Unit 1: Periodic Properties

Electronic Configuration of the elements:

The electronic configuration of an element is a symbolic notation of the way the electrons of its
atoms are distributed over different atomic orbitals. While writing electron configurations, a
standardized notation is followed in which the energy level and the type of orbital are written
first, followed by the number of electrons present in the orbital written in superscript.

For example, the electronic configuration of carbon (atomic number: 6) is 1s22s22p2 and the
electronic configuration of sodium is 1s22s22p63s1.

However, the standard notation often yields lengthy electron configurations (especially for
elements having a relatively large atomic number). In such cases, an abbreviated or condensed
notation may be used instead of the standard notation. In the abbreviated notation, the sequence
of completely filled subshells that correspond to the electronic configuration of a noble gas is
replaced with the symbol of that noble gas in square brackets. Therefore, the abbreviated electron
configuration of sodium is [Ne]3s1 (the electron configuration of neon is 1s22s22p6, which can be
abbreviated to [He]2s22p6).

This notation for the distribution of electrons in the atomic orbitals of atoms came into practice
shortly after the Bohr model of the atom was presented by Niels Bohr in the year 1913.

The three rules that dictate the way electrons are filled in atomic orbitals are:
● The Aufbau principle: electrons must completely fill the atomic orbitals of a given energy
level before occupying an orbital associated with a higher energy level. Electrons occupy
orbitals in the increasing order of orbital energy level.
● Pauli’s exclusion principle: states that no two electrons can have equal values for all four
quantum numbers. Consequently, each subshell of an orbital can accommodate a
maximum of 2 electrons and both these electrons MUST have opposite spins.
● Hund’s rule of maximum multiplicity: All the subshells in an orbital must be singly
occupied before any subshell is doubly occupied. Furthermore, the spin of all the
 electrons in the singly occupied subshells must be the same (in order to maximize the
overall spin).

Electron Configurations are useful for:

✔ Determining the valency of an element.
✔ Predicting the properties of a group of elements (elements with similar electron
configurations tend to exhibit similar properties).
✔ Interpreting atomic spectra.

Stability of Completely Filled and Half-filled Orbitals

Almost all the elements follow the same trend for writing electronic configuration. Sometimes
when two sub-shells differ in energies, an electron from the lower energy moves to higher
energy.

This is because of two reasons:

Symmetrical distribution: It is well known that symmetry leads to stability. The completely filled
or half filled subshells have symmetrical distribution of electrons in them and are therefore more
stable. Electrons in the same subshell have equal energy but different spatial distribution.
Consequently, their shielding of one-another is relatively small and the electrons are more
strongly attracted by the nucleus.

The orbitals in which the sub-shell is exactly half-filled or completely filled are more stable
because of the symmetrical distribution of electrons.
Half-filled and fully filled atomic orbitals can be represented as follows.

Exchange energy: The electrons which are there in degenerate orbitals have a parallel spin and
tend to exchange their position. Exchange energy is nothing, but the energy released during this
process. The electrons present in the different orbitals of the same sub-shell can exchange their
positions. Each such exchange leads to the decrease in energy known as Exchange Energy.
Greater the number of exchanges, greater the exchange energy and hence greater the stability. As
the number of exchanges that take place in the half-filled and fully-filled orbitals is maximum,
thus exchange energy is maximum and hence maximum stability. You may note that the
exchange energy is at the basis of Hund’s rule that electrons which enter orbitals of equal
energy have parallel spins as far as possible. In other words, the extra stability of half-filled and
completely filled subshell is due to:
(i) relatively small shielding,
(ii) smaller coulombic repulsion energy, and
(iii) larger exchange energy.
Chromium is the element that has half-filled electrons in 3d subshell and shows great stability.
Copper is the element that has fully filled electrons in 3d subshell and shows great stability.

