GENERAL CHEMISTRY II (CHE 102)

Course content

Historical survey of the development and importance of organic chemistry

Nomenclature and classes of organic compounds

Homologous series

Functional groups

Isolation and purification of organic compounds

Qualitative and quantitative organic chemistry

Stereochemistry

Determination of structure of organic compounds

Electronic theory in organic chemistry

Valence forces: structures of solids

The chemistry of selected metals and non metals

Qualitative analysis

Historical survey of the development of organic chemistry

It was believed in the early days of the chemistry of carbon compounds

that vegetable compounds like gums, sugar, resins and animal compounds
like blood, urine, honey, and fat could be produce by nature alone with the
help of some ‘vital’ force. It was believed that such substances could not be
synthesized in the laboratory. This theory is called theory of vitalism- Life
containing substances possess a vital force which man cannot control. This
theory which originated from a Swedish Chemist Berzelius was upheld for
several years. A lot of the early chemists worked successfully on the isolation
and analysis of many organic compounds but none could be prepared in the
laboratory.

However, in 1928, a German Chemist called Wohler accidentally

synthesized an organic compound (urea) in the laboratory by heating
ammonium cyannate (NH4CNO).

i.e. NH4CNO (H 2N)2C=O

This discovery led to the down fall of Vital Force Theory/ Theory of vitalism

WHAT IS ORGANIC CHEMISTRY?

Organic chemistry can be defined as the chemistry of hydrocarbons

and their derivatives. Organic compounds are treated as separate branch of
chemistry for the following reasons:

(i) Organic compounds are carbon containing compounds but not all
carbon containing compounds are organic e.g. CO 2, carbonic acid,
carbonates and bicarbonates
(ii) Carbon compounds are large in numbers(several millions of them
are known)
(iii) Carbon atom is unique. The uniqueness of carbon include
(a) Catenation: Tendency of carbon to form long open and closed carbon
chains. E.g.
C-C-C-C-C-
C

(b) Tetra valence: carbon is tetravalent in all organic compounds

(c) Existence of different possible structural and spatial arrangements

of carbon skeletons.

(Isomerism)
Importance of organic chemistry

Organic chemistry is important as it finds applications in every area of life.

The knowledge of organic chemistry is important in the following and among
other areas:

- Generation of energy from coal and petroleum products

- Production of synthetic fibres like terylene, nylon, etc as substitute for
natural fibres.
- Production of drugs, dyes, perfumes, cosmetics, photographic films,
etc.
- Production of soap, detergent and paper
- Production of explosives

CLASSES AND NOMENCLATURE OF ORGANIC COMPOUNDS

Classes of organic compounds can be distinguished according to functional

groups they contain. All organic compounds are derived from a group of
compounds known as hydrocarbons because they are made up of only
hydrogen and carbon. Organic compounds are usually classified into three
major classes

(i) Aliphatic compounds (ii) aromatic compounds (iii) Heterocyclic

compounds

The chart below gives a summary of the classes of organic compounds

 Organic compound

Hydrocarbons

Aliphatic Aromatic

Cyclic Acyclic Benzene Polynuclear

Aromatic compounds

Alkanes Alkenes Alkynes

Functional Group

A functional group is a group, of atoms that is largely responsible for the

chemical behaviour of the parent molecule. Different molecules containing
the same kind of functional group or groups undergo similar reactions. Some
functional groups and their corresponding classes of organic compounds are
listed below.

Functional group Class of organic compounds

1. -F, -Cl, -Br, -I Alkyl halides or halo-alkanes

2. -OH Alkanols or alcohols

3. -OR Ethers

4. -COH Aldehydes or alkanals

5. -C=O Ketones or alkanones

6. -C=O Carboxylic acid or alkanoic acids

OH
7. -C=O Esters

OR

8. -C=O Acid halides or acyl halides

X (X= F, Cl, Br, I)

9. -C=O Amides

NH2

10. -NH2 Amines

Nomenclature of organic compounds

The general rules for IUPAC nomenclature are numerated and illustrated
below.

