
i. Calculate the mass of sodium chloride needed (m1)
ii. Weigh a clean beaker, and record its mass (m2); with a clean spatula, add sodium chloride until the
combined mass of weighing beaker and sodium chloride is (m1 + m2).
iii. Add about 400 cm3 of distilled water, stir with a glass rod until all solids have dissolved.
iv. Pour all the solution carefully through a funnel into a 800 cm 3 volumetric flask; wash all the solution
out of the beaker and off the glass rod.
v. Add distilled water until the level is about 2 cm 3 below the graduation mark on the graduated flask. Add
the rest of distilled water from a washing bottle until the bottom of the meniscus is at the level of mark
when viewed at eye level.
vi. Insert the stopper of the flask and invert the flask several times to mix the solution.
vii. Label the solution.
Activity: Describe in details, how you can prepare the following solutions:
(a) 1L of KMnO4 0.1M

(b) 250 mL acidified potassium dichromate 1N
(c) 100 mL oxalic acid 5g/L.
(d) 50 mL of NaOH, 10%
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Preparation of solution by dilution
Apart from, dissolution method, we can prepare a solution by dilution from the stock solution.
This consists of reducing the concentration of a concentrated stock solution to less concentrated
solution by adding water.
The rationale is how we can prepare the desired solution of concentration C, with the volume V,
from the stock solution whose concentration is C o. The question consists of determination of the
volume Vo, to be pipetted from stock solution and diluted using Xml of water to get V.
So, from the conservation principle of matter, the quantity of the solute before and after dilution
should be the same.
n (before dilution) = n (after dilution)
n = c v (before dilution)
o o o
n = cv (after dilution)
Thus C V = CV and V =CV /Co

o o o
But, CoVo = C (Vo +x), solving with respect to x, we get
X= Vo (Co – C) /C but Co>C and x represents the volume of water to be added to Vo
Note:
1) The dilution factor is the concentration ratio or volume ratio defined as the number by
which the solution is diluted. It is given by:
2) The mixture of two solutions S1 and S2 of the same substance with different concentration
let C1 and C2 give the final solution S with intermediate concentration let C.
So, C1 < C < C2. Hence, from conservation rule of matter C1V1+ C2V2 = CV, therefore the new
concentration is given by:
If starting with a solution or liquid reagent one can proceed as follow:
• When diluting more concentrated solutions, decide what volume (V2) and molarity (M2) the final
solution should be.
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• Determine molarity (M1) of starting, more concentrated solution.
• Calculate volume of starting solution (V1) required using equation 2.
Note: V1 must be in the same units as V2.
eq.2. M1V1 = M2V2
Example: Prepare 100 mL of 1.0 M hydrochloric acid from concentrated (12.1 M) hydrochloric acid.
M1V1 = M2V2
(12.1 M)(V1) = (1.0 M)(100 mL)
V1 = 8.26 mL conc. HCl
Add 8.26 mL of concentrated HCl to about 50 mL of distilled water, stir, and then add water up to 100 mL.
Notice: Take care when mixing water and acid.
When you mix acid with water, it is extremely important to add the acid to the water rather than the other
way around. It is because acid and water react in a vigorous exothermic reaction, releasing heat,
sometimes boiling the liquid. If you add acid to water, the water is unlikely to splash up, but even if it did,
it is less likely to hurt you than if you add water to acid. When water is added to acid, the water boils and
the acid may splatter and splash.
Procedure:
i. Calculate the volume of the concentrated acid needed (V1) cm 3.
ii. Using a clean measuring cylinder take V1 of concentrated acid and transfer it carefully into 50 cm3 of
water into a 100 cm3 volumetric flask and shake.
iii. Make the solution up to the mark with distilled water.
iv. Insert the stopper, shake, invert and label.
TITRATION
Titration is a common laboratory method of quantitative chemical analysis that consist of determination
of the concentration of a known reactant (analyte) by the controlled addition and measurement of the
amount of a solution of known concentration (titrant) required to react completely with a measured
amount of a solution of unknown concentration(analyte).
The basis of the method is a chemical reaction of a standard solution (titrant) with a solution of an analyte.
The analyte (A) is a solution of the substance whose concentration is unknown and sought in the analysis.
The titrant (T) is a solution in which the concentration of a solute is precisely known. Because volume
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measurements play a key role in titration, it is also known as volumetric analysis. Usually it is the volume
of the titrant required to react with a given quantity of an analyte that is precisely determined during a
titration.
Using a calibrated burette to add the titrant, it is possible to determine the exact amount that has been
consumed when the endpoint of titration is reached. The endpoint is the point at which the titration is
complete, as determined by an indicator.
At the titration endpoint, the quantity of reactant in the titrant added during the titration is
stoichiometrically equivalent to the quantity of reactant in the analyte. This is ideally the same volume as
the equivalence point - the volume of added titrant at which the number of moles of titrant (nT) is equal
to the number of moles of analyte (nA), or some multiple thereof.
Titrations can be classified by the type of reaction. Different types of titration reaction include acid-base
titrations, redox titrations, etc.
I. Acid-base titration
Acid-base titrations are based on the neutralization reaction between the acid (or base) analyte and a
base (or an acid) titrant. These most commonly use a pH indicator (or pH-meters) to determine the
endpoint.
Neutralization is a chemical reaction, also called a water forming reaction, in which an acid and a base or
alkali (soluble base) react and produce a salt and water (H2O).
Acid + base → salt + water
For example, the reaction between hydrochloric acid and sodium hydroxide solutions:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
It is the determination of the concentration of an acid or base by exactly neutralizing the acid or base of
known concentration. Thus two kind of acid-base titration are known: Alkalimetry and acidimetry
 Alkalimetry is the specialized analytic use of acid-base titration to determine the concentration
of a basic substance.
 Acidimetry is the same concept of specialized analytic use of acid-base titration to determine the
concentration of an acidic substance.
Choice of indicators in acid-base titrations
Before starting the titration a suitable pH indicator must be chosen. The endpoint of the reaction, when
all the products have reacted, will have a pH dependent on the relative strengths of the acids and bases.
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pH indicators are generally very complex organic molecules (frequently weak acids or bases). When
introduced into a solution, they may bind to H+ or OH- ions. They will contain a structural component that
is called a chromophoric group. This group, or chromophore, will have a structure that changes slightly
when the pH of the system changes. The indicator will have one structure through one range of pH values,
and a second structure through a second range of pH values. When the structure changes, as a response
to pH, the chromophore will also change its color.
For more info follow this link: https://elearning.reb.rw/course/view.php?id=369&section=10
Note that the strength of an acid or base is not to be confused with the concentration of its solution.
Example of strong and weak acids and bases and choice of indicator are given in the Table below.
Examples of strong/weak acids and bases
Examples of indicators which are suitable for particular types of acid-base titrations
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Equipments and set up for Titration
The common equipment used in a titration are:
 Burette
 Pipette
 pH-indicator/acid-base indicator
 White tile: used to see a color change in the solution (a white paper can also be used)
 Conical flask (Erlenmeyer flask)
 Titrant: a standard solution of known concentration
 Analyte: a solution of unknown concentration
How to perform titrations
Knowing the use of pipette and burettes and how to handle them, the following points are useful
in order for a correct titration to be done:
1. The apparatus should be arranged as shown in the above Figure.
2. The burette tap is opened with the left hand and the right hand is used to shake the conical
flask.
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3. The equivalence-point is reached when the indicator just changes permanently the colour.
4. At the end-point, the level of the titrant is read on the burette
5. The titration is now repeated; three more times are recommended. Towards the end-point, the
titrant is added dropwise to avoid overshooting.
Notice: Before titration, check if the tip of the burette is filled with the titrant, and doesn’t contain bulb of
air. If there is a bulb of air, a quick opening and closing of the tap will expel the air out of the burette.
Titration procedure:
1. A known volume of the analyte is placed in a titration flask (Conical flask).
2. The burette is filled by a standard solution (titrant) of known concentration.
3. Before the titration is started, 1-3 drops of indicator is placed in the titration flask with the analyte. The
chosen indicator must be one color when the solution is acidic.
4.The titrant solution is then slowly added from the burette, drop by drop.
5. The titration continues, drop by drop, until the indicator suddenly change color. At that point the
titration ceases.
6. The point at which the system is neither acidic or basic is referred to as the endpoint. The endpoint will
correspond to a perfect stoichiometric relationship between the acid and the base.
7. Once the endpoint has been reached, the burette must be read. The bottom of the meniscus line
determines the quantity of the titrant that was required to reach the endpoint.
8. Once the titration is completed, the final calculations can be done.
Example: Standardization of sodium hydroxide using 0.1M Hydrochloric acid.
Reagents provided
 FA1 is 0.1M hydrochloric acid solution
 pellets
 Phenolphtalein indicator
 Distilled water.
Procedure:
Weigh accurately 1.0 g of sodium hydroxide pellets in a weighing bottle and transfer into a 250cm3
volumetric flask. Add a little distilled water and shake to dissolve. Make up the solution to the
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mark with distilled water. Label the solution FA2. Pipette 20 cm3 (or 25cm3) of FA2 into a conical
flask, add 2-3 drops of phenolphthalein indicator and titrate with FA1 from the burette. Record
your results.
Specimen results:
Mass of weighing container + NaOH pellets = 11.30 g
Mass of weighing container alone = 10.30 g
Mass of NaOH pellets = 11.30 g – 10.30 g = 1.00 g
Masses should be recorded to at least two decimal places.
Volume of pipette used = 25.0 cm3
Pipette readings should be written to one decimal places
The results of titration are summarized in a table as shown below.
Notice:
Burette readings should be written to two decimal places (for burette having precision up to hundredth).
Average volume should be obtained using values which differ not by more ± 0.10cm 3.
Questions:
a. Determine the values used to calculate average volume, and calculate the average volume of FA1 used.
b. Write the equation of the reaction between NaOH and HCl
c. Calculate the number of moles of FA1 used.
d. Calculate the concentration of FA2 in mol.dm-3.
e. Calculate the concentration of FA2 in g/L.
Answer:
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Volume of pipette used = 25.0 cm3
a. The values used to calculate average volume are 25.10 cm3 and 25.20 cm3
b. Equation: NaOH(aq) + HCl(aq)→ NaCl(aq) + H2O(l)
c. Number of moles of FA1 used: All working (calculation) should be done from first
principles:
1000 cm3 of FA1 solution contain 0.1 mole of HCl
Number of moles of FA1 = 0.002515 mol. = 0.002515 mol
d. Concentration of FA2 in mol.dm-3
From the equation of the reaction in (b); 1mole of HCl neutralizes 1mole of NaOH
Number of moles of FA2 used (reacted) = 0.002515 moles of NaOH.
25.0 cm3 of FA2 used contain 0.002515 mol
e. Concentration of FA2 in g/L (Na = 23, O =16, H=1) Molecular mass of NaOH = 23+16+1=
40g/mol
Thus 1 mole of NaOH weighs 40 g
0.1006 mole of NaOH will weigh = 40 x 0.1006g = 4.024g
Concentration of FA2 in g/l = 4.024g/L
Applications of titration
A) Determination of unknown concentration
This is the direct application of the definition of titration where the concentration of the analyte is
determined by a solution the titrant by exploiting the reaction that takes place between them.
Example: You are given 50.0 cm3 of sodium hydroxide solution of unknown concentration. You decide to
do a titration to find out the concentration of the solution. Using methyl orange indicator, you titrate the
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alkali against a 0.10 mol dm-3 solution of sulphuric acid. Having repeated the titration a suitable number
of times, you find that:
It takes 22.3 cm3 of 0.10 mol dm-3 sulphuric acid to neutralize 50.0 cm3 of sodium hydroxide solution.
Step 1
Write the balanced equation for the reaction:
2NaOH(aq) + H2SO4(aq) Na2SO4(aq) + 2H2O(l)
Step 2
Circle the information given and what you need to find out. This tells us that:
1 mole of sulphuric acid will neutralize 2 moles of sodium hydroxide.
Step 3
Find out how many moles of sulphuric acid there are in 22.3 cm3 of 0.10 mol dm-3 sulphuric acid.
In 1000 cm3 we have 0.10 moles.
0.10
So in 1 cm3 we would have moles
1000
0.10
Therefore in 22.3 cm3 we have × 22.3 moles = 0.00223 moles
1000
Step 4
Work out how many moles of sodium hydroxide must be in the unknown solution. We know from the
balanced equation that:
1 mole of sulphuric acid will neutralize 2 moles of sodium hydroxide. So 0.00223 moles of sulphuric acid
will react with 0.00223 × 2 moles of sodium hydroxide.
Therefore we know that 0.00446 moles of sodium hydroxide are present in the 50.0 cm 3 of solution.
Step 5
Work out the concentration of the solution:
We need to know how many moles there would be if we had 1000 cm 3 of the unknown solution.
From step 4 we know that:
In 50.0 cm3 of solution we have 0.00446 moles of sodium hydroxide.
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0.00446
Therefore in 1 cm3 we would have moles of sodium hydroxide.
50.0
0.00446
So in 1000 cm3 we would have × 1000 moles of sodium hydroxide = 0.089 mol dm-3 solution.
50.0
B) Determination of the molar mass
Molar masses of compounds can be determined by several experimental methods. In this experiment the
molar mass of an acid will be determined by acid-base titration.
Worked example: A chemist dissolves 0.9g of an unknown monoprotic (one acidic H) acid in water. The
chemist finds that 14.6mL of 0.426M NaOH are required to neutralize the acid.
Determine the molar mass of the acid.
Answer: suppose HX the molecular formula of the acid
So, HX +NaOH → NaX + H2O
Calculate moles of base required to reach the equivalence point

