Chapter two

General Inorganic Chemistry

Characteristics of S block elements:
The long form of periodic table has been divided into four blocks s,p,d,and f
depending upon the filling of particular shell .
The S block elements are those in which the last electron enters into the
outermost S orbital. This block includes only two group and have one or two
electrons in their outermost S shell respectively. The elements of group first
are called alkali metal and II group are called alkaline earth metals . They have
ground state electronic configuration of outermost shell is ns1 and ns2
respectively.
Characteristics:
They are soft metals having low melting and boiling point.
They have low ionisation enthalpies.
They are very reactive and readily form univalent or bivalent ions by losing one
or two electrons. So they are never found in pure state in nature.
They act as reducing agent.
Most of them imparts characteristics colour to the flame.
They mostly form ionic compounds except Lithium and beryllium

Diagonal relationship between Li and Mg

Li resembles Mg mainly due to similarity in sizes of their atoms and ions.

The main points of similarity are:

i)  Both are quite hard.

ii)  Both LiOH and Mg (OH) 2 are weak bases.
iii) Carbonates of both on heating decompose to produce oxides and
carbondioxide.
iv) Both react with nitrogen to give ionic nitrides.
v)  Nitrates of both decompose on heating to give oxides.
vi)Both Li and Mg do not form solid bicarbonates.
vii Because of covalent character LiCl and MgCl2 are soluble in ethanol.
viii) The hydroxides, bicarbonates and fluorides of both Li and Mg are
sparingly soluble in water.

General Characteristics of alkali metals.

They have one electron in S orbital and have electronic

configuration as [noble gas] ns1

They have largest atomic and ionic radii in their respective periods.
On moving down the group the atomic and ionic radii increase.

Alkali metals have lowest ionisation enthalpy in each period

The second ionisation enthalpies of alkali metals are very high

because monovalent cation have stable electronic configuration.

Alkali metals have one electron per atom so due to weak binding
energy they are soft and have low m.pt and b.pt.

The density of alkali metals is quite low as compared to other

metals it is due to larger atomic size.

All the alkali metals and their salts impart characteristic flame
colouration due to excitation of electrons.

Li Na K Rb Cs

Crimson yellow pale yellow Violet Bluish

All the alkali metals are strongly electropositive or metallic in

nature.

All the alkali metals exhibit an oxidation number of +1 in their

compound

Alkali metals salt have very high lattice enthalpies due to strong
electrostatic attraction. When size of cation increase lattice
enthalpies decreases.

They are strong reducing agent .It is due to their greater ease to
lose electrons

Biological importance of Na and K

i) Sodium ions participate in the transmission of nerve signals.
ii) Sodium ions also regulate flow of water across the cell membranes
and in transport of sugars and amino acids into the cells.
ii) Potassium ions are the most abundant cations within cell fluids, where
they activate many enzymes, participate in oxidation of glucose to
produce ATP.
iv)Potassium ions in combination with sodium ions are responsible for
transmission of nerve signals.
v) The functional features of nerve cells depend upon the sodium
potassium ion gradient that is established in the cell.

Frequently Asked Questions on S Block Elements

The first member of the s block elements differs from the rest of their members
considerably. Why?
Lithium and Beryllium, the first members of the s block family differ much
from the rest of their members. The anomaly of these elements is due to
their,

1. Low atomic and ionic size

2. Greater charge density (charge/volume of the atom)
3. Greater polarization and
4. Absence of ’d’ orbitals.
5. High I.E and electronegativity
6. High polarising power of cation

General characteristics of Alkaline earth metal

They have two electrons in the valence shell so they have electronic
configuration [noble gas] ns2

They are silvery, white, and hard metals. They are softer but harder
than alkali metals.

Some appears white but beryllium and magnesium appear greyish.

Their melting and boiling points are higher compared to alkali

metals.

They are strongly electropositive in nature.

 Except Mg and Be alkaline earth metals give different color with
flame test such as calcium gives brick red color, strontium gives
crimson color and barium gives apple green color. In Be and Mg
flame energy is not sufficient to excite electron due to smaller size.

All alkaline earth metals forms monoxide except beryllium.

They have high electrical and thermal conductivities as they have

metallic bonding.

The oxides of alkaline earth metals are basic but less basic than alkali
metals.

Hydroxides of alkaline earth metals are basic in nature except

beryllium hydroxide.

Group 2 metals forms solid carbonates. As one moves from

beryllium to barium thermal stability of carbonates increases.

