Coordination Number

❖ The number of ligand atoms that are bonded directly to the central metal ion is
called the coordination number.

❖ The coordination number is specific for a given metal ion in a particular oxidation
state and compound.

❖ [Zn(NH3)4]2+ ❖ [Co(NH3)6]3+
❖ Coordination number : 4 ❖ Coordination number : 6

SRMIST/RMP/I BTECH/CHEMISTRY
 Geometry

❖ The geometry of a complex ion depends on the coordination number and nature of
the metal ion.

❖ The geometrical pattern can be described as a polyhedron where the vertices of

the polyhedron are the centers of the coordinating atoms in the ligands.

SRMIST/RMP/I BTECH/CHEMISTRY
 Coordination Number: 2

• Geometry - Linear.
• This geometry provides the minimum ligand repulsion.
• Cu+, Ag+, Au+ and in some cases Ag2+ form such complexes.

- -
• Example: [Cu(CN)2] , [Cu(NH3)2]2+, [Hg(CN)2] , [CuCl2] [Ag(CN)2] -

SRMIST/RMP/I BTECH/CHEMISTRY
 Coordination Number: 3
• Two possible geometries are exhibited by the complexes with CN =3
(1) Equilateral triangular in which the (2) Trigonal pyramidal
ligands are arranged at the corners of a Example: [H3O]+
slightly distorted equilateral triangle
with the metal ion at its center.
Example: [Hgl3]-

SRMIST/RMP/I BTECH/CHEMISTRY
 Coordination Number: 4
• Two possible geometries exhibited by complexes with CN=4

(1) Tetrahedral - Examples: (2) Square planar – Examples:

Oxyanions

and

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Coordination Number: 5
• Complexes with coordination number 5 may be trigonal bipyramidal or square
pyramidal.
(1) Trigonal bipyramidal geometry- Examples: (2) Square pyramidal geometry- Examples:

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Coordination Number: 6
• Possible arrangements of six ligands in the complexes:
(1) Six ligands at corners of the hexagonal plane (2) Six ligands at Apices of a trigonal prism

(3) Six ligands at Apices of a regular octahedron

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Crystal Field Theory

VBT (1930 s) ’ L. Pauling

Failures of VBT

1. Tetrahedral or Square planar ??

2. Distortions in complexes – No

3. Colour of Complexes (optical spectra) ??

4. Temperature dependence of Magnetic Properties

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Crystal Field Theory (C.F.T)

• Crystal Field Theory was proposed by the physicist Hans Bethe and Van Vleck in 1929.

• This theory (CFT) largely replaced VB Theory for interpreting the chemistry of
coordination compounds.

• This theory was applied originally to ionic crystals and is therefore called crystal field
theory.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Postulates of crystal field theory
1. In a coordination compound there is the electrostatic interaction between
metal atom/ion and ligands.

2. Ligand is assumed to be a point charge.

3. In an isolated metal atom or ion, all five d-orbitals have equal energy, i.e.,
degenerate.

4. When metal atom/ion gets surrounded by ligands, there occurs interaction

between the d-electron cloud of metal atom/ion and ligand.

5. If the field due to ligand around a metal atom is spherically symmetrical, d-

orbitals of metal remain degenerated.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Crystal Field Theory (C.F.T)

6. If filed due to ligand surrounding metal is unsymmetrical the degeneracy of d-orbitals is

split into two sets of orbitals.

7. Orbitals lying in the direction of ligands are raised to a higher energy state than those
orbitals lying between the ligands.

8. The energy difference between two sets of orbitals is denoted by ∆o for octahedral and
∆t for tetrahedral.

9. The magnitude of ∆o and ∆t depends upon the field strength of the ligand around the
metal.

10. Ligands that cause larger splitting ( large ∆) are called strong field ligands while those
which cause small splitting (small ∆) are called weak field ligands.
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Limitation of Crystal field theory
▪ The crystal field model is successful in explaining the formation, structures, color, and
magnetic properties of coordination compounds to a large extent.

▪ However, from the assumptions that the ligands are point charges, it follows that anionic
ligands should exert the greatest splitting effect.

