DOUBT

CLEARING
CLASS
FOR AKSHITA SHRIVASTA
MISSION IIT-JEE

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By Prateek Khanna
QUESTION

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By Prateek Khanna
SOLUTION

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QUESTION 2

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SOLUTION 2

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LIGANDS: SPECTROCHEMICAL SERIES

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IMPORTANT POINT
When ligands have vacant π* and d orbitals of suitable energy, there is the possibility of pi
backbonding, and the ligands may be π acceptors. This addition to the bonding scheme
increases Δ. Ligands that do this very effectively include CN−, CO, and many others

The metal ions can also be arranged in order of increasing Δ, and this order is largely
independent of the identity of the ligand.
Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ < Co3+
In general, it is not possible to say whether a given ligand will exert a strong field or a weak
field on a given metal ion. However, when we consider the metal ion, the following two useful
trends are observed:
Δ increases with increasing oxidation number, and
Δ increases down a group.

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IMPORTANT POINT

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QUESTION 3

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SOLUTION

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By Prateek Khanna
QUESTION
For the square planar complex [Mabcd] where M is the central atom and a,b,c,d are monodentate
ligands, the number of possible geometrical isomers are:

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SOLUTION

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CONCEPT CIRCULAR PERMUTATION

There are some arrangements which are circular in nature. For example
consider the roundtable conference, making of a necklace with different
coloured beads. These are like arranging the items in a closed loop. The
number of ways of counting associated with the circular arrangement
gives rise to a circular permutation.

Suppose we have four chairs around the roundtable and we need to

make arrangement for four persons A, B, C, and D. Any of the persons
can take any of the positions. But as soon as one of them takes a chair,
the number of options reduces by one for the other three persons. And at
last, there is only one chair for the last person.

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or the above situation, four persons A, B, C, and D can arrange themselves in 4!
ways if they are to be arranged in a row. As in a linear permutation i.e, in a row
arrangement, there is a start and there is an end. We need to take into
consideration the position of all the persons in the arrangement. But in the
circular permutation, there is nothing like a start or an end.
In the circular permutation, we consider that one person or object is fixed and the
remaining persons are to be arranged. Suppose the position of A is fixed. The
number of ways in which the other three persons arrange themselves When one
of them has a fix position is (4 − 1)! = 3! = 6.

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QUESTION
Find the number of ways in which 10 beads can be arranged to form a necklace.

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SOLUTION

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CONCEPT OF AMBIDENTATE LIGANDS

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QUESTION

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SOLUTION
To answer this question, you must recall the concept of isomerism in coordination compounds. Coordination compounds
exhibit broadly two types of isomerism, namely structural and stereoisomerism.
The given coordination complex is given to have a square planar structure. The central metal ion has been coordinated
by four different ligands.

Since all the ligands are different, we can conclude that the compound can form 3 geometrical isomers.
However, we know that an ambidentate ligand shows linkage isomerism as well. In simpler terms if a ligand has more
than one donor atoms, the complex will have additional structural isomers.

In the given compound, we have two ambidentate ligands, namely the nitro group and the thiocyanate group. Both the
ligands are bidentate.

In the nitro group, the two donor atoms are the nitrogen atom and the oxygen atom.
In the thiocyanate group, the two donor atoms are the nitrogen atom and the sulphur atom.

Thus, it is evident that each bidentate ligand has two linkage isomers and each linkage isomer, in turn, forms three
geometrical isomers.
Therefore, the total number of isomers of the given compound =2×2×3=12=2×2×3=12.

The total number of possible isomers for the square planar coordination complex [Pt(Cl)(NO2)(NO3)(SCN)]2 -
[Pt(Cl)(NO2)(NO3)(SCN)]2 - is 12.

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IMPORTANT POINT
Coordination compounds also show optical isomerism. These are a pair of molecules which are non-superimposable
mirror images of each other. Optical isomers of a compound have identical physical and chemical properties. They
only differ in terms of the direction in which they rotate plane-polarized light.