The knowledge about the electronic configuration of elements has paved the way for various
further developments in the field of quantum mechanics.
Inert pair effect

The inert pair effect refers to the valence s- electrons of a high-atomic-number atom’s reluctance
to participate in chemical processes due to poor shielding of these electrons by inner orbital
electrons. As a result, the s-electrons are unavailable for bond formation. If we move along the
group, this effect becomes stronger. Due to the inert pair effect oxidation state of bigger elements
drops, and smaller elements’ stability improves. The inert pair effect occurs in heavier elements
of groups 13,14,15, and 16 in the periodic table.

The p-block elements display two oxidation states. This is in sharp contrast to the s-block
elements that display only one oxidation state, the group number. The higher oxidation state is
equal to the group number minus 10 (i.e. number of s and p electrons in the valence shell) and
the lower one is two units less than the group number (i.e. number of p electron in the valence
shell). The lower oxidation state becomes more stable on descending the group. This is referred
to as the inert pair effect. The higher oxidation state is displayed only when both the ns and np
electrons are involved in bond-formation. On the other hand, the lower oxidation state is
observed when only the np electron(s) participate in bond formation. On moving down the group
the ns electrons tend to remain inert and do not participate in bond formation. This reluctance of
the outermost s orbital electron pair to participate in bond formation is called inert pair effect.
The reason for this effect is explained in terms of bond energy. On one hand energy is needed to
uncouple the s-electrons and on the other hand energy is released during bond formation. If the
energy released is sufficient to unpair the s- electrons, then they participate in bond formation,
otherwise they do not. The bond energy decreases down the group and hence inert pair effect is
prominent for the lower members.
Consider as an example thallium (Tl) in group 13. The +1 oxidation state of Tl is the most stable,
while Tl3+ compounds are comparatively rare. The stability of the +1 oxidation state increases in
the following sequence.
Al+ < Ga+ < In+ < Tl+.
The same trend in stability is noted in groups 14, 15 and 16. The heaviest members of each
group, i.e. lead, bismuth and polonium are comparatively stable in oxidation states +2, +3, and
+4 respectively.

limitations of the inert pair effect

The inert pair theory possesses some limitations. Suppose we explain this in terms of electrons,
or in other words, their expected high ionisation enthalpy value. Let’s take an example of group
13 elements,

Ionization Boron (B) Aluminum (Al) Gallium (Ga) Indium (In) Thallium (Tl)
enthalpy (KJ/mol⁻¹)
 ∆H₂+∆H₃ 6086 4560 4941 4524 4848

In this ionization enthalpy will decrease as we move from up to down( B to Tl). This table shows
a few anomalies—an increase in ionization enthalpy from Al to Ga and indium to thallium.

The inert pair effect that Sidgwick proposed cannot account for this information. Their simple
explanation can be that d-block contraction affects Ga’s ionization enthalpy. Tl’s comparatively
high ionization is due to relativistic effects due to poor shielding of the d- and f- orbitals.

Periodic Law and Periodicity

The periodic properties of elements are based on the periodic law. According to Mendeleev, the
physical and chemical properties of elements are a periodic function of their atomic weights.
Later it was disproved, and the modern periodic law was formulated based on Moseley’s
experiment.

According to the modern periodic law, “the physical and chemical properties of elements are a
periodic function of their atomic numbers”.

When the elements are arranged in the modern periodic table in order of increasing atomic
number, the occurrence of similar properties of elements after a definite interval is termed as
periodicity of an element.

The periodicity of properties of the elements is caused by the periodicity in electronic structure.
The noble gases are chemically unreactive, or nearly so, because their electronic structures are
stable—their atoms hold their quota of electrons strongly, have no affinity for more electrons,
and have little tendency to share electrons with other atoms.

The properties of elements in the same group of the periodic system are, although similar, not
identical. The trend in properties from the lighter to the heavier elements may be attributed to
changes in the strength of binding of the outer electrons and especially to the increasing size of
the atoms.

