2.

1 Introduction

The group of compounds known as carbohydrates received their general name because of early
observations that they often have the formula Cx(H2O)y - that is, they appear to be hydrates of carbon.

Limitations: The above definition could not survive long due to the following reasons:
i) A number of compounds such as rhamnose, (C6H12O5) and deoxyribose (C5H10O4) are known which
are carbohydrates by their chemical behaviour but cannot be represented as hydrates of carbon.
ii) There are other substances like formaldehyde (HCHO, CH2O) and acetic acid [CH3COOH, C2 (H2O)2]
which do not behave like carbohydrates but can be represented by the general formula, C x(H2O)y.
Carbohydrates are defined as polyhydroxy aldehydes or polyhydroxy ketones or substances which give
these on hydrolysis and contain at least one chiral carbon atom. It may be noted here that aldehydic and
ketonic groups in carbohydrates are not present as such but usually exist in combination with one of the
hydroxyl group of the molecule in the form of hemiacetals and hemiketals respectively.

2.2 Classification

Chemically carbohydrates are polyhydroxy aldehydes or ketones or substances that yield these on hydrolysis.
(A) ON THE BASIS OF FUNCTIONAL GROUPS:
Carbohydrates with an aldehydic group are known as aldoses and those with ketonic group are called
ketoses. The number of carbon atoms in a carbohydrate (monomer unit) is indicated by prefix tri, tetra,
penta etc. The name of the carbohydrate containing aldehydic group end in “− ose” while suffix for
ketonic group is “− ulose”.
For example, 4−carbon containing aldehydic carbohydrate is tetrose. [OHCH2(CHOH)2CHO].
It contains two chiral carbon and the name of optical isomers are D−erythrose, D−threose, L−erythrose,
L−threose. 4−carbon containing ketonic carbohydrate is called keto tetrose [OHCH2.CO.CHOH.CH2OH].
It contains 1−chiral carbon and name of optical isomers are D− & L−erythrulose.
(B) On the basis of number of monosaccharide units (saccharide is latin name for sugar) carbohydrate
yields on hydrolysis.
Carbohydrates are divided into two main classes, sugar and polysaccharides. Sugars are crystalline
substance with a sweet taste and soluble in water. Polysaccharides are more complex than sugar, their
molecular weight being far greater, are non−crystalline substances which are not sweet and are insoluble
or less soluble in water.
Examples of sugar

i) Monosaccharides: The monosaccharides are polyhydroxy aldehydes or polyhydroxy ketones which

cannot be decomposed by hydrolysis to give simpler carbohydrates. Examples are glucose and fructose,
both of which have molecular formula, C6H12O6.
+

C6H12O6 + H2O ⎯⎯→

⎯ No reaction
H

glucose or
fructose

ii) Oligosaccharides: The oligosaccharides (Greek, oligo, few) are carbohydrates which yield a definite
number (2-9) of monosaccharide molecules on hydrolysis. They include,

a) Disaccharides, which yield two monosaccharide molecules on hydrolysis. Examples are sucrose
and maltose, both of which have molecular formula, C12H22O11.
+
C12H22O11 + H2O ⎯⎯→
⎯ C6H12O6 + C6H12O6
H

sucrose glucose fructose

 +

C12H22O11 + H2O ⎯⎯→

⎯ 2C6H12O6
H

Maltose glucose

b) Trisaccharides, which yield three monosaccharide molecules on hydrolysis. Example is, raffinose,
which has molecular formula, C18H32O16.
+

C18H32O16 + 2H2O ⎯⎯→

⎯ C6H12O6 + C6H12O6 + C6H22O6
H

raffinose glucose fructose galactose

iii) Polysaccharides: The polysaccahrides are carbohydrates of high molecular weight which yield many
monosaccharide molecules on hydrolysis. Examples are starch and cellulose, both of which have
molecular formula, (C6H10O5)n.
+

(C6H10O5)n + nH2O ⎯⎯→

⎯ nC6H12O6
H

starch glucose

In general, the monosaccharides and oligosaccharides are crystalline solids, soluble in water and
sweet to taste. They are collectively known as sugars. The polysaccharides, on the other hand, are
amorphous, insoluble in water and tasteless. They are called non-sugars. The carbohydrates may also
be classified as either reducing or non-reducing sugars. All those carbohydrates which have the ability
to reduce Fehling’s solution and Tollen’s reagent are referred to as reducing sugars, while others are
non-reducing sugars.

All monosaccharides and the disaccharides other than sucrose are reducing sugars.

3. Monosaccharides
The monosaccharides are the basis of carbohydrate chemistry since all carbohydrates are either
monosaccharides or are converted into monosaccharides on hydrolysis. The monosaccharides are
polyhydroxy aldehydes or polyhydroxy ketones. There are, therefore, two main classes of
monosaccharides.
O
||
1. the Aldoses, which contain an aldehyde group ( − C − H)
O
||
2. the Ketoses, which contain a ketone group (— C —)
The aldoses and ketoses are further divided into sub-groups on the basis of the number of carbon atoms in
their molecules, as trioses, tetroses, pentoses, hexoses, etc. To classify a monosaccharide completely, it is
necessary to specify both, the type of the carbonyl group and the number of carbon atoms present in the
molecule. Thus monosaccharides are generally referred to as aldotrioses, aldotetroses, aldopentoses,
aldohexoses, ketohexoses, etc. Glucose and fructose are specific examples of an aldose and a ketose.
 H O CH2OH
|
C C=O
| |
H – C – OH HO – C – H
| |
HO – C – H H – C – OH
| |
H – C – OH H – C – OH
| |
H – C – OH CH2OH
|
CH2OH fructose
Glucose (an aldohexose) (a ketohexose)

3.1 Trioses

D and L Terminology: The simplest of all CHO CH2OH

carbohydrates that fit the definition we have given | |
for carbohydrates are the trioses, glyceraldehyde *CHOH C=O
and dihydroxyacetone. Glyceraldehyde is | |
aldotriose, and dihydroxyacetone is a ketotriose. CH2OH CH2OH
Glyceraldehyde Dihydroxyacetone
(an aldotriose) (a ketotriose)

Glyceraldehyde contains one asymmetric carbon CHO CHO

| |
atom (marked by an asterisk) and can thus exist in H – C – OH HO – C – H
two optically active forms, called the D-form and | |
the L-form. Clearly, the two forms are mirror CH2OH CH2OH
D-Glyceraldehyde L-Glycera aldehyde
images that cannot be superimposed, that is they are
enantiomers.

O O
|| ||
1 1
CH D Means on CH
| the right |
2 2
H – C – OH HO – C – H
| | L Means on
3 3 the Left
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde

The two forms of glyceraldehyde are especially important because the more complex monosaccharides
may be considered to be derived from them. They serve as a reference point for designating and drawing
all other monosaccharides. In carbohydrate chemistry, the Fischer projection formulas are always written
with the aldehyde or ketone groups at the top of the structure. By definition, if the hydroxyl group on the
asymmetric carbon atom farthest from aldehyde or ketone group projects to the right, the compound is a
member of the D-family. If the hydroxyl group on the farthest asymmetric carbon projects to the left, the
compound is a member of the L-family. The maximum number of optical isomers of a sugar is related to
the number of asymmetric carbon atoms in the molecule and may be calculated by the following simple
equation.
Maximum Number of Optical Isomers = 2n, where n = the number of asymmetric carbon atoms.
Since glyceraldehyde contains only one asymmetric carbon atom, the number of optical isomer is 2 1. We
know that 21 is = 2, and we have seen that there are indeed two different glyceraldehydes.

3.2 Aldotetroses
 If we examine the general formula of an aldotetrose, we see that they
1. CHO
contain two asymmetric carbon atoms (marked by asterisks). |
2. *CHOH
This means that 22 or 4 optical isomers are possible. They may be |
3. *CHOH
represented as the following two pairs:
|
an aldotetrose
4. CH2OH

CHO CHO CHO CHO

| | | |
H – C – OH HO – C – H HO – C – H H – C – OH
| | | |
H – C – OH HO – C – H H – C – OH HO – C – H
| | | |
CH2OH CH2OH CH2OH CH2OH
Mirror images (recemic pair) Mirror images (recemic pair)
D (–)-erythrose L (+)-erythrose D (–)-threose L (+)-threose

All four isomers have been prepared synthetically. The D- and L-erythrose are mirror images, that is, they
are enantiomers. They have exactly the same degree of rotation but in opposite directions. Equal amounts
of the two would constitute a racemic mixture, that is, a mixture that would allow a plane-polarised light
to pass through the solution unchanged but could be separated into detrorotatory and laevorotatory
isomers. The same comments hold for D- and L-threose. However, D-erythrose and L-threose are not
images, that is, they are diastereomers (optical isomers that are not mirror images are called
diastereomers), and the degree of rotation of each would probably differ.