1. It is considered that all organic compounds are derivatives of the

hydrocarbons formed by the suitable replacements of the hydrogen(s)
by various groups or substituents. Thus the naming of any organic
compound depends on the correct selection of the parent hydrocarbon.
2. Longest carbon chain: The longest possible continuous chain of
carbon atoms is selected. This is called parent chain. The parent
hydrocarbon is then named based on the number of carbon atoms it
contains. Let’s consider the following examples:

C
C C C C C
5 4 3 2 1
C
I
C C 3 C4 C5 C
C 1 C2 C 6 C7 C8
 II
The longest continuous chains (parent chains) in structures I and II
contain 5 and 8 carbon atoms respectively.
NOTE: If there are two longest carbon chains in a molecule having the
same number of carbon atoms, the one with larger number of side
chains is selected as the parent chain
e.g.

C 7 C6 C5 C 4 C3 C2 C1 Parent Chain (It has 3 side chains)

C2
C1

3. Lowest number of locants:

(i) The carbon atoms of the longest continuous chain are numbered in
such a way that the carbon atoms carrying substituents get the lowest
numbers. If there are more than one substituent then the numbering of
carbon atoms is done in such that the sum of the numbers used to
locate the substituent is minimum.

e.g.

1
C7-2C6-3C5-4C4-5C3-6C2-7C1 Sum of locants = 2+3+6=11

Sum of locants = 2+5+6 = 11

In the example above, the numbering should be done from the right hand
end as it gives the lowest locants.

(ii) The name of the substituent is prefixed, preceded by the locant, to

the name of the parent hydrocarbon. A hyphen separates the locant
 from the name of the substituents. Thus the hydrocarbon given
below is 2-methylbutane.

CH3CH2CHCH3
CH3

4. Alphabetical order of prefixes:

(i) If there are more than one substituent, each substituent prefixed by its
locant, is put in the alphabetical order preceding the name of the
parent hydrocarbon. Note that the prefixes di, tri, etc. are not
considered when deciding the alphabetical order of substituents.

(i) If the substituent on the parent chain has itself branched chain then it
is named as the substituted alkyl group and its carbon atoms are
numbered from the carbon attached to parent chain. Such a
substituent indicating the position of the branched substituents on it is
written in parenthesis and is prefixed before the name of the parent
hydrocarbon. E.g.

(i) CH3 CH2CH2CH2CH (CH2)3CH3

CH 2

H 3C-C-CH3

CH 3

5-(2,2-dimethyl)propyl nonane

CH3CH2CH2CH2CH(CH2)2CH3

H3C-C-CH 3
 CH 3

4-(1,1dimethyl) ethyl octane.

5. Numbering of Multiple bonds:

(i) If a double bond is present in the molecule, then the longest chain of
carbon atoms is so chosen as to include the double or triple bond even
if it is not the longest continuous chain. The carbon atoms of the
parent chain are numbered in a manner that gives the least possible
number to the multiple bonds.

E.g.
6 5 4 3 2 1
(a) CH3CH2CH2CHCH=CH2

CH2CH2CH3

3-propyl hex-1-ene or 3-propyl-1-hexene

6 5 4 3 2 1
(b) CH3CH=CHCH2CH=CH2
1 2 3

CH2CH2CH2CH3
4 5 6 7
3-Butyl -1,4-hexadiene or 3-butylhexan-1,4-diene

Further Examples

Give the IUPAC nomenclature of the following compounds:

(i) (CH3)2CHCH2CH(CH3)2
(ii) CH3CH=(CH)2(CH3)2
(iii) CH2CHOHCH=CH2
 (iv) CH2=CHCH2C CH

Solution
(i) 2,4-dimethyl pentane,
(ii) 4-Methyl pent-2-ene
(iii) 3-Hydroxylbut-2-ene
(iv) Pent-2-ene-4yne OR Pent-4-yne-2-ene

6. Naming other functional group compounds:

(i) In naming monofunctional compounds the longest carbon chains is

chosen to include the functional group

(ii) The parent chain selected is numbered in such a way that the lowest
number is given to the functional group even if it violates the lowest
sum rule. The monovalent functional groups like –CHO, _COOH,
_CONH2, etc. occur at the end of the chain and their carbon atom is
always given number 1. The name of the compound ends with the
suffix representing the functional group.

