CHM 102: GENERAL CHEMISTRY II

HISTORICAL BACKGROUND OF ORGANIC CHEMISTRY

Organic chemistry is the area of chemistry that involves the study of carbon and its compounds. Carbon is
now known to form a seemingly unlimited number of compounds. The uses of organic compounds impact
our lives daily in medicine, agriculture, and general life.

In theory (Oparin, 1923) organic chemistry may have its beginnings with the big bang when the
components of ammonia, nitrogen, carbon dioxide and methane combined to form amino acids, an
experiment that has been verified in the laboratory (Miller, 1950). Organic chemicals were used in ancient
times by Romans and Egyptians as dyes, medicines and poisons from natural sources, but the chemical
composition of the substances was unknown.

In the 16th century organic compounds were isolated from nature in the pure state (Scheele, 1769) and
analytical methods were developed for determination of elemental composition (Lavoisier, 1784).

Scientists believed (Berzelius, 1807) that organic chemicals found in nature contained a special "vital force"
that directed their natural synthesis, and therefore, it would be impossible to accomplish a laboratory
synthesis of the chemicals. Fortunately, later in the century Frederich Wöhler (1828) discovered that urea, a
natural component in urine, could be synthesized in the laboratory by heating ammonium cyanate. His
discovery meant that the natural "vital force" was not required to synthesis organic compounds, and paved
the way for many chemists to synthesize organic compounds.

By the middle of the nineteenth century many advances had been made into the discovery, analysis and
synthesis of many new organic compounds. Understanding about the structures of organic chemistry began
with a theory of bonding called valence theory (Kekule, Couper, 1858).

Organic chemistry developed into a productive and exciting science in the nineteenth century. Many new
synthetic methods, reaction mechanisms, analytical techniques and structural theories have been
developed. Toward the end of the century much of the knowledge of organic chemistry has been expanded
to the study of biological systems such as proteins and DNA. Volumes of information are published monthly
in journals, books and electronic media about organic and biological chemistry.

The vast information available today means that for new students of organic chemistry a great deal of study
is required. Students must learn about organic reactions, mechanism, synthesis, analysis, and biological
function.

ELECTRONIC THEORY IN ORGANIC CHEMISTRY: BONDING, LEWIS STRUCTURES, VSEPR

THEORY, CONCEPT OF HYBRIDIZATION, VALENCE BOND THEORY AND SHAPES OF
MOLECULES.

BONDING
Bonding is the joining of two atoms in a stable arrangement. It is a favourable process because it leads to
lowered energy and increased stability. Bonding may occur between atoms of the same or different
elements. In an atom, valence electrons (outermost electrons) participate in bonding, leading to a stable
configuration of electrons (octet rule). Atoms can become bonded with each other, and their electronic
structure governs the type of bond formed. There are 2 types of bonding: ionic and covalent Ionic
bonding is the transfer of an electron from an atom (a metal) to another atom (a non-metal) to give ions.

So, ionic bond is an electrostatic attraction between oppositely charge ions. Covalent bonding involves
sharing of electrons between 2 participating atoms. Compounds that results from covalent bonding are
called molecules. E.g. CH4, H2, NH3, O2, N2 e.t.c. The major type of bonding that exist between organic

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molecules is a covalent bond. There are two types of covalent bonding: ordinary and coordinate covalent
bonding. Covalent bond could be single bond, double bond or triple bond. i.e: C-C, C=O, C=C etc.

Lewis Structures
This is the representation of covalent bonds with electron dots. It is used to show shared electron pairs
(bonding electrons) and lone pairs non-bonding electrons) in form of a dot. A covalent bond is a two
electron bond. In the Lewis structure, most atoms attain the electronic configuration of a noble gas (octet
rule) Rules for drawing Lewis structure: Arrange the atoms Count the electrons. The number of covalent
bonds can be predicted by 8-valenc e electrons. E.g the no of covalent bond around N is 8-5=3 covalent
bonds. The limitations of the Lewis structure is that the model could not give the bond angles and shapes of
molecules.
N.B: Atoms no of covalent bonds
H 1
Halogens 1
N (with one lone pair) 3
N (with a + charge) 4
C 4
C (with a + charge) 3
O 2
O (with a + charge) 3 Eg: Lewis structure of CH4
O (with a -ve charge) 1
S 6 (or less with lone pairs)
P 5 (or 3 with a lone pair).

Valence Shell Electron Pair Repulsion Theory (VSEPR)

The VSEPR theory is used to predict the shape of the molecules from the electron pairs that surround the
central atoms of the molecule. The theory was first presented by Sidgwick and Powell in 1940. This theory
gives the shape of molecules by predicting the bond angles between two bonded atoms. The VSEPR model
is based on the fact that electron pairs repel each other. The most stable arrangement keeps the groups
(atoms or lone pairs) as far away from each other as possible.

Lone pair - Lone pair repulsion > Lone pair-bond pair repulsion> bond pair - bond pair repulsion.

This order can be explained on the basis that the lone pair is under the influence of only one nucleus, hence
its electron cloud will spread out in space to a greater extent than bond pair which is under the influence of
two nuclei. This greater spread over of electron cloud in space results to a greater repulsion between a lone
pair and another lone pair than a bond pair and a lone pair.

Predicting the Shapes of Molecules:

The following steps must be followed in order to decide the shape of a molecule.
 Draw possible lewis structure
 The least electronegative atom must be selected as the central atom (since this atom has the
highest ability to share its electrons with the other atoms belonging to the molecule).
 The total number of electrons belonging to the outermost shell of the central atom must be counted.
 The total number of electrons belonging to other atoms and used in bonds with the central atom
must be counted.
 These two values must be added in order to obtain the valence shell electron pair number or the
VSEP number.
Case 1: when the central atom is surrounded by two groups:
e.g BeCl2
valence electrons of central atom( Be) = 2es
bonding electrons from chlorine = 2es, total =4es
2
electron pair = total electrons/2 =2e pair.
any atom surrounded by 2 groups is linear and has a bond angle of 180o
Cl-Be-Cl is linear and the bond angle between each Be-Cl is 180o.

Case 2: three groups surrounding an atom.

An atom surrounded by 3 groups is trigonal planar and the bond angle is 120 o
e.g BF3 (Boron trifluoride),
valencees of B= 3
bonding electrons from F= 1X 3= 3es
total electrons = 6es
electron pairs = 6/2 =3
It implies that the shape of BF3 is trigonal planar and the bond angle between each B-F is 120 o
All the B-F bonds lie in one plane (symmetrical).

Case 3: when an atom is surrounded by 4 groups.

Any atom surrounded by 4 groups is a tetrahedral and has a bond angle of 109.5o
e.g CH4
electron pair = 4es
So CH4 (has a central carbon with 4 bonds to hydrogen atoms, each pointing towards a corner of
tetrahedron).
In methane, there are four bonds of equal repulsive forces and which completely balance each other,
resulting to a tetrahedral shape.
But in ammonia NH3, there are 3 bond pairs and 1 lone pair of electrons. There is a greater repulsion
between the lone pair and the 3 bond pairs than the bond pair- bond pair repulsion. Hence the three bond
pairs are forced closer together resulting to a bond angle of 107.
Similarly, water has 2 lone pairs and 2 bond pairs, and hence there is a greater repulsion between the 2
lone pairs and also forcing the two bond pairs still closer together resulting in H-O-H bond angle of 104.5.

VALENCE BOND THEORY

According to this theory, a covalent bond is formed by overlapping of two half-filled atomic orbitals
containing electron of opposite spins. The greater the overlapping, the stronger the covalent bond. VBT
states that the overlap of incompletely filled atomic orbitals leads to the formation of a chemical bond
between two atoms. The unpaired electrons are shared and a hybrid orbital is formed. All atoms are made
up of nucleus surrounded by electrons in concentric shells. Each shell surrounding the nucleus corresponds
to a principal quantum no n. n=1, 2, 3, 4, 5, 6. Etc. each shell has sub-shells known as orbitals. An atomic
orbital is a region in space around the nucleus where there is probability of finding an electron. Types of
subshell or orbitals include: s, p, d, f.
So in n=1 level has subshell l s or s orbital.
n=2 level has s, p or orbitals

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n=3 has s,p,d.
Each orbital has its own characteristic energy and shape.

An s orbital has spherical shape. The orbital is spherically symmetrical around the nucleus.
A p orbital has two lobes forming a dumb-bell shape. The p orbital has 3 sub-orbitals of equal energy
(degenerate orbitals). They are directed perpendicular to each other just as Cartesian coordinate and are
designated as px, py and pz. Corresponding to their axes orientation.