3.3 Aldohexoses
1. CHO
If we examine the general formula of aldohexose, we see that it contains four |
asymmetric carbon atoms. 2. *CHOH
|
This means that 24 or 16 optical isomers are possible. D and L forms of altrose, allose 3. *CHOH
glucose, mannose, galactose, talose, arabinose and idose |
4. *CHOH
|
Only three of the sixteen possible aldohexoses are found in nature (all sixteen isomers
5. *CHOH
have been prepared synthetically). They are D-glucose, D- mannose, and D-galactose. |
No one of these three optical iosmers is a mirror image of any of the others, so all 6. CH2OH
three are diastereomers of each other. an aldohexose

3.4 Epimers

A pair of diastereomers that differ only in the Epimers Epimers

O H O H O H
configuration about of a single carbon atom C C C
| | |
are said to be epimers. e.g D(+)- glucose is H – C – OH H – C – OH HO– C – H
| | |
HO– C – H HO– C – H HO– C – H
epimeric with D(+) -mannose and D(+) - | | |
HO– C – H H – C – OH H – C – OH
galactose as shown below: | | |
H – C – OH H – C – OH H – C – OH
| | |
CH2OH CH2OH CH2OH
D (+)-Galactose D (+)-Glucose D (+)-Mannose

3.65 Cyclic structure of monosaccharides

We know that aldoses (and ketoses) react with alcohols to give first hemiacetals (and hemiketals) and then
acetals (and ketals), i.e.,

OH OR
| +ROH
|
– C = O + ROH – C – OR ⎯ ⎯ ⎯
⎯ → – C – OR
–H2O
| | |
H H H
Aldehyde Hemiacetal Acetal

OH OR
| | |
+ROH
– C = O + ROH – C – OR ⎯⎯ ⎯
⎯→ – C – OR
–H2O
Ketone Hemiketal ketal

Since monosaccharides contain a number of hydroxyl groups and an aldehyde or a keto group, therefore,
any one of the –OH groups (usually C4 or C5 in aldohexoses and C5 or C6
in ketohexoses) may combine with the aldehyde or the keto
group to form intramolecular hemiacetal or hemiketal. As a
result, the open chain formulae do not represent the actual
structures of the monosaccharides. Their actual structures are O O
Furan Pyran
cyclic involving five or six membered rings containing an
oxygen atom. The five
membered ring containing one oxygen atom because of its similarity with furan is called the furanose
form and the six membered ring containing one oxygen atom because of its resemblance with pyran is
called the pyranose form. In nut shell, all the monosaccharides (pentoses and hexoses) in the free state
always exist in the pyranose form. However, in the combined state some monosaccharides such as ribose,
2-deoxyribose, fructose etc., usually exist in the furanose form.

3.6 Cyclic structure of Glucose – Anomers

1 
1
H – C – OH 1
H– C=O HO – C – H
| | |
2 2 2
H – C – OH H – C – OH H – C – OH
| | |
3 3 3
HO– C – H O HO– C – H HO– C – H O
| | |
4 4 4
H – C – OH H – C – OH H – C – OH
| | |
5 5 5
H– C H– C–O–H H– C
| | |
6 6 6
CH2OH CH2OH CH2OH (II)
(I)
-D(+)-Glucose or D(+)-Glucose -D(+)-Glucose or
-D(+)-Glucopyranose (Open chain form) -D(+)-Glucopyranose

We have discussed above that monosaccharides have cyclic hemiacetal or hemiketal structures. To
illustrate, let us first consider the example of D-glucose. During hemiacetal formation C5 – OH of glucose
combines with the C1 – aldehydic group. As a result, C1 becomes chiral or asymmetric and thus has two
possible arrangements of H and OH groups around it. In other words, D-glucose exists in two
stereoisomeric forms, i.e., -D-glucose and -D-glucose as shown below:
In -D-glucose, the OH group at C1 is towards right while in -D-glucose, the OH group at C1 is towards
left. Such a pair of stereoisomers which differ in configuration only around C 1 are called anomers and the
C1 carbon is called Anomeric carbon (or glycosidic carbon. The cyclic structures of monosaccharides can
be better represented by Haworth Projection formulae. To get such a formula for any monosaccharide (say
-and -D-glucose), draw a hexagon with its oxygen atom at the upper right hand corner. Place all the
groups (on C1, C2, C3 and C4) which are present on left hand side in structures I and II, above the plane of
the ring and all those groups on the right hand side below the plane of the ring.

The terminal – CH2OH group is always placed above the plane of the hexagon ring (in D-series).
Following the above procedure, Haworth Projection Formulae for -D-glucose (I) and -D-glucose (II)
are obtained as shown below:

6 CH2OH 6 CH2OH

5 5
H H H OH
H 
H
4 1 4 1
OH H  OH H
OH OH OH H
3 2 3 2
I II
H -D-Glucose OH H -D-Glucose OH
or -D(+)-Glucopyranose or -D(+)-Glucopyranose

3.7 Cyclic structure of Fructose

Like glucose, fructose also has a cyclic structure. Since fructose contains a keto group, it forms an
intramolecular hemiketal. In the hemiketal formation, C5– OH of the fructose combines with C2-keto
group. As a result, C2 becomes chiral and thus has two possible arrangements of CH2OH and OH group
around it. Thus, D-fructose exists in two stereoisomeric forms, i.e., -D-fructopyranose and -D
fructopyranose. However in the combined state (such as sucrose), fructose exists in furanose form as
shown below:

6
2 1 CH2OH O
HO – C – CH2OH OH
| 
3
H – C – OH O 5 2
| 1
4
H – C – OH H H H CH2OH
| 1
5
H– C
4 3
| 1
6
CH2OH  -D-Fructofuranose
OH OH

3.8 Mutarotation

The two stereoisomeric forms of glucose, i.e., -D-glucose and -D-glucose exist in separate crystalline
forms and thus have different melting points and specific roations. For example -D-glucose has a m.p. of
419 K with a specific rotation of +112° while -D-glucose has a m.p. of 424 K and has a specific rotation
of +19°. However, when either of these two forms is dissolved in water and allowed to stand, it gets
converted into an equilibrium mixture of -and -forms through a small amount of the open chain form.
 -D-Glucose Open chain form -D-Glucose
(36%) (0.02%) (64%)

As a result of this equilibrium, the specific rotation of a freshly prepared solution of -D-glucose gradually
decreases from of +112° to +52.7° and that of -D-glucose gradually increases from +19° to +52.7°.

This change in specific rotation of an optically active compound in solution with time, to an equilibrium
value, is called mutarotation. During mutarotation, the ring opens and then recloses either in the inverted
position or in the original position giving a mixture of -and--forms. All reducing carbohydrates, i.e.,
monosaccharides and disacchardies (maltose, lactose etc.) undergo mutarotation in aqueous solution.

3.9 Reactions of Glucose

1. MILD OXIDATION
Mild oxidation of aldoses gives aldonic acid. Br2 water or alkaline solution of iodine oxidises only the
aldehydic group to give aldonic acids.

2. STRONG OXIDATION
Strong oxidation of aldoses oxidise both −CHO group and terminal −CH2OH group into −COOH to give
aldaric acid.

3. REDUCTION OF SUGAR
Sugar can be reduced into corresponding alcohols by variety of reducing agents like high pressure
catalytic hydrogenation (Ni/H2), NaBH4, (iii) Na/Hg (iv) electrolytic reduction in acidic medium.

4. REACTION OF ALDOSE AND KETOSE WITH PHENYL HYDRAZINE

Aldose and ketose both react with phenyl hydrazine (excess) to form osazones, which contain two
phenylhydrazone group and also give aniline and ammonia. The overall reaction may be represented as.

N
CHO HC=NNH−Ph H−C NHPh
PhNHNH2
CHOH CHOH HO−C−H

N NH NH
H−C NHPh NHPh H−C + PhNH2
H−C
C−H C C=O
H
OH O

Ketoses (for example, Fructose) also react with phenyl hydrazine in similar way
O O
CHOH H H
CH C
C=O PhNHNH2 −PhNH2
C=NNH−Ph C NH−Ph
NH

O NNHPh
+2PhNHNH2
H−C H−C + NH3 + H2O
−PhNH2
C=NH C=NNHPh
 Only C−1 and C−2 in glucose and fructose are involved in osazone formation and the reaction do not run
throughout the chain. This is because osazone formed is stabilised by chelation.
NHPh
6
HOH2C O N
5 1 H
4 2 N
3
OH N Ph
OH
Fig. 5.1

Glucose and fructose both form same osazone. This means configuration of glucose and fructose is similar
at all the carbons except C−1 and C−2.

5. REACTION WITH CONCENTRATED HCl

This reaction is only given by aldohexoses and aldopentoses. When aldohexoses are treated with conc.
HCl (or H2SO4), they first give hydroxymethyl furfural, which then decomposes into other products.

HOCH2(CHOH)4CHO ⎯⎯ ⎯⎯→ 3H2O +

conc . HCl

HOH2C O CHO

6. REACTION WITH ACID CHLORIDES AND ACID ANHYDRIDES

When monosaccharides are acylated with acetyl chloride in presence of anhydrous ZnCl2, all the hydroxyl
groups are acylated. For example, glucose gives a penta−acetate.

CHO Anhydrous CHO

ZnCl2
(CH−OH)4 + 5CH3COCl (CHOOCCH3)4 + 5HCl
CH2OH Acetyl chloride CH2OOCCH3
Glucose Glucose penta−acetate

7. REACTION WITH PCl5

When treated with PCl5, all the hydroxyl groups are chlorinated.
CHO CHO
(CH−OH)4 + 5PCl5 (CHCl)4 + 5POCl3 + 5HCl
CH2OH CH2Cl
Glucose Penta−chloroglucose
(Glucose penta−chloride)

8. REACTION WITH METALLIC HYDROXIDES

Glucose reacts as a weak acid and on reaction with calcium hydroxide to form calcium gluocosate.
C6H11O5−OH + HO−Ca−OH C6H11O5OCaOH + H2O
Calcium hydroxide  and −Calcium glucosate

9. FORMATION OF GLYCOSIDES
Glucose reacts with methyl alcohol in presence of dry HCl to form  and −methyl glycoside of glucose.
The reaction takes place only on OH of hemi−acetylic carbon. Other hydroxyl groups are unreactive.

To methylate all the OH groups, methylating agent used is dimethyl sulphate.