▪ The anionic ligands are found at the low end of the spectrochemical series.

▪ Further, it does not consider the covalent character of bonding between the ligand and
the central atom.

▪ These are some of the weaknesses of CFT, which are explained by ligand field theory
(LFT) and molecular orbital theory
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 The shape of ‘d’-Orbitals

❑ Five d- orbitals of the center metal ion can be

divided into two different sets of orbitals.
❑ Three orbitals namely dxy dyz and dzx orbitals
are known as t2g set of d orbitals. All these
orbitals are present between the axis which is
also known as the Nonaxial set of d- orbitals.
❑ Two orbitals namely dx2-y2 and dz2 are
combinedly known as eg set of d orbitals.
❑ Both these orbitals are present over the axis due
to which they are also known as an axial set of d-
orbitals.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 ‘d’ orbital splitting in octahedral complexes
The octahedral arrangement of six ligands surrounding the central metal ion can be shown as:

• It is obvious from the figure, that ligands approaching the x, y, and

z-axis.

• The two d-orbitals namely d(x2 –y2 ) and d(z2 ) will suffer more
electrostatic repulsion and hence their energy will be greater than
the other three orbitals d(xy), d(yx), and d(xz) which will have
their lobes lying between the axis.

• Thus the degenerate set of d-orbitals split into two sets:

• eg orbitals of higher energy including d(x2 –y2) and d(z2).

• t2g orbitals of lower energy including d(xy), d(yx), and d(xz).

SRMIST/RMP/I BTECH/CHEMISTRY
 ‘d’ orbital splitting in octahedral complexes
• The crystal field splitting is
measured in terms of the energy
difference between t2g and eg
orbital and is denoted by a symbol
∆o.

• It is generally measured in terms of

Dq.

• It is called crystal field splitting

energy (or) crystal field stabilization
energy (CFSE).
CFSE= −0.4 x n(t2g) + 0.6 x n(eg)o

▪ Where n(t2g) and n(eg) are the no. of electrons occupying the respective levels.
▪ If CFSE is very large, pairing occurs (i.e. CFSE > P).
▪ If CFSE is rather small, no pairing occurs (i.e P > CFSE).
SRMIST/RMP/I BTECH/CHEMISTRY
 Spectrochemical series
▪ Crystal field splitting is greatly influenced by the nature of ligands.

▪ Different ligand causes different degrees of splitting of d-orbital of metal ion in the complexes.

▪ Ligands that cause larger crystal field splitting are called strong field ligands.

▪ Similarly, those ligands which cause smaller crystal field splitting are called weak field ligands.
▪ The experimental observation of spectra of a series of complexes of the same metal ion with different ligands
shows that the values of crystal field splitting energy vary depending on the ligands’ nature.

• The arrangement of ligands in a series in the order of increasing crystal field splitting is
called spectrochemical series.

• (Weak field ligands)

• I− < Br− < S2− < SCN− < Cl− < NO3− < N3− < F− < OH− < C2O42− < H2O <NCS− <CH3CN < py < NH3< en < bipy < phen < NO2− < PPh3 < CN− < CO
(Strong field ligands)

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Factor affecting the position of Ligands in series

• The series is experimentally determined but it is difficult to explain theoretically.

However, the relative position is based on their increasing σ donation.
• The ligands with a high negative charge and small size and having good σ donor and π-
acceptor properties give large crystal field splitting and occupy the top position of the
series as strong ligands.
• In contrast, ligands that act as π-donor occupy a bottom position as weak field
ligands.

• A pattern of increasing σ donation is as follows:

Halides donors < O donors < N donors < C donors

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Significance of Spectrochemical series

• Spectrochemical series can be used to predict the relative d-orbital splitting of

two complexes containing the same metal ion with different ligands.

• Similarly, the relative frequency of the absorption band can be predicted.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Limitation of Spectrochemical series

1.The anionic ligands would exert the greatest effect, but they are at the low end.

2.OH– should lie above neutral H2O but the order is reversed.