(iii) The number indicating the position of the functional group is always
included in naming the compound.

Example

Give the IUPAC names of the following monofunctional compounds:

CH 3

(1)CH3CH2CHCH2CH2CHCH2OH

C2H5
 (2)

OH

O
(3) H

Solution

1. 5-Ethyl-2-methylheptan-1-ol
2. 2-Methyl hexan-2-ol or 2-Methyl-2-hexanol
3. 2-Methyl-3-hexenal

Work to do

1. Give the IUPAC names of the following compounds

(i) CH3CHCH=CH2
OH

(ii)

Br

(iii) CH2=CHCH2C CH (iv)

2. Write the structural formulae of the following compounds:

(i) 4-methylpentene
(ii) 1,3-butadiene
(iii) 1,2,3propanetriol
(iv) 2,7-dimethylocta-2,4,6-triene
 (v) 3-Ethyl-2,2-dimethylpentane
(vi) 5-Ethyl-2,4,6-trimethyl octane

HOMOLOGOUS SERIES

A homologous series is a group of closely related organic compounds having

the same functional group. Members of different homologous series have
different functional groups. Individual member of a homologous series is
characterized by the following features:

1. Every member of the series has the same functional group

2. Each member differs in molecular formula from the preceding and
succeeding members by –CH2- group.
3. The series can be represented by a general formula e.g. Alkenes
conform to the general molecular of CnH2n.
4. The physical properties of the homologues show a regular gradation
with increase in molecular weight.
5. Members of a homologous series can be prepared by almost similar
methods.
6. Members of a homologous series have similar chemical properties

PURIFICATION OF ORGANIC COMPOUNDS

An organic compound when obtained from natural sources or by synthesis is

contaminated with other substances produced in side reactions of the
process. For determination of the molecular composition and formula of the
substance it is very to obtain it in pure form.

Purification of Solid Organic Compounds

(A) Extraction
(i) The first step in the purification is the extraction of the compound. If
the impurities present are solids then a solvent that will dissolve only
the compound and not the impurities is chosen. The solution of the
compound is separated from solid particles by ordinary filtration or
centrifugation. The filtrate obtained is evaporated to get the organic
solid being purified.

(ii) Use of water immiscible solvent: this is used when the organic
compound to be extracted is soluble in water and also in a solvent
which is immiscible with water. It usually involves the use of separating
funnel.

(B) Crystallization

The next step the purification of solid organic compounds is

crystallization. There are two types of crystallization namely:

(i) Simple crystallization

(ii) Fractional crystallization

Simple crystallization: Simple crystallization is carried out in four

stages

(a) Preparation of a hot saturated solution of the substance in a suitable

solvent (A solvent in which the substance dissolves les at room
temperature and more at high temperature)

(b) Filtration of the hot solution

(c) Crystals are allowed to form as the hot solution cools down

(d) Isolation by filtration, and drying of the purified organic substance.

The crystals obtained may again be dissolved for re-crystallization if further

purification is needed.
(ii) Fractional crystallization: fractional crystallization is used when an
organic compound is contaminated with another substance that has a high
difference in its solubility and the solubility of the organic substance in a
given solvent. Let A be the organic compound contaminated with B which is
less soluble in the solvent X. dissolve A and b in the solvent X and allow the
solution to crystallize. B will crystallize first being less soluble and A will
remain in the mother liquor. The crystals of B are then filtered. The mother
liquor is now concentrated since the little amount of B in it has been filtered.
Then the mother liquor is evaporated to get A. The crystals of A can be
further purified by dissolving it in just sufficient quantity of the solvent and
repeating the fractional crystallization again.

(C) Sublimation: Some solid organic compounds when heated pass into
vapour state without melting and return o solid state when cooled. Examples
of such substances are naphthalene, anthracene, benzoic acid, camphor, etc.
the property of sublimation possessed by organic compounds may be used
for their purification when the impurities present along with them do no
sublime.