 H OCH3 CH3O H
C C

(CHOH)3 O (CHOH)3 O

CH CH

CH2OH CH2OH
−Methyl glucose −Methyl glucose

Fig. 5.2

10. REACTION OF CARBONYL GROUP (ALDEHYDIC GROUP)

Glucose is reduced by sodium−amalgam in presence of acid into corresponding hydroxyl compound,
sorbitol.
Na−Hg
CH2OH(CHOH)4CHO + 2H CH2OH(CHOH)4CH2OH
H2O
Glucose H2O Sorbitol

11. REACTION WITH HCN

HCN reacts with glucose to form an addition product, glucose cyanohydrin.
CN
CH2OH(CHOH)4CHO + HCN CH2OH(CHOH)4CH
Glucose H2O
Glucose cyanohydrin OH
12. REACTION WITH HIO4
Glucose consumes five moles of HIO4 to give five moles of formic acid and one mole of formaldehyde.
Fructose consumes five moles of HIO4 to give three moles of formic acid, two moles of formaldehyde and
one mole of CO2.

13. KILIANI FISCHER SYNTHESIS

The aldoses can be stepped up with the help of following sequence of reactions. Aldose is treated with
NaCN /HCN (cyanohydrin formation) and hydrolysed producing aldonic acid.
Theoretically, one isomer of an aldose produces two diastereomeric aldonic acid, however one of this is
obtained in greater yield in practice. The aldonic acid is separated at this stage and separated acids when
heated forms −lactone, which when reduced which sodium−amalgam gives higher aldose.

CN COOH O=C HC=O

HC=O HCOH HCOH HCOH HCOH
(HCOH)2 O
(HCOH)2 (HCOH)2 (HCOH)2 (HCOH)2
CN−/HCN H3O+ Na/Hg
HCOH HCOH HCOH HC CO2
HCOH
CH2OH CH2OH CH2OH CH2OH CH2OH
a D−aldopentose a cyanohydrin a glyconic acid a −lactone a D−aldohexose

14. RUFF’S DEGRADATION METHOD

In this method, aldose is oxidised by bromine water to corresponding aldaric acid (only CHO is oxidised
into COOH) and calcium salt of this acid when treated with Fenton’s reagent (H2O2/Fe2+) the aldose is
converted into corresponding lower aldose.
 CHO COOH CO2−
CHO
CHOH CHOH CHOH
Br2 water Ca salt H2O2/Fe2+
(CH−OH)3
(CH−OH)3 (CH−OH)3 (CH−OH)3
CH2OH
CH2OH CH2OH CH2OH
(Aldopentose)
(Aldohexose)
This method involves oxidative decarboxylation, where −CHOH in oxidised to −CH=O without any
configurational changes of the other chiral carbons.

4. Disaccharides
Carbohydrates which upon hydrolysis give two molecules of the same or different monosaccharides are
called disaccharides. Their general formula is C12H22O11. The three most important disaccharides are
sucrose, maltose, and lactose. Each one of these on hydrolysis with either an acid or an enzyme gives two
molecules of the same or different monosaccharides as shown below:
+
C12H22 O11 + H2O ⎯⎯
⎯→ C6H12 O6 + C6H12 O6
H

Sucrose or invertase Glu cos e Fructrose

C12H22O11 + H2O ⎯ ⎯→
⎯ C6H12O6 + C6H12O6
H
or Maltase
Maltose Glucose Glucose
+

C12H22O11 + H2O ⎯ ⎯→
⎯ C6H12O6 + C6H12O6
H
or Lactase
Lactose Glucose Galactose

Disaccharides may also be considered to be formed by a condensation reaction between two molecules of
the same or different monosaccharides with the eliminatioin of a molecule of water. This reaction involves
the formation of an acetal from a hemiacetal and an alcohol in which one of the monosaccharides acts as
the hemiacetal while the other acts as the alcohol.

4.1 Maltose

Maltose is another disaccharide, which is made up of two −D−glucose units joined together by glycosidic
linkage in such a way that one anomeric OH (C−1) is joined with OH (C−4) in other unit.
6
6 CH2OH
CH2OH
O H O OH
H 5
H 5
H 4
H 1
4 1 OH H
OH H 2 H
3 2 O 3
OH
H OH H OH

−D−glucopyranose −D−glucopyranose

Structure of Maltose (−D− glucopyranose −D− glucopyranose

4.2 Sucrose

It is formed by condensation of one molecule of glucose and one molecule of fructose. Unlike maltose and
lactose, it is non-reducing sugar since both glucose (C1 - ) and fructose (C2 - ) are connected to each
other through their reducing centres. Its structure is shown below:
4.1.1 Hydrolysis 6
CH2OH
(Invert Sugar or Invertose). Hydrolysis of sucrose with hot
dilute acid yields D-glucose and D-fructose. 5
H O
1 H
H+
C12H22O11 + H2O ⎯⎯→
⎯ C6H12O6 + C6H12O6
4
H
1
Sucrose D-glucose D-fructose OH H
[ ] D = +66.5° [ ] D = +53° [ ] D = –92°
 -link
Invert Sugar
HO 2
3
[ ] D = (+53°) – (–92°) = –39°
Sucr O  Glycosidic
H OH
ose is dextrorotatory, its specific rotation being +66.5%, linkage
(Glucose unit)
D-glucose is also dextrorotatory, []D = +53°, but D-
CH2OH O  -link
fructose has a large negative rotation, []D = -92°. Since
D-fructose has a greater specific rotation than D-glucose,
the resulting mixture is laevorotatory. Because of this
the hydrolysis of sucrose is known as the inversion of H H OH CH2OH
sucrose, and the equimolecular mixture of glucose and
fructose is known is invert sugar or invertose. 1
OH H
(Fructose unit) Sucrose

5. Polysaccharides
Polysaccharides are formed when a large number (hundreds to even thousands) of monosaccharide
molecules join together with the elimination of water molecule. Thus, polysaccharides may be regarded as
condensation polymers in which the monosaccharides are joined together by glycosidic linkages. Some
important polysaccharides are:

1. Cellulose 2. Starch
3. Glycogen 4. Gums and
5. Pectins

5.1 Starch

It is a polymer of glucose. Its molecular formula is (C6H10O5)n where the value of

n (200 – 1000) varies from source to source. It is the chief food reserve material or storage polysaccharide
of plants and is found mainly in seeds, roots, tubers, etc. Wheat, rice, potatoes, corn, bananas etc., are rich
sources of starch.

Starch is not a single compound but is a mixture of two components – a water soluble component called
amylose (20%) and a water insoluble component called amylopectin (80%). Both amylose and
amylopectin are polymers of -D-glucose.

Amylose is a linear polymer of -D-glucose. It contains about 200 glucose units which are linked to one
another through -linkage involving C1 of one glucose unit with C4 of the other as shown below:
C1 – C4 – -linkage

(– Glucose – Glucose – Glucose – Glucose –)n

Linear Polymer
Amylopectin, on the other hand, is a highly branched polymer. It consists of a large number (several
branches) of short chains each containing 20-25 glucose units which are joined together through -
linkages involving C1 of one glucose unit with C4 of the other. The C1 of terminal glucose unit in each
chain is further linked to C6 of the other glucose unit in the next chain through C1 – C6 -linkage. This
gives amylopectin a highly branched structure as shown below.-

C1 ⎯ C4 -linkage
Glucose ⎯ Glucose ⎯ Glucose
 C1 ⎯ C6 -linkage
Glucose ⎯ Glucose ⎯ Glucose
 C1 ⎯ C6 -linkage
Glucose ⎯ Glucose ⎯ Glucose

Hydrolyis: Hydrolysis of starch with hot dilute acids or by enzymes gives dextrins of varying complexity,
maltose and finally D-glucose. Starch does not reduce Tollen’s reagent and Fehling’s solution.

Uses: It is used as a food. It is encountered daily in the form of potatoes, bread, cakes, rice etc. It is used
in coating and sizing paper to improve the writing qualities. Starch is used to treat textile fibres before
they are woven into cloth so that they can be woven without breaking. It is used in manufacture of
dextrins, glucose and ethyl alcohol. Starch is also used in manufacture of starch nitrate, which is used as
an explosive.

6. Amino Acids
6.1 Introduction and Nomenclature

Amino acids are molecules, which contain two functional groups, one is carboxylic group and another is
amino group. Amino acids are derivatives of carboxylic acids in which one hydrogen atom of carbon
chain is substituted by Amino group.

Amino group may be at , ,  position with respect to carboxylic group

H2N ⎯ CH2 ⎯ COOH Amino acetic acid, or Glycine

CH3 ⎯ CH (NH2) ⎯ COOH  - Amino propionic acid or Alanine

H2N ⎯ CH2 ⎯ CH2 ⎯COOH  - Amino propionic acid

H2N ⎯ CH2 ⎯ (CH2)2 ⎯ COOH  - Amino butyric acid

Some amino acids contain a second carboxyl group or a potential carboxyl group in the form of
carboxamide: these are called acidic amino acid some contain a second basic group which may be an
amino group these are called basic amino acids.