3.NH3 produces a greater splitting than H2O although their dipole moments are in reverse
order (μNH3 = 4.90 × 10-30 cm; μH2O = 6.17 × 10-30 cm)

4.The model is also unable to account for the fact that with certain strong field ligands
(such as CN-) , Δo varies only slightly for the analogous complexes within a group.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 CRYSTAL FIELD STABILIZATION ENERGY (CFSE)

• The energy difference between the distribution of electrons in a particular crystal field and that

for all electrons in the hypothetical spherical or uniform field levels is called the crystal field

stabilization energy (CFSE).

• As we have seen, the energy difference between t2g and eg orbital is defined as Δo.

• The energy level of each of the two eg orbital would be 0.6 Δo above the zero of energy

(barycenter) .

• whereas the energy level of each of the three t2g orbitals would be 0.4 Δo below the zero energy.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 CRYSTAL FIELD STABILIZATION ENERGY (CFSE)
CFSE= −0.4 x n(t2g) + 0.6 x n(eg)o

• Consider the example, the Ti (H2O)6 3+ ion . Ti3+ has a d1 electron configuration with the
electron occupying t2g, the crystal field stabilization energy (CFSE) is -0.4 Δo .

• For d2 , the CFSE = -0.8 Δo. For d3 , CFSE = -1.2 Δo.

• Upon reaching the d3 configuration, however, the t2g level becomes half-filled and there are no
further orbital of this energy to accept electrons without pairing.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 CRYSTAL FIELD STABILIZATION ENERGY (CFSE)

• For configurations d4 , d5 , d6 and d7 two possibilities arise.

• The determining factor whether high-spin or low-spin complexes arise is the ligand-field splitting
parameter.

• When Δo is larger than the pairing energy P for the electrons, the electron pair in the t2g orbitals
as far as possible.

• If the energy required for pairing up the electrons (electrostatic repulsion) is greater than Δo, the
electrons will be distributed between t2g and eg levels.

• In the former case we have the strong-field (Δo> P) arrangement with low-spin complexes.

• While in the latter we have the weak-field (Δo< P) arrangement with high-spin complexes.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 CRYSTAL FIELD STABILIZATION ENERGY (CFSE)

• With d8 , d9 and d10 configurations there is only one possible way for distributing the electrons
between the t2g and eg orbital.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
Calculation of CFSE in an Octahedral Complex

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 ‘d’ orbital splitting in tetrahedral complexes
The tetrahedral arrangement of four ligands surrounding the metal ions can be shown as:
• It is obvious from the figure that none of the d-orbital points
exactly towards the ligands.

• However, three d-orbitals d(xy), d(yz), and d(zx) are pointing close
towards ligands.

• As a result of this, the energy of these three orbitals increases

much more than the other two d- orbitals d(x2 –y2 ) and d(z2 ).

• The d-orbitals thus split into two sets of orbitals: t2g orbitals of
higher energy including d(xy), d(yz), d(xz), and eg orbitals of lower
energy including d(x2 –y2 ) and d(z2 ).

• However, splitting is much smaller than that in octahedral

complexes.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 ‘d’ orbital splitting in tetrahedral complexes
• The crystal field splitting is
measured in terms of the energy
difference between eg and t2g
orbital and is denoted by a symbol
∆t.

• It is generally measured in terms of

Dq.

• It is called crystal field splitting

energy (or) crystal field stabilization
energy (CFSE).

▪ Negative sign denotes that the order of splitting in tetrahedral complexes is reverse of that in
octahedral complexes.
▪ Because of the small value of ∆t, electrons generally do not pair and result in the formation of a high-
spin complex.
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Why Tetrahedral complexes are High Spin?
▪ There are only 4 ligands in the tetrahedral complex and hence the ligand field is roughly 2/3 of the
octahedral field.

▪ The direction of the ligand approach in the tetrahedral complex does not coincide with the d-
orbitals. This reduces the field by a factor of 2/3.

▪ Therefore, Δt is roughly 2/3 × 2/3 = 4/9 of Δo.

▪ As a result, all tetrahedral complexes are high-spin since the Δt is normally smaller than the paring
energy (P).

▪ Hence, low spin configurations are rarely observed.

▪ Usually, if a very strong field ligand is present, square planar geometry will be favored.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 When do we expect tetrahedral geometry?