nb=MbxVb
nb=0.426mol/L x 0.0146L=0.006219mol. Therefore, 6.219 x 10 -3 mol of NaOH are required.
The acid base reaction is in the ratio 1:1; Therefore, 6.219 x 10 -3 mol of acid are present initially.
Calculation of the molar mass of the acid Mm of the acid in g/mol
Mm= (0.9g)/(0.006219mol)
Mm= 144.72g/mol
C) Determination of atomic masses
The atomic masses of an unknown element in a compound can be determined by the similar method as
above in B.
Worked example: A compound with the formula XOCl2 reacts violently with water, yielding HCl and the
diprotic acid H2XO3. When 0.350g of XOCl2 was added to 50.0 ml of water and the resultant solution was
titrated, 96.1 ml of NaOH 0.1225M was required to react with all the acid.
Find the atomic mass and identity of element X?
Answer:
the reaction of the compound with water is represented by:
XOCl2 + 2H20 →2HCl + H2XO3
The NaOH react with the two acid as follow
H2XO3 + 2NaOH →2H2O +Na2XO3
2HCl + 2NaOH→2NaCl +H2O, add the two equation to see well in which ration these will react.
So, four mol NaOH is equivalent to only one mol of H2XO3.
Now from the titration you should be able to calculate how much mol of XO Cl 2 will weight 0.350g.
Number of mol of NaOH= 0.0961L x 0.1225M= 1.177 x 10 -2 mol
1.177 x 10-2 mol of NaOH X 1 mol of H2XO3/ 4 mols of NaOH= 2.94 x 10-3mols
2.94 x 10-3mols H2XO3 x 1 mol of XOCl2/ 1 mol of H2XO3= 2.94 x 10-3 mol of XOCl2
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molar mass= 0.350g/2.94 x 10-3= 119.047 g/mol
Mass of element X=119.047g- {(35.5g x 2)+ 16.0g}= or32.047 g which is close to the mass of sulphur.
D) Determination of the number of moles of water of crystallization
Water of crystallization is defined as that definite amount of water which a substance associate
with on crystallizing out of an aqueous solution. Many crystals cannot form without the presence
of water i.e. water of hydration.
Examples of some hydrated substances
BaCl2.2H2O: Barium chloride
CuSO4.5H2O: Copper (II) sulphate
Na2CO3.10H2O: Sodium carbonate
Na2S2O3.5H2O: Sodium thiosulphate
Water of crystallization can be determined by using two different methods.
a) Weighing method
This method is preferably used when the crystals are neutral, and they cannot react with acid or
basic solution.
Procedure: (For example, CuSO4. xH2O)
 Weigh the mass of a clean dry crucible with lid.
 Two or three grams of hydrated CuSO4.XH2O are added and the whole set up is weighed.
 The crucible, lid and the content are heated on a pipe-clay triangle on a tripod stand, gently
at first and later strongly, to drive off water of crystallization.
 The set up is allowed to cool in a dessicator (to exclude moisture) and reweighed.
 Heat again the crucible, lid and content and then cool as before and weigh again.
 Repeat the process of heating, cooling and reweighing until a constant mass is reached
which shows that all water has been expelled.
 Using calculations, it is possible to get x moles of water of crystallization found in one

mole of substance. See the following example:
Example 1: If 2.465g of hydrated magnesium sulfate loses 1.26g of water by heating. Determine the
crystallization number.
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Answer: Let us consider the reaction
Therefore, the crystallization number can be

determined as follow:
From stoichiometry ratio of the reaction of heating effect, we remark that:
Hence, we get Mg SO4.7 H2O. It is obvious that water content is 51.12% for this compound.
Example2: 4.99g of hydrated copper (II) sulphate, CuSO4.x H2O was strongly heated until all
water of crystallization was eliminated. The mass of anhydrous copper sulphate was found to be
3.19g. Calculate the number of moles of water of crystallization contained in one mole of
CuSO4.xH2O (Cu = 63.5, S = 32, O =16, H = 1)
Answer: Mass of water = 4.99g – 3.19g = 1.8g
Mr for CuSO4 = 63.5 +32 +64 = 159.5
Number of moles of anhydrous CuSO4= 3.19/159.5 = 0.02 mol
Number of moles of water = 1.8/18 = 0.1mol
Number of moles of water of crystallization =0.1/0.02 = 5
So, we may write: CuSO4.5H2O.
b) Using titration
Titration is used for crystals substance which are either basic or acidic for example H2C2O4.x H2O,
Na2CO3.x H2O. This method obeys all the titration principles used in acid-base titration.
Example: 400 ml of zinc sulphate solution 0.5N is prepared by dissolving 28.76g de ZnSO 4 . xH2O, but x is
the crystallization number to be determined.
Answer: 400 ml that is 0.4 L ; with N= 0.5eq/l→M=0.5/2=0.25,

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ZnSO4(aq)→ Zn2+(aq)+ SO42- (aq), nf=2
 Calculation, the number of mole of the salt in solution, n=MxV; 0.4x0.25=0.1mol

 Calculate the molar mass of the hydrated salt=m/n=28.76g/0.1mol=287.6g
 Determine the value of x in the salt:
Mass of ZnSO4 in 1 mole of ZnSO4 . xH2O=161.4g
Mass of water in 1 mole of ZnSO4 . xH2O=287.6-161.4=126.2g
Value of x= 126.2/18=7 . so the formula of hydrated salt is ZnSO4 . 7H2O
Exercise2: The determination of the number of water crystallization of ethanedioic acid or oxalic acid:
C2H2O4.x H2O.
Procedure: 1.6 g of acid crystals are dissolved in distilled water and then made up to the 250Cm 3 mark in
a volumetric flask. 25Cm3 portions of this solution is then titrated with 0.1M sodium hydroxide solution
using phenolphthalein as indicator.
Results: 25Cm3 of acid solution required 25.04 Cm3 of the sodium hydroxide solution.
Calculations:
i. Write down the balanced chemical reaction
ii. Calculate the number of moles of hydrated oxalic acid contained in 250Cm3.
iii. Calculate the molecular mass of hydrated oxalic acid.
iv. Calculate the number of moles of water of crystallization(x).
v. Calculate the percentage of water in the hydrated oxalic acid.
Answer: x=2
BACK TITRATION (INDIRECT TITRATION) CALCULATIONS
A back titration, or indirect titration, is generally a two-stage analytical technique:
1. Reactant A of unknown concentration is reacted with excess reactant B of known concentration.
2. A titration is then performed to determine the amount of reactant B in excess.
Back titrations are used when:
 one of the reactants is volatile, for example ammonia.
 an acid or a base is an insoluble salt, for example calcium carbonate
 a particular reaction is too slow
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 direct titration would involve a weak acid - weak base titration
(the end-point of this type of direct titration is very difficult to observe)
Example: Back (Indirect) Titration to Determine the Concentration of a Volatile Substance
A student was asked to determine the concentration of ammonia, a volatile substance, in a

commercially available cloudy ammonia solution used for cleaning.
First the student pipetted 25.00mL of the cloudy ammonia solution into a 250.0mL conical flask.
50.00mL of 0.100M HCl(aq) was immediately added to the conical flask which reacted with the ammonia
in solution.
The excess (unreacted) HCl was then titrated with 0.050M Na2CO3(aq).
21.50mL of Na2CO3(aq) was required.
Calculate the concentration of the ammonia in the cloudy ammonia solution.
Step 1: Determine the amount of HCl in excess from the titration results
1. Write the equation for the titration:
2HCl(aq)+ Na2CO3(aq) → 2NaCl(aq) + CO2(g)+ H2O(l)
2. Calculate the moles, n, of Na2CO3(aq) that reacted in the titration:

n=MxV
M = 0.050 molL-1
V = 21.50mL = 21.50 x 10-3L
n(Na2CO3(aq)) = 0.050 x 21.50 x 10-3 = 1.075 x 10-3 mol
3. Use the balanced chemical reaction for the titration to determine the moles of HCl that reacted
in the titration.
From the balanced chemical equation, 1 mole Na2CO3 react with 2 moles of HCl
So, 1.075 x 10-3 mole Na2CO3 reacted with 2 x 1.075 x 10-3 moles HCl
n(HCltitrated) = 2 x 1.075 x 10-3 = 2.150 x 10-3 mol
4. The amount of HCl that was added to the cloudy ammonia solution in excess was
2.150 x 10-3 mol
Step 2: Determine the amount of ammonia in the cloudy ammonia solution
1. Calculate the total moles of HCl originally added to the diluted cloudy ammonia solution:
n(HCltotal added) = M x V
M = 0.100 molL-1
V = 50.00mL = 50.00 x 10-3L
n(HCltotal added) = 0.100 x 50.00 x 10-3 = 5.00 x 10-3 mol
2. Calculate the moles of HCl that reacted with the ammonia in the diluted cloudy ammonia
solution
n(HCltitrated) + n(HClreacted with ammonia) = n(HCltotal added)
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n(HCltotal added) = 5.00 x 10-3 mol
n(HCltitrated) = 2.150 x 10-3 mol
2.150 x 10-3 + n(HClreacted with ammonia) = 5.00 x 10-3
n(HClreacted with ammonia) = 5.00 x 10-3 - 2.150 x 10-3 = 2.85 x 10-3 mol
3. Write the balanced chemical equation for the reaction between ammonia in the cloudy
ammonia solution and the HCl(aq).
NH3(aq) + HCl(aq) → NH4Cl(aq)
4. From the balanced chemical equation, calculate the moles of NH3 that reacted with HCl.
From the equation, 1 mol HCl reacts with 1 mol NH3
So, 2.85 x 10-3 mol HCl had reacted with 2.85 x 10-3 mol NH3 in the cloudy ammonia solution.
5. Calculate the ammonia concentration in the cloudy ammonia solution.

M=n÷V
n = 2.85 x 10-3 mol (moles of NH3 that reacted with HCl)
V = 25.00mL = 25.00 x 10-3L (volume of ammonia solution that reacted with HCl)
M = 2.85 x 10-3 ÷ 25.00 x 10-3 = 0.114 M
6. The concentration of ammonia in the cloudy ammonia solution was 0.114M
Example: Back (Indirect) Titration to Determine the Amount of an Insoluble Salt
A student was asked to determine the mass, in grams, of calcium carbonate present in a 0.125g sample
of chalk.
The student placed the chalk sample in a 250mL conical flask and added 50.00mL 0.200M HCl using a
pipette.
The excess HCl was then titrated with 0.250M NaOH.
The average NaOH titre was 32.12mL
Calculate the mass of calcium carbonate, in grams, present in the chalk sample.
Step 1: Determine the amount of HCl in excess from the titration results
1. Write the equation for the titration:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
acid base → salt water
2. Calculate the moles, n, of NaOH(aq) that reacted in the titration:

n=MxV
M = 0.250 molL-1
V = 32.12mL = 32.12 x 10-3L
n(NaOH(aq)) = 0.250 x 32.12 x 10-3 = 8.03 x 10-3 mol
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3. Use the balanced chemical reaction for the titration to determine the moles of HCl that reacted
in the titration.
From the balanced chemical equation, 1 mole NaOH reacts with 1 mole of HCl
So, 8.03 x 10-3 mole NaOH reacted with 8.03 x 10-3 moles HCl
4. The amount of HCl that was added to the chalk in excess was
8.03 x 10-3 mol
Step 2: Determine the amount of calcium carbonate in chalk
1. Calculate the total moles of HCl originally added to the chalk:

n(HCltotal added) = M x V
M = 0.200 molL-1
V = 50.00mL = 50.00 x 10-3L
n(HCltotal added) = 0.200 x 50.00 x 10-3 = 0.010 mol
2. Calculate the moles of HCl that reacted with the calcium carbonate in the chalk
n(HCltitrated) + n(HClreacted with calcium carbonate) = n(HCltotal added)
n(HCltotal added) = 0.010 mol
n(HCltitrated) = 8.03 x 10-3 mol
8.03 x 10-3 + n(HClreacted with calcium carbonate) = 0.010
n(HClreacted with calcium carbonate) = 0.010 - 8.03 x 10-3 = 1.97 x 10-3 mol
3. Write the balanced chemical equation for the reaction between calcium carbonate in the chalk
and the HCl(aq).
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
4. From the balanced chemical equation, calculate the moles of CaCO3 that reacted with HCl.
From the equation, 1 mol CaCO3 reacts with 2 mol HCl so, 1 mol HCl reacts with ½ mol CaCO3
So, 1.97 x 10-3 mol HCl had reacted with ½ x 1.97 x 10-3 = 9.85 x 10-4 mol CaCO3 in the chalk.
5. Calculate the mass of calcium carbonate in the chalk.

n = mass ÷ MM
n = 9.85 x 10-4 mol (moles of CaCO3 that reacted with HCl)
MM(CaCO3) = 40.08 + 12.01 + (3 x 16.00) = 100.09 g/mol
mass = n x MM = 9.85 x 10-4 x 100.09 = 0.099g
6. The mass of calcium carbonate in the chalk was 0.099g
II. REDOX TITRATION
Introduction
We can use the method of titration to measure the concentrations of acids and bases in acid-base
reactions. A redox titration uses the same technique but is applied to the reactants in a redox reaction.
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There are three reagents most commonly used in redox titration: manganate (VII) ion, dichromate (VI)
ion, and thiosulphate ion.
A. The manganate (VII) ion as an oxidant
Potassium manganate(VII), KMnO4 is used to titrate:
(i) iron(II) ions,
(ii) (ii) ethanedioates,
(iii) (iii) hydrogen peroxide and
(iv) (iv) nitrate(III) ions (old name 'nitrite').
The titrations are done with dilute sulphuric acid present to prevent side reactions e.g. MnO 2 formation
(brown colouration or black precipitate).
The choice of acid is very important; The mineral acid must be dilute sulfuric acid because potassium
manganate(VII) will oxidise hydrochloric acid
(2MnO4-(aq) + 16H+(aq) + 10Cl-(aq) → 2Mn2+(aq) + 8H2O(l) + 5Cl2(g) ) and nitric(V) acid is an oxidising agent itself,
so use of either of these acids leads to inaccurate false titration results.
Weak acid such as ethanoic acid cannot be used since they do not provide a high enough concentration of
H+ ions.
Notice that no indicator is used in this titration. The potassium manganate (VII) acts as its own indicator.
As the reaction proceeds the purple manganate (VII) is reduced to manganese (II),
which is pale pink but practically colorless. At the end point one drop of excess manganate (VII) will produce
a permanent pale pink coloration of the solution.
(i) MnO4-(aq) + 8H+(aq) + 5Fe2+(aq) → Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)
Theoretically, there are actually two simultaneous colour changes, both masked by the redox indicator
change.
The purple manganate(VII) ion changes on reduction to the very pale pink manganese (II) ion, and the pale
green iron(II) ion changes on oxidation to the orange iron(III) ion, However, in the dilute solution of the
titration mixture, the first permanent pink colour does stand out from the pale orange of the iron(III) ion
plus the very pale pink of the manganese(II) ion.
In the other examples (ii) to (iv) below, the reductants and oxidation products are colourless, so the colour
of the very pale pink manganese(II) ion is visually overridden by the first drop of excess of the bright purple
potassium manganate(VII).
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(ii) 2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq) →2Mn2+(aq) + 8H2O(l) + 10CO2(g)
(iii) 2MnO4-(aq) + 6H+(aq) + 5H2O2(aq) → 2Mn2+(aq) + 8H2O(l) + 5O2(g)
(iv) 2MnO4-(aq) + 6H+(aq) + 5NO2-(aq) → Mn2+(aq) + 5NO3-(aq) + 3H2O(l)
(i) Titration of Fe2+ by Potassium manganate (VII), KMnO4
Most redox titration labs utilize an iron (II) salt, frequently iron (II) sulphate heptahydrate. This
compound is used for two reasons. First, it has a large molar mass, making it a good (but not the
best) primary standard. Second, its solution is near colorless, so the pink/purple endpoint is easy
to detect. Color proves to be an issue when dealing with many other compounds. Iron (II) salts are
an excellent choice for a titration utilizing potassium permanganate.
MnO (aq) +8H (aq) +5e →Mn (aq) +4H O(l)