HOOC ⎯ CH2 ⎯ CH ⎯ COOH H2N ⎯ CH2 ⎯ CH2 ⎯ CH2 ⎯ CH2 ⎯ CH ⎯ COOH

 
NH2 NH2
Aspartic acid Lysine
(Acidic amino acid) (Basic amino acid)

6.2 Physical Properties and Structure

Although the amino acids are commonly shown as containing an amino group and a carboxyl group,
certain properties are not consistent with this structure.
1. In contrast to amines and carboxylic acids, the amino acids are nonvolatile solids, which melt at fairly
high temperatures.
2. They are insoluble in organic solvents [i.e. non polar solvents] and are highly soluble in water.
3. Their aqueous solution is neutral.
4. Their aqueous solutions behave like solutions of substances of high dipole moment.
5. Acidity and basicity constants are ridiculously low for - COOH and – NH2 groups
All these properties are quite consistent with a dipolar ion structure for the amino acids (I)
+
H3N ⎯ CHR ⎯ COO––
(I)
Amino acid : dipolar ions
In the physical properties melting points, solubility, and high dipole moment are just what would be
expected of such a salt.
The acid base properties also become understandable when it is realized that the measured Ka actually
refers to the acidity of an ammonium ion, RNH3+
H3NCHRCOO– + H2O
+
H3O+ + H2NCHRCOO–
[H3O + ][H2NCHRCOO − ]
Ka =
[ + H3N − CH − RCOO − ]
and Kb actually refers to the basicity of a carboxylate ion, RCOO–
H3N ⎯ CH ⎯ RCOO– + H2O
+
H3N ⎯ CHR ⎯COOH + OH–
+

[ + H3N − CHR − COOH][OH− ]

Kb =
[ + H3NCHRCOO − ]
When the solution of an amino acid is made alkaline, the dipolar ion(I) is converted to the anion (II); the
stronger base, hydroxide ion, removes a proton from the ammonium ion and displaces the weaker base,
the amine
+
H3N ⎯ CHRCOO– + OH– H2N CHRCOO– + H2O
(I) (II)
Stronger Stronger Weaker Weaker
acid base base acid
When the solution of an amino acid is made acidic; the dipolar ion I is converted into the cation (III); the
stronger acid H3+ O , gives up a proton to the carboxylate ion, and displaces the weaker carboxylic acid.
+
H3N CHRCOO– + H3O+ +
H3N CHRCOOH + H2O
(I) (III)
Stronger Stronger Weaker Weaker
base acid acid base
In summary, the acidic group of a simple amino acid like glycine is − NH 3+ not –COOH, and basic group
is –COO- not –NH2.
6.3 Iso Electric Point

What happens when a solution of an amino acid is placed in an electric field depends upon the acidity or
basicity of solution. In quite alkaline solution.
– H+ + – H+ +
H2N-CHRCOO H3N.CHRCOO H3N.CHRCOOH
OH– OH–
(II) (I) (III)
Anions (II) exceed cations (III), and there is a net migration of amino acid toward the anode. In quite
acidic solution cations (III) are in excess, and there is a net migration of amino acid towards the cathode.
If (II) and (III) are exactly balanced, there is no net migration; under such conditions any one molecule
exists as a positive ion and as a negative ion for exactly the same amount of time and any small movement
in the direction of one electrode is subsequently cancelled by an equal movement back towards the other
electrode. The hydrogen ion concentration of the solution in which a particular amino acid does not
migrate under the influence of an electric field is called the isoelectric point of that amino acid.
An amino acid shows its lowest solubility in a solution at the isoelectric point, since here there is the
highest concentration of the dipolar ion. As the solution is made more alkaline or more acidic, the
concentration of one of the more soluble ions, II or III increases.
If an amino acid has amino group and one carboxyl group, it has two pK values. The isoelectric point (PI)
of this amino acid has the average value of the both pK values.
We take example of glycine.
H3+N ⎯ CH2 ⎯ COOH H3N+ ⎯ CH2 ⎯ COO– + H+ …(1)
Conjugated acid (CA) Dipolar Ion (DI)

[D I][H+ ]
At equilibrium K1 =
[CA ]
H3N+ ⎯ CH2 ⎯ COO– H2N ⎯ CH2 ⎯ COO– + H+ …(2)
DI Conjugated Base (CB)
+
[CB][H ]
At equilibrium K 2 =
[DI]

[DI][H + ]
[CA] =
K1

K 2 [DI]
[CB] =
[H + ]
At isoelectric point [CA] = [CB]
[DI][[Hi+ ] K 2 [DI]
= +
Where [Hi+ ] = conc. of [H+] at isoelectric point.
K1 [Hi ]

or, [Hi+ ] 2 = K1 K2
or, 2log [Hi+] = log K1 + log K2
or –2 log (Hi+] = - log k1 – logK2
or 2pHi = pK1 + pK2
pK1 + pK 2
or pHi =
2
7. Peptides
As the amino acid molecules contain both basic as well as acidic group it might be expected that an
intermolecular reaction may take place between the carboxyl group of one amino acid and the amino
group of another amino acid, with the elimination of a molecule of water.
R R R R
   
H2N ⎯ CH ⎯ COOH + H2N ⎯ CH ⎯ COOH ⎯→ H2 N ⎯ CHCO ⎯ NH ⎯ CHCOOH
Since the resulting molecule still has a free amino and a carboxyl group, it may react with other amino
acids at either of the ends to give a higher molecular weight linear or condensation product. Every two
amino acids are linked by means of a –CO-NH group, which is commonly referred as peptide bond. So
now we can define a peptides as the amides formed by interaction between amino groups and
carboxyl groups of amino acids.
Depending upon the number of amino acid residues per molecule, they are known as dipeptides,
tripeptides and so on and finally polypeptides.

7.1 Naming of Polypeptide

A convenient way of representing peptide structures by use of standard abbreviations. According to

convention the N-terminal amino acid residue [having the free amino group] is written as the left and the
C terminal amino acid residue (having the free carboxyl group) at the right end.

A peptide is named by indicating its sequence of amino acids beginning with the N-terminal residue.

H2N ⎯ CH ⎯ CONH ⎯ CH ⎯ CONH ⎯ CH ⎯ CONH ⎯ CH ⎯ CONHCH2 COOH

| | | |
CH3 CH2-OH CH2-C6H5 CH2-CONH2
Alanine Serine Phenylalamine Asparagine glycine

This pentapeptide is called alanyl-sery-phenylalanyl-asparaginyl-glycine or using the common

abbreviations as H-Ala-Ser-phe-Asn-gly-OH. All naturally occurring important peptides, however, posses
a shorter individual name.

7.2 Structure of Poly peptides

To identify the structure of a peptide, the peptide in question is first hydrolysed to its constituent amino
acids, which are separated and identified. The amount of each amino acid is measured, and hence the
number of each kind of amino acid can be calculated.

The next problem is to determine the sequence of the various amino acids constituting the peptide. This is
very difficult task, because there is a large number of possibilities in which the constituent amino acids
may be linked in the peptide, e.g. even is a dipeptide, having glycine and alanine, the two amino-acids
may be present in either of the two ways.

CH3 CH3
 
H2N – CH2 – CO – NH – CH – COOH H2N – CH – CO – NH – CH2 – COOH
Glycylalanine Alanylaglycine

The two structures differ in the respect that in the first the N-terminal amino acid is glycine (i.e. the amino
group of glycine is free) and C-terminal amino acid is alanine, while in the latter the N-terminal amino
acid is alanine and C-terminal acid is glycine. Various chemical methods have been developed to remove
either of the two terminal amino acid residues of a polypeptide in a stepwise manner and hence the
arrangement of the various amino acids in a polypeptide can be established.
8. Polymers
8.1 Introduction

Sit quietly and think about your activities today from the morning. You wake up in the morning, You
want to brush your teeth. You fetch your toothpaste. The tube is made up of a polymer. Your brush is
made up of a polymer. When you want to rinse your mouth, you open your plastic(polymer) tap. The pipe
lines used to bring water to your tap is made of PVC(polymer). Skip it. You start preparing your break
fast. You take a non-stick tawa. Non-stick? What does that mean? What is it made of? It is poly
tetrafluoro ethylene abbreviated as teflon, a polymer. See, how polymers play an important role in our
daily life from dawn to dusk. The molded chair in which you are sitting is a polymer. The pen with which
I'm writing this is a polymer. Want to know more about polymers? Read further.

Polymers can be called as macromolecules. Macromolecules can be considered as an association of small

molecules to give a big molecule. Macromolecules can be man-made, too. The first syntheses were aimed
at making substitutes for the natural macromolecules, rubber and silk; but a vast technology has grown up
that now produces hundreds of substances that have no natural counterparts. Synthetic macromolecular
compounds include: elastomers, which have the particular kind of elasticity characteristic of rubber;
fibers, long, thin and threadlike, with the great strength along the fiber that characterizes cotton, wool,
and silk; and plastics, which can be extruded as sheets or pipes, painted on surfaces, or molded to form
countless objects. We wear these manmade materials, eat and drink from them, sleep between them, sit
and stand on them; turn knobs, pull switches, and grasp handles made of them; with their help we hear
sounds and see sights remote from us in time and space; we live in houses and move about in vehicles that
are increasingly made of them.

8.2 Polymers and polymerization

Macromolecules, both natural and man-made, owe their great size to the fact that they are polymers
(Greek: many parts); that is, each one is made up of a great many simpler units — identical to each other
or at least chemically similar — joined together in a regular way. They are formed by a process we
touched on earlier: polymerization, the joining together of many small molecules to form very large
molecules. The simple compounds from which polymers are made are called monomers.

Polymers are formed in two general ways.

a) In chain-reaction polymerization, there is a series of reactions each of which consumes a reactive

particle and produces another, similar particle; each individual reaction thus depends upon the
previous one. The reactive particles can be free radicals, cations, or anions. A typical example is the
polymerization of ethylene. Here the chain-carrying particles are free radicals, each of which adds to a
monomer molecule to form a new, bigger free radical.