General group trends of s, p and d block elements

Ionization Enthalpy

Ionization Enthalpy is the energy required to remove the most loosely bound electron from an
isolated atom in the gaseous state for one mole of an element. It is an absolute value and can be
determined experimentally. It is expressed in kJ mol-1 (kilojoules per mole).
M(g) + IE → M+ (g) + e–

The variation in the magnitude of ionization enthalpy of elements in the periodic table is mainly
dependent on the following factors:
(a) The size of the atom
(b) The magnitude of the nuclear charge on the atom,
(c) The extent of screening (Screening effect)
(d) The type of orbital involved (s, p, d, or f).(Penetration effect)

● In small atoms, the electrons are tightly held whereas in large atoms the electron are less
strongly held. Thus, the ionization enthalpy decreases as the size of the atom increases.
● When an electron is removed from an atom, the effective nuclear charge, i.e., the ratio of
the number of charges on the nucleus to the number of electrons, increases. As a result
the remaining electrons come closer to the nucleus and are held more tightly. The
removal of a second electron, therefore, requires more energy. e.g., Mg+ is smaller than
the Mg atom The remaining electrons in Mg+ are more tightly held. The second
ionisation enthalpy is, therefore, more than the first ionisation enthalpy.
● Since the orbitals (s, p, d and f) have different shapes, the ionization enthalpy depends on
the type of electrons removed. e.g. an electron in an s orbital is more tighly held as
compared to an electron in a p orbital. It is because an s electron is nearer to the nucleus
as compared to a p electron. Similarily a pelectron is more tightly held than a d-electron,
and a d-electron is more tightly held than a f-electron. If all other factors are equal, the
ionization enthalpies are in the order s > p > d > f.

These factors taken together contribute largely to decide the extent of the force of
attraction between the nucleus and the electrons around it. The resultant of these factors
thus determine the magnitude of ionization enthalpy of any element.

As we move from left to right in the periodic table, there is a nearly regular increase in the
magnitude of the ionization enthalpy of elements. Similarly, on moving down a group the
magnitude of the ionization enthalpy indicates a regular decline.
The ionization enthalpy of the first member of any group is the highest within that group and the
ionization enthalpy of the last member in the same group, is the least.

✔ The metals of group 1 (Li, Na, K, Rb, etc.) have the lowest ionization enthalpies in their
respective periods.
✔ The noble gases (He, Ne, Ar, Kr, Xe and Rn) have the highest ionization enthalpies in
their respective periods. It is because the energy required to remove an electron from a
stable fully filled shell is very large.
✔ The values of ionization energies do not increase smoothly. e.g. the first ionization
enthalpy of B (boron) is lower than that of Be (beryllium); the ionization enthalpy of Al
(aluminium) is lower than that of Mg (magnesium); the first ionization enthalpy of
O(oxygen) is lower than that of N (nitrogen). It can be explained as follows.:
▪ The first ionization enthalpies of Be and Mg are higher than those of their
preceding elements because the electrons are removed from the fully filled s
orbitals.
▪ The first ionization enthalpy of N is higher than that of O because from N, the
electron is to be removed from a half-filled p-orbitals.
▪
 ⮚ With the decrease in ionization enthalpies down the group, main group metals/elements
show increasing chemical reactivity.
⮚ There are some exceptions also. The first ionization energy of Ga31, an element of fourth
period is slightly higher than that of Al13, the element of third period [(IE)1 of Al = 577.6
kJ/mole and (IE)1 of Ga= 578.8 kJ/mole]This is perhaps due to the poor shielding effect
of 3d10 electrons. Also, the third row of transition elements shows higher value of
ionization energy as compared to second row elements. This is due to the decrease in
size of these elements as a result of insertion of lanthanides in 6th period (Lanthanide
contraction).