▪ Small metal ions and large ligands (Cl-, Br- and I- ) because then ligand-ligand repulsions cancel the
energy advantage of forming more metal-ligand bonds.

▪ Metal ions with zero CFSE (d0 , d5 , d10) or small CFSE (d2 and d7 ).

• Examples:

▪ MnO4 - (d0 )

▪ FeCl4 - (d5 , H.S.)

▪ CoCl4 2- (d7 , H.S.)

▪ ZnCl4 2- (d10)

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Crystal Field Stabilization Energy in Tetrahedral Complexes
▪ The CFSE value in the case of tetrahedral complexes can be calculated by using the relation

▪ Where x and y represent the number of electrons in the lower eg and the upper t2g level and n is
number of electron pairs present in both the levels.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Introduction to optical property
▪ The human eye perceives a mixture of all the colors, in sunlight, as white light.

Complementary colour wheel

▪ Complementary colors, those located across from each other on a color wheel, are
also used in color vision.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪The eye perceives a mixture of two complementary colors,
in the proper proportions, as white light.

▪when a one of colour is missing from white light, the eye

sees its complement.

▪ when violet photons are absorbed from white light, the

eyes see the lemon yellow colour.

▪When red photons are removed from white light, the eyes
see the green colour
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪If the white light (ordinary sunlight) passed
through [Cu(NH3)4]SO4 solution it appears to
be blue colour .

▪The [Cu(NH3)4]2 ions in the solution absorb

light in the red region of the spectrum leaving
the complementary colors of blue
▪

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪ The colour what we observe at an object or a compound is due to
light that is transmitted or reflected, not light that is absorbed

▪ The reflected or transmitted light from the object is complementary

in color to the light that is absorbed.

▪ Thus a green compound absorbs light in the red portion of the visible
spectrum and vice versa, as indicated by the complementary color
wheel.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
Optical property of transisition elements
▪ The striking colors exhibited by transition-metal complexes are
caused by excitation of an electron from a lower-energy d
orbital to a higher-energy d orbital - d–d transition
▪ For a photon to effect such a transition, its energy must be
equal to the difference in energy between the two d orbitals,
which depends on the magnitude of Δ . o

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
In a d–d transition of an octahedral complex, an electron in one of the
t2g orbitals of an octahedral complex such as the [Cr(H2O)6]3+ ion absorbs a
photon of light with energy equal to Δo, causes the electron to move to an
empty or singly occupied eg orbital.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪Small changes in the relative energies of the orbitals that
electrons are transitioning between can lead to drastic shifts
in the color of light absorbed.
▪The colors of coordination compounds depend on many
factors.
▪Different aqueous metal ions can have different colors.
▪ Different oxidation states of one metal can produce
different colors,

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪ The specific ligands coordinated to the metal center also influence the
color of coordination complexes.
▪ Because the energy of a photon of light is inversely proportional to its
wavelength, the color of a complex depends on the magnitude of Δo,
which depends on the structure of the complex.
▪ Strong-field ligands cause a large split in the energies of d orbitals of
the central metal atom (large Δoct).
▪ Transition metal coordination compounds with these ligands are
yellow, orange, or red because they absorb higher-energy violet or
blue light.
▪ On the other hand, coordination compounds of transition metals with
weak-field ligands are often blue-green, blue, or indigo because they
absorb lower-energy yellow, orange, or red light.
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪The complex [Cr(NH3)6]3+ has strong-field ligands relatively large
Δo. Consequently, it absorbs relatively high-energy photons,
corresponding to blue-violet light, which gives it a yellow color.

▪ A related complex [Cr(H2O)6]3 weak-field ligands, the + ion,

absorbs lower-energy photons corresponding to the yellow-green
portion of the visible spectrum, giving it a deep violet color.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Introduction to Magnetic property

▪ One of the most valuable fields of application of magneto chemistry is

the investigation of transition metal complexes.

▪ Magnetic measurements indicate the electronic configuration of the d-

shell of the transition metal.

▪ Magnetic measurements can provide information on the electronic

structure and oxidation state, and in some cases on the symmetry
properties of the transition metal central

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 What isMagnetism?