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OPTICAL ISOMERISM

Optical isomers are two compounds which contain the same number and kinds of atoms, and bonds (i.e., the
connectivity between atoms is the same), and different spatial arrangements of the atoms, but which have non-
superimposable mirror images. Each non-superimposable mirror image structure is called an enantiomer.
Molecules or ions that exist as optical isomers are called chiral.

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 OPTICAL ISOMERISM IN COORDINATION
COMPOUNDS
Optical activity refers to whether or not a compound has optical isomers.

A coordinate compound that is optically active has optical isomers and a coordinate compound that
is not optically active does not have optical isomers.

Optical isomers have the unique property of rotating light. When light is shot through a polarimeter,
optical isomers can rotate the light so it comes out in a different direction on the other end. Armed
with the knowledge of symmetry and mirror images, optical isomers should not be very difficult.

There are two ways optical isomers can be determined: using mirror images or using planes of
symmetry.

Optical isomers do not exhibit symmetry and do not have identical mirror images. Let's go through a
quick review of symmetry and mirror images. A mirror image of an object is that object flipped or
the way the object would look in front of a mirror. For example, the mirror image of your left hand
would be your right hand. Symmetry on the other hand refers to when an object looks exactly the
same when sliced in a certain direction with a plane. For example imagine the shape of a square. No
matter in what direction it is sliced, the two resulting images will be the same

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METHOD 1: THE "MIRROR IMAGE METHOD"
The mirror images method uses a mirror image of the molecule to determined whether optical isomers exist or not. If the mirror
image can be rotated in such a way that it looks identical to the original molecule, then the molecule is said to be superimposable
and has no optical isomers. On the other hand, if the mirror image cannot be rotated in any way such that it looks identical to the
original molecule, then the molecule is said to be non-superimposable and the molecule has optical isomers. Once again, if the
mirror image is superimposable, then no optical isomers but if the mirror image is non-superimposable, then optical isomers exist.
Definition of Non-superimposable
Non-superimposable means the structure cannot be rotated in a way that one can be put on top of another. This means that no
matter how the structure is rotated, it cannot be put on top of another with all points matching. An example of this is your hands.
Both left and right hands are identical, but they cannot be put on top of each other with all points matching.

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METHOD 2: THE "PLANE OF SYMMETRY METHOD"
The plane of symmetry method uses symmetry, as it's name indicates, to identify optical isomers. In this method, one
tries to see if such a plane exists which when cut through the coordinate compound produces two exact images. In other
words, one looks for the existence of a plane of symmetry within the coordinate compound. If a plane of symmetry
exists, then no optical isomers exist. On the other hand, if there is no plane of symmetry, the coordinate compound has
optical isomers. Furthermore, if a plane of symmetry exists around the central atom, then that molecule is
called achiral but if a plane of symmetry does not exist around the central molecule, then that molecule has chiral
center.

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WHAT IS A POLARIMETER?
A polarimeter is a scientific instrument used to measure the angle of rotation caused by passing polarized light
through an optically active substance. Some chemical substances are optically active, and polarized (uni-directional)
light will rotate either to the left (counter-clockwise) or right (clockwise) when passed through these substances. The
amount by which the light is rotated is known as the angle of rotation. The angle of rotation is basically known as
observed angle.

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 Schematic of a polarimeter showing the
principles behind it's operation.
Unpolarized light is passed through a
polarizing filter before traveling through
a sample.

The degree of rotation of polarization is

determined by a second, rotatable filter.

The polarimeter is made up of a polarizer (#3 on Figure) and an analyzer (#7 on Figure).

The polarizer allows only those light waves which move in a single plane.

This causes the light to become plane polarized. When the analyzer is also placed in a similar position

it allows the light waves coming from the polarizer to pass through it. When it is rotated through the right angle no waves can pass through the right angle
and the field appears to be dark.

If now a glass tube containing an optically active solution is placed between the polarizer and analyzer the light now rotates through the plane of polarization
through a certain angle, the analyzer will have to be rotated in same angle.

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QUESTION

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SOLUTION

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IMPORTANT POINTS

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QUESTION

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SOLUTION

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SOLUTION

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QUESTION

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SOLUTION

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QUESTION

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SOLUTION

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QUESTION

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SOLUTION

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