CH2 = CH2
Rad. + CH2 = CH2 ⎯→ RadCH2CH2 ⎯⎯ ⎯⎯ ⎯→ RadCH2CH2CH2CH2 ⎯→ etc.

b) In step reaction polymerization, there is a series of reactions each of which is essentially

independent of the preceding one; a polymer is formed simply because the monomer happens to
undergo reaction at more than one functional group. A diol, for example, reacts with a dicarboxylic
acid to form an ester; but each moiety of the simple ester still contains a group that can react to
generate another ester linkage and hence a larger molecule, which itself can react further, and so on.
 HOCH2CH2OH + HOOC COOH
1,2-Ethanediol Terephthalic acid

HOCH2CH – O – C – – C – OH
|| ||
O O
HOCH2CH2OH

HOCH2CH2 – O – C – – C – O – CH2CH2OH
|| ||
O O
p-C6H4(COOH)2

HO– C – – C – O – CH2CH2 – O – C – – C – O – CH2CH2OH

|| || || ||
O O O O

a) Free-radical vinyl polymerization: In we discussed briefly the polymerization of ethylene and

substituted ethylenes under conditions where free radicals are generated — typically in the presence
of small amounts of an initiator, such as a peroxide. Reaction occurs.

nCH2 = CH ⎯⎯ ⎯ ⎯→ – CH2CHCH2CHCH2CHCH2CH –
initiator

| | | | |
G G G G G

Vinyl monomer or (– CH2CH –)n

|
G
Polymer

At the doubly bonded carbons — the vinyl groups — and is called vinyl polymerization. A wide
variety of unsaturated monomers may be used, to yield polymers with different pendant groups (G)
attached to the polymer backbone. For example.

CH2 = CH ⎯→ – CH2 – CH – CH2 – CH – CH2 – CH –

| | | |
Cl Cl Cl Cl
Vinyl chloride Poly (vinyl chloride)
(PVC)

CH2 = CH ⎯→ CH2 – CH – CH2 – CH – CH2 – CH – CH2 – CH –

| | | | |
CN CN CN CN CN
Acrylonitrile Polyacrylonitrile
(Orlon)

CH2 = CH ⎯→ CH2 – CH – CH2 – CH – CH2 – CH –

| | | |
C6H5 C6H5 C6H5 C6H5
Styrene Polystyrene
b) Copolymerization: So far, we have discussed only polymerisation of a single monomeric compound
to form a homopolymer, a polymer made up — except, of course, at the two ends of the long
molecule — of identical units.

Now, if a mixture of two (or more) monomers is allowed to undergo polymerization, there is obtained
a copolymer a polymer that contains two (or more) kinds of monomeric units in the same molecule.
For example:

CH3 CH3
| |
CH2 = CH + CH2 = C ⎯⎯ ⎯ ⎯→ – CH2 – CH – CH2 – C –
initiator

| | | |
Ph COOCH3 Ph COOCH3
Styrene Methyl methacrylate Polystyrene (co-methyl methacrylate)

Through copolymerization there can be made materials with different properties than those of either
homopolymer, and thus another dimension is added to the technology. Consider, for example, styrene.
Polymerized alone, it gives a good electric insulator that is molded into parts for radios, television sets,
and automobiles. Copolymerization with butadiene (30%) adds toughness; with acrylonitrile (20-30%)
increases resistance to impact and to hydrocarbon; with maleic anhyride yeilds a material that, on
hydrolysis, is water-soluble, and is used as a dispersant and sizing agent. The copolymer in which
butadiene predominates (75%) butadiene, 25% styrene) is an elastomer, and since World War II has been
the principal rubber substitute manufactured in the United States.

Copolymers can be made not just from two different monomers but from three, four, or even more. They
can be made not only by free-radical chain reactions, but by any of the polymerization methods we shall
take up; ionic, coordination, or step-reaction. The monomer units may be distributed in various ways,
depending on the technique used. As we have seen, they may alternate along a chain, either randomly or
with varying degrees of regularity. In block copolymers sections made up of one monomer alternate with
sections of another:

— M1M1M1M1M1 – M2M2M2M2 — Block copolymer

If graft copolymers, a branch of one kind is grafted to a chain of another kind:

— M1M1M1M1M1M1M1 —
|
M2M2M2M2

Fibres are long thin, threadlike bits of material that are characterized by great tensile (pulling) strength in
the direction of the fiber. The natural fibres – cotton, wool, silk – are typical. Fibres are twisted into
threads, which can then be woven into cloth, or embedded in plastic material to impart strength. The
tensile strength can be enormous, some synthetic fibres rivaling – on a weight basis – steel.

The gross characteristics of fibres are reflected on the molecular level – the molecules, too, are long, thin,
and threadlike. Furthermore, and most essential, they lie stretched out alongside each other, lined up in the
direction of the fiber. The strength of the fiber resides, ultimately, in the strength of the chemical bonds of
the polymer chains. The lining-up is brought about by drawing – stretching — the return to random
looping and coiling is overcome by strong intermolecular attractions. In a fiber, enthalpy wins out over
entropy. This high degree of molecular orientation is usually — although not always — accompanied by
appreciable crystallinity.

An elastomer possesses the high degree of elasticity that is characteristic of rubber: it can be greatly
deformed — stretched to eight times its original length, for example — and yet return to its original shape.
Here, as in fibres, the molecules are long and thin; as in fibres, they become lined up when the material is
stretched. The big difference is this: when the stretching force is removed, the molecular chains of an
elastomer do not remain extended and aligned but return to their original random conformations favored
by entropy. They do not remain aligned because the intermolecular forces necessary to hold them that way
are weaker than in a fiber. In general, elastomers do not contain highly polar groups or sites for hydrogen
bonding; the extended chains do not fit together well enough for Vander Waals forces to do the job. In an
elastomer entropy beats enthalpy.

One further requirement the long chains of an elastomer must be connected to each other by occasional
cross – links: enough of them to prevent slipping of molecules past one another; not so many as to deprive
the chains of the flexibility that is need for ready extension and return to randomness.

Natural rubber illustrates these structural requirements of an elastomer; long flexible chains; weak
intermoecular forces and occasional cross – linking. Rubber is cis 1,4-polyisoprene . With no highly polar
substituents, intermolecular attraction is largely limited to van der Waals forces. But these are weak
because of the all – cis configuration about the double bond. Figure below compares the extended chains
of rubber with those of its trans stereoisomer. As we can see, the trans configuration permits highly
regular zig – zags that fit together well; the cis configuration does not. The all-trans stereoisomer occurs
naturally as gutta percha; it is highly crystalline and non-elastic.

(a)

(b)

Extended chains of (a) natural rubber, cis-1,4 –polyisoprene, and of (b) gutta
percha, its trans stereoiosmer.

Chief among the synthetic elastomers is SBR, a copolymer of butadiene (75%) and styrene (25%)
produced under free-radical conditions; it competes with natural rubber in the main use of elastomers, the
making of automobile tires. All-cis polybutadiene and polyisoprene can be made by Ziegler – Natta
polymerization.

An elastomer that is entirely or mostly polydiene is, of course, highly unsaturated. All that is required of
an elastomer, however, is enough unsaturation to permit cross-linking. In making butyl rubber for
example, only 5% of isoprene is copolymerized with isobutylene.

Some Important Polymers:

a) Natural Rubber: Natural rubber is an addition polymer of isoprene (2-methyl-1,3-butadiene)

Rubber has an average chain length of 5000 monomer units of isoprene.
The rubber in which the arrangement of carbon chain is trans with respect to the double bond is
known as Gutta Percha and this is the natural rubber obtained from bark of various trees. Natural
rubber is sticky material. This disadvantage is removed by 'VULCANISATION' which involves
addition of sulphur to rubber and heating the mixture. sulphur forms short chains of sulphur atoms
that link two hydrocarbon (isoprene) units together.
 CH3 CH3

----CH—C=CH—CH2—CH—C=CH—CH2----
S
S

----CH—C=CH—CH2—CH2—C=CH—CH—CH------
CH3 CH3
When tension is applied the chains can strengthen out but they cannot slip past each other because of
sulphur bridges. Thus rubber can be stretched only to a certain extent and hydrocarbon chains have
the tendency to regain their shape when tension is removed.
Vulcanised rubber is thus stronger and less sticky than the natural rubber.
b) Synthetic rubber: (Polychloroprene) or Neoprene) It is obtained by free radical polymerisation of
chloroprene in
Cl Cl

nCH2=C—CH=CH2 ⎯→ (–CH2—C=CH—CH2—)n
Neoprene
it is a thermoplastic and need not to be vulcanised. It is a good general purpose rubber and superior to
natural rubber as it is resistant to the reaction of aire, heat, light chemicals, alkalis and acids below
50% strength. It is used for making transmission belts, printing rolls and flexible tubing employed for
conveyence of oil and petrol.
c) Buna rubbers: Butadiene polymerises in the presence of sodium to give a rubber substitute viz. BuNa. It
is of two types
i) Buna - N or GRA: it is synthetic rubber obtained by copolymerisation of one part of acryl nitrile
and two parts of butadiene.
nCH2=CH—CH=CH2 + nCH2=CH ⎯→ —CH2—CH=CH—CH2—CH2—CH

CN BUNA-S CN n

It is more rigid responds less to heat and very resistant to swelling action of petorol, oils and other
organic solvents.
ii) Buna -S or GRS (General purpose Styrene rubber): It is a copolymer of three moles of butadiene
and one mole of styrene\ and is an elastomer. It is obtained as a result of free radical
copolymerisation of its monomers.
nC6H5CH=CH2 + nCH2=CH—CH=CH2→ [–CH2–CH=CH–CH2–CH–CH2–]n

C6H5
BUNA-S
It is generally compounded with carbon black and vulcanised with sulphur. It is extremely
resistant to wear and tear and finds use in manufacture of tyres and other mechanical rubber
goods.
d) Teflon: It is polymer of tetrafluorethylene (F2C=CF2) which on polymerisation gives Telfon.
nCF2=CF2 ⎯⎯ ⎯−⎯
870 1020
⎯⎯ K → (—CF —CF —)
2 2 n

It is thermoplastic polymer with a high softening point (600K). It is very tough and difficult to work.
It is inert to most chemicals except fluorine and molten alkali metals. It withstands high temperatures.
Its electrical properties make it an ideal insulating material for high frequency installation.

e) Nylon -66: It is a polymer resin. It is a condensation polymer formed by reaction between adipic acid
and hexamethylene diamine. Both monomer units consist of 6 carbon atoms and therefore named
nylon -66.
 O H
|| |
−H2O
HO − C − (CH2 )4 − C− OH + H − N− (CH2 )6 − NH2 ⎯⎯ ⎯⎯→

 O O H 
 || || | 
− − C− (CH2 )4 − C− N− (CH2 )6 − NH − − −
 
 
Nylon− 66
( A condensation copolymer)

It is thermoplastic polymer when extruded above its melting point (536 K) through spinneret, it gives
nylon fiber which is extremely tough and resistant to friction. It possess greater tensile strength,
elasticity and lusture than any natural fiber. It is chemically inert and is fabricated into sheet, bristles
and textile fibres.

f) Nylon 6 or Perolon - L: A polyamide is prepared by prolonged heating of caprolactam at 530 - 540 K.