4- + - 2+
2
5xFe (aq) → 5xFe (aq) + 5xe

2+ 3+ -
MnO (aq) + 5Fe (aq) +8H (aq) →Mn (aq) +5Fe (aq) +4H O(l)
4
- 2+ + 2+ 3+
2
Reaction ratio MnO4-: Fe2+ is 1: 5
Example: A solution contains both iron(II) and iron(III) ions. A 50.0 mL sample of the solution is titrated
with 35.0 mL of 0.00280 M KMnO4, which oxidizes Fe2+ to Fe3+. The permangante ion is reduced to
manganese(II) ion. Another 50.0 mL sample of solution is treated with zinc metal, which reduces all the
Fe3+ to Fe2+. The resulting solution is again titrated with 0.00280 M KMnO4, this time 48.0 mL is required.
What are the concentrations of Fe2+ and Fe3+ in the solution?
Solution:
1) The stoichiometric relationship of permangante to Fe(II):
5Fe2+ + 8H+ + MnO4¯ →5 Fe3+ + Mn2+ + 4 H2O
The ratio is five to one (5:1).
2) Calculate moles of Fe(II) reacted:
(0.00280 mol / L) (0.0350 L) = 0.000098 mol of MnO4¯
(0.0000980 mol Mn) (5 mol Fe / 1 mol Mn) = 0.000490 mol Fe(II)
3) Determine the total iron content:
(0.00280 mol / L) (0.0480 L) = 0.0001344 mol of MnO4¯
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(0.0000980 mol Mn) (5 mol Fe / 1 mol Mn) = 0.000672 mol of total Fe
4) Determine Fe(III) in solution and its molarity:
0.000672 mol - 0.000490 mol = 0.000182 mol
0.000182 mol / 0.050 L = 0.00364 M
5) Determine molarity of Fe(II):
0.000490 mol / 0.050 L = 0.0098 M
(ii) Titration of oxalic acid or oxalates by potassium manganate (VII)
The reducing agent is the oxalate ion, C O . Oxalic acid is a white crystalline solid of formula
2 4
2-
H C O .2H O
2 2 4 2
The reaction between the oxalate ion and manganate (VII) ion is kinetically slow at temperature
below 60 C. Titrations at room temperature take too long time for the purple color of the manganate
0
(VII) ion to disappear. In the oxalate ion, carbon has the oxidation state of +3; when reacted with
potassium permanganate the oxidation state changes into +4. The reaction below describes the
overall redox reaction:
2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq) →2Mn2+(aq) + 8H2O(l) + 10CO2(g)
The reaction ratio is MnO4- : C2O42- = 2: 5
Example: 0.2640 g of sodium oxalate is dissolved in a flask and requires 30.74 mL of potassium
permanganate (from a buret) to titrate it and cause it to turn pink (the end point).
The equation for this reaction is:
5Na2C2O4(aq) + 2KMnO4(aq) + 8H2SO4(aq) → 2MnSO4(aq) + K2SO4(aq) + 5Na2SO4(aq) + 10 CO2(g) + 8 H2O(l)
(a) How many moles of sodium oxalate are present in the flask?
(b) How many moles of potassium permanganate have been titrated into the flask to reach the end
point?
(c) What is the molarity of the potassium permanganate?
Solution to (a):
0.2640 g / 134.00 g/mol = 0.001970149 mol to four sig figs, this would be 0.001970 mol
Solution to (b):
From the balanced equation, the oxalate-permanganate molar ratio is five to two.
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0.001970149 mol oxalate times (2 mol permanganate / 5 mol oxalate) = 0.00078806 mol permanganate
to four sig figs, this is 0.0007881 mol
Solution to (c):
0.00078806 mol / 0.03074 L = 0.02564 M (to four sig figs)
(iii)Titration of hydrogen peroxide by potassium manganate (VII), KMnO 4
Hydrogen peroxide is a powerful reducing agent in the presence of a strong oxidizing agent such as
potassium permanganate. For this reason, dilute concentrations of both compounds must be used. A
common laboratory experiment determines the concentration of commercially sold hydrogen peroxide
(about 3%) via titration with potassium permanganate (usually prepared to be approximately 0.02 M).
Concentrated solutions of these reactants will react explosively and must be avoided.
H2O2(aq) → 2H+(aq) + O2(g) +2e- (Oxidation)
MnO4-(aq) + 8H+(aq) + 5e-→ Mn2+(aq) + 4H2O(l) (Reduction)
Overall equation is:
2MnO4-(aq) + 6H+(aq) + 5H2O2(aq) → 2Mn2+(aq) + 8H2O(l) + 5O2(g)
Reaction ratio is MnO4- : H2O2 = 2: 5
The concentration of H2O2 solution is usually expressed in terms of volume of oxygen measured at s.t.p,
available from a fixed amount (or mass) of H2O2.
This unit of concentration is called volume strength or volume concentration.
Thus, volume strength is defined as, the volume of oxygen available from a unit volume of the H 2O2
solution measured at s.t.p.
Therefore, a volume solution of H2O2 is one, which yields 1volume of O2 for each volume of the H2O2
solution decomposed, example: 1cm3 of 100 volume H2O2decomposes to yield 100cm3 of O2 measured at
s.t.p. from the equation:
2H2O2 (aq)→ 2H2O (l) + O2 (g)
By definition; 2moles of H2O2 produces 1mole of O2 which has volume strength of 22.4 litres at
s.t.p.
1mole of H2O2 has volume strength of 11.2 litres at s.t.p or 22.4 volume solution contains 68g/l
H2O2.
Example: 100 cm3 of H2O2 was dissolved in 1dm3 of solution. 25 cm3 of the solution was titrated
with 44cm3 of 0.02M KMnO4 acidified with H2SO4.
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a. Calculate the concentration of H2O2 solution in mol dm-3.
b. Calculate the volume of oxygen produced
Answer:
Write the balanced equation
2MnO4-(aq) + 6H+(aq) + 5H2O2(aq) → 2Mn2+(aq) + 8H2O(l) + 5O2(g)
a. Moles of MnO4- = 44x10-3 x 0.02 =0.88x10-3 mole
Mole ratio is MnO4- : H2O2 = 2: 5
2moles of MnO4- titrate 5moles of H2O2
0.88x10-3 moles of MnO4- = x 0.88x10-3 moles = 2.2x10-3 moles of H2O2 in 25cm3
1000cm3 of H2O2 contain = =0.088M
b. Volume of oxygen:
Mole of O2: 1Mole H2O2 decomposes to give mole of O2
0.088 Mole of H2O2 = 0 .088 Mole x0.5 =0.044 moles of O2
But 1mole of O2 occupies 22.4 dm3
0.044 mole of O2 = 0.044 mole x22.4 dm3/mole = 0.9856 dm3 = 985.6cm3
Note: The advantages of potassium permanganate as oxidizing agent are:
i. It acts as its own indicator (i.e. purple color)
ii. The crystals are obtained at high state of purity
iii. The crystals are anhydrous and not deliquescent
iv. It has a fairly high relative molecular mass
v. A wide range of substances can be oxidized by it.
However, potassium permanganate has disadvantages:
i. The crystals are not very soluble in water
ii. The compound is decomposed by the light

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iii. The compound is reduced by water and organic matter from atmosphere
iv. The meniscus of the solution may be difficult to see.
Activity: This Question has many parts covering the titration of iron(II) ions with a standard solution of
potassium manganate(VII).
The relative atomic mass of iron = 55.9
Here are the two half equation: MnO4-(aq) + 8H+(aq) + 5e-→ Mn2+(aq) + 4H2O(l)
and ( Fe3+(aq) + e- →Fe2+(aq)
(a) Construct the fully balanced redox ionic equation for the manganate(VII) ion oxidising the iron(II) ion
(b) 24.3 cm3 of 0.0200 mol dm-3 KMnO4 reacted with 20.0 cm3 of an iron(II) solution.
(i) Calculate the molarity of the iron(II) ion.
(ii) How do recognise the end-point in the titration?
(c) Calculate the percentage of iron in a sample of steel wire if 1.51 g of the wire was dissolved in excess
of dilute sulphuric acid and the solution made up to 250 cm3 in a standard graduated flask. A 25.0 cm3
aliquot of this solution was pipetted into a conical flask and needed 25.45 cm3 of 0.0200 mol dm-3 KMnO4
for complete oxidation.
(d) Suggest reasons why the presence of dil. sulfuric acid is essential for an accurate titration and why dil.
hydrochloric and nitric acids are unsuitable to be used in this context.
(e) The analysis of a soluble iron(II) salt to obtain the percentage of iron in it.
8.25g of an iron(II) salt was dissolved in 250 cm3 of pure water. 25.0 cm3 aliquots were pipetted from this
stock solution and titrated with 0.0200 mol dm-3 potassium manganate(VII) solution.
The titration values obtained were 23.95 cm3, 23.80 cm3 and 23.85 cm3.
(i) What titration value should be used in the calculation and why?
(ii) Calculate the moles of manganate(VII) used in the titration.
(iii) calculate the moles of iron(II) ion titrated
(iv) Calculate the mass of iron(II) titrated
(v) Calculate the total mass of iron in the original sample of the iron(II) salt.
(vi) calculate the % iron in the salt.
B. Titration with potassium dichromate (VI), K2Cr2O7

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Potassium dichromate (VI) unlike potassium manganate (VII) is a primary standard. In the titration of
potassium dichromate (VI), the color change is from orange to green and this makes it not possible to
detect the sharp end-point.
Thus, an indicator is necessary for this reaction. Therefore, redox indicator such as barium diphenylamine
sulphonate must be used, which changes its colour to blue at the end point.
Potassium dichromate (VI) is a weaker oxidizing agent than potassium manganate (VII). As such it cannot
oxidize the chloride ion to chlorine, and therefore hydrochloric acid in addition to sulphuric acid can be
used to acidify solution of potassium dichromate (VI).
The reactions of potassium dichromate (VI) are similar to those of potassium manganate (VII), however at
the end-point the color is green due to the presence of chromium (III) ions that is;
Cr2O72-(aq) + 14H+(aq) +6e- →2Cr3+(aq)+7H2O(l)
In volumetric analysis, K2Cr2O7 is commonly used in:
a. Determination of the concentration of iodide ions.
Since iodide ions can be oxidized to molecular iodine by dichromate (VI) ion, potassium dichromate
(VI) can be used as a primary standard in this reaction.
2I (aq) → I (aq) +2e

-
2
-
Oxidation half-reaction
Cr O (aq) + 14H (aq) +6e →Cr (aq) + 7H O(l)