Based on this, there are 2 types covalent bonds based on the type of overlapping:
Sigma and pi bond.
Types of overlapping
s-s overlapping e.g
s-p
p-p linear overlapping
p-p parallel overlapping
Summarily, sigma bond results from
a) Hybrid –hybrid overlap
b) Hybrid –s overlap
c) Hybrid-p overlap
d) s-s overlap
 bond results from p-p orbital overlap that are parallel to each other. E.g Cl2.
Sigma bond is stronger than a pi bond.

Orbitals
Shell s p d f Total Electrons Possible
1 1 2
2 2 3 8
3 3 3 5 18
4 1 3 5 7 32

*energy level 1 contains up to two electrons in a spherical orbital called a 1s orbital.

*energy level 2 contains up to eight electrons; two in a 2s-orbital and two in each of three orbitals
designated as 2p-orbitals. The p-orbitals have a barbell type shape and are aligned along the x, y, and z
axes. They are thus called the px, py, and pz orbitals.

*energy level 3 contains up to eighteen electrons, two electrons in a 3s-orbitals, and ten electrons in the
five 3d Orbitals.
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*energy level 4 contains up to thirty-two electrons, two electrons in a 4s-orbital, six electrons in the three
4p-orbitals, ten electrons in the five 4d-orbitals, and fourteen electrons in the seven 4f-orbitals.

Electrons fill the lower energy levels first until all of the electrons are used (Aufbau Principle). An element
contains the number of electrons equal to its atomic number. For the first and second row elements the
electron configurations are relatively simple.

Element (atomic number) Electron Configuration

H (1) 1s1 (1st shell, s orbital, one electron)
He (2) 1s2
Li (3) 1s2, 2s1
Be (4) 1s2, 2s2
B (5) 1s2, 2s2, 2p1
C (6) 1s2, 2s2, 2p2
N (7) 1s2, 2s2, 2p3
O (8) 1s2, 2s2, 2p4
F (9) 1s2, 2s2, 2p5
Ne (10) 1s2, 2s2, 2p6 (inert, completely filled)

Electronegativity is the ability of an atom to attract electrons to itself, and generally increases as one moves
from left to the right across the periodic table.
Least most
electronegative Li < Be < B < C < N < O < F electronegative
Electronegativity also increases as we go from the bottom to the top of a column in the periodic table.
Least most
electronegative I < Br < Cl < F electronegative
Elements that easily lose electrons and attain a positive charge are called electropositive elements. Alkali
metals are electropositive elements.

Saturated and unsaturated compounds

When all the bonds between the carbon atoms (may involve other elements) are single, the compound is
said to be saturated e.g. Pentane. If, however, multiple bonds e.g. the double bond in alkenes and triple
bond in alkynes is present in the molecule, the compound is said to be unsaturated.

Bonding in Carbon Compounds

The property of carbon that makes it unique is its ability to form bonds with itself and therefore allows a
large number of organic chemicals with many diverse properties. Carbon has the property of forming single,
double and triple bonds with itself and with other atoms. This multiple-bond ability allows carbon
compounds to have a variety of shapes. In all carbon compounds, carbon forms four bonds. The types of
bonds used by the carbon atom are known as sigma () and pi () bonds. Different combinations of these
bonds lead to carbon single bonds, double bonds and triple bonds.
The uniqueness of carbon atom stems from its ability to form:
i. A variety of strong covalent carbon-carbons bond
ii. Long chains or rings of carbon atoms bonded to one another called CATENATION.
iii. strong covalent bonds with other elements
iv. Multiple bonds (double and triple) with another carbon atom or other elements.
In all these bonds, carbon shows a valency of four. The special properties of carbon can be attributed to its
being a relatively small atom with four valence electrons. The energy changes involved in gaining or losing
four electrons, to form a stable configuration, are very high so that simple C4 f and C4- ions do not exist, but
customarily, carbon completes its valence-shell octet by sharing electrons (covalent bond formation) with
other atoms (carbon or other elements).

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Types of covalent bonds formed by carbon

The Carbon-Hydrogen Single Bond-The Sigma () Bond

By far most of the bonds in carbon compounds are covalent bonds found commonly in the carbon-hydrogen
single bond. In carbon (1s2, 2s2, 2p2) one of the electrons of the 2s2 orbital is promoted to the third 2p0
orbital. The s and three p orbitals hybridize to form four new orbitals of equal energy called sp 3 hybrid
orbitals. The electrons in the four sp3 hybridized orbitals bond by overlap with the 1s 1 hydrogen orbital. The
single covalent bond is called a sigma () bond. The sp3 bonds arrange themselves as far from each other
as possible. The shape of a molecule of methane, CH4, is tetrahedral with 109.5o bond angles.
Addition of another atom to methane results in ethane which has covalent sigma bonds to the hydrogen
atoms and a covalent sigma bond between the carbon atoms. Addition of more carbon atoms leads to many
more compounds.

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The Carbon-Carbon Double Bond-The Pi () Bond
Carbon forms a wide variety of compounds that contain carbon bonded to another carbon with a double
bond between the two atoms. These compounds are classified as alkenes (older naming calls them olefins).
The orbital model below explains the carbon-carbon double bond. The carbon electron configuration shows
one s electron being promoted to a p orbital. But now only three orbitals are mixed, a s orbital and two p

orbital, that are called sp2 hybrid orbitals and are used to form single bonds (sigma bonds). The p orbital
contains one electron.

The combination of two of the sp2 hybridized carbon atom leads to two carbon atoms being joined by
overlap of sp2 orbitals to form a C-C single bond, and the side-to-side overlap of the p orbitals to form
another bond known as a pi () bond. In the molecule of ethene shown below there are a total of 5 sigma
bonds and one pi bond. As a result of the bonding in an ethene, the molecule is planar with bond angles of
120o and a C=C bond length that is longer than the C-H bond length.
When carbon forms a bond with an electronegative atom such as oxygen, nitrogen, sulfur or a halogen, the
bond is a polar covalent bond with the electrons of the bond residing closer to the electronegative atom.

The Carbon-Carbon Triple Bond

Another type of bond that carbon forms with itself is the triple bond found in a class of compounds called
alkynes. After promotion of the 2s electron to a 2p orbital, one s orbital mixes with one p orbital to give two
hybrid sp orbitals. The two remaining p orbitals are used to make  bonds. Thus the carbon is bound by a
sigma bond to hydrogen from one of the sp hybrid orbital, to the other carbon atom by a sigma bond from
one of the sp hybrid orbitals, and the two carbon atoms are bound by two pi bonds from side-to-side
overlap of the two p orbitals. The sp hybrid orbitals position themselves 180o apart and thus a molecule of
ethyne is linear with the hydrogen atoms 180o apart.

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NOMENCLATURE OF ORGANIC COMOUNDS
The earliest attempts to name organic compounds were based either on their origin or on their properties.
For example, citric acid was named so because of its occurrence in citrus fruits. The aromatic compounds
were called so because of their characteristic odour (Greek: aroma, fragrant smell). Examples are oil of
wintergreen and vanillin (a constituent of vanilla also used as a flavouring agent) which were called
aromatic due to their characteristic fragrance. With the advancement and growth in the knowledge of
chemistry, the number of known organic compounds has increased rapidly. Also, with the increase in the
number of carbon atoms, the number of possible isomers for hydrocarbons (without any functional group)
becomes very large. Isomers are the compounds that have identical molecular formulas but differ in the
ways in which the atoms are bonded to each other. For example, four carbons in a hydrocarbon having
molecular formula C4H10 can be arranged in the two different ways:

Straight chain H3C – CH2 – CH2 – Ch3

Common name; normal butane or n-butane Branched chain
CH3
|
H3C – CH – CH3 with a common name 150 – butane.
Thus, n-butane and isobutene are isomers.

Number of 4 5 6 7 8 9 10 12 15 20
carbon Atoms in
the Hydrocarbon
Number of 2 3 5 9 18 35 75 355 4,347 366,319
possible Isomers
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Having learned about the variety of functional groups, you can imagine that the nature and position of
functional groups present can raise these numbers many fold. Under such a situation, it is next to
impossible to learn the names randomly assigned to the compounds, especially when there is no correlation
of the name to the structure of the compound. This necessitated the need to have a systematic
nomenclature for which the International Committee of Chemists met at Geneva in 1892. The work was
carried on by the International Union of Chemists (I.U.C.) which gave its report in 1931, known as the
I.U.C. system of nomenclature. As the nomenclature is always undergoing modifications and revisions, the
latest rules which are widely accepted were recommended by the Commission on Nomenclature of Organic
Chemistry of the International Union of Pure and Applied Chemistry (I.U.P.A.C.).

Classification of Organic Compounds

A. Classification based on structure

B. Classification based on solubility

Polar organic compounds are those that can dissolve in water and polar organic solvents.
Non polar organic compounds do not dissolve in water and polar organic solvents. They dissolve in
non-polar organic solvents such as benzene, n-hexane. Examples of polar organic compounds are
alkanols (alcohols), phenols, carboxylic acid, ether, aldehydes e.t.c. Examples of non-polar
organic compounds are: alkanes, alkenes e.t.c.