▪ Magnetism is a phenomenon of attracting magnetic substances like

iron, nickel, cobalt, etc.

▪ Magnetism is a property of materials that respond to an applied

magnetic field that cause the material to be either attracted or repelled.

▪ A body possessing the property of magnetism is called a magnet.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
Elements that can be magnet

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
Types of Magnetisms

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪ Diamagnetism, which is shown by every molecule. This is
due to the inductive action of the external magnetic field on
the electron cloud.

▪ Paramagnetism, which is shown only by molecules

containing unpaired electrons. It arises from the spin and
orbital moments of the unpaired electrons. The external
magnetic field tends to align the intrinsic magnetic moment
of the molecule in the direction of the field.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Where does the magnetic moment come from?
Each electron has a magnetic moment

spin angular momentum orbital angular momentum

µtotal = µorbital +µspin

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 STEREOISOMERISM

❑ Consider two compounds containing the same ligands attached to the same central metal ion, but
the arrangement of ligands in space about the central metal ion is different, then these two
compounds are said to be stereoisomers and this phenomenon is known as stereoisomerism.

❑ There are two different types of stereoisomerism.

❑ Geometrical isomerism

❑ Optical isomerism

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 STEREOISOMERISM

Geometrical (or) cis-trans isomerism

❑ Geometrical isomerism is due to ligands occupying different positions around the central ion.

❑ The ligands occupy positions either adjacent to one another or opposite to one another.

❑ These are referred to as cis-trans forms, respectively.

❑ This type of isomerism is, therefore, also referred to as cis-trans isomerism.

❑ Geometric isomers are possible for both square planar and octahedral complexes, but not
tetrahedral.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Geometrical isomerism in 4-coordinate complex
(1) [Ma2b2] type complexes - Square planar:

• In a cis-isomer two identical (or) similar groups are adjacent to each

other whereas in a trans-isomer they are diametrically opposite to
each other.
• Square planar complexes of the type [Ma2b2] n+ where a and b are
monodentate ligands, exist as cis and trans-isomers as shown.

Example:
[Pt (NH3)2 Cl2] and [Pd(NH3)2 (NO2)2]
The cis-trans isomers of these compounds are represented as
cis-diamminedichloroplatinum(II) and
trans-diamminedichloroplatinum(II)
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Geometrical isomerism in 4-coordinate complex
(2) [Mabcd] type complexes:

❑ Square planar complex of this type exists in three isomeric forms.

❑ For example [Pt(NH3)(Py)(Cl)(Br)] exists in the following structures

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Geometrical isomerism in 4-coordinate complex
(3) [ Ma2bc] type complexes:

❑ Square planar complexes of this type also show cis-trans isomerism.

❑ For example [Pd (Cl)2B. I]2- exists in the following cis-trans.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Geometrical isomerism in 4-coordinate complex
(4) [M(AB)2] n± type complex:

❑ Here M is the central metal ion.

❑ (AB) represents an unsymmetrical bidentate ligand.

❑ (A) and (B) are the two ends (i.e. coordinating atoms) of the bidentate ligands.

❑ Such types of complexes also show trans and cis isomerism.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Geometrical isomerism in a 6-coordinate complex (octahedral complex)

❑ A complex compound having the central metal ion with ❑ An octahedral complex of the
a coordination number equal to 6 has an octahedral type [Ma4b2] where a and b are
shape. monodentate ligands, exists as
two geometrical Isomers:
❑ The system is used for numbering different positions of
ligands and generally it is assumed that the 1,2 positions
are cis-positions.

❑ Normally it is taken that 1,6 positions are trans-

positions.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Optical Isomerism
▪ This is a phenomenon in which certain organic or inorganic compounds have the property of rotating
plane polarized light. The compounds which exhibit this property are called optical isomers.

▪ The optical isomers of a compound have identical physical and chemical properties.

▪ The only distinguishing property is that the isomers rotate the plane of polarized light either to the left or
right.

▪ If the rotation is on the left side, then that isomer is levo, and if on the right side, then the isomer is
dextro.