In sublimation method of purification, the crude organic solid is placed in

a dish covered with wet cotton or filter paper. The dish is heated on a sand
bath to produce the vapour of the crude organic compound. The vapour of
the organic substance cools to form pure crystals of the substance on the
funnel. The impurities are left inside the dish.

PURIFICATION OF LIQUIDS

The methods employed in the purification of crude organic liquids are;

(a) Distillation
(b)Fractional distillation
(c) Distillation under reduced pressure
(d)Steam distillation
A popular method for the purification of both solid and liquid
substances is chromatography.

TEST OF PURITY

The purity of an organic compound can be ascertained by

determining some physical constant associated with that substance.
Such physical constants are melting or boiling point, specific gravity,
refractive index and viscosity. For a substance to be declared pure, it
must show those values for these constants which are known to exist
for pure substances. In the presence of impurities, the values of these
constants will vary from the standard value.
In usual practice, the melting point of a solid and the boiling
point of liquid are used to determine their purity.

1. Melting point Determination

The melting point of substance is defined as the temperature at
which the solid and the liquid phases of the substance exist together.
A pure organic substance has a sharp melting point. The apparatus
used for determination of melting point include capillary tube,
thermometer, H2SO4 bath, retort stand and Bunsen burner.

A capillary tube (about 5cm long) sealed at one end is filled with
finely powdered organic substance. The organic substance should be
enough to fill 1cm length of the capillary tube. The bulb of the
thermometer is dipped in sulphuric acid bath and the taken out. The
capillary tube is then placed along the thermometer with sealed end
near the bulb. The capillary tube clings to the thermometer due to
surface tension and viscosity of the acid. The thermometer is then
carefully lowered into the bath and held in a position that keeps half of
the capillary tube out of the bath. The bath is heated slowly to keep
the temperature of the liquid uniform. When the opaque solid
substance in the tube becomes transparent, the temperature is noted.
This is the melting point of the substance. If this melting point is the
same with that of the pure substance, then the substance prepared is
also pure.

In case of a newly discovered substance, it is recrystallized and its

melting point is determined again. If the two melting points are
concordant and sharp, then the newly discovered compound is pure.

Determination of Melting point

Boiling point determination can also be used to determine the purity

of liquids. It must, however, be noted that boiling point is not a
reliable measure of purity of a liquid.
Now days the ultimate criterion for determining the purity of a
compound is its ability to give a single spot in a chromatogram.

QUALITATIVE AND QUANTITATIVE ORGANIC CHEMISTRY

 Having obtained an organic compound in its pure form, the next
step is the detection of the elements present in the organic
substance. Qualitative organic analysis is defined as the process of
detecting the constituent elements of an organic compound. In
general, an organic compound may contain two or more elements
from among carbon, oxygen, hydrogen, nitrogen, sulphur, halogens,
phosphorous and metal. Carbon is present in all organic compounds.

Detection of carbon and hydrogen

The presence of carbon and hydrogen in an organic compound can be

detected as follows:

The organic compound is intimately mixed with freshly ignited copper

oxide in a hard test tube. Copper oxide is ignited before use because
it is hygroscopic. The test tube is clamped and fitted with a delivery
tube carrying a bulb in the horizontal length. The end of the delivery
tube is dipped into a vessel containing lime water. The mixture is
heated strongly so that’s the carbon And hydrogen present in the
compound are converted into CO2 and H2O respectively. The water
formed condenses in small droplets in the bulb while the CO 2
produced turns the lime water milky. The water droplets can be
tested with an anhydrous CuSO4
 C + 2CuO CO 2 + 2Cu
2H + CuO H 2O + Cu.
If the organic substance under investigation is a volatile liquid or gas,
the vapours are passed over heated copper oxide kept in a
combustion tube and the product tested as above.

Detection of nitrogen, sulphur and halogens

Nitrogen, sulphur and halogens are usually detected by converting them

into ionizable inorganic substances. This is best done by fusing the
organic substance with sodium metal. This method gives cyanide,
sulphide and the halide of sodium.