C. Classification based on Structural formula

The structural formula of a compound is its Lewis structure, which shows how various atoms are
connected or linked to each other in a compound. i.e. bonding sequence.
e.g: butane has a molecular formula C4H10 has a structural formula:

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What is Homologous series?
Homologous series is a series of compounds with similar chemical properties and some functional groups
differing from the successive member by CH2. Carbon chains of varying lengths have been observed in
organic compounds having the same general formula.
Such organic compounds that vary from one another by a repeating unit and have the same general
formula form a series of compounds. Alkanes with general formula CnH2n+2, alkenes with general formula
CnH2n and alkynes with general formula CnH2n-2 form the most basic homologous series in organic chemistry.
All the members belonging to this series have the same functional groups. They have similar physical
properties that follow a fixed gradation with increasing mass. The properties of CH 3OH, C2H5OH, and
C3H7OH are similar and follow a gradual change with increasing molecular mass of the successive members
of the series. This is because, with the increase in the molecular mass of the compounds, the number of
bonds also increases. Therefore, properties such as melting and boiling point, solubility, etc. that depend on
the mass and the total number of bonds in a compound show a gradual change with an increase in
molecular masses of the compounds. The Chemical properties of the members of a homologous series are
the same due to the fact that they all have the same functional groups in them.

Functional Groups
With over twenty million known organic compounds in existence, it would be very challenging to memorize
chemical reactions for each one. Fortunately, molecules with similar functional groups tend to undergo
similar reactions. A functional group is defined as an atom or group of atoms within a molecule that has
similar chemical properties whenever it appears in various compounds. Even if other parts of the molecule
are quite different, certain functional groups tend to react in certain ways.

We've already looked at alkanes, but they are generally unreactive. We primarily use alkanes as a source of
energy when they are combusted. While the majority of functional groups involve atoms other than carbon
and hydrogen, we will also look at some that include only carbon and hydrogen. Some of the most common
functional groups are presented in the following sections.

Organic molecules vary greatly in size and when focusing on functional groups, we want to direct our
attention to the atoms involved in the functional group. As a result, the abbreviation R is used in some
examples. The letter R is used in molecular structures to represent the “Rest of the molecule”. It consists of
a group of carbon and hydrogen atoms of any size. It is used as an abbreviation since a group of carbon
and hydrogen atoms does not affect the functionality of the compound. In some molecules, you will see R,
R’, or R’’ which indicates that the R groups in the molecule can be different from one another. For example,
R might be –CH2CH3 while R’ is –CH2CH2CH2CH3.

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 alkyl halide R-X X= halogens CH3Br C-X
Alcohols R-OH CH3CH2OH -OH (hydroxyl group)
Ether R-O-R H3C-O-C2H5 -OR (alkoxy)
Amines R-NH2, R2NH, R3N CH3NH2 -NH2 (amino group)
Thiols R-SH -SH (mercapto group)
Sulphide R-S-R -S-R (alkylthiol group)

Alkane
Since the nomenclature of other classes of compounds is based on the nomenclature of alkanes, let us start
the study of nomenclature with the alkanes. Alkanes are represented by the general formula CnH2n+2
where n can be 1,2,3,4… etc. The first four alkanes retain their original or nonsystematic names. The
names of alkanes higher than these start with a prefix (Greek or Latin words) which indicates the number of
carbon atoms in the chain and end with suffix-ane. The unbranched alkanes have their common names as
normal alkanes or n-alkanes.
The branched chain alkanes are named by using the following steps:
1. The longest continuous chain of carbon atoms is taken as the parent hydrocarbon. For example, in
compound shown below, the parent
hydrocarbon is heptane and not the
hexane.

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 2. Identify the substituent alkyl groups attached to the parent chain. Some common alkyl groups are
listed below. Can locate that both the substituents in the example cited above are methyl groups.

Note that the numbering of carbon atoms is from the point of attachment of the group to the parent chain.

3. The parent carbon chain is then numbered in such a way that the substituents get the lowest
possible numbers. The carbon atoms in the above compound can be numbered as;

The first possibility locates the methyl groups at carbons 4 and 5 and the second, at carbons 3 and 4.
Certainly, the second way of numbering the carbon chain is correct.

4. Perfixes di, tri, tetra, penta etc, are used when the substituents occur more than once. Since in the
above compound the methyl substituent is occurring twice, the name is prefixed with di for the
above compound.
5. The name of the compound is written by writing the location and name of the substituents followed
by the name of the parent alkane. The above compound can be named as 3, 4-dimethylheptane.
Note that a comma is used to separate the two numbers and the numbers are separated from
names of groups by a hyphen. Also note that there is no blank space between the name of the last
substituent and the parent alkane.
6. When more than one type of alkyl groups are present, then they are cited in the name in the
alphabetical order, regardless of their location in the principal chain.
The numerical prefixes di, tri, tetra, etc. and hyphenated prefixes such as sec-tert – are not considered in
determining the alphabetical order but prefixes iso, neo, cyclo are considered for alphabetizing. To
understand it, let us consider the examples given below:

Note that here ethyl is cited before methyl, in spite of its higher location number.

Similarly, the compound below can be named as;

4-isopropyl- 5,5-dimethylnonane or 4-(1- methylethy1)- 5, 5-dimethylnonane.

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 7. The branched chain substituents, such as 1-methylethyl shown in step 6, are numbered starting
from the carbon attached directly to the parent chain. We already saw the numbering pattern for
branched substituents. The longest carbon chain is selected and the substituents are named
according to the rules listed above for compounds having unbranched substituents. Note that the
name and numbering of branched substituent is written in brackets in order to separate it from the
numbering of the main chain.
8. The alkyl substituents can be further classified as primary, secondary or tertiary. An alkyl group is
called a primary alkyl group if the carbon atom at the point of attachment is bonded to only one
other carbon. For example, R – CH2 – is a primary alkyl group. Similarly, a secondary alkyl group has
two alkyl groups bonded to the carbon atom taken as the point of attachment to the main chain.
Similarly, a tertiary alkyl group has three carbon atoms bonded to the carbon atom taken as point of
attachment. Thus, a secondary and tertiary alkyl group can be represented as shown below:

9. When more than one carbon chains of equal length are available, the numbering is done considering
the following points:
a) The principal chain should have the greatest number of side chains. For example, in the
compound shown below;

The chain having numbering from left to right has four side chains while the chain marked with numbers
from right to left has three side chains. So the principal chain is the one which is marked in the red colour.
Hence, the name is 3-ethyl-2,5,6-trimethyloctane.
b) The chain having the lowest number for substituents is chosen as the principal chain. In the
compound shown below;

Black

Red

If the numbering is done as shown in black colour, the name would have substituents at positions 3,4 and
5. But, if the carbon chain numbered in red colour is taken as the principal chain, then the substituents get
the numbers 2, 3 and 4, which is obviously the correct choice.
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Till now we were studying the nomenclature of alkanes. Let us now study how various compounds having
different functional groups are named. In case of compounds which have a functional group, the functional
group gets precedence over the alkyl substituents. At this stage, you refer back to where IUPAC prefixes
and suffixes for various classes of compounds are given.

Alkenes:
The suffix ane of the parent hydrocarbon is changed to ene and the functional group (a double bond in this
case) is given the lowest possible number.
Some examples are:

Alkynes:
In this case suffix ane of the parent hydrocarbon is changed to yne. As expected, here also the functional
group is given the lowest number.
When both double and triple bonds are present, then the double bond gets the lower number. Thus, for the
compound show below;

Alkyl halides:
The alkyl halides are the halogen derivatives of alkanes also known as haloalkanes. The halogens present
are usually F, Cl, Br and I. The common names are arrived at by writing the name of alkyl group followed
by the name of the halide. Examples are shown below:

In the IUPAC system of nomenclature, prefix halo- (i.e., fluoro, chloro-, bromo or iodo-) is used to give the
lowest number to the carbon atom to which the halogen is attached. For example, some halogen
compounds are named below:

When more than one type of halogen atoms are present, their names are arranged in alphabetical order as
shown in the next example,

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Haloalkanes are found in fire extinguishers, refrigerants, propellants, solvents, and medications. They are
also a significant source of pollution and their use has been reduced or eliminated in some products.
Chlorofluorocarbons (CFCs) were used as refrigerants in air-conditioners but were found to be a major
cause of the depletion of the ozone layer. Research and development of alternatives began in the 1970s.
Hydrochlorofluorocarbons (HCFCs) have been used for many years since they cause less damage to the
ozone layer, but many countries agreed to eliminate HCFCs by 2020.

Alcohols
Alcohols: Alcohols are the compounds having hydroxyl (-OH) group attached to the alkyl chain. The
common names of the alcohols are written by specifying the alkyl group followed by the word alcohol, e.g.