2 7
2- + - 3+
2 Reduction half-reaction
Overall reaction equation is:
Cr O (aq) +14H (aq) + 6I (aq) → 2Cr (aq) +3I (aq) +7H O (l)
2 7
2- + - 3+
2 2
The amount of iodine liberated in the reaction is determined by titrating it against a standard solution of
sodium thiosulphate using starch indicator.
b. Analysis of iron (II) salts
In this titration the iron(III) ions formed affect the indicator to give an inaccurate end point so
phosphoric(V) acid is also added at the start to complex the Fe3+ ions as they form.
Fe2+(aq) Fe3+(aq) +e- oxidation half-reaction
Cr2O72- (aq) +14H+ (aq) +6Fe2+ (aq) 2Cr3+ (aq) +6Fe3+ (aq) +7H2O (l)
c. Analysis of nitrite salts
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NO- (aq) +2H2O (l) NO3- (aq) +4H+ (aq) +4e-
d. Analysis of tin (II) salts
Sn2+ (aq) Sn4+ (aq) +2e-
Advantages of K2Cr2O7 over KMnO4
Unlike KMnO4, K2Cr2O7 is used as a primary standard i.e. it can always be obtained pure; it is stable under
ordinary conditions, its aqueous solution can be stored for long time if sufficiently protected from
evaporation.
Example: 4.0 g of hydrated ammonium ferrous sulphate (NH4)2SO4.FeSO4.6H2O (Mohr’s salt) are
dissolved in 25.0 cm3 of 2 M H2SO4 and made up to 250.0 cm3 with distilled water. 25.0 cm3 of the
resultant solution required 15.0 cm3 of potassium dichromate (VI) during the titration. Calculate
concentration of potassium dichromate (VI).
Answer:
Molar mass of ammonium ferrous sulphate = 392 g/mol
Mass of Fe2+ salt in 1 dm3 = = 16.0 g Molarity of iron (II) salt = = 0.04 M
Cr2O72-(aq) + 14H+(aq) +6Fe2+(aq) →2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l)
Number of moles of Fe2+ in 25.0 cm3 = (0.04x25.0)/1000 = 0.001 mol
Number of moles of Cr2O72- = x number of moles of Fe2+ i.e.: x 0.001 = 0.000167 mol
Concentration of Cr2O72- = = 0.01 M
C. Titrations involving sodium thiosulphate and iodine
Sodium thiosulphate is a white crystalline solid with the formula Na 2S2O3.5H2O. It is not a primary
standard as the water content of the crystals is variable. The solid acts as a reducing agent in a redox
reaction and the reducing agent being the thiosulphate ion, S2O3-2.
2S2O32-(aq) S4O62-(aq)
However, the thiosulphate ion is very sensitive to acid (weak or strong). In presence of an acid
(hydrogen ions), it decomposes to sulphur dioxide and elemental sulphur (which settles as a yellow
precipitate).
S2O32-(aq) +2H+(aq) SO2(g) +S(s) + H2O(l)
Therefore, solutions of sodium thiosulphate should never be acidified.
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The thiosulphate ions reduce iodine according to the reaction below:
I2 (aq) +2e- 2I- (aq)
2S2O32- (aq) +I2 (aq) S4O62- (aq) + 2I- (aq)
a. Detection of the end point:
In titrations involving iodine and sodium thiosulphate, starch is normally used as an indicator.
Addition of the starch produces iodine-starch complex which is blue. Further drop by drop addition of
the thiosulphate solution is continued until the solution turns colorless which marks the end point of
titration.
Thiosulphate titration has important applications in the laboratory and water treatment plants.
Potassium iodate (V), potassium dichromate (VI), iodine, potassium manganate (VII) solutions can be
used to standardize sodium thiosulphate solutions.
For example, potassium iodate (V) reacts with iodide ions in presence of an acid to liberate iodine.
2IO3-(aq) + 12H+(aq) + 10e- → I2(aq) + 6H2O(l) Reduction half reaction
2I- (aq) → I2 (aq) +2e- Oxidation half reaction
2IO3-(aq) + 12H+(aq) + 10I-(aq) → 6I2(aq) + 6H2O(l) Overall reaction
The liberated iodine is then titrated against standard sodium thiosulphate using the starch indicator.
2S2O32- (aq) +I2 (aq) S4O62- (aq) + 2I- (aq)
b. Preparation of starch solution:
0.5g of soluble starch powder is mixed with water into a thin smooth paste which is then poured into
300cm3 of boiling water. The mixture is then boiled after for about a minute. The solution is then cooled
and used when still fresh. But starch solution may be preserved by addition of few crystals of mercuric
iodide.
Example: 1 g of solid potassium iodate V was dissolved and made up to 250 cm3 of solution. 25.0 cm3 of
the resultant solution is pipetted into a conical flask containing a mixture of 10% solution potassium iodide
and 10 cm3 of 2 M sulphuric acid. The solution in the flask is then titrated with sodium thiosulphate in the
presence of starch indicator. This solution required 20.0 cm 3 of thiosulphate solution. Calculate the
concentration of the thiosulphate solution in g/dm3.
Answer:
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Molar mass of KIO3 = 214.1 g/mol
Mass of KIO3 in 1 dm3 = = 4.0 g
Molarity of KIO3 = = 0.0187 M
Number of moles of KIO3 in 25 cm3 = = 0.0004675 mol
Reactions:
2IO3- (aq) + 12H+ (aq) + 10I-(aq) 6I2 (aq) + 6H2O (l)
2S2O32- (aq) +I2 (aq) S4O62- (aq) + 2I- (aq)
Combining the above equations with elimination of iodine (I 2) we get:
IO3- (aq) + 6H+ (aq) + 6S2O32- (aq) 3S4O62- (aq) + I- (aq) + 3H2O (l)
Number of moles of thiosulphate = 6 x number of moles of IO3-i.e.: 6 x 0.0004675 = 0.002805 moles
Concentration of thiosulphate = = 0.14025 M
Molar mass of Na2S2O3.5H2O = 248 g/mole
Concentration in g.dm-3 = Molarity x molar mass = 0.14025 x 248 = 34.8 g.dm-3
Activity: 1.01g of an impure sample of potassium dichromate(VI), K2Cr2O7, was dissolved in dil. sulphuric
acid and made up to 250 cm3 in a calibrated volumetric flask. A 25.0 cm3 aliquot of this solution pipetted
into a conical flask and excess potassium iodide solution and starch indicator were added. The liberated
iodine was titrated with 0.100 mol dm-3 sodium thiosulphate and the starch turned colourless after 20.0
cm3 was added.
(a) Using the half-equations, construct the full balanced equation for the reaction between the
dichromate(VI) ion and the iodide ion.
(b) Using the half-equations, construct the balanced redox equation for the reaction between the
thiosulphate ion and iodine.
(c) Calculate the moles of sodium thiosulphate used in the titration and hence the number of moles of
iodine titrated.
(d) Calculate the moles of dichromate(VI) ion that reacted to give the iodine titrated in the titration.
(e) Calculate the formula mass of potassium dichromate(VI) and the mass of it in the 25.0 cm 3 aliquot
titrated.
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(f) Calculate the total mass of potassium dichromate(VI) in the original sample and hence its % purity.
c. Finding the percentage of copper in copper ore or in its salt
There are two possible methods depending on the copper ore (or salts).
1. In the first method which is applicable to any copper salt, a solution of excess potassium iodide is
added to a solution of the copper salt. A dark brown mixture is produced (white precipitate
stained brown). The brown colour is due to iodine liberated.
2Cu2+(aq) +4I-(aq) 2CuI (s) +I2(aq) (ionic equation)
The iodine liberated in the reaction is now titrated with a standard solution of sodium thiosulphate in the
second reaction according to the following equation.
2S2O32- (aq) +I2 (aq) S4O62- (aq) +2I- (aq)
2. The second applicable method is to liberate iodine from iodate (V) ions, then titrate it with
thiosulphate ions as indicated by the following equations:
2IO3- (aq) + 12H+ (aq) + 10I-(aq) → 6I2 (aq) + 6H2O (l) (1)
2S2O32- (aq) +I2 (aq) → S4O62- (aq) +2I- (aq) (2)
Examples: An experiment was carried out in a laboratory to determine the percentage of copper in sample
of impure copper metal. Nitric acid was added to a sample of impure copper metal. The resulting copper
(II) nitrate was reacted with excess of potassium iodide. The iodine liberated was titrated with a solution
of sodium thiosulphate of concentration 0.480M. The volume of sodium thiosulphate required was 23.7
cm3. Use the following equations in your calculations.
2Cu2+(aq) +4I-(aq) 2CuI (s) +I2(aq)
2S2O32- (aq) +I2 (aq) S4O62- (aq) +2I- (aq)
a. Calculate the number of moles of thiosulphate ions in 23.7 cm 3 of solution.
b. Deduce the number of moles of Cu2+ in the copper (II) nitrate solution.
c. The mass of the impure copper was 0.900g. Calculate the percentage of copper in the sample of
impure copper (cu= 63.5).
d. Give the oxidation number and the electronic configuration of copper in CuI (Atomic number of
Cu =29).
Answer:
a. Number of moles of S2O3 2- = = 11.376x10-3 moles

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b. Number of moles of Cu2+
In equation (2), molar ratio between S2O32- : I2= 2:1
2 moles of S2O3 2- react with 1mole of I2
11.376 x10-3 moles of S2O32- = =5.688x10-3moles I2
In equation (1), molar ratio I2 : Cu2+ = 1: 2
1mole of I2 is produced by 2 moles of Cu2+
5.688x10-3 moles of I2 is from 5.688x10-3 x2= 11.376x10-3 moles of Cu2+
c. Mass of Cu2+ = 11.376x10-3 moles x 63.5g/mole = 0.72g
Percentage of Cu2+ = = 80%
d. Oxidation number of copper in CuI; X-1=0 => X= +1
Electronic configuration of copper, in CuI is: 1s2 2s2 2p6 3s2 3p6 3d10
d. Determination of the percentage of available chlorine in a liquid
The method consists of measuring a fixed volume of the original liquid and then dilute it to 250cm 3 with
distilled water. Aliquot portions of this solution is pipetted and added to an excess of KI solution
acidified with ethanoic acid.
The iodine liberated is then titrated, for example, with a standard solution of sodium thiosulphate. This
is a displacement (redox) reaction in which, aqueous potassium iodide reacts with chlorine to form
potassium chloride and iodine. The equation for the reaction is:
2KI (aq) + Cl2 (g) 2KCl (aq) + I2 (aq)
Example: The concentration of chlorine in treated water for domestic use can be monitored by testing
water samples. In one such test, excess potassium iodide (KI) was added to 1000cm 3 sample of water.
The liberated iodine reacted with 14.00cm3 of 0.00100M sodium thiosulphate solution.
a. Calculate the number of moles of sodium thiosulphate used in the reaction and hence the
number of moles of iodine liberated.
b. Write an equation for the reaction between Cl2 (aq) and I- (aq) ions. Identify the reducing agent
in this reaction.
c. Calculate the number of moles of Cl2 and hence the mass of chlorine molecule in the original
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sample of water (Cl= 35.5).
d. Write an equation for the reaction between Cl2 and water and show that this is a
disproportionation reaction.
e. Give the name of a suitable indicator to use in the titration of iodine solution with thiosulphate
solution.
Answer:
a. Number of moles of S2O32- = (14.00 x 0.001)/1000=0.000014mol
Number of moles of I2:
2S2O32- (aq) +I2 (aq) S4O62- (aq) +2I- (aq)
Mole ratio between S2O32-: I2= 2:1
2 moles of S2O32- titrate 1 mole of I2
0.000014moles of S2O32- titrate = 0.000007mol
b. Equation for the reaction between Cl2 and I- ions.
Cl2 (aq) + 2I- (aq) 2Cl- (aq) + I2 (aq)
Reducing agent is I- (iodide ions)
c. Equations:
(i) Cl2 (aq) +2I- (aq) I2 (aq) +2Cl- (aq)
(ii) 2S2032- (aq) + I2 (aq) S2O62- (aq) + 2I-(aq)
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In the above reaction, chlorine underwent both oxidation and reduction, hence it is a disproportionation
reaction.
e. Starch solution, which changes colour from dark blue to colorless.
e. Determination of the percentage of available chlorine in bleaching powder.
Procedure:
Solution FA1 was made by weighing 2.5g of bleaching powder. This is stirred in a little water and the
supernatant milk suspension poured into 250cm3 volumetric flask. The solid residue is then mixed again
with little water and the fine suspension decanted into the volumetric flask.
This process is continued until most of the sample has been transferred. The solution is then made up to
250cm3 mark.
The flask is then shaken vigorously and immediately 25 cm3 of the suspension in pipetted into a clean
conical flask. 20 cm3 of 2M sulphulic acid or 2M ethanoic acid is added followed by 10 cm 3 of 0.5M
potassium iodide. The liberated iodine is then titrated with solution FA 2 which is 0.1M sodium
thiosulphate solutions using starch indicator.
Specimen results:
Calculations:
b. Calculate the number of moles of available chlorine in 250 cm 3.
c. Calculate the mass of the available chlorine in the sample of bleaching powder weighed.
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d. Hence calculate the percentage of available chlorine bleaching powder.
Theory:
In the presence of H+, bleaching powder releases chlorine by the following equation of reaction:
CaOCl2(aq) + 2H (aq) +
Ca 2+(aq) + H2O(l) + Cl2 (g) (i)
Chlorine being more electronegative than iodine, it displaces iodine from KI:
Cl2 (g) + 2KI (aq) 2KCl (aq) +I2 (aq) (ii)
The iodine produced is then titrated with S2O32- and reacts following the equation:
2S2032- (aq) + I2 (aq) S2O62- (aq) + 2I-(aq) (iii)
Note: Since 1 mole of Cl2 produces 1 mole of I2
Number of moles of iodine is equal to the amount of chlorine set free.
Answers:
UNIT 12: CONDUCTIVITY OF SOLUTIONS

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Conductance of electrolytic solutions
The conductance of material or solution is the property of materials due to which a material allows the
flow of ions or electrons through itself and thus conducts electricity. It is generally defined as the reciprocal
of resistance of that material. i.e.,
Units of conductance: Ω-1 or S (Siemens), named after the 19th century German engineer and
industrialist Ernst Werner von Siemens.
It used to be called the mho, which is just ohm written backwards because the resistance is
expressed in (Ohm). The symbol for conductance is L or G. Thus G = 1/R. R = V/I so conductance
is just the inverse of R: G = I/V. where R= Resistance (Ω, Ohm), I= Current Intensity (A,
Amperes) and V=Voltage (V, Volts)
How well a solution conducts electricity depends on a number of factors:

 Concentration
 Mobility of ions
 Valence of ions
 Temperature
All substances possess some degree of conductivity. In aqueous solutions the level of ionic strength
varies from the low conductivity of ultrapure water (because there are very little ions (H+ and OH-
). to the high conductivity of concentrated chemical samples of electrolyte.
The presence of electrolytes further enhances the conductivity as they supply their ions to the
solution. The conductance of electricity by ions present in the solutions is called electrolytic or
ionic conductance.
Measurement of Conductance
The conductance is the inverse of resistance; therefore, it is determined by calculating the

resistance of the electrolytic solution or using the conductance cell.
Electrical conductivity meter
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Principle of the measurement
The electrical conductivity of a solution of an electrolyte is measured by determining the

resistance of the solution between two flat or cylindrical electrodes separated by a fixed
distance. An alternating voltage is used in order to avoid electrolysis. The resistance is
measured by a conductivity meter. Typical frequencies used are in the range 1–3kHz.
The dependence on the frequency is usually small, but may become appreciable at very
high frequencies.
A wide variety of instrumentation is commercially available. There are two types of cell, the
classical type with flat or cylindrical electrodes and a second type based on induction. Many
commercial systems offer automatic temperature correction. Tables of reference conductivities are
available for many common solutions.
Definition of terms
Resistance
The resistance of the solution (R) can be calculated using Ohm’s law
(V = R x I). R = V/I
where:
V = voltage (volts)
I = current (amperes)
R = resistance of the solution (ohms)
Conductance
Conductance (G) is defined as the reciprocal of the electrical resistance (R) of a solution between
two electrodes.
G = 1/R (S)
The conductivity meter in fact measures the conductance, and displays the reading converted into
conductivity.
Specific Conductance or Conductivity
The resistance of any conductor varies directly with its length (l) and inversely with its cross-sectional area
(A), i.e.,Mathematically
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Where:
ρ is called the specific resistance.
l/A is known as cell constant.
If l = 1 cm and A = 1 cm2, then R = ρ ; The specific resistance is, thus defined as the resistance of one
centimeter cube of a conductor.
The reciprocal of specific resistance is termed the specific conductance or it is the conductance of one
centimeter cube of a conductor. It is denoted by the symbol κ (kappa) .
Thus, Where kappa → the specific conductance
Specific conductance is also called conductivity.
Further,
Specific conductance or conductivity of an electrolytic solution at any given concentration is the