Electron gain Enthalpy

Every atom, in general, has a tendency to gain or loose electrons in order to acquire a noble gas
configuration. The atom which have five, six or seven electrons in their outermost shell show
tendency to accept electrons and attain the nearest noble gas configuration. The energy change
(ΔE) for this process is called electron gain enthalpy of that atom.
Electron gain enthalpy is the energy released for one mole of neutral atoms in a gaseous state
when electron is accepted by each atom.

X(g) + e– ⎯⎯→ X- (g)

where X represents an atom. For example;

Cl (g) + e– ⎯⎯→ Cl- (g): ΔE = –349 kJ /mol

The negative value shows release of energy and hence tendency to greater stabilisation. The
electron gain enthalpy becomes more in negative from left to right in a period. This is because it
is easier to add an electron to a smaller atom since the added electron would be closer to the
positively charged nucleus. Halogens release maximum energy when they accept an electron. On
the other hand, metals do not accept electrons and show a high positive value for ΔE. Thus
electron gain enthalpy can be positive or negative.

● Electron gain enthalpies becomes less in negative as we go down the group showing that
the electropositive character of the atoms increases. This is because the size of the atom
increases down the group and the electron added goes to the higher shells. The electron
gain enthalpy of chlorine is more in negative value as compared to that of fluroine. This
is due to the small size of the F atom. As the electron approaches the small F atom, it
expriences a repulsion from other electrons. (In between Sulphur and Oxygen, Sulphur
has a higher negative value than oxygen.)
● Among the two non-metals Sulphur and Chlorine. The electronic configuration of
Chlorine is 3p5 and Sulphur has the configuration of 3p4. If we add one electron to these
non-metals than Chlorine will accept it first. After acquiring one electron it will achieve
its noble gas configuration. After acquiring one electron, the stability of Chlorine will be
more. So, it will remove the maximum amount of energy. Hence, the electron gain
enthalpy of chlorine is more negative as compared to Sulphur. The atomic radius of
chlorine is smaller than that of Sulphur so the effective nuclear charge on an electron in
 the case of chlorine will be more than that of Sulphur. Thus, the chlorine will have more
negative electron gain enthalpy.
Electron gain enthalpy depends on three factors:

● Electronic configuration
● Atomic radius
● Nuclear charge.
Electron gain enthalpy is sometimes also referred to as Electron affinity although there is a
minute difference between them. Electron affinity means love for electron. It is the negative of
the electron gain enthalpy. By using the concepts of thermodynamics, we find a relationship
between electron gain enthalpy and electron affinity i.e.

𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑔𝑎𝑖𝑛 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 affinity −5/2𝑅𝑇

where, R= universal gas constant & T= temperature in Kelvin scale.

Electronegativity

Electronegativity was developed by Linus Pauling, who won the Noble prize twice. Pauling set
the definition of electronegativity as “the power of an atom in a molecule to attract electrons to
itself”.

It is an indicator of the extent of attraction by which electrons of the bond pair are attracted by an
atom linked by this bond. Different elements have different electronegativities based on a
number of factors such as size and number of protons, neutrons, and electrons. It is often viewed
on an electronegativity chart of the elements, where trends and values can easily be seen. The
higher the electronegativity, the stronger an atom attracts electrons. The value of
electronegativity is assigned arbitrarily to one atom such as hydrogen. Then the value of
electronegativity is assigned to all other atoms with respect to hydrogen. One such scale is the
Pauling Scale of electronegativity.

Electronegativity is defined as a measure of the ability of an atom to attract the shared electron
pair in a covalent bond towards itself. Greater the ability of an atom to attract electrons, larger is
the value of electronegativity. Thus , it is different from electron affinity/electron gain enthalpy
which is a quantitative property associated with an isolated atom. Electronegativity, on the other
hand, is a qualitative property and is not the property of an isolated atom but of an atom that may
be bonded to one or more atoms in a molecule or a complex ion. It may, however, be mentioned
that although electronegativity is not the property of an isolated atom yet often it is considered so
and related to some of the properties of an isolated atom.