▪ The equal proportion of levo and dextro mixture is called a racemic mixture.

▪ It is generally found in octahedral chelate ions.

▪ The two isomers of this type of complex are a mirror image of each other and cannot superimpose on
each other, hence they possess a chirality character.
SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Optical Isomerism

❑ coordination compound of type [PtCl2(en)2]2+

two geometrical isomers are possible.
❑ They are cis and trans.
❑ Among these two isomers, cis isomer shows
optical activity because the whole molecule is
asymmetric.

The optical isomers of [CoCl2(en)(NH3)2] + are as follows: Optical isomeric structure of [Cr(ox)3]3-
or [Cr(C2O4)3]3- as follows:

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Optical Isomerism

❑ Another type of geometrical isomerism occurs in

octahedral coordination entities of the type [Ma3b3 ]
like [Co(NH3)3 (NO2)3].
❑ If three donor atoms of the same ligands occupy
adjacent positions at the corners of an octahedral face,
we have the facial (fac) isomer.
❑ When the positions are around the meridian of the
octahedron, we get the meridional (mer) isomer.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 ISOMERISM

▪ Compounds having the same chemical formula but different physical and
chemical properties due to the different structural arrangements are called
isomers.

▪ This phenomenon is known as isomerism.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Types of Isomerism

Isomerism

Structural
Stereoisomerism
Isomerism

Ionization Hydrate or Coordination Geometrical Optical

Linkage Ligand Isomerism
Isomerism
Isomerism Isomerism Solvate Isomerism Isomerism
Isomerism

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Structural Isomerism
1. Ionization Isomerism
Coordination compounds having the same molecular formula but forming
different ions in solution are called ionization isomers.

Example:
[Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
Red violet Isomer-yields sulphate ion Red Isomer-yields bromide ion
in solution in solution

• [Co(NH3)4Cl2]NO2 and [Co(NH3)4NO2Cl]Cl

• [Co(NH3)5NO3]SO4 and [Co(NH3)5 SO4]NO3

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Structural Isomerism
2. Linkage Isomerism

▪ Linkage isomerism occurs with ambidentate ligands.

▪ These ligands are capable of coordinating in more than one way.

▪ The best-known cases involve the monodentate ligands SCN- /NCS and NO2-/ONO.

Example:

▪ [Co (NH3)5 ONO] Cl2 the nitrito isomer – red color - O attached.

▪ [Co (NH3)5 NO2] Cl2 the nitro isomer - yellow color - N attached.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Structural Isomerism
3. Hydrate Isomerism or Solvate Isomerism:

▪ The best-known examples of this type of isomerism occur for chromium chloride “CrCl3.6H2O” which may
contain 4, 5, (or) 6 coordinated water molecules.

1. [Cr (H2O)4 Cl2] Cl.2H2O - Bright green -Tetraaquadichlorochromium(III)chloride dihydrate

2. [Cr (H2O)5 Cl] Cl2.H2O - Grey-green - Pentaaquachlorochromium(III)chloride monohydrate

3. [Cr(H2O)6] Cl3 - Violet - Hexaaquachromium(III) chloride.

▪ These isomers have very different chemical properties and on reaction with AgNO3 to test for Cl- ions,
would find 1,2, and 3 Cl- ions in solution, respectively.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Structural Isomerism
4. Coordination Isomerism
• In a bimetallic complex, both complex cation and complex anion may be present.
• In such a case the distribution of ligands between the two coordination spheres can vary, giving rise to
isomers called the coordination isomers.
• This phenomenon is called coordination isomerism.
• This isomerism is illustrated by the following pairs of complexes where the complex cation and anion
contain different metal centers.
Example:
[Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
Hexammine hexacyanocobalt(III)chromate(III) Hexammine hexacyanochromium(III)cobaltate(III)

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 Structural Isomerism

5. Ligand Isomerism

• Ligand isomerism arises from the presence of ligands that can adopt different isomeric forms.

• Example: Diaminopropane, which may have the amine groups in the terminal (1,3-) positions or in

the 1,2-positions.