conductance of one-unit volume of solution kept between two platinum electrodes with the unit area
of cross section and at a distance of unit length.
Or, the specific conductance is defined as the conductance of a solution of definite dilution enclosed in a
cell having two electrodes of unit area separated by a distance of unit length.
Unit of specific conductance (κ): Ω-1cm-1 or S/cm
The conductivity of an electrolyte indicates how well an electrolyte conducts electricity.
What is the difference between Conductance and Conductivity?
 Conductance depends on the dimensions of the conductor, but conductivity does not depend on the
dimensions.
 Conductance is measured in Siemens while conductivity is measured in Siemens per meter
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Measurement of specific Conductance
It is now known to us that when the solution of an electrolyte is taken between two parallel
electrodes of cross-sectional area 'A' and 'l' cm apart, then the specific conductance, k, should be:
Thus, knowing the values of R, l and A, the specific conductance can be measured. The quantity l/A is
called cell constant and is expressed in cm-1
Specific conductance = Conductance × cell constant
The cell constant is calculate using the following expression:
Cell constant, x=
The resistance of cell, i.e., conductance is measured when filled with a standard solution at a given
temperature.
The standard values of specific conductance of KCl solutions of various concentrations at different
temperature are known.
Thus, the cell constant is calculated by using the above equation. The same cell constant applies to a
measurement with any other solution.
The determination of specific conductance of an electrolytic solution, thus, consists of two steps:
 Determination of cell constant by using a standard KCl solution of known concentration in the
conductivity cell.
 Determination of resistance of the given solution using the same cell. The reciprocal of this gives
the value of conductance.
Multiplication of conductance and cell constant gives the value of specific conductance of the solution.
Example: A conductivity cell was filled with 0.01M KCl which was known to have a specific conductivity
of 0.1413S.cm-1 at 298K. It is measured resistance at 298K was 94.3ohms. When the cell filled with 0.02M
AgNO3 its resistance was 50.3ohms. Calculate: i. The cell constant ii. The specific conductance of AgNO 3
solution.
Equivalent conductance (or equivalent Conductivity)
One of the factors on which the conductance of an electrolytic solution depends is the concentration of the
solution.
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In order to obtain comparable results for different electrolytes, it is necessary to take equivalent
conductance's.
Equivalent conductance of a solution at any given concentration is the conductance of the volume of
solution containing one gram equivalent of electrolyte kept between two electrodes with the unit area of
cross section and distance of unit length.
Equivalent conductance, is also defined as the conductance of all the ions produced by one gram
equivalent of an electrolyte in a given solution.
It is denoted by. (Λeq)
In general, Λeq= k × V
where V is the volume in mL containing 1 g equivalent of the electrolyte.
In case, if the concentration of the solution is gram equivalent per litre, then the volume containing 1 g
equivalent of the electrolyte will be 1000/eq.
So equivalent conductance
Λeq = κ × 1000/N
where N = normality
Unit of equivalent conductance: Ω-1cm2eq-1
Molar Conductance
The molar conductivity of a solution at any given concentration is the conductance of the volume of
solution containing one mole of electrolyte kept between two electrodes with the unit area of cross section
and distance of unit length.
The molar conductivity can also be defined as the conductance of all the ions produced by ionization of 1
mole of an electrolyte when present in V mL of solution. It is denoted by Λm .
Λm = κ ×V where V is the volume in mL containing 1mole of the electrolyte.
If C is the concentration of the solution in mole per litre, then the volume containing 1 mole of the
electrolyte will be 1000/C.
Λm = k ×1000/C (Where C=n/v so v=n/C)
In general terms, it is defined as the ratio of specific conductivity and the concentration of the electrolyte.
Units of molar conductance: Ω-1cm2mol-1
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In order to determine equivalent conductance or molar conductance, the concentration of the experimental
solution should be known.
Example1. A solution of 0.108 mol dm-3 of ethanoic acid has a conductivity of 4.95x 10-
2Ω m-1. What is the molar conductivity of this solution?
Solution
Λ = κ /C
C = 0.108 mol dm = (0.108 x 1000) mol m-
-3 3
Λ= 4.95x10 /0.108 x 1000 = 4.58 x 10 Ω m mol

-2 -4 -1 2 -1
Example2. A cell with electrodes of 0.0002 m2 of area and 0.1m apart is filled with 0.1M aqueous
solution of NaCl. The molar conductance is 106.7x10 -4 Sm2 mol-1 at 298K. If the applied emf
across section is 50 volts, calculate the current in ampere flowing through the cell.
Note: Molar conductivity is often expressed as Siemens centimeter squared per mole
in CGS unit.
In conductance measurements, the solutions are always prepared in conductivity water which has no
conductance due to dissolved impurities.
Conductivity measurements are used routinely in many industrial and environmental applications as a fast,
inexpensive and reliable way of measuring the ionic content in a solution. For example, the measurement
of conductivity is a typical way to monitor and continuously trend the performance of water purification
systems.
Variation of Conductivity and Molar Conductivity with concentration
Conductivity decreases with a decrease in concentration as the number of ions per unit volume that carries
the current in a solution decrease on dilution.
Example: Variation of conductivity in terms of concentration at different temperatures
This table shows that the conductivity increases with increasing concentration and
temperature.
Change in Molar Conductivity
Molar conductivity increases with a decrease in concentration. This happens because the total volume, V,
of the solution containing one mole of electrolyte also increases. Upon dilution, the concentration decreases.
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In summary, The conductivity and molar conductivity of an electrolyte change with the
concentration of the electrolyte.
As concentration decreases, conductivity decreases for both strong and weak electrolytes.
But molar conductivity increases as concentration decreases. The variation is different for strong
electrolytes and weak electrolytes.
Variation of Conductivity and Molar Conductivity with Dilution
following variations on molar conductance are observed:
The value of molar conductance increases on dilution. The increase is due to the fact that molar conductance
is the product of specific conductance (k) and the volume (V) of the solution containing 1 mole of the
electrolyte. As the decreasing value of specific conductance is more than compensated by the increasing
value of ‘V’, thus the value of molar conductance (Λ m) will increase with dilution.
The variation of molar conductance at different dilutions of some common electrolytes are shown Table
below:
Explanation of Increase in Conductivity with Dilution:
Strong electrolytes
For strong electrolyte, molar conductivity increases steadily with dilution until it reaches the maximum
value at infinite dilution (at high concentration, the lower molar conductivity values are due to ionic
interference). The formation of ionic pairs or triplet and symmetrical spheres greatly reduces the mobility
of ions however as the dilution increases, there is reduced ionic interference as result of many solvent
molecules surrounding the oppositely charged ions thus an increase in molar conductivity.
At infinite, there is independent migration of ions that is ions experience negligible ionic interference and
move independent of each other.
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The molar conductivities of strong electrolytes are high. This is because, by nature, strong electrolytes are
highly dissociated when molten or when in solution into large number of ions. These ions are mobile, hence
they migrate to the electrodes, resulting in the high conduction of electricity: the higher the number of ions
are free in solution, the higher the conductivity.
From this graph it is clear that strong electrolytes such as KCl, can have limiting value of molar conductivity
by extrapolation of the graph to zero concentration (i.e. at infinite dilution).
Weak electrolytes
Weak electrolytes show partial dissociation in solution, producing few ions, which results in low conduction
of electricity.
A weak electrolyte dissociates to a much lesser extent so its conductance is lower than that of a strong
electrolyte at the same concentration.
With increase in dilution (decrease in concentration), ions become farther apart, and inter-ionic forces (i.e.
forces of attraction between unlike ions and forces of repulsion between like ions) decrease considerably,
so that greater number of ions are able to migrate to the electrodes. In addition, due to change in equilibrium,
the electrolyte undergoes further ionization from the same mass in solution (in order to balance the effect).
Hence, more ions (conducting species) are introduced into the solution
From this graph it is clear that weak electrolyte such as acetic acid, there is no indication that a limiting
value can be obtained by the extrapolation of the graph to zero concentration. It means we can not
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experimentally determine molar conductivity of weak electrolytes at infinite dilution. It is obtained by
applying Kohlrausch’s law (see later)
The very large increase at infinite dilution is because the ionization increases and so the number of ions in
solution increases.
Summary:
The higher the number of ions per unit volume in solution, the greater the conductivity of the electrolytic
solution. This means that the conductivity increases with concentration of ions in solution up to an optimum
level over which it starts decreasing.
On the other hand when the conductivity has decreased due to very high concentration of ions, it can be
increased with dilution (i.e. lower concentrations) up to its optimum, beyond which further dilution will
decrease conductivity.
The decrease or increase of conductivity by concentrating or diluting the solution is sharp in strong
electrolytes while it is gradual in weak electrolytes. The following graph shows
Λ values for strong electrolytes are larger than weak electrolytes for the same concentration.
Increase Λ for strong electrolyte is quite small as compared to that for weak electrolyte towards dilution.
Kohlrausch’s Law of Independent Migration of Ions
It has been observed that the molar conductivity of solution increases with dilution until it reaches its
limiting value at infinite dilution it is represented as ∧∞. Kohlrausch made a systematic study of ∧∞ for
different electrolytes and concluded that each ion contributes a characteristic value of its own to molar
conductivity at infinite dilution irrespective of the nature of the other ion present.
Kohlrausch’s law of independent migration of ions states that “at infinite dilution, where ionization of all
electrolytes is complete and where all interionic effects are absent, the molar conductivity of an
electrolyte is the sum of the molar conductivities of its constituent ions at constant temperature”.
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According to the law, the molar conductivity at infinite dilution for the following electrolytes will be
obtained as;
Activity 1 The molar conductivity of chloride ion is 1.264 x 10 -2 Sm2mol-1. What is the molar conductivity
of sodium ions given that the molar conductivity of NaCl is 1.264 x 10 -2 S m2mol-1?
Asnwer:
According to Kohlrausch’s law,
Λ∞ (NaCl) = Λ∞ (Na+) + Λ∞ (Cl-)
Λ∞ (Na+) = Λ∞ (NaCl) - Λ∞ (Cl-)
=1.264x10-2 – 7.63 x 10-3
= 5.01 x 10-3 Sm2mol-1
Activity 2: The molar conductivities at infinite dilution of KCl, KNO 3and AgNO3 at 298K are
0.01499Sm2.mol-1; 0.01450Sm2mol-1and 0.01334 Sm2mol respectively, calculate the molar conductivity of
AgCl at infinite dilution at this temperature.
Example 3: Calculate the molar conductance of aqueous BaSO4 solution at infinite

dilution. Given
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Factors that affect molar conductivity of solutions
1. Temperature
The increase of temperature decreases inter-ionic attractions and increases kinetic energy of ions and their
speed. Thus, Λm increases with temperature.
2. Concentration of the solution
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It is obtained by applying Kohlrausch’s law.
The very large increase at infinite dilution is because the ionization increases and so the number of ions in
solution increases.
3. Nature of electrolyte
The strong electrolytes like KNO3, KCl, NaOH, etc are completelyionized in aqueous solution and have
high values of molar conductivity. The weak electrolytes are ionized to a lesser extent in aqueous solution
and have lower values of molar conductivity. Solvents of high dielectric constant yield more conducting
solution. The viscosity is inversely proportional to the conductance.
4. Ionic charge and size
Generally, the ions move at very low speeds. The velocities of hydrogen ions and hydroxyl ions are
relatively high. They contribute greatly to high conductivities of aqueous solutions of strong acids and
alkalis.
The differences in speeds of ions under similar conditions are as a result of their difference in charge and
size.
a. Ionic charge
Multiple charged ions get strongly attracted to the oppositely charged electrode. This increases their speeds
compared to singly charged ions.
b. Ionic size
Velocities of smaller ions are higher than those of larger ions of the same charge.
This is because larger ions meet many obstacles compared to small ones. However, as ions exist in aqueous
solution in a solvated form, the radius of the hydrated ion is considerably larger than the crystal radius.
Small ions get more hydrated than larger ones due to high charge density. This reverses the expected order
of ionic velocities. Thus for group 1cations, the ionic radius increases in the order
Li+<Na+<K+<Rb+<Cs+and the electric mobility increases in the same order (Li+<Na+<K+<Rb+<Cs+). This
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is because of the effect of hydration. This explains why lithium ions have a lower molar ionic conductivity
than potassium ions.
5. Pressure
The molar conductance increases slightly with increase in pressure.
Molar conductivity at a given concentration (Λ or ΛmC)
Remember that the molar conductivity, Λ m is the ratio of specific conductivity and the
concentration of the electrolyte.
Λ and Λ∞ are the molar conductivity at a given concentration and at infinite dilution respectively.
Λm = К /c Where, К = specific conductivity and c = concentration of electrolyte.
Example 1
A solution of 0.108 mol dm-3 of ethanoic acid has a conductivity of 4.95x 10-2Ω m-1. What is
the molar conductivity of this solution?
Solution
Λ = κ /C
C = 0.108 mol dm-3 = (0.108 x 1000) mol m-3
Λ= 4.95x10-2/0.108 x 1000 = 4.58 x 10-4 Ω-1m2mol-1
Note: Molar conductivity is often expressed as Siemens centimeter squared per mole in CGS
unit.
Relation between molar conductivity, degree of ionization and ionization constant
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At infinite dilution, the electrolyte is completely ionized and all the ions take part in conducting
the current. At appreciable concentration, only a fraction of the electrolyte is ionized.
Having the degree of ionization α, the dissociation constant Ka can be obtained as follow:
From the above equations, also the pH of the solution can be calculated. For example, for a weak
acid such as ethanoic acid,
Note that: pKa = -logKa
Activity: The resistance of 0.02M solution of an organic acid in a cell (cell constant = 0.2063
cm-1) was found to be 888 Ω.
a. What is the degree of ionization of that organic acid at this concentration given that its
molar conductivity at infinite dilution is 387.9 x 10 -4 Sm2mol-1
b. Calculate pKa for that organic acid.
c. Calculate the pH of that solution
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Use of conductivity measurement in titration and solubility product
What is Conductometric Titration?
Conductometric titration is a laboratory method of quantitative analysis used to identify the

concentration of a given analyte in a mixture.
Conductometric titration involves the continuous addition of the titrant to a reaction mixture and
the continuous recording of the corresponding change in electrolytic conductivity of the reaction
mixture.
It can be noted that the electrical conductivity of an electrolytic solution is dependent on the
number of free ions in the solution and the charge corresponding to each of these ions.
In this type of titration, upon the continuous addition of the titrant (and the continuous recording
of the corresponding change in electrolytic conductivity), a sudden change in the conductivity
implies that the stoichiometric point has been reached.
a) Using conductivity to find the end point of a titration
The end-point in titration experiment can be determined using conductivity.
For example, the strength of a base can be determined via conductometric titration with a standard
solution of an acid. The procedure of the technique is:
At the start of this titration the conical flask contains a strong alkali that is fully ionized in
water. If electrodes are placed inside the conical flask the ions in the water will conduct
electricity and a current will flow. The more ions there are the better the conductivity and
the higher the current will be. The current can be measured using an ammeter.
As acid is added to the alkali hydrogen ions and hydroxide ions react together to form
water molecules. The number of ions in the conical flask starts to decrease and the
current flowing through the solution will decrease. At neutralization all of the hydrogen
ions and hydroxide ions have reacted together to form water molecules. The neutral
solution contains only salt ions dissolved in water molecules. The solution will still conduct
electricity because of the salt ions but the current will be at a minimum.
As more acid is added the current will start to increase because there will now be
unreacted hydrogen ions in the solution as well as the salt ions. The solution is now no
longer neutral but has become acidic.
 If you draw a graph of current against the amount of acid added, you can see where the
minimum is. This is the end point of the titration at neutralization.
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 If you draw a graph of the electrolytic conductivity against the amount of the titrant added,
you can see where the minimum is. This is the end point of the titration at neutralization.
An example of a curve plotted for such a titration process is given below.
Principle
The principle of the conductometric titration process can be stated as follows – During a titration process,
one ion is replaced with another and the difference in the ionic conductivities of these ions directly
impacts the overall electrolytic conductivity of the solution.
b) Determination of solubility and solubility product by conductivity measurement.
Conductance measurement can be used for measurements of solubility of slightly soluble