Variation of electronegativity can be related to orbital type and charge.

i) For the orbitals of a given atom or ion, electronegativity decreases as:
1s > 2s > 2p > 3s > ……
(it is the electronegativity of valence orbitals that is of greatest importance)

ii) For a given element, electronegativity decreases with the number of electrons:
 M2+ > M+ > M > M- > M2-
i.e., the more electron-poor a species is, the greater its electronegativity.

In a homonuclear diatomic molecule such as hydrogen (H2 ) or fluorine (F2 ), the electron pair of
the covalent bond in each molecule experiences equal attraction by each atom. Thus, neither of
the two atoms is able to shift the bond pair of electrons to itself. However, in a heteronuclear
diatomic molecule, the bond pair electrons get shifted towards the atom which is more
electronegative than the other. For example, in HF or HCl the bond pair of electrons are not
shared equally but the more electronegative atom F or Cl is able to shift the bond pair towards
itself, resulting in the polarization of the molecule. A large difference between electronegativities
of the two atoms indicates highly ionic character of the bond between them, for example in Cs+
F-. On the other hand, zero difference in the electronegativities between the two atoms indicates
that the percentage ionic character is zero. Therefore the molecule is purely covalent e.g. H2, Cl2 ,
N2 etc.

● The most electronegative elements have been placed on the farthest right hand upper
corner (noble gases are not included).
● The value of electronegativity decreases as we go down in any group and increases from
left to right in the period. Thus, fluorine is the most electronegative and cesium is the
least electronegative element. (Francium (radioactive) not considered).

Factors affecting the magnitude of electronegativity:

1. Size of the atom:
In a particular bond, the shared pair of electron is attracted more towards the atom wit
smaller size thus the electronegativity is greater for the atom of smaller size. For
example, along the period ( Li to F) size decreases the value of electronegativity
increases( Li size 123pm, EN 1.0 ; F size 72pm, EN 4.0). Similarly, down the group (H to
Cs) as size increases the electronegativity value decreases ( H size 37pm, EN 2.1; Cs size
235pm, EN 0.7).
2. Charge on the ion (oxidation state):
The cation(M+) of the same atom(M) is smaller in size, lesser the size of the cation, more
is the electronegativity value. On the other hand, an anion(X-) of the same atom(X) is
larger in size and shows lesser value of electronegativity. Higher the positive charge of
cation, lesser is the size and more is the electronegativity. For example, EN of Li and Li+
are 1.0 and 2.5 respectively. EN of Fe, Fe2+,Fe3+ are 1.8, 1.83 & 1.96 respectively.
3. Hybridisation:
More the penetration effects of an orbital, more tightly it is held to the nucleus. Taking an
account of the penetration power, s orbitals are more nearer to the nucleus compared to p,
d and f orbitals. Thus electronegativity has more value with increasing s – character in
relation to different hybridization i.e., sp3 , sp2 and sp of organic/ inorganic compounds.
For example; in methane, ethane and ethyne as hybridization changes from sp3 to sp , the
s-character increase from 25% to 50% and electronegativity increases simultaneously (
 Methane 2.48, ethane 2.75, ethyne 3.29). Similarly, in ammonia, hydrazine and alkyl
cyanide.
4. Bond Order:
With increasing bond order, electronegativity increases for the atom under consideration.
Triply bonded C2H2 ( B.O. = 3) is more electronegative than doubly bonded C2H4
(B.O.=2).

Heat/Enthalpy of Atomization:
Each spontaneous process tends to result in the production of novel products. Some processes,
out of all the ones we know about, tend to absorb energy, while others simply result in energy
evolution. As a result, when we complete these activities, we usually experience enthalpy or heat
change. When the bonds of a compound tend to break, and elements of that complex are reduced
to singular atoms, the enthalpy of atomization refers to the amount of change in heat.
The heat of atomization is always a positive number and can never be negative. The symbol for
the enthalpy of atomization is ΔaH . During the process of atomisation, all types of chemical
bonds are broken down, and none are formed. Therefore, the enthalpy of atomisation is always a
positive value. The standard enthalpy value for this enthalpy change is “standard enthalpy of
atomisation”. The standard conditions considered in this context are the 268.15 K temperature
and 1 bar pressure.