In the IUPAC nomenclature, suffix ol is used instead of final e of the parent hydrocarbon. The position of
the hydroxyl group is given by assigning the lowest possible number to the carbon atom carrying it.

Some examples are:

Alcohols can be classified as primary, secondary, or tertiary based on the characteristics of the carbon to
which it is attached. In a primary alcohol, the carbon bonded directly to the oxygen atom is also bonded to
exactly one carbon atom, with the other bonds generally going to hydrogen atoms. In a secondary alcohol,
the carbon is attached to two other carbon atoms, and in a tertiary alcohol, the carbon is bonded to three
other carbon atoms. The type of alcohol being used will determine the product of certain reactions. Note
the naming of alcohols as illustrated in the figure below. The location of the −OH group is indicated with
the number of the carbon to which it is attached.

We are already familiar with several common alcohols. For example, ethanol (CH 3CH2OH) is the alcohol
present in alcoholic beverages. It is also widely used in the industrial manufacture of other chemicals.
Methanol (CH3OH) is used as a gasoline additive or alternative. Additionally, methanol can be used to
manufacture formaldehyde, which is employed in the production of plastics, paints, and other useful
substances. Isopropanol is commonly known as rubbing alcohol. In addition to its industrial uses,

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isopropanol is used to clean various surfaces, including computer monitors, whiteboards, and even skin
(e.g., before getting blood drawn).

Ethers
The common names for ethers are derived by naming the two alkyl groups in alphabetical order followed by
the word ether. This is illustrated in the examples given below:

In the IUPAC system, ethers are named as alkoxyalkanes. The larger of the two alkyl groups is chosen as
the hydrocarbon chain. For example, the compound below is named is named as 1-methoxyethane and not
as ethoxymethane. Similarly, the second compound has the name 1-ethoxy-2-methylpropane.

Ethers are good solvents for other organic compounds because of their low reactivity. They readily dissolve
nonpolar molecules. Diethyl ether is perhaps the best known ether. It is widely used as a solvent and has
been used as an inhalable anesthetic.

Although ethers themselves are relatively unreactive, they can be converted to peroxides after prolonged
exposure to oxygen. Peroxides are very reactive and are often explosive at elevated temperatures. Many
commercially available ethers come with a small amount of a peroxide scavenger dissolved in them to help

Aldehydes

Lower members of this class are commonly named after the acids that they form on oxidation. For example,
HCHO, formaldehyde is named so because it forms formic acid (HCOOH) on oxidation.

In the IUPAC system of nomenclature, they are named as alkanals. The simplest aldehyde is methanal.
Since the aldehyde group – CHO) is always at the end of the chain, it is always numbered as C – 1 in the
chain, but this number is not specified in the name, i.e. the compound.

Aldehyde

An aldehyde is a carbonyl in which the carbon atom is bonded to at least one hydrogen atom. The other
group attached to the carbonyl may be an RR-group or a hydrogen atom. Because the hydrogen atom is so
small, the partial positive charge on the carbonyl carbon is very easy for other molecules to approach,
making aldehydes a particularly reactive type of carbonyl. Aldehydes are versatile reactants for a wide
variety of organic syntheses. Many aldehydes also have distinctive flavors and aromas. For example, the
flavor of cinnamon is primarily due to the molecule cinnamaldehyde, and vanillin is the aldehyde most
responsible for the smell and taste of vanilla extract.

A special aldehyde is the molecule in which the carbonyl is bonded to two hydrogen atoms. This molecule,
called formaldehyde, has a wide variety of uses. By itself, it can be used as a tissue preservative or as a
very harsh disinfectant. It is also used as a precursor to various materials, including plastics, resins, and
other polymers.
16
Examples of molecules with aldehyde functional groups.

Ketones

The common names for ketones are written similar to ethers, i.e. the two alkyl groups are written
alphabetically followed by the word ketone. For example, the compound below is known as, ethyl methyl
ketone

Thus, acetone, CH3COCH3 is also known as dimethyl ketone. The IUPAC names for ketones are derived by
using the suffix one instead of final e of the parent hydrocarbon. As usual, the position of the carbonyl
group is indicated by the lowest possible number. A few examples are,

This ketone is commonly used to remove fingernail polish and serves as an industrial solvent. Ethyl methyl
ketone is used as a paint stripper and a solvent. Ketones are also used in the production of various
polymers, either as a building block or as a solvent.

Sulphonic acids

The names of sulphonic acids use the suffix sulphonic acid with the name of the corresponding
hydrocarbon.

Carboxylic Acids

Nowhere else in organic chemistry, the common names are so prevalent as they are among carboxylic
acids. Carboxylic acids are another carbonyl-containing functional group, in which the carbon atom is
bonded to an OH group on one side and either a carbon or hydrogen atom on the other. Some examples

17
are listed in Table below along with both their common and IUPAC names. For monocarboxylic acids, [i.e.
acids having one carboxy (- C – OH) group], the IUPAC names are derived by replacing e ending of the
alkane by oic acid. As for aldehydes, the carboxyl carbon is numbered 1. However, in case of the
dicarboxylic acids, the final e of the hydrocarbon is not dropped.

Carboxylic acid

As the name implies, carboxylic acids

are weak acids. An OHOH group that is
directly connected to a carbonyl will
ionize to a small extent when dissolved
in water. The reason for this is the
relative stability of the resulting anion.
A carboxylate ion (see figure below), in
which the negative charge is spread
over two different oxygen atoms
through resonance structures, is more
stable than an isolated oxygen-centered
anion. The carboxylic acid and
carboxylate ion are interchangeable.
Carboxylate ions are often present in
amino acids.

Carboxylate ion

Carboxylic acids are used in a variety of environments. Formic acid acts as a protective chemical for many
stinging insects and plants. Acetic acid gives vinegar its characteristic smell and flavor and is a fundamental
biological and industrial building block. Carboxylic acids with longer carbon chains (fatty acids) are used by
animals as a way of storing energy and are widely used in the manufacture of soaps. Some compounds
contain multiple carboxylic acids within a single molecule. For example, citric acid (three carboxyl groups) is
especially abundant in citrus fruits and it used as a flavoring and preservative in many foods and beverages.

Acyl halides

Acyl halides are commonly named by placing the names of the halide after the name of the acyl group. The
acyl group is obtained from the carboxylic acid by removal of its hydroxyl portion, i.e. R – C=O – OH leads
to R–CO – acyl group. The acyl group is named by using yl as the ending instead of ending ic in the
carboxylic acid. Some examples are:

18
IUPAC names for acyl groups use the ending oyl instead of ending e in the name of the corresponding
hydrocarbon. Acetyl chloride has the IUPAC name ethanoyl chloride. Another
example is which is named as 2-methylpropanoyl chloride,

Amides

An amide is a carbonyl in which the carbon is attached to one nitrogen atom and one carbon or hydrogen
atom. Alternatively, we could define an amide as an amine in which one of the carbon atoms attached to
the nitrogen is part of a carbonyl.

Amide

An amide can be formed by combining a carboxylic acid and an amine. Only primary and secondary amines
can be sued to form amides, since they have a hydrogen that can be replaced with the carbonyl carbon;
tertiary amines will not form amides. The amide shown in the figure above was formed from a carboxylic
acid and a primary amine.

The common names for acid amides are derived by replacing the suffix ic or oic of the carboxylic acid by
the suffix amide as shown below:

The compounds are called ethanamide (acetic - acetamide) and methanamide respectively.

Amides are used as coloring agents in crayons, pencils, and ink. They are employed in the paper, plastic,
and rubber industries. Polyacrylamide is a very widely used amide; it is involved in the treatment of drinking
water and sewage, and in plastics manufacture. The amide Kevlar is widely employed for the production of
body armor, and nylon is another type of amide-based polymer.

Acid anhydrides

A symmetrical anhydride is named as anhydride of the parent acid. Thus, CH3 – C=O – O – C=O – CH3, the
anhydride which is obtained from ethanic acid (common name: acetic acid) is commonly known as acetic
anhydride. The IUPAC name for this anhydride is ethanoic anhydride.

For mixed anhydrides, both the parent carboxylic acids are cited in alphabetical order, followed by the word
anhydride, as illustrated below:

ethanoic methanoic anhydride (common name: acetic formic anhydride)

Esters

An ester is similar to a carboxylic acid, in that it contains a carbonyl where the carbon is bonded to one
additional oxygen atom and one carbon or hydrogen atom. However, the second oxygen atom is bonded to
19
another carbon instead of to an acidic hydrogen atom. Structurally, carboxylic acids and esters are related
to one another in the same way as alcohols and ethers. As the ethers contain alkyl and alkanoyl (acyl)
groups, they are named as alkyl alkanoates. The alkyl group is cited first, followed by the name of the
alkanoyl (acyl) portion which is named by replacing the ic ending of the carboxylic acid by the suffix ate.