substances like BaSO4, PbSO4, AgCl etc. The method is based on the difference in the conductance
of the ions of the salts.
When a sparingly soluble salt is placed in water, a very little amount of the salt dissolves in the
water and a solution is created.
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Their solutions may be taken as infinite dilute. Moreover, because their solutions are saturated,
their concentrations may be taken equal to their solubility. Thus by determining the specific
conductance κ and molar conductivity of such solutions, we can easily calculate the solubility.
For the purpose, a saturated solution of the salt is prepared in conductivity water and allowed to
stand until almost all the insoluble fraction settles down. The clear solution from the top is taken
and its conductance is measured in a conductance cell. The cell is thoroughly washed and filled
with the same conductivity water and the conductance of the water measured in the same cell. The
conductance of water is then subtracted from the conductance of the solution. The value so
obtained is the conductance due to the salt. The observed conductance is then converted to specific
conductance.
The solubility of such salts is then calculated by the application of Kholrausch’s law and
conductance measurements. The molar conductance (Λ m) of a saturated solution as given by
equation-
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What is Solubility Product, Ksp?
The solubility product, Ksp, applies in situations where salts do not fully dissolve in a solvent. The
solvent is generally water.
The solubility product, KSP, determines the equilibrium that exists between the sparingly soluble
salt and the ions that are dissolved in water.
A substance's solubility product is the mathematical product of its dissolved ion concentrations
raised to the power of their stoichiometric coefficients.
Ksp represents the level at which a solute dissolves in solution. The more soluble a substance is,
the higher the Ksp value it has.
Consider the general dissolution reaction below (in aqueous solutions):
aA(s)⇌cC(aq)+dD(aq)
To solve for the Ksp it is necessary to take the molarities or concentrations of the products (cC and
dD) and multiply them. If there are coefficients in front of any of the products, it is necessary to
raise the product to that coefficient power. This is shown below:
Ksp=[C]c[D]d
Note that the reactant, aA, is not included in the Ksp equation. Solids are not included when
calculating equilibrium constant expressions, because their concentrations do not change the
expression; any change in their concentrations are insignificant, and therefore omitted.
Hence, Ksp represents the maximum extent that a solid can dissolve in solution. Let us consider
the following equilibrium:
Example 1: PbSO4.
Assume concentration of solid is a constant.
Concentration of Pb2+= concentration of SO42- = C
Ksp = [Pb2+aq] [SO42-aq] Ksp = C2
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Example 2: CaF2
Let [Ca2+] = x [F-] =2x
Ksp = [Ca2+][F-]2 = x(2x)2 = 4x3 = 4C3
These concentrations can be determined via conductivity measurements, as discussed above and
therefore the Ksp can be calculated. Consider the following examples:
Example 1.
The specific conductance of saturated aqueous solution of barium sulfate at 298K is 1.84x10-
4
Sm-1and that of water is 1.60x10-4Sm-1. The ionic conductivities at infinite dilution of Ba 2+ and
SO42- ions at 298 K are 63.6x10-4Sm2mol-1 and 79.8x10-4Sm2mol-1 respectively. Calculate the
solubility and solubility product of barium sulphate at 298K
Example 2.
The conductivity of a saturated solution of a sparingly soluble salt MX in water at 298K is 1.88x10 -
4
Sm-1. The molar conductivity of MX at infinite dilution at this temperature is 138.3x10-4Sm-1.
Calculate the solubility and the solubility product of MX at this temperature.
Example 3.
Explain how the solubility product affect the conductivity.
Difference between metallic conductivity and electrolytic conductivity
The substances, which allow the passage of electric current, are called conductors. The best metal
conductors are such as copper, silver, tin, etc. On the other hand, the substances, which do not
allow the passage of electric current through them, are called non-conductors or insulators. Some
common examples of insulators are rubber, wood, wax, etc.
The conductors are broadly classified into two types, Metallic and electrolytic conductors.
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The electrolyte may, therefore, be defined as the substance whose aqueous solution or fused state
conducts electricity accompanied by chemical decomposition. The conduction of current through
electrolyte is due to the movement of ions. On the contrary, substances, which in the form of their
solutions or in their molten state do not conduct electricity, are called non-electrolytes.
UNIT 13: ELECTROLYSIS
Key unit competence: Predict the products of given electrolytes during electrolysis and work
out quantitatively to determine how much is liberated at a given electrode using Faraday’s law.
Learning Objectives:
 Define electrolysis, cathode and anode.
 Explain the electrolysis of different substances.
 State Faraday’s laws and define the Faraday’s constant.
 Develop practical experimental skills related to electrolysis, interpret results, and draw
valid conclusions.
 Carry out a practical activity to explain the phenomenon of electrolysis.
 Compare the electrolysis of dilute solutions and concentrated solutions.
 Calculate the masses and volumes of substances liberated during electrolysis.
 Relate the nature of electrode, reactivity of metal ion in solution to the products of
electrolysis.
 Perform electroplating of graphite by copper metal
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Definition of electrolysis and Description of electrolytic cells.
1.Definition of electrolysis.
In galvanic cells, chemical energy is converted into electrical energy. The opposite is true for
electrolytic cells. In electrolytic cells, electrical energy causes nonspontaneous reactions to occur
in a process known as electrolysis. Electrical energy is converted into the chemical energy in the
battery as it is charged. Once charged, the battery can be used to power the automobile.
A spontaneous reaction is a reaction that favors the formation of products without external
energy. It is a process that will occur on its own. For example, a ball will roll down an incline,
water will flow downhill, radioisotopes will decay, and iron will rust. No intervention is required
because these processes are thermodynamically favorable.
A non spontaneous reaction (also called an unfavorable reaction) is a chemical reaction that
necessitates external energy to occur. For example, without an external energy source, water will
remain water forever. Under the right conditions, using electricity (direct current) will help to
produce hydrogen gas and oxygen gas from water. Cooking foods is not spontaneous reaction that
is why heat is used.
Electrolysis is defined as the decomposition of an electrolyte by passage of an electric current

through it.
Electrolyte are substances that allow the flow of electric current when in molten or in solution and
non-electrolytes are substances that cannot allow the flow of electric current when in molten or
in solution.
Electrolysis: Basics
 When an electric current is passed through a molten ionic compound the compound
decomposes or breaks down
 The process also occurs for aqueous solutions of ionic compounds
 Covalent compounds cannot conduct electricity hence they do not undergo electrolysis
 Ionic compounds in the solid state cannot conduct electricity either since they have no free
ions that can move and carry the charge
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2. Description of electrolytic cells.
An electrolytic cell is an electrochemical cell that drives a non-spontaneous redox reaction

through the application of external electrical energy. They are often used to decompose chemical
compounds, in a process called electrolysis. The Greek word lysis means to break up.
An electrolytic cell has three component parts:
 An electrolyte (The electrolyte is usually a solution of water or other solvents in which ions
are dissolved. Molten salts such as sodium chloride are also electrolytes).
When driven by an external voltage applied to the electrodes, the ions in the electrolyte are
attracted to an electrode with the opposite charge, where charge-transferring (also called
faradaic or redox) reactions can take place.
Only with an external electrical potential (i.e. voltage) of correct polarity and sufficient
magnitude can an electrolytic cell decompose a normally stable, or inert chemical compound
in the solution. The electrical energy provided can produce a chemical reaction which would
not occur spontaneously otherwise.
 A source of direct current (Alternating current (AC) would not be appropriate for
electrolysis. Because the “cathode” and “anode” are constantly switching places, AC
produces explosive mixtures of hydrogen and oxygen).
The direct current is conveyed from its source to the electrolyte by means of electrodes
 Electrodes (electrical conductors which provides the physical interface between the
electrical circuit providing the energy and the electrolyte). The electrode connected to the
positive terminal of the direct current is called the anode and the one connected to the
negative terminal is the cathode.
By convention, the electric current enters the electrolyte by the anode and leaves by the cathode.
When the current passes through an electrolytic solution, ions migrate and electrons are gained or
lost by ions on the electrodes surface. Electrode that is positively charged has deficit of electrons
is called anode and the other electrode negatively charged has excess of electrons and is called
cathode.
Use the PANIC mnemonic to remember which electrode is the positive and which is the negative:
Positive (is) Anode Negative Is Cathode
Cations are attracted to the cathode and anions are attracted to the anode. Electron flow in
electrochemistry occurs in alphabetical order as electrons flow from the Anode to the Cathode.
Chemical changes at the electrodes due to the passage of electric current are called electrolysis.
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Electrolytic cell
In the process of electrolysis, there is an interchange of ions and atoms due to the addition or
removal of electrons from the external circuit. Basically, on passing current, cations move to the
cathode, take electrons from the cathode (given by the supply source-battery), and is discharged
into the neutral atom. The neutral atom, if solid, is deposited on the cathode and if gas, move
upwards. This is a reduction process and the cation is, reduced at the cathode.
At the same time anions, give up their extra electrons to the anode and is oxidized to neutral atoms
at the anode. Electrons released by the anions travel across the electrical circuit and reach the
cathode completing the circuit. Electrolysis involves a simultaneous oxidation reaction at anode
and a reduction reaction at the cathode.
The products of electrolysis are in some different physical states from the electrolyte and can be
removed by some physical processes.
Electrodes of metal, graphite and semi-conductor material are widely used. Choice of suitable
electrode depends on chemical reactivity between the electrode and electrolyte and the cost of
manufacture.
Note:
The suitable electrode in electrolysis should be inert (C, Pt, etc.) therefore it will not participate in
the chemical reaction.
It is very easy to be confused about the names CATHODE and ANODE and what their properties
are, both with electrochemical cells and electrolytic cells.
(To help you to remember, Cathode is the site of reduction, or, if you prefer, CCC = Cathode
Collects Cations. Anode is the site of oxidation, or, AAA = Anode Attracts Anions.)ssaz
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For example, Electrolysis of molten compounds eg: Lead (II) Bromide:
Diagram showing the electrolysis of lead (II) bromide
Method:
 Add lead (II) bromide into a beaker and heat so it will turn molten, allowing ions to be free
to move and conduct an electric charge
 Add two graphite rods as the electrodes and connect this to a power pack or battery
 Turn on power pack or battery and allow electrolysis to take place
 Negative bromide ions move to the positive electrode (anode) and lose two electrons to
form bromine molecules. There is bubbling at the anode as brown bromine gas is given off
 Positive lead ions move to the negative electrode (cathode) and gain electrons to form a
grey lead metal which deposits on the surface of the electrode
Reaction at electrodes:
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Electrolysis process, while useful to get elemental forms from compounds directly, it can also be
used indirectly in the metallurgy of alkali and alkaline earth metals, purification of metals,
deposition of metals, preparation of compounds etc.
Cell Potential or Voltage
The minimum potential needed for the electrolysis process depends on the ability of individual
ions to absorb or release electrons. This ability is, measured as an electrode potential of the ions
present in the electrolytic cell. The cell potential is the sum of the potential required for the
reduction and oxidation reaction. The potential involved in various redox reactions is available in
literature as standard reduction potential.
Reaction with positive redox cell potentials only will be feasible as per thermodynamic Gibbs free
energy (or standard potential). Generally, the electrolysis is thermodynamically controlled. In
electrolysis, a potential equal to or slightly more than that, is, applied externally.
The ions, which are stable and not reacting, are made to undergo reaction in the presence of
externally applied potential. External potential hence makes an unfavorable reaction to take place.
In electrolysis, chemical bonds connecting atoms are either made or broken and so, electrolysis
involves the conversion of electrical energy into chemical energy.
Example: The Electrolysis of Molten Sodium Chloride
In molten sodium chloride, the ions are free to migrate to the electrodes of an electrolytic cell; The reactions
at different electrodes are:
anode: 2Cl−(l) →Cl2(g) + 2e− E∘Cl2/Cl−=+1.3V
cathode: Na+(l) + e−→Na(l) E∘Na+/Na=−2.7V
overall: 2Na+(l) + 2Cl−(l) →2Na(l) + Cl2(g) E∘cell=−4.0V
The power supply (battery) must supply a minimum of 4 V, but, in practice, the applied voltages are
typically higher because of inefficiencies in the process itself.
Passing an electric current through molten sodium chloride decomposes the material into sodium metal and
chlorine gas. Care must be taken to keep the products separated to prevent the spontaneous formation of
sodium chloride.
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Electrolysis: General Principles
Electrolysis of molten compound
 For a binary molten compound of a metal and a nonmetal, the cathode product will always
be the metal
 The product formed at the anode will always be the non-metal
Aqueous solutions
Aqueous solutions will always have water (H2O) therefore H+ and OH– ions from the water
are involved as well
 Positive electrode (anode)
 OH– ions and non-metal ions (anions) are attracted to the positive electrode
 Either OH– or non-metal ions will lose electrons and oxygen gas or gas of non-metal in
question is released, eg. chlorine, bromine, nitrogen
 The product formed depends on which ion loses electrons more readily, with the
more reactive ion remaining in solution
A reactivity series of anions is shown below:
 Negative electrode (cathode)
 H+ and metal ions attracted to the negative electrode but only one will gain electrons
 Either hydrogen or metal will be produced
 If the metal is above hydrogen in reactivity series, then hydrogen will be produced and
bubbling will be seen at the cathode
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The reactivity series of metals including hydrogen and carbon
Concentrated and dilute solutions
 Concentrated and dilute solutions of the same compound give different products
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 For anions, the more concentrated ion will tend to get discharged over a more dilute ion
EXAMPLES OF ELECTROLYSIS
A. Electrolysis of sodium chloride
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Sodium chloride may be in different forms that can be electrolytes. It may be in its molten
state, dilute solution or concentrated solution. In each case, the products of electrolysis differ
because of different factors.
1. Electrolysis of molten sodium chloride
The molten salt is introduced in a container called electrolytic cell (or electrolysis cell) in
which there are two inert electrodes (platinum or graphite). Electrodes are connected to a
DC generator.
• Cations (Na+) move toward the cathode (negative electrode), where they take electrons
and are reduced. On cathode metallic sodium is deposited: Na+ + 1 e- →Na
• Anions (Cl-) move towards the anode (positive electrode), where they give up electrons
and are oxidized. On the anode Cl2 is released: 2 Cl- - 2 e- →Cl2
The overall reaction is the addition of half reactions at electrodes:
Cathode: 2x Na+ + 2x1 e-→ 2Na

Anode: 2 Cl- → Cl2 + 2e-
------------------------------------------------------
Overall reaction 2 Na+ + 2 Cl- → 2 Na + Cl2
Electrolysis of molten sodium chloride solution
2. Electrolysis of Dilute Sodium Chloride Solution
An aqueous solution of sodium chloride contains four different types of ions.
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They are:
 Ions from sodium chloride: Na+ (aq) and Cl- (aq)

 Ions from water: H+ (aq) and OH- (aq)
When dilute sodium chloride solution is electrolysed using inert electrodes, the Na+ and H+
ions are attracted to the cathode. The Cl - and OH- ions are attracted to the anode.
At the cathode:
The H and Na ions are attracted to the platinum cathode. H ions gains electrons from the cathode
+ + +
to form hydrogen gas. (The hydrogen ions accept electrons more readily than the sodium ions. As
a result, H ions are discharged as hydrogen gas, which bubbles off.
+
2H (aq) + 2e- → H2(g) ,

+
Na ions remain in solution.
+
At the anode:
OH and Cl are attracted to the platinum anode. OH ions give up electrons to the anode to form
- - -
water and oxygen gas.
4OH (aq) →2H2O (l) + O2(g) + 4e-

-
Cl- ions remain in solution.
Adding the two reactions and balancing the terms:
2x2H (aq) + 2x2e- →2H2(g)

+
at the cathode
-
4OH (aq) →2H O(l) + O (g) + 4e-
2 2 at the anode
Overall reaction: 4H2O(l) →2H2O(l) + 2H2(g) + O2(g)
If we remove 2 molecules of water on both sides, we get:
2H2O(l) →2H2(g) + O2(g)
Note:
Since water is being removed (by decomposition into hydrogen and oxygen), the
concentration of sodium chloride solution increases gradually. The overall reaction shows
that the electrolysis of dilute sodium chloride solution is equivalent to the electrolysis
of water.
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Electrolysis of
dilute sodium chloride
solution
Another important thing to note is that twice as much hydrogen is produced as oxygen. Thus
the volume of hydrogen produced is twice that of oxygen. Refer to the equations above and note
the number of electrons involved to help you understand.
3. Electrolysis of Concentrated Sodium Chloride Solution

The only difference with dilute NaCl solution is that at the anode, Cl ions are more numerous than
-
OH ions. Consequently, Cl ions are discharged as chlorine gas, which bubbles off.
- -
A half-equation shows you what happens at one of the electrodes during electrolysis.
Anode: 2Cl – 2e– →Cl2 (oxidation)

–
Cathode: 2H + 2e– →H2 (reduction).