NH  
540K→
− − − (CH ) C− NH − (CH) C− NH − − − 
(CH2)5 ⎯⎯ ⎯⎯  2 5 5 
|| ||
C=O  O O 
Nylon−6

The fiber is practically identical to Nylon in properties

9. Practical Organic Chemistry

9.1 Introduction

This lesson is an extremely useful exercise for the structure elucidation of newly synthesized organic
\

molecules. The technique involved is elemental detection, determination of functional groups, number of such
functional groups, determination of molecular formula, preparation of derivatives and determining their
melting and boiling points. All these steps are to be followed in the same sequence, as one leads to another.

The ultimate portion of the lesson deals with the procedure for separating a mixture of organic
compounds (containing monofunctional groups) into its constituents in pure form, so that the above procedure
can be carried out effectively.

9.2 Qualitative Analysis

Qualitative analysis of an organic compound involves following operations.

(i) Preliminary examination:

(A) Physical state (B) Colour (C) Odour (D) Ignition test (e) Solubility test
(ii) Detection of elements

(iii) Detection of functional groups

(iv) Determination of melting or boiling point and
(v) Preparation of derivatives.

9.2.2 Detection of Elements

 The elements generally present in organic compounds are carbon, hydrogen and oxygen. The detection of
these elements in the organic compounds is not essential. Organic compounds also contain nitrogen, halogens,
phosphorus and sulphur, in addition to these elements.
Thus, detection of elements basically refers to nitrogen, halogens, phosphorous & sulphur.

Detection of Carbon and Hydrogen

The organic compound is mixed with an equal amount of dry copper oxide and strongly heated. The carbon
present in the compound is oxidised to carbon dioxide (turns limewater milky) and hydrogen to water (turns
anhydrous copper sulphate blue).

C + 2CuO ⎯⎯→ CO2 + 2Cu

2H + CuO ⎯⎯→ H2O + Cu
CO2 + Ca(OH)2 ⎯→ CaCO3 + H2O
limewater white

CuSO4H2O + 4H2O ⎯→ CuSO45H2O

white blue

Lassaigne’s test
Nitrogen, sulphur and halogens in an organic compound are detected by Lassaigne’s test through Lassaigne’s
extract. Organic compounds contain these elements mostly linked through covalent bonds. In order to make them
free, we convert them into ionic form by treating the compound with sodium. The ionic compound formed are
water−soluble and releases the element in ionic form, which is easy to detect.

(A) Preparation of Lassaigne’s Extract

A small piece of dry sodium metal is heated gently in a fusion tube till it melts to a shining globule. Then,
a small amount of organic substance is added and the tube is heated strongly till it becomes red hot. The
red hot tube is plunged into distilled water contained in a china dish. The fusion tube should break into
pieces on adding to water. If it is not broken, it is broken using a glass rod. Then the solution is boiled for
some time. It is then cooled and filtered. The filtrate is known as sodium extract or Lassaigne’s extract.
Sodium reacts with elements of the organic compound to give following reactions.
C + N + Na ⎯→ NaCN
S + 2Na ⎯→ Na2S
X + Na ⎯→ NaX (where X = Cl, Br or I)
When nitrogen and sulphur both are present in the organic compound, then sodium thiocynate is formed.
Na + C + N + S ⎯→ NaSCN
All the sodium salts being soluble in water, can be easily detected.

Detection of Nitrogen
If the organic compound contains nitrogen, the sodium fusion extract will contain sodium cyanide
(NaCN). A small portion of the extract is boiled with ferrous sulphate solution and acidified with dilute
sulphuric acid. A blue precipitate of Prussian blue (ferric ferrocyanide) confirms the presence of nitrogen.
2NaCN + FeSO4 ⎯→ Fe(CN)2 + Na2SO4
Fe(CN)2 + 4NaCN ⎯→ Na4[Fe(CN)6]
(excess)
Oxidised by
FeSO4 ⎯⎯⎯⎯⎯
⎯→ Fe2(SO4)3
H2SO 4
 3Na4[Fe(CN)6] + 2Fe2(SO4)3 ⎯→ Fe4[Fe(CN)6]3 + 6Na2SO4
Prussian blue

If the organic compound contains sulphur along with nitrogen and the sodium, present is in insufficient
amount then sodium thiocynate is formed, which gives blood red colouration by reaction with ferric ions.
3NaSCN + Fe3+ ⎯→ [Fe(SCN)3] + 3Na+
Blood red colour

However, the absence of blood red colouration does not necessarily mean that sulphur is absent in the
organic compound because NaCNS combines with Na to give NaCN and Na2S.
NaSCN + HCl ⎯→ HSCN + NaCl
4HSCN + Co(NO3)2 ⎯→ H2[Co(SCN)4] + 2HNO3
Blue colour

Detection of Sulphur
If the organic compound contains sulphur, the sodium fusion extract will contain sodium sulphide. It is
divided into two portions and following tests are performed.

Sodium Nitroprusside Test:

Add freshly prepared sodium nitroprusside solution to one portion. A deep violet colour confirms the
presence of sulphur.

Na 2 S + Na 2 [Fe(CN) 5 NO] ⎯⎯→ Na 4 [Fe(CN) 5 NOS]

Violet colour

Lead Acetate Test:

Acidify the second portion with acetic acid and then add lead acetate solution. A black precipitate of lead
sulphide confirms the presence of sulphur.

Na 2 S + (CH3 COO) 2 Pb ⎯⎯→ PbS  + 2CH3 COONa

lead acetate black ppt.

Detection of Halogens
If the organic compound contains halogen, the sodium fusion extract will contain sodium halide. The
sodium fusion extract is boiled with dilute nitric acid to decompose sodium cyanide or sodium sulphide,
(if present) otherwise a white precipitate of silver cyanide or silver sulphide will be formed even in the
absence of halogen. The solution is then cooled and silver nitrate solution is added. The characteristic
precipitate confirms the presence of a halide.
NaX + AgNO 3 ⎯⎯→ AgX  + NaNO 3
(A) White precipitate, soluble in aqueous ammonia indicates chlorine.
(b) Light yellow precipitate, sparingly soluble in aqueous ammonia indicates bromine.
(c) Pale yellow precipitate, insoluble in aqueous ammonia indicates iodine.

Detection of Phosphorus
The organic compound containing phosphorus is fused with sodium peroxide and extracted with water. The
aqueous solution is boiled with concentrated nitric acid and ammonium molybdate is added. A canary
yellow precipitate indicates the presence of phosphorus.

9.2.3 Detection of Functional groups

Detection of functional groups is an important step in the analysis of organic compounds.
It entirely depends on the correct determination of the constituent elements.
1. Tests for Carboxylic Acid Group
(i) Litmus test: Place a small quantity of the organic compound or its aqueous solution on a piece of
moist blue litmus paper. If the litmus paper turns red, carboxylic acid group may be present.
(ii) Sodium bicarbonate test: Add a small quantity of the organic compound to sodium bicarbonate
solution taken in a test−tube. Compound dissolves with brisk effervescences.
RCOOH + NaHCO3 ⎯→ RCOONa + H2O + CO2 
(iii) Take a small quantity of the organic compound and add some alcohol in a test−tube. Add a few drops
of conc. sulphuric acid and warm on a water bath, a fruity smell indicates the formation of an ester.
RCOOH + ROH ⎯⎯ ⎯⎯→ RCOOR+ H2 O
H2SO 4
Ester

2. Tests for Aldehyde Group

(i) Schiff’s test: Take small amount of Schiff’s reagent in a test−tube and shake with organic compound
(do not heat). A pink colour appears instantaneously.
(ii) Fehling’s test: Mix equal volumes of Fehling’s (A) and Fehling’s (B) solution in a test−tube. Add a
small amount of the organic compound and boil for some time. A red precipitate of Cu2O is
obtained.
RCHO + 2CuO ⎯⎯→ RCOOH + Cu 2 O 
Re d ppt.
(iii) Tollen’s test: Add few drops of Tollen’s reagent ppt. to a small quantity of the organic compound
and heat on a water bath. A shining silver mirror is formed on the inner walls of test−tube.
RCHO + 2 [ Ag(NH3 ) 2 ]OH + H2 O ⎯⎯→ RCOONH 4 + NH3 + 2NH 4 OH + 2Ag 
Tollen ' s reagent Silver mirror

(iv) Benedict’s test: Take small amount of Benedict’s reagent in a test−tube. Add a few ml of the
organic compound (or a solution prepared in alcohol or water). Heat the mixture to boiling.
Formation of red precipitate indicates the presence of aldehydic group.
RCHO + 2Cu(OH) 2 + NaOH ⎯⎯→ Cu 2 O + RCOO − Na + + 3H2 O
3. Tests for Ketone Group
(i) Ketones, unlike aldehydes, do not restore the pink colour of Schiff’s reagent nor do they reduce
Fehling’s solution or ammoniacal silver nitrate solution. However, they form yellow or red
crystalline precipitate with 2,4−dinitro phenylhydrazine and also with sodium bisulphite reagent.
This test should be conduct only after the confirmation of absence of aldehydes.
NO2 NO2
R R
C=O + H2NHN NO2 ⎯→ C=NHN NO2
R R
(2,4 DNP)

Ketones add on sodium hydrogen sulphite to form crystalline bisulphite compounds.