For example, enthalpy of atomisation for water molecule refers to the energy required to separate
the two hydrogen atoms and the oxygen atom in the water molecule. In other words, the enthalpy
of atomisation for water is the sum of the bond dissociation energies of two O-H bonds.
Similarly, the enthalpy of atomisation for an elemental solid is the enthalpy of sublimation for
that substance because sublimation involves the conversion of the solid into a monoatomic gas
upon evaporation.

Among alkali metals, enthalpy of atomization is maximum in case of Li & is much lower in the
case of the next element which is Na. The fall in the case of the subsequent elements is relatively
small.
Among alkaline earth elements, the heat/enthalpy of atomization falls considerably on moving
from Be to Mg. The subsequent change is rather small.

The energy required to form a 1 mole of gaseous atoms from its elements in its standard state is
called standard enthalpy of atomization. The transition elements have high enthalpies of
atomization because of presence of strong bonds between the atoms. The enthalpy of atomization
increases with the increase in number of unpaired electrons which results in formation of strong
bonds due to strong interatomic interactions. The elements of 4d and 5d series have greater
enthalpy of atomization than corresponding elements of first transition series which results in
much more metal-metal bonding in compounds of the heavy transition elements.

In first transition series, Zn has minimum enthalpy of atomization because of absence of

unpaired electrons.
Oxidation States:

The oxidation state of an atom is equal to the total number of electrons which have been
removed from an element (producing a positive oxidation state) or added to an element
(producing a negative oxidation state) to reach its present state.

The oxidation state of an atom can be defined as the hypothetical charge that would be held by
that atom if all of its bonds to other atoms were completely ionic in nature. For example, the
oxidation state of carbon in CO2 would be +4 since the hypothetical charge held by the carbon
atom if both of the carbon-oxygen double bonds were completely ionic would be equal to +4
(each oxygen atom would hold a charge of -2 since oxygen is more electronegative than carbon).

Oxidation state and oxidation number are terms frequently used interchangeably. They are the
quantities which describe the number of electrons lost in an atom. Ideally, the oxidation state is
either zero, positive, or negative.

Antoine Lavoisier was the first to use the term oxidation to denote the reaction between a
substance and oxygen. Later, it was noticed that when the substance is oxidized it loses electrons.
Therefore, the elucidation diversified to include other reactions as well where the electrons are
lost, irrespective of the involvement of oxygen atom.

The value of the oxidation state usually constitutes integers. Sometimes the oxidation state is a
fraction. For example,The element iron in Fe3O4 (magnetite) is 8/3.

The oxidation state of an atom is not regarded as the real charge of the atom. In a chemical
reaction if there is an increase in oxidation state then it is known as oxidation whereas if there is
a decrease in oxidation state, it is known as reduction. The lowest known oxidation state is −4,
for carbon in CH4 (methane). The highest known oxidation state is +9 in the tetroxoiridium (IX).

● Halogens in the periodic table commonly show negative, and alkali metals or
alkaline earth metals commonly show positive oxidation states.
● The s-block elements commonly show +1 and +2 oxidation states.
● p-block elements commonly show +3, +4, -3, -2 and -1 oxidation states.
● One of the most important properties that distinguish transition metals or d-block
elements from non-transition elements is variable oxidation states.( d orbitals not
completely filled )
● f-block elements also show variable oxidation states. (incompletely filled f
orbitals)

Metallic Character:

Metallic character refers to the level of reactivity of a metal. Metals tend to lose electrons
in chemical reactions, as indicated by their low ionization energies. Within a compound, metal
atoms have a relatively low attraction for electrons. This is indicated by their low
electronegativities.
The most reactive metals reside in the lower left portion of the periodic table. The most reactive
metal is cesium, which is not found in nature as a free element. It reacts explosively
with water and ignites spontaneously in the air.
Francium is below cesium in the alkali metal group. However, it is so rare that most of its
properties have never been observed.