+
Sodium ions Na and hydroxide OH are also present in the sodium chloride solution. They are
+ –
not discharged at the electrodes. Instead, they make sodium hydroxide solution.
These products are reactive, so it is important to use inert (unreactive) materials for the
electrodes.
One volume of hydrogen gas is given off at the cathode and one volume of chlorine gas is
produced at the anode. The resulting solution becomes alkaline because there are more
OH- than H+ ions left in the solution.
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B. Electrolysis of water
Water can be decomposed by passing an electric current through it. When this happens, the
electrons from the electric current cause an oxidation-reduction reaction. At one electrode, called
the cathode, electrons cause a reduction. At the other electrode, called the anode, electrons leave
their ions completing the circuit, and cause an oxidation.
In order to carry out electrolysis the solution must conduct electric current. Pure water is a very
poor conductor. To make the water conduct better we can add an electrolyte to the water. The
electrolyte added must not be more electrolyzable than water. Sulfate ions do not electrolyse as
easily as water, so sulfates are often used to enhance the conductivity of the water
Water may be electrolyzed in the apparatus shown below. Pure water is however a very poor
conductor of electricity and one has to add dilute sulphuric acid in order to have a significant
current flow.
The electrodes consist of platinum foil. The electrolyte is dilute sulphuric acid. Hydrogen gas
is evolved at the cathode, and oxygen at the anode. The ratio, by volume, of hydrogen to
oxygen, is exactly 2:1.
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Remember that electron flow in the circuit is opposite to the conventional current flow.
The reaction at the cathode (tube A) is the reduction of protons:
2H+ + 2e → H2(g)
Oxidation takes place at the anode (tube B). There are two anions competing to give up their
electrons, namely sulphate (SO42-) from sulphuric acid, and hydroxide (OH-) from the ionization
of water. Here, the activity series is used to know the ion to be discharged.
The oxidation of OH- according to the reaction:
4OH- →O2 + 2 H2O + 4e
In pure water at the negatively charged cathode, a reduction reaction takes place, with electrons
(e−) from the cathode being given to hydrogen cations to form hydrogen gas. The half reaction,
balanced with acid, is:
Reduction at cathode: 2 H+ (aq) + 2e− →H2 (g)
At the positively charged anode, an oxidation reaction occurs, generating oxygen gas and giving
electrons to the anode to complete the circuit:
Oxidation at anode: 2 H2O (l) →O2 (g) + 4 H+ (aq) + 4e−
(4OH- →O2 + 2 H2O + 4e)
Cathode 2 H2O(l) + 2e− → H2(g) + 2 OH−(aq)

(reduction):
Anode 4 OH−(aq) → O2(g) + 2 H2O(l) + 4 e−

(oxidation):
Combining either half reaction pair yields the same overall decomposition of water into oxygen
and hydrogen:
Overall reaction: 2 H2O (l) →2 H2 (g) + O2 (g)
The number of hydrogen molecules produced is thus twice the number of oxygen molecules.
Assuming equal temperature and pressure for both gases, the produced hydrogen gas has
therefore twice the volume of the produced oxygen gas.
C. Electrolysis of concentrated copper (II) sulphate solution
1. Electrolysis of concentrated copper (II) sulphate solution using inert electrode
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Using the simple apparatus (diagram below) and inert carbon (graphite) electrodes, you
can observe the products of the electrolysis of copper sulfate solution are a copper deposit
on the negative cathode electrode and oxygen gas at the positive anode electrode.
The electrolysis of copper (II) sulphate solution with carbon electrodes.
The blue colour fades as more and more copper is deposited, depleting the concentration of blue
copper ion Cu in solution.
2+
The electrode products from the electrolysis of copper sulphate with inert graphite (carbon)
electrodes
The negative cathode electrode attracts Cu ions (from copper sulphate) and H ions (from water).
2+ +
Only the copper ion is discharged, being reduced into copper metal. The less reactive a metal, the
more readily its ion is reduced on the electrode surface.
A copper deposit forms as the positive copper ions are attracted to the negative electrode
(cathode)
Cu (aq) + 2e– →Cu(s) positive ion reduction by electron gain.

2+
The traces of hydrogen ions are not discharged, so you do not see any gas collected above the
negative electrode.
At the positive anode reaction with graphite electrodes Oxygen gas is formed.
The negative sulphate ions (SO4 ) and the traces of hydroxide ions (OH ) are attracted to the
2- –
positive electrode. But the sulphate ion is too stable and nothing happens. Instead hydroxide ions
are discharged and oxidised to form oxygen.
4OH (aq) → 2H2O(l) + O2(g) + 4e- : negative ion oxidation by electron loss
–
2H2O(l) → 4H (aq) + O2(g)+ 4e- : molecule oxidation by electron loss

+
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Cathode reaction: 2xCu (aq) + 2e- →2xCu(s)
2+
Anode reaction: 2H2O(l) →O2(g) + 4H (aq) + 4e-

+
Overall reaction: 2Cu (aq) + 2H2O(l) → 2Cu(s) + O2(g) + 4H (aq)

2+ +
2. Electrolysis of concentrated copper (II) sulphate solution using copper electrodes
The products of electrolysis of copper sulfate solution with copper electrodes are copper metal
and copper ions (the copper anode dissolves).
The electrolysis of copper (II) sulphate solution using copper electrodes is shown below.
The electrolysis of copper (II) sulphate solution with a copper anode and a copper cathode.
Using the simple apparatus and two copper electrodes the products of the electrolysis of copper
sulphate solution are a copper deposit on the negative cathode electrode and copper dissolves,
Cu , at the positive anode electrode.
+2
The electrode products from the electrolysis of copper sulphate with copper electrodes
The negative cathode electrode attracts Cu ions (from copper sulphate) and H ions (from water).
2+ +
Only the copper ion is discharged, being reduced to copper metal.
A reduction electrode reaction at the negative cathode: Cu (aq) + 2e– → Cu(s)

2+
The positive anode (with copper electrodes) attracts the negative sulphate ions SO 4 (from2-
copper sulphate) and the traces of hydroxide ions OH (from water) but both the sulphate ion
–
and hydroxide ion are too stable and nothing happens to them because the copper anode is
preferentially oxidised to Cu copper ions.
2+
An oxidation electrode reaction at the positive anode: Cu (s)→ Cu2+ (aq) + 2e-
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When Copper (II) sulphate is electrolysed with a copper anode electrode (the cathode can
be carbon or copper), the copper deposit on the cathode (–) equals the copper dissolves at
the anode (+). Therefore, the blue colour of the Cu ions stay constant because Cu deposited
2+
= Cu dissolved. Both involve a two electron transfer so it means mass of Cu deposited = mass
of Cu dissolving for the same quantity of current flowing (flow of electrons). You can check
this out by weighing the dry electrodes before and after the electrolysis has taken place.
The electrode reactions and products of the electrolysis of copper sulfate solution (with
a copper anode) are illustrated by the theory diagram above - it doesn't matter whether
the cathode is carbon or copper - you get the same copper deposit
Electrolysis: Reactions at the Electrodes

370 | P a g e
Determining what gas is produced
 If the gas produced at the cathode burns with a ‘pop’ when a sample is lit with a lighted
splint then the gas is hydrogen
 If the gas produced at the anode relights a glowing splint dipped into a sample of the gas
then the gas is oxygen
 The halogen gases all produce their own colours (bromine is red-brown, chlorine
is yellow-green and fluorine is pale yellow)
371 | P a g e
Faraday’s Laws
The relationship between the mass of product formed at an electrode and the quantity of electricity
passed through an electrolyte is given by Faraday’s laws of electrolysis.
Michael Faraday (1791-1867) did the first work on electrolysis and formulated what is known
today as Faraday’s laws of electrolysis.
These laws express the quantitative results of electrolysis. They assert that the amount (expressed
in moles) of an element liberated during electrolysis depends upon:
1. The time of passing the steady current, t

2. The magnitude of the steady current passed, I
3. The charge of the ions
Faraday’s First Law

This law states that “the mass of a substance deposited or liberated at any electrode is directly
proportional to the amount of charge passed”
i.e., M α Q (where M is the mass of the substance deposited or liberated and Q is the amount of charge
passed). This proportionality can be made into an equality by,
M = ZQ
where z is the proportionality constant called the electrochemical equivalent. It is the mass of the
substance in grams deposited or liberated by passing one coulomb of charge.
Since Q = I.t; Where I = Current in Ampere and t = time in second. Therefore;
and
Thus or M= Mm x n →n=Q/nF
Faraday’s Second Law
According to this law, “if same quantity of electricity is passed through different electrolytes, then
the amount of substances liberated at the respective electrodes are in the ratio of their equivalent
masses”. Or
When the same quantity of electricity passes through solutions of different electrolytes, the amounts of the
substances liberated at the electrodes are directly proportional to their chemical equivalents.
, where E is the mass equivalent.

For example, when the same current is passed through the solutions of sulphuric acid (H2SO4),
copper sulphate (CuSO4), and silver nitrate (AgNO3) for the same period of time then:
 Mass of copper deposited/Mass of silver deposited = Equivalent mass of

copper/Equivalent mass of silver and,
372 | P a g e
 Mass of copper deposited/Mass of hydrogen gas liberated =Equivalent mass of
copper/Equivalent mass of hydrogen
Therefore, the same quantity of electricity is required to liberate one equivalent of any material
during electrolysis. This quantity of electricity is called Faraday (F). One Faraday is equal to
96487 coulomb per mole of electrical charges. For the sake of convenience, we generally use a
value 96500 C mol–1 for the Faraday constant (F).
So, 1 Faraday = 1 F= Electrical charge carried by one mole of electrons