R R OH
C=O + NaHSO3 ⎯→ C
R R SO3Na
(Bisulphite addition
compound)

(ii) Sodium nitroprusside test: Treat some organic compound with few drops of freshly prepared
solution of sodium nitroprusside followed by excess of NaOH solution. A wine−red colour is
obtained.

4. Tests for Phenol Group

(i) Litmus test: Place a trace of the organic compound on the moist blue litmus paper. It turns red.
(ii) Neutral FeCl3 test: When phenols are treated with neutral ferric chloride solution, they form
coloured complexes. The colour of the complex may be violet, red, blue or green. This is a
 characteristic reaction of compounds having enolic group (=C−OH). All stable enols respond to this
test.
With relatively milder oxidizing agents such as ferric chloride (Fe3+), a resonance stabilized
phenoxyl radical is formed. This radical soon undergoes dimerization, which may take place by
ortho−ortho, ortho−para, para−para coupling.
OH O O O O
H H
+ Fe3+ ⎯→ ⎯→ ⎯→ ⎯→

+ Fe+2 + H+

O O O
H H H
O
+ +O O
H
H H

The phenoxyl radicals are highly coloured and therefore, products are also coloured.
(iii) Aniline Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in ice−cold water and add
aqueous solution of sodium nitrite dropwise. To this cold solution, add organic compound already
dissolved in sodium hydroxide solution.
A red or orange precipitate is obtained.

NaNO 2 + HCl ⎯⎯→ HNO 2 + NaCl

This test is applicable for the detection of small quantities of phenols with the para position free.
(iv) Phthalein test (Fluorescein test) : Heat some organic compound and phthalic anhydride with a few
drops of concentrated sulphuric acid in a test−tube. Pour the heated mixture into water taken in a
beaker and then add sodium hydroxide solution, till it became alkaline. A beautiful pink or purple
colour appears.

OH
OH
C
C=O H2SO4
+ −H2O OH
O C O
O C O OH

2NaOH
O−Na+
C
O
− +
O=C−O Na
(Pink or purple)

(v) Bromine water test: Take aqueous or alcoholic solution of the organic compound in a test−tube.
Add excess of bromine water. A yellowish white precipitate is obtained.
 OH OH
Br Br
+ 3Br2 ⎯→

Phenol
Br
(2,4,6−tribromophenol)

(vi) Ceric ammonium nitrate test: Add few drops of the ceric ammonium nitrate to hot aqueous
solution of the organic compound. A green or brown precipitate is obtained.
(NH 4 ) 2 [Ce(NO 3 ) 6 ] + 2C 6H5 OH ⎯⎯→ [Ce(NO 3 ) 4 (C 6H5 OH) 2 ] + 2NH 4NO 3
Phenol Green or brown ppt.
(vii) Liebermann’s test: Take a small amount of the compound and fuse with a few crystals of NaNO2 in
a test−tube. Cool the test−tube and add some concentrated H2SO4. A deep green colour is obtained
and when poured into large excess of water, green colour changes to red. When a little NaOH
solution is added to the aqueous solution, the solution becomes deep blue coloured.

NaNO2 + H2SO4 Tautomerize

HO HO N=O O N−OH

(Green colour)

Phenol NaOH
H2SO4
O N OH O N O−Na+
+
Indophenol (red) Indophenol salt (blue)

5. Tests for Alcohol Group

Alcohols may be considered as neutral compounds. They are soluble in water or dioxane.
(i) Sodium test: Take some organic compound in a test−tube. Add a thin slice of sodium metal to it. A
brisk effervescence due to the evolution of hydrogen takes place. (Organic compound should be free
from water).
2ROH + 2Na ⎯⎯→ 2RO− Na + + H 2 
(ii) Ester test: Warm the given liquid with acetic acid in presence of sulphuric acid.
A fragrant fruity smell indicates the formation of ester.
ROH + CH 3 COOH ⎯⎯ ⎯⎯→ CH 3 CO 2R + H 2 O
H2SO 4

Alcohols give crystalline esters with 3,5−dinitrobenzoyl chloride. These esters have sharp melting
points and can be used for testing a given alcohol.
NO2 NO2
R−OH + Cl−C R−O−C + HCl
O NO2 O NO2
(iii) Oxidation test: Take some organic compound in a test tube, add to it K2Cr2O7 solution and
concentrated H2SO4. Heat the test−tube after fitting a delivery tube. The distillate is passed into
another test−tube containing water. The solution becomes green coloured. Test the aqueous solution
of the distillate for carboxylic acid group. A positive test indicates the presence of primary alcoholic
group in the given compound.
RCH 2 OH ⎯⎯⎯→ RCO 2H + H 2 O
[O]

(iv) Ceric ammonium nitrate test: Shake a few drops of ceric ammonium nitrate with the organic
compound. A red colour is produced. This test is useful only when the compound contains less than
10 carbon atoms per molecule.
 2ROH + (NH 4 ) 2 [Ce(NO 3 ) 6 ] ⎯⎯→ [Ce(NO 3 ) 4 (ROH) 2 ] + 2NH 4 NO 3

Distinction between primary, secondary and tertiary alcohols

Lucas test: Add some amount of alcohol to 2 ml of Lucas reagent (anhydrous ZnCl 2 + concentrated HCl)
in a test−tube. Shake the mixture and allow it to stand at room temperature. If a cloudy precipitate of
alkyl chloride is obtained immediately then it is a tertiary alcohol, if obtained within 5 minutes then it is
a secondary alcohol, while no cloudy precipitate even after long standing means it is a primary alcohol.
This test is applicable for alcohols with less than 6 carbon atoms.
+ − 
R−O…..ZnCl2 ⎯→ R
−
Cl
R−OH + ZnCl2 ⎯→ R−Cl
+ −
[Zn(OH)Cl
a 2] Cloudy ppt.
H

6. Tests for Primary Amines (−NH2)

(i) Carbylamine test: Heat the organic compound with alcoholic KOH and chloroform in a test−tube.
A highly offensive smell is evolved due to the formation of isocyanides.

RNH2 + CHCl3 + 3KOH R−N C + 3KCl + 3H2O

This test is applicable for aliphatic and aromatic primary amines but not for 2° and 3° amines.
(ii) Dye test: This test is applicable only for aromatic primary amines. Dissolve a small amount of the
organic compound in dilute HCl. Cool it in ice−cold water bath. Add cold solution of sodium nitrite
with constant stirring and then alkaline −naphthol solution. An orange−red dye is obtained.

7. Tests for Secondary Amines (−NH−)

Liebermann’s nitroso test:
Dissolve some organic compound concentrated HCl and then add small amount of water. Cool the
solution in ice−cold water bath and then add cold dilute NaNO2 solution.
A yellow oily emulsion is produced. Take above emulsion in a test tube and add phenol and concentrated
H2SO4 to it. A green colour appears. Addition of water changes green colour to red, which changes to
deep blue on adding NaOH solution.

8. Tests for Nitro Group

(i) Reduction test: Take a small amount of the organic compound in a test−tube. Add a few ml of
concentrated hydrochloric acid and one or two pieces of granulated zinc or tin. Heat the mixture
gently for few minutes. Decant the clear liquid into a test−tube. Cool it in ice−cold water bath and
then add cold dilute solution of sodium nitrite. Pour this cold solution into an alkaline solution of
−naphthol. An orange−red dye is obtained. This test is applicable only to aromatic nitro
compounds.

Zn + 2HCl ⎯⎯→ ZnCl 2 + 2[H]

C 6 H5 NO 2 + 6[H] ⎯⎯→ C 6 H5 NH 2 + 2H 2 O

NaNO 2 + HCl ⎯⎯→ HNO 2 + NaCl

C 6 H5 NH 2 + HNO 2 + HCl ⎯⎯→ C 6 H5 N 2+ Cl − + 2H 2 O

(ii) Mulliken’s test: Take a small amount of the organic compound in a test−tube. Add a few ml of
water or alcohol, 1 ml of calcium chloride or ammonium chloride solution and then a pinch of zinc
dust. Boil the mixture for few minutes. Cool and then filter. Treat this filtrate with ammoniacal silver
nitrate solution. A grey or black precipitate is obtained.
 Zn + 2H2O ⎯→ Zn(OH)2 + 2[H]
C6H5NO2 + 4[H] ⎯→ C6H5NHOH + H2O
C6H5NHOH + Ag2O ⎯→ C6H5NO + H2O + 2Ag 
Grey or black ppt.
This test is applicable for aliphatic as well as aromatic nitro compounds.

9.3 Quantative Analysis

After determining the elements present in the organic compound, the subsequent step is to find out the
percentages of elements in the compound. The methods used for determining the percentage of elements
involve combustion, oxidation and precipitation etc. of an organic compound such that they are converted into
inorganic compounds, which can be easily estimated by gravimetric or volumetric techniques.

9. 3.1 ESTIMATION OF CARBON AND HYDROGEN

Liebig’s Combustion Method

A known mass of the organic compound is heated in a current of dry oxygen
(free from CO2) in the presence of cupric oxide till all the carbon is oxidised to carbon dioxide and all the
oxygen is oxidised to water.

 y
CxHy +  x +  O2 ⎯→ xCO2 + y/2 H2O
 4

Oxidised copper spiral

dry O2 ............
.