Esters can be formed by heating carboxylic acids and alcohols in the presence of an acid catalyst. This
process is reversible, and the starting materials can be regenerated by reacting an ester with water in the
presence of a weak base.

Some esters have very pleasant odors, so they are used in the manufacture of many perfumes. Propyl
acetate contributes to the odor of pears, while isoamyl acetate gives bananas their smell. This ester also
serves as an alarm signal for honeybees. Esters are employed in the manufacture of fabrics (polyesters) and
Plexiglass. Anesthetics such as procaine and benzocaine also contain esters.

Thiol
The thiol functional group contains a sulfur atom bonded to a hydrogen atom. It is very similar to an alcohol
functional group with the sulfur replacing the O. In naming thiols, an ending thiol is used as a suffix to the
name of the corresponding hydrocarbon; for example,

Thiols are also called mercaptans which is derived from the Latin phrase for "capturing mercury" because of
the strong bonds it forms with mercury-containing compounds. Some thiol compounds have a distinctive
smell similar to rotten eggs. They are often added to natural gas, which itself has no odor, as a way to
detect leaks since its odor can be detected by humans in very small amounts. A thiol group is also present
in the amino acid cysteine.

Amines
An amine consists of a nitrogen atom bonded to some combination of carbons and hydrogens.
Like alcohols, amines can be classified as primary, secondary, or tertiary. However, the rules for assigning
these categories are slightly different. In an alcohol, the oxygen atom is always bonded to exactly one
carbon atom, so we look at the branching on the adjacent carbon, not the oxygen atom itself. In a neutral
amine, the nitrogen can be bonded to one, two, or three carbon atoms, and this is how we decide whether
it is called a primary, secondary, or tertiary amine.

There are two systems of naming amines. One method names them as alkylamines and the other calls them
as alkanamines. The alkanamine naming system was introduced by Chemical Abstracts and is easier to use
as compared to the earlier IUPAC system of alkylamine names. The latest revision of IUPAC rules accepts
both systems and examples below are named in both ways.

20
(Note that the numbering starts at the carbon and not at the nitrogen of the amine part).

Primary diamines are named by using the suffix diamine after the name of the hydrocarbon.

For the secondary and the tertiary amines, the longest alkyl group present is considered as the parent
chain. The remaining alkyl groups are named as substituents attached to the nitrogen and a prefix N- is
used with the name of the alkyl group.

When used as a substituent, the – NH2 group is named as amino and is prefixed with a number indicating
the carbon atom to which it is attached.

Neutral amines are weak bases, because the lone pair on nitrogen can act as a proton acceptor. Many
smaller amines have very strong and offensive odors. For example, the aptly-named compounds cadaverine
and putrescine are foul-smelling amines, formed as a part of the decay process after death.

Amines serve a wide variety of uses. Diphenylamine acts as a stabilizer for certain types of explosives.
Amines are found as components in some lubricating materials, in developers, and are a part of
waterproofing textiles. Some amines, such as novocaine, are used as anesthetics. Many pharmaceutical
compounds contain amines, including 8 of the 10 most prescribed medications in 2012.

Nitriles
Nitriles are named in the IUPAC system by using the suffix – nitrile to the name of the hydrocarbon
corresponding to the longest carbon chain. Note that here the carbon of the nitrile group is included in the
numbering of carbon chain and is numbered as position 1. Some examples are given below:

21
When named as a substituent, the – CH group is called a cyano group. For example, the compound

is named as cyanomethyl ethanoate.

QUALITATIVE AND QUANTITATIVE CHEMISTRY

The main difference between qualitative and quantitative analysis chemistry is that qualitative analysis
determines whether or not different chemical components are present in a sample, whereas quantitative
analysis determines the amount of different chemical components present in a sample.

What Is Qualitative Analysis?

In chemistry, qualitative analysis is a branch of the subject that examines the chemical makeup of a
material. It denotes the presence of several elements or groupings of elements in the sample, such as
functional groups. As a result, a qualitative analysis of a sample can be utilized to establish whether or not a
specific component is present. However, no information regarding the quantity of that chemical component
is provided by this examination. Colour, aroma, melting point, boiling point, reactivity, precipitation, and
other characteristics of the sample are frequently evaluated in the analysis. There are two forms of
qualitative analysis: organic qualitative analysis and inorganic qualitative analysis. Organic qualitative
analysis, for example, determines the sample’s functional groups and chemical bonds, whereas inorganic
qualitative analysis, for the most part, determines the ions present in the sample.
The following chemical procedures can be employed in the qualitative examination of a sample:

 Variation in colour

 Extraction

 Precipitation

 Chromatography

 Spectroscopy

Qualitative Analysis in Chemistry Examples

Let’s look at a few examples to see how a sample’s qualitative analysis works.

1. Test for Iodine (An Organic Qualitative Analysis Technique) – The iodine test is used to determine
whether or not starch is present. Sugar is a type of organic substance. The indication is liquid iodine
in this case. To test, utilize a spot test (take a white tile and drop some drops of the samples to be
examined on it.) Then, for each drop of sample, add a drop of iodine solution. The presence of
starch is indicated by a change in the colour of the sample to a brown colour.

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 2. Test with a flame (An Inorganic Qualitative Analysis Technique) – The existence of a certain metal
or its ions can be determined via a flame test. The flame takes on varied hues depending on which
metal atoms are present. The presence of some metal ions can be determined based on the flame
colour produced when a part of the sample is burned in the Bunsen burner. Zinc, for example,
produces a green flame.

In Chemistry, What Is Quantitative Analysis?

In chemistry, quantitative analysis is a section of the subject that deals with the quantities of various
components in a sample. The quantity can be expressed as a mass, volume, concentration, relative
abundance, or any other number of ways. Quantitative analysis is carried out using chemical or physical
procedures.
There are two methods in quantitative analysis which are:

 Chemical methods – Chemical methods include titration methods, gravimetric methods, combustion
analysis techniques, and chemical reactions (for example, oxidation, reduction, precipitation,
neutralization, and so on).

 Physical methods – Physical methods examine one or more of a sample’s physical attributes. AES
(Atomic emission spectroscopy), x-ray fluorescence spectroscopy, mass spectroscopy, and other
techniques are examples. Most of the time, physical and chemical analysis techniques, together with
certain computations, are employed to identify the exact amount of a component in a sample.
However, several inferences and experimental errors can lead to erroneous final results.

Importance of Quantitative Analysis

For a variety of reasons, quantitative analysis of a sample is critical. It specifies how much reactant should
be used to perform a chemical synthesis reaction in order to obtain a specific amount of product, reducing
chemical waste (increasing atom economy). It can also be used to determine the quality of food or any
other product by indicating the presence of appropriate amounts of ingredients, as well as determining the
purity of a sample.

What Are The Similarities And Differences Between Qualitative And Quantitative Chemistry
Analysis?

Similarities:

 In chemistry, both qualitative vs quantitative analysis in chemistry are analytical procedures

 In chemistry, both qualitative and quantitative analysis techniques provide information on the
components of a sample
 The majority of the time, these strategies are combined (Ex: use qualitative analysis followed by
quantitative analysis).
Differences:

Qualitative Analysis Quantitative Analysis

In chemistry, qualitative analysis is a branch of the In chemistry, quantitative analysis is a section of
subject that examines the chemical makeup of a the subject that deals with the quantities of various
material components in a sample
Qualitative analysis determines the presence or Quantitative analysis determines the amount of
absence of several chemical components in a various chemical components contained in a sample
sample through analytical techniques
Employs procedures such as distillation, extraction, Titrations, gravimetric analysis, combustion
colour change, chromatography, and so on analysis, AES, and other techniques are used in
quantitative analysis in chemistry

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INSTRUMENTAL METHODS OF STRUCTURE DETERMINATION

 Nuclear Magnetic Resonance (NMR) – Excitation of the nucleus of atoms through

radiofrequency irradiation. Provides extensive information about molecular structure and atom
connectivity.
 Infrared Spectroscopy (IR) – Triggering molecular vibrations through irradiation with infrared
light. Provides mostly information about the presence or absence of certain functional groups.
 Mass spectrometry – Bombardment of the sample with electrons and detection of resulting
molecular fragments. Provides information about molecular mass and atom connectivity.
 Ultraviolet spectroscopy (UV) – Promotion of electrons to higher energy levels through
irradiation of the molecule with ultraviolet light. Provides mostly information about the presence of
conjugated π systems and the presence of double and triple bonds.