Nonmetals tend to gain electrons in chemical reactions and have a high attraction
for electrons within a compound. The most reactive nonmetals reside in the upper right portion
of the periodic table. Noble gases are a special group because of their lack of reactivity.
However, the element fluorine is the most reactive nonmetal. It is not found in nature as a free
element.
There is no clear division between metallic and non-metallic character. As we move across the
periodic table, there is an increasing tendency to accept electrons (non-metallic) and a decrease
in the possibility that an atom would give up one or more electrons(metallic).

The metallic character increases as you go down a group. Since the ionization energy decreases
going down a group (or increases going up a group), the increased ability for metals lower in a
group to lose electrons makes them more reactive. In addition, the atomic radius increases going
down a group, placing the outer electrons further away from the nucleus and making that
electron less attracted by the nucleus.
p-block contains a wide range of elements i.e. metals, non-metals, and metalloids. The p-block
is the main locale of the periodic table to contain metalloids. The nonmetallic character
diminishes down the group though there is a progressive increment in non-metallic character
from left to right in the p-block. The metallic character tends to increment down every group
while it diminishes as we go from left to right over a period. As a matter of fact, the heaviest
element in every p-block group is the most metallic in nature.

Magnetic Property:

The p block elements Radon, Astatine, Iodine, and Polonium are Non-Magnetic in nature. Only
Tin is Paramagnetic and the rest all elements of the p-block are Diamagnetic in nature.

Many compounds of d-block elements exhibit magnetic properties. Qualitatively speaking, there
are several kinds of magnetism. The substances which are weakly repelled by the strong
magnetic field are termed as diamagnetic while those which are weakly attracted by the strong
magnetic field are called paramagnetic. These substances lose their magnetism on removing the
magnetic field. Diamagnetism is the property of the completely filled electronic subshells and is
shown by all substances to more or less extent. Paramagnetism is produced by the presence of
unpaired electrons and because most of the d-block metal atoms and ions have unpaired
electrons, they are paramagnetic in behaviour. In some transition metals (e.g. Fe, Co, Ni)
unpaired electron spins are more pronounced and show much more paramagnetism than the other
d-block metals. Such metals are called ferromagnetic metals and magnetic property shown by
them is known as ferromagnetism. Such metals can be permanently magnetized.

Formation of Coloured Ions/ Compounds:

The majority of compounds of d-block elements, whether ionic or covalent, are coloured in solid
or solution state. This property of d-block elements is markedly different from those of s or
p-block elements which are white or light coloured. The colour of a substance arises from the
property of the substance to absorb light of certain wavelength in the region of visible light
(white light) when the latter interacts with the substance. The coloure of the substance is the
colour of the transmitted light component and is complementary to the colour of light component
absorbed.
The colour of d-block metal ions is associated with
(a) an incomplete d-subshell in the metal ion,
(b) the nature of surrounding groups around the metal ion.

The whole act of exhibition of colour by d-block ions/compounds can be explained as follows. In
a free gaseous or isolated ion the five d-orbitals are degenerate, i.e. of same energy. Since five
d-orbitals are oriented differently in space, the surrounding groups affect the energy of some
orbitals more than others in the compounds. This destroys their degeneracy.

Thus, in d-block metal ions with partially filled d-subshell, it is possible to promote electron(s)
from one set of d-orbitals to another set (group) of higher energy by fairly small energy absorbed
from the visible light. The colour of the compounds depends on the energy difference (gap)
between the two groups (sets) of d-orbitals. This in turn depends on the nature of ligands and
their arrangement around the metal ion in the compound / complex.