C, H, O, N, S, halogen + Na NaCN + Na 2S + NaX +NaOH

(Organic compound)

Sodium should be in slight excess otherwise in compounds containing N

and S together, sodium thiocynate is formed. If sodium is present in
excess, the thiocynate formed decomposes to produce sodium cyanide
and sodium sulphide.

Na + NaCNS NaCN + Na 2S
 Lassaigne’s Filtrate or Extract

A small piece of sodium (0.04g) is freshly cut and dried between

folds of filter paper. It is then transferred into a fusion tube and heated
gently. The fusion tube is removed from the flame when the sodium
inside it melts. A little quantity (about 0.05g) of the organic solid is
added to the molten sodium inside the fusion tube. The tube is now
heated over the flame, first slowly and then strongly until the tube. The
fusion tube is plunged directly into 5-10ml of distilled water in a
porcelain dish and crushed by the tip of a pair of tongs. The content is
then boiled for a few minutes and filtered. The filtrate is known as
Lassaigne’s filtrate or extract.

Detection of nitrogen using Lassaigne’s test

Detection of nitrogen

Lassaigne’s test: two cubic centimetres of lassaigne’s filtrate is taken

into a test tube and 2ml of freshly prepared saturated ferrous sulphate is
added and the mixture boiled. Dilute H2SO4 is added to dissolve the green
ferrous hydroxide solution. Prussian blue colour/precipitate indicates the
presences of nitrogen.

Detection of sulphur

Take about 3ml of Lassaigne’s filtrate and mixed with a drop of ferric
chloride solution. A blood red colouration confirms the presence of nitrogen
and sulphur.

3NaCNS + FeCl3 NaCl + Fe(CNS) 3

2. To another portion of Lassaigne’s filtrate, add acetic acid and lead acetate
are added; a black precipitate of lead sulphide confirms the presence of
sulphur.
Detection of halogens

If nitrogen and sulphur have been detected in the organic compound,

then it is boiled with excess of dilute HNO3 to remove hydrogen cyanide and
hydrogen sulphide. The boiling continues until the volume is reduced to half.
It is then cooled, diluted with water and silver nitrate added; a white,
yellowish white or yellow precipitate indicates the presence of chlorine,
bromine or iodine respectively. If sulphur and nitrogen were not detected in
the organic compound, boiling is not essential after acidifying the
Lassaigne’s filtrate with HNO3.

Detection of oxygen

The presence of oxygen can be established by testing for the

presence of functional groups known to contain oxygen e.g. hydroxyl (-OH),
aldehydes (-CHO), etc

Detection of metals

The organic compound is heated strongly in a platinum crucible. If a

residue is left it may be a metal. The residue is dissolved in an acid and
inorganic qualitative analysis carried out to detect the metallic radical as in
the case of metallic salts.

Quantitative Organic Analysis

After qualitative detection of the elements, the next step is the estimation of
elements by weight.

Estimation of carbon and hydrogen

The estimation of carbon and hydrogen is carried out in one experiment.
Carbon and hydrogen are oxidized to carbon dioxide and water by heating
the compound or its vapour with pure dry copper oxide. The resultant carbon
dioxide and water vapour are absorbed in proper absorbents and their
weights determined. Thus, the weights of carbon and hydrogen in the known
weight of the compound are obtained. The percentage of carbon and
hydrogen present in the organic compound can be calculated from the data
obtained from experimental runs. An example is illustrated below:

Weight of the organic substance= x g

Weight of water formed= yg

Weight of carbon dioxide formed= zg

Since 44g of carbon dioxide contain 12g of carbon

12
:. Zg of carbon dioxide will contain x zg of carbon
44

:. % of carbon in the compound= (12/44)x (z/x) x 100

Or percentage of carbon = ¿ ¿ x (12/44) x 100

weight of H 2 O formed
Similarly, % hydrogen = x (2/18) x100
weight of compound

Estimation of oxygen

The method given below is one used to estimate the amount of oxygen in an
organic compound.