ISOLATION AND PURIFICATION OF ORGANIC COMPOUNDS

The isolation of organic compounds is of particular interest to the oil, pharmaceutical, cosmetic, and alcohol
production industries. Achieving a good separation requires a conscious selection of the technique to be
used, depending on the physical properties of the organic compounds. The purification of organic
compounds is necessary, though complex, step after its extraction from a natural source or synthesis in the
laboratory. The method of purification of the organic compound depends mainly on the nature of the
compound and the impurities present. One easy method to check the purity of an organic compound is to
either melt or boil it as organic compounds tend to have sharp melting and boiling points. Purification
means the removal of unwanted impurities present in an organic compound. The general methods of
purification are:
 Sublimation
 Crystallisation
 Distillation
 Differential Extraction
 Chromatography
Methods of Purification

a) Sublimation
Some solids can directly pass to the vapour state without going through the liquid phase. The purification
technique which exploits this property is called sublimation. It is helpful in separating sublimable
compounds from non-sublimable ones.

Methods of Purification - Sublimation

24
The substance is heated in a china dish above which an inverted funnel is kept to collect the sublimable
compounds. The funnel is kept cool so as to hasten the process. Vapours of the substance solidify on the
funnel.

b) Crystallisation
The principle here is that the compound and the impurities have different solubilities in a solvent. A solvent
is chosen where the compound to be purified is sparingly soluble, that is, it is sparingly soluble at lower
temperature and soluble at a higher temperature. The solution is heated to get a saturated solution, and on
cooling, the crystals of the compounds are removed via filtration.
For example, crystals of benzoic acid can be crystallised with water. Benzoic acid is sparingly soluble in cold
water and soluble in hot water. If the mixture contains impurities that have the same solubility as of the
compound to be purified, repeated crystallisation is performed.

c) Purification of Liquids - Distillation

The underlying principle behind distillation is that the mixture of liquids can be separated by the difference
in their boiling points. The boiling point is defined as that temperature at which the vapour pressure of the
liquid is equal to the atmospheric pressure. This method separates volatile liquids from non-volatile liquids.
The setup is given below.

Purification of Liquids – Distillation

The mixture is taken in the RB flask and boiled. The more volatile or the component with lower boiling point
evaporates faster and is collected in a separate container. A condenser is used to hasten the process of
condensation. For example, a mixture of chloroform and aniline can be separated by distillation. The boiling
point of chloroform is 60°C and that of aniline is 189°C. Therefore distillation can be used to separate a
mixture of chloroform and aniline.

Fractional Distillation

This method is employed when the difference between the boiling points of the liquids isn’t much. Since the
vapours of such liquids might condense together, a fractionating column is fixed to the mouth of the RB
flask.

25
Purification of Liquids – Fractional Distillation

Vacuum Distillation

Since the boiling point is dependent on the atmospheric pressure, the liquids will boil at a temperature
lesser than their boiling points if they were distilled in an atmosphere having lower pressure. This is
achieved by using a vacuum pump. Since the atmospheric pressure is reduced, the liquids also boil faster
and hence the whole process of distillation is made fast.

Process of Vacuum Distillation

26
 Steam Distillation
In this variant, steam is passed into the flask containing the liquids to be separated. The principle here is
that the liquids will boil faster because of aqueous tension (vapour pressure of water) helps in equalising
the atmospheric pressure.
Total pressure = Aqueous tension + vapour pressure of liquid components

In the absence of aqueous tension, the process of boiling would have been continued until it equalises the
atmospheric pressure. Now with the addition of steam, that process is expedited.

Purification of Liquids by Steam

Distillation

d) Differential Extraction
This method is used for immiscible liquids, that is, liquids that do not mix together. For example, oil and
water are immiscible.
The immiscible liquids are taken in a separating funnel and left undisturbed. After a while, they separate out
according to their specific gravities, with the heavier liquid at the bottom. Then they are later collected.

27
Substances can also be separated according to their preferential solubilities in the liquid. For example, if
phenol is to be extracted, it can be preferentially extracted using NaOH solution as one of the liquids used.

e) Chromatography

Chromatography is an important separation technique used to separate constituent particles of a mixture of

substances, to purify the compounds and check the purity of organic compounds. In this technique on a
stationary phase (solid or a liquid) a mixture of substance is applied. The mixture of gas or the pure solvent
is allowed to move slowly on the stationary phase. Due to which the components of the mixture start
separating from one another.

Principle of Chromatography

 Chromatography is a separation method where the analyte is contained within a liquid or gaseous
mobile phase, which is pumped through a stationary phase.
 Usually, one phase is hydrophilic and the other lipophilic. The components of the analyte interact
differently with these two phases.
 Depending on the polarity they spend more or less time interacting with the stationary phase and
are thus retarded to a greater or lesser extent.
 This leads to the separation of the different components present in the sample.

Chromatography is of two types:

Adsorption Chromatography and Partition Chromatography

1. Adsorption Chromatography

It is based on the principle that the constituents are adsorbed on an adsorbent in varying degrees. The
adsorbents used are generally silica gel or alumina. When a mobile phase moves over the fixed phase,
different constituents of the mixture get adsorbed at various distances over the fixed phase.

Adsorption Chromatography is further classified into:

 Column Chromatography
 Thin Layer Chromatography

Column Chromatography
Here, a mixture is separated over a column of either silica gel or alumina, packed in a glass column. The
constituent with the most affinity with the fixed phase is adsorbed at the top, and so on. It is then retrieved
by using an eluant. The solvent is then evaporated to get the constituent.

28
Thin Layer Chromatography

Here a sheet of alumina is taken (0.2 mm thick) over which a small spot of the mixture is placed and it is
kept in a suitable solvent. The solvent rises due to capillary action and the constituents also rise with the
solvent depending on their differential adsorption, and thereby, they are separated.

2. Partition Chromatography

Partition Chromatography technique is defined as the separation of components between two liquid phases
viz original solvent and the film of solvent used in the column.

Partition Chromatography Principle

The separation of the components from the sample mixture is carried out by the process of partition of the
components between 2 phases. Both phases are in liquid form. In this process, the immiscible solid surface
coated with the liquid surface on the stationary phase is in the mobile phase. The liquid surface is
immobilised by a stationary phase which results in making it a stationary phase. The mobile phase moves
from the stationary phase and components get separated. The separation depends on different partition
coefficients.

Partition Chromatography Diagram

29
Partition Chromatography Procedure;
Below we have explained the procedure to conduct Paper Chromatography Experiment for easy
understanding.
Apparatus required – chromatography jar, liquid impregnated paper (stationary phase), capillary tube (to
apply sample mixture), mobile phase (example chloroform, methanol, acetone, ethanol).

1. Take a clean and dry chromatography jar.

2. To make sure that the environment of the jar is saturated with solvent vapours, a paper
impregnated in the mobile phase is set to the walls.
3. Add the mobile phase to the jar. Around 0.5 cm to 1 cm from the bottom of the jar.
4. Close the jar.
5. Allow attaining equilibrium.
6. Mark the baseline on the adsorbent.
7. Apply sample to the paper with the help of a capillary tube.
8. Air-dry the sample spot.
9. Place the paper in the jar and close it.
10. Allow the system to stand till the solvent moves to some distance from the baseline.
11. Take out the paper and dry it.
12. If the sample components are separated, showing colours, then dry them in ordinary light. If it is a
colourless component, then dry it in a UV lamp.
13. Store the chromatogram
14. Calculate the Rf value.

Partition Chromatography Applications,

There are various applications of Paper Chromatography. Some of the applications are mentioned below:
 To separate and identify amino acids.
 To separate and identify tannins.
 To separate and identify alkaloids.
 To separate and identify carbohydrates.
 To separate and identify glycosides.

Types of Partition Chromatography,

1. Liquid-liquid Chromatography – It is a chromatography technique where a sheet of blotting paper, is
used instead of adsorption column. The components are separated based on their differential
migratory velocities. On separating, they are stained to make the chromatogram visible.
2. Gas-liquid Chromatography – A chromatography technique in which the separation of the mixture is
done by an inert gas along a tube. The tube is filled with finely divided inert solid. The solid is
coated with a non-volatile oil. The migration of each component occurs at a rate determined by its
solubility in oil as well as its vapour pressure.

Application of partition chromatography,

 Remove the detergent from the protein solution.
 Steroids, bile acids, and mycotoxins are separated.
 Pesticides, phenols, and insecticides are all being removed.
 Concentration of trace metals in aqueous solutions

30
PERIODIC PROPERTIES OF ELEMENTS

The basic law governing modern periodic table states that the properties of elements are periodic functions
of their atomic number. These properties reappear at regular intervals or follow a particular trend at regular
intervals. This phenomenon is known as the periodicity of elements.
The periodic properties of elements occur due to the recurrence of similar electronic configuration that is
having the same number of electrons in the outermost orbit. In a particular group, the number of valence
electrons remains the same. On the other hand, the number of valence electrons increases, as we move from
left to right across a period. The chemical property of an element depends on the number of electrons in the
valence shell.

The periodic properties of an element depend on valency and number of shells in an atom. As we move
down a group the number of shell increases successively such that the number of the shell of an element is
equal to the number of periods to which it belongs. As we move across a period, the number of shell
remains the same. For example, elements of the second period have two shells.