Catalytic Property:

The catalytic activity of d-block elements and their compounds is associated with their variable
oxidation states and their capability of forming interstitial compounds. A number of d-block
metals and their compounds are known to catalyse various reactions of industrial importance, For
example, finely divided Ni is used as a catalyst in hydrogenation reactions; MnO2 catalyses the
decomposition of H2O2; TiCl4 is used as a catalyst for polymerisation of ethene in the
manufacture of polythene; V2O5 is employed in the catalytic oxidation of SO2 to SO3 in the
contact process of manufacture of H2SO4; Fe is used in the manufacture of NH3 by Haber’s
process; Cu acts as a catalyst in the manufacture of (CH3)2 SiCl2 during the synthesis of silicones.
Cu/V is used in the large-scale production of Nylon-66. Fe(III) ions catalyse the reaction
between iodide and peroxodisulphate ions.
An important view of the mechanism of catalysis is that at solid surface of the catalyst, bonds
would be formed between the molecules of the reactants and atoms of the catalysts thereby
increasing the concentration of the reactants at the surface. This weakens the bonds of the
reactant molecules due to lowering of the activation energy.

Complex Formation Tendency:

Alkali metal ions with the exception of Li+ have very little polarizing power due to their large
size and only a unit positive charge. As a result, they have only a weak tendency to form
complexes with unidentate ligands. However, alkali metal ions form reasonably stable complexes
with some of the bidentate and polydentate ligands such as salicyaldehyde, beta-diketones, nitro
phenols etc.

Because of their higher positive charge (+2) and smaller ionic radii, the alkaline earth metals
have a much greater tendency to form complexes with Lewis bases than do the alkali metals.
This tendency is most important for the lightest cation (Be2+) and decreases rapidly with the
increasing radius of the metal ion. For example, Be2+ forms complexes with unidentate ligands (
BeF42-), with oxalic acid and acetic acid. Well known complex of Mg2+ is green pigments of
plants ( chlorophyll), Mg2+, Ca2+,Sr2+ and Ba2+ form complexes with EDTA.

The small size and the more noteworthy charge of the elements of various groups of p-block
empower them to have a more prominent propensity to form complexes as compared to the
s-block elements. This tendency of forming complex diminishes down the group as the size of
the atoms increments down the group.
The cations of d-block elements are unique in their tendency to form complexes with several
molecules such as ammonia, water, etc. or different ions such as cyanide, NO2, halide ions, etc.
These molecules or ions are called ligands.
The complex forming tendency of these elements is attributed to the following factors:
a) Small size and high positive charge density,
(b) Availability of vacant d-orbitals of right energy to accept the lone pairs of electrons from the
approaching ligands,
(c) Exhibition of variable oxidation states.

The elements of first transition series fulfill all conditions of complex formation and are, thus,
most suitable for this purpose. As a result, the cations of these elements have a strong tendency
to form complexes with certain molecules (e.g. CO, NO, NH3, etc.) or several ions (e.g. F-, Cl- ,
CN- etc.). These molecules and ions are called ligands (L) and have one or more lone pairs of
electrons on their donor atom (usually central atom) which they donate to the metal ion/atom (M)
during the process of complex formation via M←L coordinate covalent bonds. This happens
because the metal ions are electron deficient in most of their oxidation states or even the atoms
are electron acceptors. Small size and high charge density of the metal ions facilitate the
formation of the complexes which also depends on the basicity of the ligands. The complex
formation tendency increases as the positive oxidation state of the metal ion increases.

References:
1. Principles of Inorganic Chemistry- Puri, Sharma and Kalia
2. Concise Inorganic Chemistry- J. D. Lee
3. Advanced Inorganic Chemistry- Cotton and Wilkinson
4. Basic Principles of Inorganic Chemistry- A. K. Das.