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 The Periodic Table

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• Introduction
▪ The periodic table is made up of rows of elements and
columns.
▪ An element is identified by its chemical symbol.
▪ The number above the symbol is the atomic number
▪ The number below the symbol is the rounded
atomic weight of the element.
▪ A row is called a period
▪ A column is called a group

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 Effective Nuclear charge

▪Net positive charge experienced by an electron in a poly electronic atom.

▪There are two factors responsible for increasing the effective nuclear charge,
which is electrons and protons.
▪The net positive charge from the nucleus that an electron can “feel” attractions
▪The core electrons are said to shield the valence electrons from the full attractive
forces of the protons in the nucleus.

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▪ The effective nuclear charge, Z eff = Z−S

▪ Zeff is higher for valence electrons farther from the nucleus (Zeff Z)

▪ Zeff is lower for valence electrons farther from the nucleus (Zeff Z)

▪ Zeff is equal to Z for valence electrons because Z is constant (Zeff Z)

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
 Slater's Rule

The actual charge felt by an electron is equal to the expected charge of the
certain number of protons, but minus a certain amount of charge from
other electrons.
Slater's rule is used to calculate shielding constant $ .
$ = (0.35 \times n) + (0.85 \times m) + (1.00 \times p)
where
n is number of electrons in n shell,
m is number of electrons in n-1 shell,
p is number of electrons in the remaining inner shells.
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 Energy of an orbital

▪ The energy required to remove an electron present in that orbital to infinity or the

release of energy when an electron from an infinity to added in that orbital referred
to as the energy of orbitals.

▪ Energy level Varies in s,p,d and f orbitals of atoms in the periodic table

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▪ Orbital energy is dependent upon the principle of the quantum number (n)
and azimuthal quantum number (l) which depends on the shell and subshells.

▪ All orbitals belongs to the same subshell, has the same energy and those
orbitals having same energy are stated as degenerate orbitals.

The order of the increase in energy along the various orbitals is stated as –
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f

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SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
▪The s orbital electron is more tightly bound to the nucleus than p orbital
electron, which is more tightly bound than d orbital electron for a given
value of the principal quantum number.

▪ s orbital electrons are having lesser amount of energy than p orbital

electrons which in turn lesser amount of energy than d orbital electrons

▪With the increase in the atomic number (Zeff), the orbital energy decreases in
the same subshell.

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▪Extent of shielding from the nucleus is different for the electrons in different
orbitals, it leads to the splitting of energy levels that have the same principal
quantum number.

▪The orbital energy would depend on the values of both the principal quantum
number and azimuthal quantum number, symbolized as n and l respectively.
Hence, the lower value of (n + 1) for an orbital , the lower is its energy.

SRMIST/RMP/I BTECH/22CYB101J/CHEMISTRY
• Introduction
▪ The periodic table is made up of rows of elements and
columns.
▪ An element is identified by its chemical symbol.
▪ The number above the symbol is the atomic number
▪ The number below the symbol is the rounded
atomic weight of the element.
▪ A row is called a period
▪ A column is called a group

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 ATOMIC AND IONIC RADII

Atomic or ionic radius is generally used for the distance between the
nucleus and the outer most shell of electrons of the atomic or ionic particle.
It is not possible to isolate an individual atoms or an ion.

In a period the atomic size of the elements decreases from the left to the
right because the nuclear charge (number of protons) increases and so the
electrons are pulled closer to the nucleus.

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 Variation in 2nd period

Elements Li Be B C N O F

Covalent 1.23 0.90 0.82 0.77 0.75 0.73 0.72

radii ( A*)

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 Variation in group

In a group the atomic size of the elements increases from top to

bottom because the number of shells increases and the distance
between the nucleus and shells also increases.

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 Variation in 2nd period

Elements of IIA Be Mg Ca Sr Ba
Group

Covalent radii ( Å) 0.90 1.36 1.74 1.91 1.98

Ionic radii of M2+

cations (Å) 0.31 0.65 0.99 1.13 1.35

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 IONISATION POTENTIAL or IONISATION ENERGY

▪ The amount of energy required to remove the most loosely bound electron (i.e.,
the outermost electron) from an isolated gaseous atom of an element in its lowest
energy state (i.e., ground state) to produce a cation is known as ionisation potential
or ionisation energy of that element.