The combining capacity of an atom is known as its valency. It is equal to the number of electrons that an
atom can accept or donate in order to complete its octet. As we move down a group, the number of
electrons in the valence shell remains the same. Hence, the valency of a group is constant. Valency
depends on the number of electrons in the outermost shell of an atom. If the number of electrons is 1, 2, 3,
4 then the respective valences will be 1, 2, 3, 4. If the number of electrons in the outermost shell will be 5,
6, 7 then the valency will be 8 – 5 = 3, 8 – 6 = 2 and 8 – 7 = 1. Valency is the combining capacity of an
atom hence will always have a positive value and largely affects the periodic properties.

In a period, the number of electrons increases from left to right. As a result, the number of electrons
needed to complete the octet also changes. Hence, the valency successively increases to four in group 14
and then subsequently decreases to 1 in group 17.

STRUCTURE OF SOLIDS

Solid is one of the three main states of matter, along with liquid and gas. Matter is the "stuff" of the
universe, the atoms, molecules and ions that make up all physical substances. In a solid, these particles are
packed closely together and are not free to move about within the substance. Molecular motion for the
particles in a solid is confined to very small vibrations of the atoms around their fixed positions; therefore,
solids have a fixed shape that is difficult to change. Solids also have a definite volume; that is, they keep
their size no matter how you try to change them.

However, the main focus of this topic is to consider the solid phase of matter. A large majority of
substances around us are solids. The distinctive features of solids are:

 They have a definite shape.

 They are rigid and hard.
 They have fixed volume.

These characteristics can be explained on the basis of following facts:

 The constituent units of solids are held very close to each other so that the packing of the
constituents is very efficient. Consequently, solids have high densities.
 Since the constituents of solids are closely packed, it imparts rigidity and hardness to solids.
 The constituents of solids are held together by strong forces of attraction. This results in their having
definite shape and fixed volume.

31
Classification of solids
Solids are classified into categories
 Amorphous solids
 Crystalline solids

The two types of solids have different characteristics.

1. Amorphous Solids: An amorphous solid is a substance whose constituents do not possess an

orderly arrangement. Important examples of amorphous solids are glass and plastics. Although
amorphous solids consist of microcrystalline substance but the orderly arrangement is restricted to
very short distances. These distances are of the same order of magnitude as the interatomic
distances.
2. Crystalline Solids: A crystalline solid is a substance whose constituents possess an orderly
arrangement in a definite geometric pattern. Some very common examples of crystalline substances
are sodium chloride, sugar and diamond. The main characteristics of crystalline substances are:

 Orderly arrangement. The constituent units of crystalline solids are arranged in an orderly
fashion which repeats itself over very long distances as compared to interatomic distances.
The arrangement of bricks in a wall can be considered as an example. The arrangement is so
well defined that the entire pattern can be repeated provided the arrangement of a few
atoms is known.
 Crystals are always bounded by plane faces.
 The faces of crystals always meet at some fixed angles.

THE CHEMISTRY OF SELECTED METALS AND NON-METALS

Metals and Nonmetals are different types of materials present around us. Elements can be divided into
metals and nonmetals and it is important to know whether a particular element is a metal or nonmetal.
Metals (like copper and aluminium) are good conductors of heat and electricity, while nonmetals (such
as phosphorus and sulfur) are insulators. Materials are distinguished as above, based on their properties.
The Majority elements in the periodic table are metals. This includes alkali metals, transition metals,
lanthanides, actinides and alkaline earth metals. Metals are separated by non-metals on a periodic table
through a zigzag line starting from carbon, till radon. The elements between the two are phosphorus,
selenium and iodine.
These elements and elements right to them in the periodic table are non-metals. Elements present just to
the left of the line are termed as semimetals or metalloids. These will have the combined properties of both
metals and non-metals.
Non-metals occupy the upper right-hand portion of the periodic table. Considering the properties of non-
metals it is not shiny, malleable or ductile nor are they good conductors of electricity. These properties of
non-metals provide one means by which we can distinguish metals from non-metals.
Properties of Non-metals have less in common with each other than metals. Their physical and chemical
properties vary widely. Some non-metals are solids and some are gases at room temperature.

Physical Properties of Metals

 Shiny (lustrous) in nature
 Metal is a good conductor of electricity and heat
 Density and melting point is high
 Mouldable (Malleable)
 Ductile
 At room temperature, it is in solid form except for mercury
 Opaque
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Chemical Properties of Metals
 Easily corrodible
 Can lose electrons
 Form basic oxides
 Have low electronegativities
 Good reducing agents

Physical Properties of Non-metals

 Poor conductors of electricity and heat
 Non-Ductile metals
 Brittle solids
 Maybe solids, liquids or gases at room temperature
 These are not sonorous
 Transparent

Chemical Properties of Non-metals

 The number of electrons in the outer shell is generally 4-8
 Easily gain or lose valence electrons
 Form acidic oxides whenever they come in contact with oxygen
 High electronegative elements
 Great oxidizing agents

Non-metals and metals take different forms (allotropes). They have different shapes and properties.
Allotropes are elements that exist in two or more than two different physical forms.

 Example 1: A non-metal carbon – two allotropes of carbon are diamond and graphite.
 Example 2: A metal such as iron – two allotropes of iron are austenite and ferrite

Differences between Metals and Non-metals

Metals Non-metals
These are solids at room temperature except
These exist in all three states
mercury
These are very hard except sodium These are soft except diamond
These are malleable and ductile These are brittle and can break down into pieces
These are shiny These are non-lustrous except iodine
Electropositive in nature Electronegative in nature
Have high densities Have low densities

The Metalloids
The distinction between metals and nonmetals is somewhat fuzzy. Elements with properties of both metals
and nonmetals are called semimetals or metalloids. A stair-step line roughly divides metals from nonmetals
on the periodic table. But, chemists recognize that naming one element a "metal" and the one next to it a
"metalloid" is a judgement call. In truth, most metals display the properties of nonmetals under certain
conditions, and nonmetals act like metals in some situations.
Hydrogen is a good example of an element that acts as a non-metals sometimes, but as a metal other
times. Under normal conditions, hydrogen is a gas. As such, it acts like a nonmetal. But, under high
pressure it becomes a solid metal. Even as a gas, hydrogen often forms the +1 cation (a metallic property).
Yet, sometimes it forms the -1 anion (a nonmetal property).

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TRANSITION METALS

Transition metals (also known as transition elements) are metals that have partially filled d orbitals. IUPAC
defines transition elements as an element having a d subshell that is partially filled with electrons, or an
element that has the ability to form stable cations with an incompletely filled d orbital.

In general, any element which corresponds to the d-block of the modern periodic table (which consists of
groups 3-12) is considered to be a transition element. Even the f-block elements comprising the lanthanides
and the actinides can be considered as transition metals. However, since the f-block elements have
incompletely filled f-orbitals, they are often referred to as inner transition elements or inner transition
metals. It is important to note that the element’s mercury, cadmium, and zinc are not considered transition
elements because of their electronic configurations, which corresponds to (n-1)d 10 ns2.These elements have
completely filled d orbitals in their ground states and even in some of their oxidation states. One such
example is the +2 oxidation state of mercury, which corresponds to an electronic configuration of (n-1)d 10.

Electronic Configuration of Transition Elements

The list of the first two rows of transition elements with their corresponding electronic configurations is
tabulated below. It can be noted that in some of these elements, the configuration of electrons corresponds
to (n-1)d5 ns1 or (n-1)d10 ns1. This is because of the stability provided by the half-filled or completely filled
electron orbitals.
Transition Elements Atomic Number Electronic Configuration
Sc 21 [Ar] 3d1 4s2
Ti 22 [Ar] 3d2 4s2
V 23 [Ar] 3d3 4s2
Cr 24 [Ar] 3d5 4s1
Mn 25 [Ar] 3d5 4s2
Fe 26 [Ar] 3d6 4s2
Co 27 [Ar] 3d7 4s2

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 Ni 28 [Ar] 3d8 4s2
Cu 29 [Ar] 3d10 4s1
Zn 30 [Ar] 3d10 4s2
Y 39 [Kr] 4d1 5s2
Zr 40 [Kr] 4d2 5s2
Nb 41 [Kr] 4d4 5s1
Mo 42 [Kr] 4d5 5s1
Tc 43 [Kr] 4d5 5s2
Ru 44 [Kr] 4d7 5s1
Rh 45 [Kr] 4d8 5s1
Pd 46 [Kr] 4d10
Ag 47 [Kr] 4d10 5s1
Cd 48 [Kr] 4d10 5s2

It can be observed that the Aufbau principle is not followed by many transition elements like chromium. The
reason for this is believed to be the relatively low energy gap between the 3d and 4s orbitals, and the 4d
and 5s orbitals.