Boat with Copper Guard tube

organic Oxidised
substance

Calcium chloride tube KOH tube

Figure 1

Water is absorbed in a previously weighed U−tube containing anhydrous calcium chloride or anhydrous
magnesium perchlorate. Carbon dioxide is absorbed in a previously weighed U−tube containing a strong
solution of potassium hydroxide or ascarite (NaOH + CaO). The weights of carbon dioxide and water thus
formed are determined and the amounts of carbon and hydrogen in the organic compound can be
calculated as

Mass of CO 2 formed
Moles of CO2 formed = = Moles of C in CO2
44
= Moles of C in organic compound
Moles of CO 2 formed
 Mass of carbon in organic compound =  12
44
12 Mass of CO 2 formed
 Percentage of carbon in organic compound =   100
44 Mass of organic compound

Mass of H 2 O formed
Moles of H2O formed =
18
 Mass of H 2 O formed
Moles of H in H2O =  2 = Moles of H in the organic compound.
18
Mass of H 2 O formed  2  1
Mass of hydrogen in the organic compound =
18
2 Mass of H2 O formed
 Percentage of hydrogen in organic compound =   100
18 Mass of organic compound
9. 3.2 ESTIMATION OF NITROGEN
Nitrogen can be estimated either by Dumas’ method or Kjeldahl’s method.

Duma’s Method
Known mass of an organic compound is heated with cupric oxide in an atmosphere of carbon dioxide.
The carbon and the hydrogen get oxidised to carbon dioxide and water while the nitrogen is set free. Traces of
oxides of nitrogen, which may be formed in some cases are reduced to elemental nitrogen by passing over heated
copper spiral. The gaseous mixture is collected over an aqueous solution of potassium hydroxide. CO2 is absorbed
by the caustic potash solution while H2O condenses and nitrogen is collected by downward displacement of KOH
solution.
The volume of nitrogen is measured and this is equivalent to the nitrogen present in the compound. The
volume of nitrogen is reduced to STP, its weight calculated and from this the percentage of nitrogen present in the
organic compound is estimated.
The following reactions take place during Duma’s process.
C + 2CuO ⎯→ CO2 + 2Cu ; 2H + CuO ⎯→ H2O + Cu
2N + CuO ⎯→ N2 + Oxides of nitrogen

Oxides of nitrogen + Cu ⎯→ CuO + N2

Nitrogen
CuO + Organic Copper
compound Coarse CuO gauze KOH solution
compound
CuO Gauze
CO2

Furnace Nitrometer

Mercury
Seal

Figure 2. Estimation of nitrogen by Duma’s method

Let the mass of organic compound = w g,

Volume of nitrogen collected = V cm3,
Pressure of moist N2 = P mm of Hg,
Room temperature = t°C,
Aqueous tension at t°C = a mm of Hg,
 Pressure of dry nitrogen = (P − a) mm of Hg,
Let us first convert the volume of nitrogen at given temperature & pressure to the volume of N2 at STP.
PN2  VN2 = n N2  RT
 (P − a)  V  10 −3
nN2 =
760  0.0821  (273 + t )

(P − a)  V  10 −3  22.4
 Volume of N2 at STP = = x L (say)
760  0.0821  (273 + t )
Now, 22.4 L of N2 at STP weigh = 28 g
 28 
 x L of N2 at STP will weigh =   x g
 22.4 
Mass of nitrogen 28 x  100
Percentage of nitrogen =  100 =
Mass of organic compound 22.4  w

Kjeldahl’s Method
This method is simpler and more convenient than Duma’s method. This method is largely used for the
estimation of nitrogen in food stuffs, drugs, fertilizers and many other organic compounds. However, this
method cannot be used for

(i) organic compounds containing nitrogen in the ring such as pyridine, quinoline etc.
(ii) organic compounds containing nitro (−NO2) and diazo (−N=N−) groups.

Principle: A known weight of the organic compound is heated with concentrated H2SO4 so that nitrogen
is quantitatively converted into ammonium sulphate. The solution is then heated with excess of sodium
hydroxide. The ammonia gas evolved is passed into a known but excess volume of standard acid (HCl or
H2SO4). The acid left unused is estimated by titrating the solution with standard alkali. From the amount
of acid left unused, the amount of acid used for neutralization of ammonia can be calculated. From this,
percentage of nitrogen can be calculated. The chemical reactions involved are
Conc . H SO
C, H, S ⎯⎯ ⎯ ⎯
2
⎯
⎯4
→ CO2 + H2O + SO2
(From organic compound)

Conc . H SO
N ⎯⎯ ⎯ ⎯
2
⎯
⎯4
→ (NH4)2SO4
(From organic compound) Ammonium sulphate

(NH4)2SO4 + 2NaOH ⎯→ Na2SO4 + 2NH3 + 2H2O

2NH3 + H2SO4 ⎯→ (NH4)2SO4
(n = 1)

H2SO4 + 2NaOH ⎯→ Na2SO4 + 2H2O

 NH3 + Steam

Kjeldahl Trap

Water

Kjeldahl’s flask

Substance + conc. Kjeldahlised

H2SO4 + K2SO4 + CuSO4 liquid + NaOH
in excess Water

Known volume
of standard acid

Figure 3. Estimation of nitrogen by Kjeldahl’s method.

Let the mass of organic compound = w g,
Total volume of standard acid taken = V1 cm3,
Normality of acid = N1
Now, the excess acid after dilution is titrated against standard alkali.
Volume of standard alkali used for neutralization of unused acid = V2 cm3,
Normality of standard alkali = N2,
Equivalents of unused acid = Equivalents of alkali = N2V2  10−3
Initial equivalents of acid = N1V1  10−3
Equivalents of acid consumed by NH3 = (N1V1 − N2V2)10−3 = Equivalents of NH3 reacted.
Moles of NH3 reacted = (N1V1 −N2V2)  10−3
Moles of NH3 liberated = (N1V1 − N2V2)  10−3 = Moles of nitrogen in NH3
= Moles of nitrogen in organic compound.
Mass of nitrogen in the organic compound = (N1V1 − N2V2)  10−3  14
Mass of nitrogen
Percentage of nitrogen =  100
Mass of organic compound
(N1V1 − N2 V2 )  10 −3  14 1.4 (N1 V1 − N2 V2 )
=  100 =
w w
where V1 and V2 are the volume of standard acid and alkali respectively, in cm3.

9.3.3 ESTIMATION OF HALOGENS

Carius Method
In this method, a known mass of the organic substance is heated with fuming nitric acid in the presence of
silver nitrate in a special sealed tube known as Carius tube. Carbon, hydrogen or sulphur present in the
compound will be oxidised to CO2, H2O and H2SO4 respectively. The halogen forms a precipitate of silver
halide (AgX). The precipitate is filtered, washed, dried and weighed.

C + 2O ⎯⎯⎯ → CO2
3 HNO

2H + O ⎯⎯⎯ → H2O
3 HNO

S + H2O + 3O ⎯⎯⎯ → H2SO4

3 HNO

X + AgNO3 ⎯→ AgX 
(halogen)
 Carius tube Iron tube

Organic
substance Glass stopper

Furnace

HNO3 + AgNO3
Figure 4. Carius method for the estimation of halogens
The Carius tube is a long narrow tube closed at one end and (during the experiment) sealed at the other end.
A weighed quantity of the organic substance is taken in the tube with fuming nitric acid and silver nitrate,
then the open end is sealed and the tube is heated in a furnace. The organic compound decomposes and
silver halide is formed. At the end of the experiment, the tube is cooled, the sealed end broken and the
contents are transferred to a filter. The precipitated silver halide is filtered, washed, dried and weighed.

Weight of AgX
Moles of AgX = = Moles of halogen in AgX
Molar mass of AgX

= Moles of halogen in organic compound

Weight of AgX  atomic mass of ha log en

Mass of halogen in organic compound =
Molar mass of AgX

Atomic mass of halogen  wt. of AgX

 Percentage of ha log en =  100
(108 + atomic mass of halogen)  wt. of organic compound

9 3.4
9. ESTIMATION OF SULPHUR

Sulphur is estimated by Carius method. The organic compound containing sulphur is heated with fuming
nitric acid. The sulphur in the compound is oxidised to sulphuric acid, which is then precipitated as
barium sulphate by adding excess of barium chloride solution. The precipitate is filtered, washed and
dried. From the weight of barium sulphate formed, the percentage of sulphur in the organic compound can
be estimated.

Weight of BaSO 4
Moles of BaSO4 = = Moles of S in BaSO4
Molar mass of BaSO 4

= Moles of S in organic compound.

Weight of BaSO 4
Mass of sulphur in organic compound =  32
Molar mass of BaSO 4

32  weight of BaSO 4
 Percentage of sulphur =  100
Molar mass of BaSO 4  weight of organic compound

32  weight of BaSO 4
=  100
233  weight of organic compound
9.3.5 ESTIMATION OF PHOSPHORUS
A known mass of the organic compound is heated with fuming nitric acid, when the phosphorus present in
the organic compound is oxidised to phosphoric acid. The phosphoric acid obtained is treated with
magnesia mixture (a mixture of MgCl2, NH4CI and NH4OH) to give a precipitate of Mg(NH4)PO4, which
on ignition gives Mg2P2O7.

Weight of Mg 2P2 O 7
Moles of Mg2P2O7 =
Molar mass of Mg 2P2 O 7

2  weight of Mg 2P2 O 7
Moles P in Mg2P2O7 = = Moles of P in organic compound
Molar mass of Mg 2P2 O 7

2  weight of Mg 2P2 O 7
 Mass of phosphorous in organic compound =  31
Molar mass of Mg 2P2 O 7

2  31  weight of Mg 2P2 O 7
Percentage of phosphorus =  100
Molar mass of Mg 2P2 O 7  weight of organic compound

62  weight of Mg2 P2 O 7
=  100
222  weight of organic compound

9.3.6 ESTIMATION OF OXYGEN

There is no direct method for the estimation of oxygen in a given organic compound. It is estimated by
subtracting the sum of the percentages of all other elements in the compound from 100.

Percentage of oxygen = 100 − (% of all other elements)