M(g) + Energy supplied (Ionisation energy, I) →M+ (g) + e-

Isolated gaseous atom Cation

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 Successive ionisation potentials
• Elements with atomic number
• Electronic configuration
• Successive Ionisation potentials( eV)
• I1 I2 I3 I4 I5 I6 I7 I8
• H1 1s1 13.6
• He2 1s2 24.6 54.4
• Li3 1s2 ,2s1 5.4 75.6 122.4
• Be4 1s2 ,2s2 9.3 18.2 153.9 217.7
• B5 1s2,2s2 p1 8.3 25.1 37.9 259.3 340.1
• C6 1s2 ,2s2 p2 11.3 24.4 47.9 64.5 39.2 489.8
• N7 1s2 ,2s2 p3 14.5 29.6 47.4 77.59 7.95 51.9 666.8
• O8 1s2,2s2 p4 13.6 35.1 54.9 77.4 113.9 138.1 739.1 871.1

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 Charge on the nucleus (i.e., nuclear charge) and variation in period

Elements of 2nd period : Li Be B C N O F Ne

Nuclear charge : +3 +4 +5 +6 +7 +8 +9 +10

Ionisation potential (eV) : 5.4 9.3 8.3 11.3 14 13.6 17.4 21.7

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 Ionisation potential variation in period

II A No. of inner- Ionisation

group shells potential (eV)
Be 1 9.3
Mg 2 7.6
Ca 3 6.1
Sr 4 5.7
Ba 5 5.2

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 ELECTRONEGATIVITY

• The electronegativityof a bonded atom is defined as its relative

tendency (or ability) to attract the shared electron pair towards itself.

• Electronegativity of an atom A is generally represented as xA.

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 PERIODIC VARIATIONS in Periods
• Electronegativity increases on moving in a period of the periodic table from
left to right. This is due to the increase in nuclear charge as a result of which
the added electrons can be held more tightly. Thus the C—N bond should be
shown as C + -N -or C N, the arrow head being to element N.
• Elements of 2nd period : Li Be B C N O
• Valence-shell configuration : 1s1 2s2 2s2p1 2s2p2 2s2p3 2s2p4 No.
of valence-shell electrons : 1 2 3 4 5 6
• Electronegativity values : 1.0 1.5 2.0 2.5 3.0 3.5
Increasing downwards the more electronegative

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 PERIODIC VARIATIONS- in groups

▪ In moving down through a group of the periodic table, since the

nuclear charge again increases, the electronegativity of a lower
element should be more than that of upper element.
▪ Actually it is not so because of the electron shielding effects.
▪ Therefore a lower element of a group is less electronegative than the
upper element of the same group.
▪ In general, the small atoms attract electrons more strongly than large
ones and are, therefore, more electronegative

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 ELECTRON AFFINITY

▪ The amount of energy released when an electron is added to an

isolated neutral gaseous atom in its lowest energy state (i.e. ground
state) to produce an anion is called its electron affinity or affinity
▪ It is represented as EA or E and is measured in electron energy.
▪ electron affinity can be expressed by the following equation:
A(g) + e- (g) A- (g)+ Energy released (electron affinity E)
Neutral gaseous atom Anion

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 PERIODIC VARIATIONS- in Periods
• Electron affinity values generally increase on moving from left to right
in a period in the periodic table.
• IA IIA III A IV A VA VI A VII A Zero
• H 0.75 He 0.0
• Li -0.61 Be 0.0 B -0.30 C -1.25 N -1.20 O-1.48 (+7.3) F -3.6 Ne 0.0
• Na-0.82 Mg 0.0 Al -0.52 Si -1.39 P -0.80 S -2.0 (+3.4) Cl -3.8 Ar 0.0
• K -0.69 Br -3.5 Kr 0.0
• I -3.2 Xe 0.0

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PERIODIC VARIATIONS- in Groups

• In moving down a group, electron affinity values generally decrease.

• For example E Cl > E Br > EI

• This is because of the steady increase in the atomic radius of the

elements
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