General Properties of Transition Elements

As discussed earlier, the elements zinc, cadmium, and mercury are not considered transition elements since
their electronic configurations are different from other transition metals. However, the rest of the d-block
elements are somewhat similar in properties and this similarity can be observed along each specific row of
the periodic table. These properties of the transition elements are listed below;

 These elements form coloured compounds and ions. This colour is explained by the d-d transition of
electrons.
 There is a relatively low gap in energy between the possible oxidation states of these elements. The
transition elements, therefore, exhibit many oxidation states.
 Many paramagnetic compounds are formed by these elements, because of the unpaired electrons in
the d orbital.
 A large variety of ligands can bind themselves to these elements. Due to this, a wide variety of
stable complexes are formed by transition elements.
 These elements have a large ratio of charge to the radius.
 Transition metals tend to be hard and they have relatively high densities when compared to other
elements.
 The boiling points and the melting points of these elements are high, due to the participation of the
delocalized d electrons in metallic bonding.
 This metallic bonding of the delocalized d electrons also causes the transition elements to be good
conductors of electricity.

Uses of Transition Metals?

Several transition metals have catalytic properties that are very useful in the industrial production of some
chemicals. For example, iron is used as a catalyst in the Haber process of preparing ammonia. Similarly,
vanadium pentoxide is used as a catalyst in the industrial production of sulfuric acid. Iron, a transition
metal, is widely used in the construction industry. It is usually alloyed into steel, which exhibits greater
tensile strength and versatility. Iron is also used as a catalyst for the industrial production of ammonia via
the Haber process. Titanium, another transition metal, is used in aircrafts, piping for nuclear power plants,
and in artificial hip replacements. The primary application of the transition element nickel is in the
production of stainless steel. Copper, a transition metal, is widely used in electrical wiring because of its
high tensile strength, malleability, ductility, and electrical conductivity.

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Why some Transition Metals referred to as Noble Metals
Some elements in the lower right corner of the d-block on the modern periodic table (such as gold, silver,
and platinum) are often referred to as noble metals. These metals are highly unreactive owing to their low
enthalpies of hydration and high ionization enthalpies. These metals are highly resilient towards acids.
However, metals like platinum, mercury, and gold can be dissolved in some acid mixtures such as aqua
regia (a mixture of hydrochloric acid and nitric acid). It can be noted that silver does not dissolve in aqua
regia.

Reason behind the High Melting/Boiling Points of Transition Elements

The presence of unpaired electrons leads to the formation of metal-metal covalent bonds along with the
metallic bonds. These strong bonds attribute high melting and boiling points to the elements. The presence
of a partially filled d-orbital enables the transition elements to have a greater number of unpaired electrons,
which in turn increases their ability to form covalent bonds along with metallic bonds. For example, the
elements with the greatest number of unpaired electrons (chromium, molybdenum, and tungsten) have the
greatest melting and boiling points in their respective rows. On the other hand, metals such as zinc and
mercury do not hold any unpaired electrons and hence have relatively low boiling and melting points.

Group 1 or 1A Elements

The alkali metals make up Group 1 of the periodic table. This family consists of the elements lithium,
sodium, potassium, rubidium, cesium, and francium (Li, Na, K, Rb, Cs, and Fr, respectively). Group one
elements share common characteristics. They are all soft, silver metals. Due to their low ionization energy,
these metals have low melting points and are highly reactive. The reactivity of this family increases as you
move down the table. Alkali metals are noted for how vigorously they react with water.
The alkali metals (again, except for hydrogen) react vigorously with water, producing the metal hydroxide,
hydrogen gas, and heat.
2M(s) + H2O(l)  MOH(aq) + H2(g)

Ionic Meltin
Electron Usual Atomic (M+) Ionization g
Symb Configurati Oxidatio Radius/p Radius/p Energy/MJ Density/ Electronegativi Point
Element ol on n State m m mol–1 g cm–3 ty (in °C)
First Second
0.52
Lithium Li [He]2s1 +1 122 60 6 7.305 0.534 1 179
0.50
Sodium Na [Ne]3s1 +1 157 95 2 4.569 0.97 0.9 98
Potassiu 0.42
m K [Ar]4s1 +1 202 133 5 3.058 0.86 0.8 64
Rubidiu 0.40
m Rb [Kr]5s1 +1 216 148 9 2.638 1.52 0.8 39
0.38
Cesium Cs [Xe]6s1 +1 235 169 2 2.43 1.87 0.7 28

The alkali metals are so named because when they react with water they form alkalies. Alkalies are
hydroxide compounds of these elements, such as sodium hydroxide and potassium hydroxide. Alkalies are
very strong bases that are caustic. Alkalies react with acids to form salts.

2Na (s) + 2HCl (aq) → 2 NaCl (aq) + H2 (g) ↑

General properties of the first group elements (Alkali metals)

1. The presence of a single electron in the outer energy level.
2. Their atoms have the largest atomic volume.

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 3. They give characteristic colours (atomic spectra) when the electron of these elements is excited to a
higher energy level.
4. They react with water, oxygen, hydrogen, acids, non-metals, atmospheric air etc.
5. Most of their oxygenated salts are thermally stable.

Group IV-A Elements

This group of elements is placed in middle of periodic table. Group 4A (or IVA or group 14) elements of the
modern periodic table includes the nonmetal carbon (C), the metalloids silicon (Si) and germanium (Ge), the
metals tin (Sn) and lead (Pb), and ununquadium (Uuq).

Melting and Boiling Point of group 4 A elements:

Carbon, Silicon and Germanium have giant atomic structures and they have strong covalent bonds so their
melting points are high. A decrease in melting point from C to Ge is due to increasing atomic size because
of which covalent bonds are weakened. Sn and lead are metals and their atoms are bigger so their metallic
bonding is weak hence their melting points are low.
Metallic character decreases down the group. In group IV-A Change from non-metal occurs. Carbon and
Silicon are non-metals, Ge is metalloid while Sn and Pb are metals.

Oxidation states:
Carbon shows +4 (as in CCl4), -4 (as in Be2C), -1 (as in Na2C2) oxidation states.
Silicon shows a +4 oxidation state.
Ge, S, and Pb show +2 and +4 oxidation states. So the most common oxidation state is +4.

Inert Pair Effect:

“The tendency of an element not to involve its pair of electrons of s orbital in bond formation is named as
inert pair effect.”

If hybridization occurs then electrons of the s-orbital will not be inert and if no hybridization occurs then
electrons of the s-orbital will be inert.

1. Promotion of one of s-electron to p-orbital followed by sp3 hybridization of orbitals needs energy to
be provided for the process.
2. The formation of four covalent bonds involving the hybrid orbitals releases energy.

If the energy released in the formation of four covalent bonds is more than the energy absorbed in the
promotion of an electron from s-orbital to p-orbital, then hybridization will occur and the element will not
show an inert pair effect.
On the other hand, If the energy released in the formation of four covalent bonds is less than the energy
absorbed in the promotion of an electron from s-orbital to p-orbital, then no hybridization will occur and the
element will show an inert pair effect.
Inert pair effect increases down the group. As atomic radius increases down the group and bigger atoms
make weak covalent bonds so energy released during bond formation is less than the energy absorbed
during the promotion of an electron from s to p so no hybridization occurs and s-electrons remain inert.
Elements on the top of group 4 show no inert pair effect thus their oxidation state in the compounds will be
+4 while lead being a larger atom often shows inert pair effect and in its most compounds its oxidation
state is +2. Higher oxidation state tends to the covalent bond formation while a lower oxidation state tends
to ionic bond formation. So Carbon forms covalent bonds while lead (Pb) forms ionic bonds.

Oxides:
Group IV-A elements make two types of oxides i.e. monoxides (CO, SnO and PbO) and dioxides (CO 2, SnO2
and PbO2).

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Nature of oxides:
Carbon and Silicon are non-metals so their oxides are covalent. Whereas Tin and Lead are metals so their
oxides are ionic.

Chlorides:
Carbon, silicon and lead form tetrachlorides (CCl4, SiCl4 and PbCl4). As these elements are sp3 hybridized so
their tetrachlorides are tetrahedral. The stability of chlorides decreases from CCl4 to PbCl4. Thus PbCl4
decomposes to give PbCl2. PbCl4 → PbCl2 + Cl2.
Stability of +4 oxidation state decreases down the group so C and Si form only CCl 4, SiCl4 while Pb often
forms PbCl2.
CCl4 does not react with water as water cannot reach carbon as carbon is a small atom and four big Cl
atoms are around it. SiCl4 to PbCl4 reacts violently with water producing their oxides.
SiCl4 + 2H2O → SiO2 (White) + 4HCl
PbCl4 + 2H2O → PbO2 + 4HCl
PbCl2 is ionic so it just gets dissolves in water.
PbCl2 ⇌ Pb2+ + 2Cl–

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