1 F= Charge on an electron × Avogadro’s number or,
1 F=e–× NA= (1.602 × 10–19C) × (6.02 × 1023mol–1),1 F= 96488 C mol–1
Example
In the following diagram the number of moles of silver deposited will be twice the number of moles
of copper deposited. The number of moles of copper deposited will be equal to the number of moles
of nickel deposited.
Cu2+(aq) + 2e Cu(s)
Ni2+(aq) + 2e Ni(s)
Ag+(aq) + 1e Ag(s)
If we pass one Faraday of charge, it means that we are passing one mole of electron and by passing 1
Faraday of charge 1gm equivalent weight of the substance will be deposited or liberated.
Factors affecting Electrolysis
In an electrolysis where there are more than one species which can be discharged at the same electrode,
only one of them is discharged at a time; for example, in an aqueous sodium chloride solution, we have
four species that is, Na+ and Cl- ions from sodium chloride and H+ and OH- ions from water. During
electrolysis Na+ ions and H+ ions migrate to the cathode while Cl - ions and OH- migrate to the anode. Now
373 | P a g e
the question is, which species of ions will be discharged at the cathode and which ones will be discharged
at the anode first?
The factors which decide the selective discharge of ions are:
• Nature of electrodes
• Position of the ion in electrochemical series
• Concentration
• The state of the electrolyte
1. Nature of Electrodes
In the electrolysis of sodium chloride solution using a platinum cathode, H + ions are discharged first in
aqueous solution.
2H+ + 2e- → H2(g)
However, if the cathode is mercury, sodium is discharged. The sodium atom discharged combines with
mercury cathode to form sodium amalgam.
Na+(aq) +e- → Na(s)
Na(s) +Hg (l) → Na/Hg (l)
Electrolysis of copper sulphate using copper anode
In this electrolysis, the anions, SO42- and OH- migrate to the anode but none of them is discharged. Instead
the copper atoms of the anode ionise and enter the solution.
Cu(s) → Cu2+(aq) +2e-
The copper (II) ions are attracted to the cathode and copper is deposited as a brown layer. The use of
platinum anode gives oxygen as the product due to the reaction;
4OH-(aq) → 2H2O (l) + O2 (g) + 4e-
2. Position of ion in Electrochemical Series
When solving for the standard cell potential, the species oxidized and the species reduced must be identified.
This can be done using the activity series. Looking simply at a table of standard reduction potentials in
decreasing order, The species at the top have a greater likelihood of being reduced while the ones at the
374 | P a g e
bottom have a greater likelihood of being oxidized. Therefore, when a species at the top is coupled with a
species at the bottom, the one at the top will become reduced while the one at the bottom will become
oxidized.
During electrolysis of solution containing a mixture of ions, the ion lower in electrochemical series is
discharged first in preference to the one high in the series.
Let us look at the role of water in electrolysis products.
Water molecules to a small extent (degree) ionize as
H2O(l) → H+(aq) + OH-(aq)
Due to the above ionization, aqueous solutions of electrolytes contain two sets of ions; those from the salt
dissolved and the H+ and OH- ions from partial dissociation of water molecules.
Example: Electrolysis of aqueous copper (II) sulphate solution using platinum electrodes.
Ions present in solution:
CuSO4 (aq) → Cu2+ (aq) + SO42- (aq)
2H2O (l) →H3O+ (aq) + OH- (aq)
Cathode
Cu2+ and H3O+ ions migrate to the cathode. Cu2+ ions being lower than H3O+ ions in electrochemical series
are discharged in preference to hydrogen ions.
Cu2+(aq) + 2e- → Cu(s)
The cathode gets coated with a brown layer of copper as the solution loses its blue colour.
Anode
Hydroxyl ions (OH-) being lower than sulphate ions (SO42-) in the electrochemical series are discharged at
the anode. Oxygen is evolved.
4OH-(aq) → 2H2O (l) + O2 (g) +4e-
375 | P a g e
3. Concentration of electrolyte solution
Increase of concentration of an ion tends to promote its discharge, for example in concentrated hydrochloric
acid, containing OH- (from water) and Cl- as negative ions, the highly concentrated Cl- is discharged in
preference.
However, if the acid is very dilute, some discharge of OH - will also occur. It is important to know that as
the acid is diluted, there will not be a point at which chlorine ceases to be produced and oxygen replaces it.
Instead a mixture of the two gases will come off, with the proportion of oxygen gradually increasing.
Another case in which the order of discharge according to the electrochemical series is reversed by a
concentration effect is that of sodium chloride solution.
In concentrated solution of sodium chloride called brine, the following reactions occur.
At the anode: 2Cl- →Cl2(g) + 2e-
At the cathode: 2H+(aq) + 2e-→ H2(g)
The hydroxyl ions OH- from water are attracted by Na+ ions to form NaOH solution.
Na+(aq) + OH-(aq) →NaOH(aq)
However, when sodium chloride solution is dilute, oxygen and hydrogen are formed in accordance with the
electrochemical series.
At the anode: OH- is oxidized in preference to chloride ions;
4OH-(aq) →2H2O + O2(g) + 4e-
At the cathode: H+ is reduced in preference to sodium ions;
2H+(aq) + 2e- → H2(g)
So in the electrolysis of dilute sodium chloride, water is decomposed into its elements rather than NaCl
being decomposed. This theory is applied in dilute solutions of the electrolytes such as dilute H 2SO4, dilute
HCl and dilute NaOH.
4. The state of the electrolyte
The half reactions taking place at the electrode depends on whether the electrolyte is in a molten or an
aqueous state, and if in aqueous state its concentration. For example, the electrode reactions that take place
during the electrolysis of molten potassium iodide are:
376 | P a g e
At the anode: 2I- → I2 (g) + 2e- (oxidation)
At the cathode: K+(l) + 1e- → K (l) (reduction)
However, if aqueous potassium iodide is used, the following electrode reactions take place:
At the anode: 2I-(l) → I2 (g) + 2e- (oxidation)
At the cathode: 2H+(aq) + 1e- → H2 (g) (reduction)
Application of electrolysis
Electrolysis has a number of important industrial applications. These include the extraction and purification
of metals, electroplating and anodizing and the manufacture of other chemicals for example sodium
hydroxide (NaOH).
Extraction of metals
Metals are extracted from their ores using a method dependent on the position of the metal in the reactivity
series. More reactive metals are extracted using electrolysis while less reactive metals can be heated with
carbon.
Unreactive metals, such as silver and gold, can be found in the Earth’s crust in a pure form, uncombined
to other elements. However, more reactive metals, such as aluminium and magnesium, will usually be
found combined to another element in a compound. An ore is a rock that contains enough of the metal to
make it economically worth extracting.
If a metal is less reactive than carbon, it can be extracted by reacting it with carbon in a displacement
reaction. In a displacement reaction, the more reactive metal is able to take the place of a less reactive metal
in a compound, since the more reactive metal forms stronger bonds. Carbon replaces the less reactive metal
in a redox reaction, where the carbon is oxidised and the metal is reduced. We therefore refer to this
method as reduction using carbon.
377 | P a g e
Elements which are more reactive than carbon will be extracted using electrolysis. Aluminium is more
reactive than carbon so it must be extracted from ores containing aluminium oxide using this method.
Sodium is obtained by electrolysis of molten sodium chloride in the Dawn cell. Magnesium is obtained by
electrolysis of MgCl2, generated from dolomite and sea water.
Extraction of Aluminium
The chief ore of Aluminium is bauxite, Al2O3.2H2O, it contains silica and iron (III) oxide as impurities.
Bauxite is dissolved in a strong solution of sodium hydroxide:
Al2O3(s) + 2OH-(aq) → 2AlO2-(aq) + H2O (l)
The impurities are not affected by the presence of sodium hydroxide because they are not amphoteric and
they are thus filtered off. The solution is diluted, cooled and seed by adding a few crystals of pure Al(OH)3.
On seeding, the aqueous tetrahydroxoaluminate is precipitated as pure Al(OH) 3 from the solution:
The precipitate is filtered off, washed, dried and heated strongly 1000 0C to form the pure oxide.
2Al (OH)3(s) → Al2O3 + 3H2O
378 | P a g e
The electrolytic cell is an iron tank lined with carbon, which acts as the cathode. The anodes are blocks of
carbon dipped into the electrolyte. The electrolyte is a solution of molten aluminum oxide in molten cryolite.
Cryolite acts as a solvent to dissolve aluminium oxide and as an impurity to lower the melting point of
aluminium oxide. The electrolytic cell is maintained at around 900°C
Electrodes: Carbon
Ions present in electrolyte: Al3+, O2−
Reaction at cathode: Al3+ (l) +3e− → Al (l)
Reaction at anode: 2O2− (l) → O2 (g) +4e−
Aluminium ions are discharged at the cathode, forming a pool of molten aluminium at the bottom of the
tank.
At high temperature, oxygen reacts with the carbon anode to form carbon dioxide gas. Hence, the anodes
are slowly burnt away as carbon dioxide gas and needs to be replaced frequently.
Extraction of Sodium
Sodium, like many of the most reactive metals, can be extracted by electrolysis of its molten chloride. This
can be done in the 'Down's Cell' shown in the diagram.
379 | P a g e
Construction of Down’s cell
 Down’s cell consists of a rectangular container of steel.

 Inside of the tank is lined with firebricks.
 Anode is a graphite rod which projects centrally up through the base of the cell.
 Cathode is a ring of iron, which surrounds the anode.
 The anode and cathode are separated from each other by a cylindrical steel gauze diaphragm; so
that Na and Cl2 are kept apart.
 A bell like hood is submerged over the anode
Sodium chloride has a high melting point, ~800 oC, so calcium chloride or sodium carbonate is added to
reduce the melting point to around 600oC.
When an electric current is passed through the molten mixture of NaCl and CaCl 2, NaCl decomposes in
to Na+ and Cl- ion. Na+ ions migrate towards cathode while Cl- ions towards the anode. The molten sodium
collects in the cathode compartment where it rises to the top and is tapped off by a pipe. Chlorine is collected
at the anode.
Ions present in electrolyte: Na+, Ca2+, 2Cl−

Reaction at cathode: Na+(l) + e−→Na(l)
Reaction at anode: 2Cl−(l) →Cl2(g)+2e−
Overall Reaction: 2Cl-(l) + 2Na+(l)→Cl2(g) + 2Na(l)
During electrolysis, calcium is also obtained at cathode but sodium and calcium are separated from each
other due to the difference in density. Density of Na is 0.67 g cm-3 and the density of Ca is 2.54 g cm-
3i.e.much higher than that of Na. That is why they do not mix with each other.
Purification of metals
Metals such as copper, zinc and aluminium can be purified by electrolysis. The purification of metals is
known as refining. The copper obtained after the reduction process is not very pure. It contains small
amounts of impurities such as iron. This copper is called blister copper and is refined by an electrolytic
method. It is cast into bars which are used as anodes in acidified copper (II) sulphate solution.
The cathode is made of thin pure copper. During the electrolysis, Cu2+ ions are transferred from the anode
to the cathode where they are discharged and copper is deposited.
At the anode: Cu(s) → Cu2+ (aq)+ 2e- impure copper

At the cathode: Cu2+ (aq) + 2e-→Cu (s) pure copper
The net effect is to dissolve the anode made of impure copper and thicken the cathode (pure copper) with
purer copper.
380 | P a g e
Electroplating
Another important use of electrolytic cells is in the electroplating
Electroplating is the process of plating (coating) one metal onto another by electrolysis, most
commonly for decorative purposes or to prevent corrosion of a metal.
Electroplating allows manufacturers to use inexpensive metals such as steel or zinc for the majority of the
product and then apply different metals on the outside to account for appearance, protection, and other
properties desired for the product.
Common plating metals are gold, nickel and silver as well as chromium and zinc. Electroplating produces
a very thin coating of these expensive metals on the surfaces of cheaper metals, to give them the appearance
and the chemical resistance of the expensive ones.
In general;
 The metal being plated (coated) is made the cathode and the plating (coating) metal is the anode
 The solution used is made of the ions of a metal that is coating, so that the anode can dissolve. Anode
is the pure plating metal.
Silver plating could be done in the cell below.
Set up for silver plating spoon
o At cathode: Ag+(aq) + e- →Ag(s) (silver deposits)

o At anode: Ag(s) →Ag+(aq) + e- ( silver dissolves)
381 | P a g e
A good electroplating requires steady electric current, appropriate concentration of electrolyte and
temperature. The metal to electroplate must be clean.
USES OF ELECTROPLATING
While electroplating is often used to improve the aesthetic appearance of a base material, this technique is
used for several other purposes across multiple industries. These uses include the following:
Build thickness: Electroplating is often used to build up the thickness of a substrate through the progressive
use of thin layers.
Protect substrate: Electroplated layers serve as sacrificial metal coatings. This means that when a part is
placed in a harmful environment, the plated layer breaks down before the base material, protecting the
substrate from damage.
Lend surface properties: Electroplating allows substrates to benefit from the properties of the metals they
are plated with. For example, some metals protect against corrosion, improve electrical conductivity, reduce
friction or prepare a surface for better paint adhesion. Different metals lend different properties.
Improve appearance: Of course, electroplating is also commonly used to improve the aesthetic appearance
of a substrate. This can mean plating the substrate with an aesthetically pleasing metal or simply applying
a layer to improve surface uniformity and quality.
Production of chemicals
Many chemicals, such as caustic soda, chlorine, hydrogen and oxygen etc. are produced by electrolysis on
a large scale. The most important is production of caustic soda by electrolysis of brine.
Production of caustic soda by electrolysis of brine
These are manufactured by electrolysis of concentrated sodium chloride, called brine. Hydrogen and
chlorine are also obtained as by products. In solution, sodium chloride ionizes:
NaCl (aq) → Na+ (aq) + Cl-(aq) and water partially ionizes as: H2O →H+ + OH-
Using carbon electrodes, the products of electrolysis are chlorine at the anode and hydrogen at the cathode.
Hydrogen is discharged in preference to sodium.
Anode: 2Cl – 2e– →Cl2

–
Cathode: 2H + 2e– →H2

+
Over all reaction 2NaCl + 2H2O→ Cl2 +2NaOH + H2
Using mercury cathode, the products of electrolysis are chlorine at the anode and sodium at the cathode.
382 | P a g e
(Anodic reaction) 2Cl- → Cl2 + 2e-
(Cathodic reaction) 2Na+ + 2Hg + 2e- →2Na/Hg (l)
(Overall cell reaction) 2Cl- + 2Na+ + 2Hg →Cl2 + 2Na/Hg (l)
The sodium discharged at the mercury cathode forms a solution of sodium amalgam in mercury. The sodium
amalgam is collected in a reservoir in which it reacts with water to form sodium hydroxide solution and
hydrogen gas. Mercury is also recovered and returned to the electrolytic cell to pass through the process
again.
(Decomposer reaction) 2Na/Hg (l) + 2H2O → H2 +2NaOH + Hg

(overall process reaction) 2NaCl + 2H2O → Cl2 +2NaOH + H2
The sodium hydroxide produced is crystallized. It is used in:
o Manufacture of soap
o The paper industry-wood contains lignin, which is a nitrogenous compound, in addition to cellulose.
Wood chips are converted into pulp by boiling the chips with sodium hydroxide solution to remove
the lignin. The digested material is bleached with chlorine.
383 | P a g e

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CHEMISTRY FOR S5 MCB, PCM& PCB

Key competences by the end of Senior Five

Key competences by the end of Senior Five

SUB-TOPIC AREA: ALIPHATIC COMPOUNDS

Unit 1: Introduction to organic chemistry

2. General properties of organic compounds

A. Classification of Organic Compounds Based on Structure

2. Aromatic heterocyclic compounds: Heterocyclic compounds which resemble benzene and

i. The percentage of each element is divided by its atomic mass.

% composition 39.13 8.64 52.23

Relative Ratio of 39.13

Atomic ratio 3.26

Empirical formula 3 7.95=8 3

% composition 31.9 6.8 42.79 18.51

Relative Ratio of 31.9

Atomic ratio 2.658

Empirical formula C2H5NO2

 molecular weight = 2 x vapour density= 2x37.5= 75gr/mol

hence molecular formule=empirical formula= C2H5NO2

 Percentage of oxygen = 100-26.66-2.22=71.12%

Relative Ratio of 26.66

Atomic ratio 2.22

Empirical formula CHO2

Molecular formula n= 90/45=2 C 2H 2O4 Acide oxalique

% of Oxygen  100  (% of H 2  % of carbone)

Activity: The laboratory analyses of an organic compounds A containing carbon, hydrogen,

(i) Determine its empirical formula

A gaseous hydrocarbon exploded in air by the reaction

Volume of hydrocarbon reacting: 15cm3

45= x.15 → x=3

The molecular formula is C3H8 (propane) CH3CH2CH3

 Displayed Formulae (also called developed Formulae)

 Semi- Displayed Formulae (also called "Semi-Developed Formulae" or "condensed

 Skeletal Formulae(also called stick Formulae)

Examples of Displayed Formulae

Propanoic Acid Hexanenitrile Propyl Pentanoate

Propanoic Acid Hexanenitrile Propyl Pentanoate

OR, even shorter OR, even shorter OR, even shorter

A skeletal formula does not explicitly show:

A skeletal formula does explicitly show:

 bonds between carbon atoms

Drawing and Interpreting Skeletal Formula

To draw a skeletal formula:

a. Draw the 2-dimensional structural formula

To draw a 2-dimensional structural formula given the skeletal formula:

a. Place a carbon atom at the end of each line

Examples of Skeletal Formulae

Propanoic Acid Hexanenitrile Propyl Pentanoate

1. Geometrical isomerism ( cis-trans isomerism)

H3C CH3 H3C H

Exemple. 1,4 butenedioic acid C4H4O4

HOOC COOH HOOC H

Table: Properties of maleic and fumaric acid

Cis but-2-enedioic FOCUSED Trans1,4 but-2-enedioic

135°C Melting points 287°C

79 Solubility(g/100g H2O) 0,7

Optical activity is measured using an instrument called polarimeter.

How a polarimeter works

7. General rules of nomenclature of organic compounds according to IUPAC system.

1. Alkanes (saturated hydrocarbon)