Ter Meuler method

 A known weight of the organic compound is heated in a current of dry
hydrogen and the gases produced are passed over red hot platinized
asbestos. In this way, the oxygen of the organic compound I converted into
CO, CO2 and water vapour. This gaseous mixture is then passed over finely
divided nickel at temperature o9f 3500C the oxides of carbon are reduced to
methane and oxygen is converted into water vapour.

CO + 3H2 CH4 + H2O

CO2 + 4H2 CH4 + 2H2O

The water vapour produced in the experiment is absorbed in weighed

calcium chloride tube. The % of oxygen can be calculated from the weight of
water produced.

weight of H 2 O 16
% Oxygen = x 100
weight of theorganic cmpd 18

NOTE: In most cases the percentage of oxygen is calculated by difference

Example

0.1435g of an organic compound containing carbon, hydrogen and oxygen

on analysis gave 0,3235g of CO2 and 0.1339g of water. Calculate the
percentage of carbon, hydrogen and oxygen in the organic compound.

solution

Weight of organic compound = 0.1435g

,, ,, CO2 = 0.34253g

,, ,, H2O = 0.1339g

10.3253 6 12
%carbon = x x100 = 61.83%
10.14358 44
 0.1339 2
% hydrogen = x x 100 = 10.37%
0.1435 18

% oxygen = 100- (61.83-10.37)

= 27.8%

Estimation of nitrogen

Estimation of nitrogen is carried out generally by two methods:

(a) Dumas’ method

[(b)] Kjeldah’s ,,

Dumas’ method
The method is based on the fact that when an organic compound is
heated with copper oxide carbon, hydrogen and sulphur are converted
into their oxides and nitrogen is set free. Any nitrogen which may be
oxidized is again reduced by bright reduced copper gauze. CO 2, H2O
vapour, and sulphur dioxide are absorbed in caustic potash solution and
free nitrogen is collected in a nitrometre.
The amount of nitrogen in the compound can be estimated from the
data obtained from the experiment.

Calculation
The volume of nitrogen at S.T.P. can be calculated by using
(P−p)v x 273
V=
( 273+T ) x 760
Where v = volume of nitrogen in nitrometre (ml),
T= room temperature (0C),
P = pressure of nitrogenatmospheric pressure (mm) and
pP = aqueous tension at room temperature.
 Since 22,400ml of nitrogen at STP = 28g
:. v ml of nitrogen at STP = 28xv/22400 = x g

If the weight of the organic substance = w, the percentage of nitrogen =

(x/w) x 100

Estimation of halogen
Carius method
This method involves the heating of a known weight of the organic
substance with conc. nitric acid and silver nitrate. Thus, the carbon and
hydrogen are oxidized to CO2 and H2O respectively while the halogen
present is converted to silver halide. The weight of the halogen in the
silver halide is obtained. The percentage of halogen in the organic
compound can be determined as follows:

Weight of the substance taken = w g

,, ,, dry silver halide = a g

Atomic weight of the halogen = x

Molecular weight of the silver halide = 108 + x
Since (108 + x) of silver halide contain x g of halogen
x
:. a g of siver halide contain xa
108+ x
x a
% halogen = x x100
108+ x w

atomic wt of halogen
= x (a/w) x 100
molecular wt .of silver halide

Example 2
In Dumas’ method of nitrogen estimation 0.31g of an organic compound
gave 35.5ml of moist nitrogen at 170C and 750mm pressure. Determine the
percentage of nitrogen in the compound (Aqueous tension at 17 0C =
13.4mm)

Solution

P= 750mm, T= 17, p =13.44mm, v =35.5ml

(750−13.4)x 35.5 x 273

V=
( 273+17 ) x 760

= 33.32ml

Weight of 33.32 ml of nitrogen at STP

33.32
= x 28
22400

33.32 100
Percentage of nitrogen = x 28 x
22400 0.31

13.44%

Example 3

In Carius method 0.369g of an organic compound gave 0.345g of silver

bromide. Calculate the percentage of bromine in the compound (Br =80)