Alkaline earth metals also form sulphates such as BeSO 4, and MgSO4.
Beryllium sulphate and magnesium suphate is soluble in water as
compared to other suphates of alkaline earth metals.

Group 2 elements form hydrated, crystallized nitrates. Heating of

nitrates form oxides, Barium nitrate crystallizes to form anhydrous
salt whereas magnesium nitrate crystallizes with six molecules of
water.

2Ba (NO3)2 + heat → 2BaO + 4NO2 + O2

Alkaline earth metals forms halides after reacting with halogens.

Beryllium chloride polymerizes in solid phase. There is a formation of
coordinate bond between beryllium and chloride. Halides of
beryllium are covalent. But halides of calcium, barium and strontium
are ionic or electrovalent in nature

They have low I.E due to fairly large size but I. E of group II elements
is higher than alkali metals.
The group II elements have to form stable complexes. Be and Mg
have maximum tendency to form complexes due to small size and
higher charge density eg. [BeF4]2-,Chlorophyll .

P- Block Elements

The elements in which the last electrons enters the P subshell of

their outermost energy level are called p block elements .There are
six group of p block elements from 13-18 .The general electronic
configuration for the atom of this block is ns2np1-6

General characteristics

 General electronic configuration of p block element is ns2np1-6

 The oxidation number is closely related to group number. The
highest oxidation number is group number 10.On descending
the group, a lower oxidation state which is two less than the
highest oxidation state becomes more stable in group 13-16.
This is due to inert pair effect .For example, the highest
oxidation number for gr. 13 is +3 however in addition to +3
these elements show +1 while moving down the group.
 The non-participation of the two s electrons in bonding due to the
high energy needed for un-pairing them i.e the reluctance of S-
electrons pair to take part in a chemical combination is called
inert pair effect .As a result of inert pair effect the heavier
elements of p block show oxidation state two units less than
group oxidation state. This helps to explain the stability of
lower oxidation state for heavier elements of a group, Thallium
+1 O.S is more stable than +3 although electronic configuration
is ns2np1  likewise Sn2+ and Pb2+ and Sb3+ and Bi3+ which are
the lower oxidation states of the elements are formed because of
the inert pair effect. The inert pair effect increases down the group
with an increase in the atomic number.

o Stability of elements and compounds changes due to inert

pair effect.or example, SnCl2 compound is more stable
than SnCl4compound.Because, in the formation
 of SnCl2 compound, ‘Sn’ metal utilize two ‘5p’-electrons
only.While, in the formation of SnCl4 compound, ‘Sn’ metal
used both ‘5s’ and ‘5p’ electrons.But, ‘5s’ electron of ‘Sn’ is not
available for compound formation due to inert pair effect.
Hence, SnCl4 compound becomes unstable.

o ( II )  Inert pair effect cause the variable valency of elements.

Both tin and lead show +2 and +4 oxidation state due to inert
pair effect. ‘Tl’ element shows +3 and +1 oxidation state for
same cause.

o ( III ) Inert pair effect, influence the oxidizing and reducing

properties of compounds. For example, +5 oxidation state of
Bi is less stable than +3 oxidation state of bismuth element .

o ( IV ) Inert pair effect, affect their melting and boiling point of

elements. For example, the melting and boiling point of
polonium [Po] is less than ‘Te’ .

 The p block elements contain both metallic and non- metallic

elements. The nom metallic character increases along a period but
decreases down the group.The non-metallic elements are present at
right top and metallic elements are present at lower left. In between
these elements like B Al, Si Ge, Sb etc show both metallic and non-
metallic characteristics are called metalloids.
 The first members of each group of p block element s differ in many
aspects from surrounding members (called congeners ) of their
respective groups due to

o i small size of an atom and its ion

o ii high electronegativity

o iii absence of d orbitals in their valence shell.

 Their ionisation energy are relatively higher as compared to S block

elements.

 They form mostly covalent compounds

 Some of them show more than one oxidation state in their

compounds

 There occur a graduation from reducing to oxidising properties as

we move across the period of this block.

 Group 18 elements with ns2 np6 electronic configuration are

known as noble gases.

 Group 17 elements are called halogens and group 16 are called

chalcogens ( ore former)
  Many elements like carbon sulphur silicon phosphorous show the
phenomenon of allotropy, they have no colour on flame, some of
them show catenation, and form acidic oxide.

Diagonal relationship

Some elements of second period show similarities with element of

third period present diagonally to each other though they are
belonging to different groups known as diagonal relationship.
A diagonal relationship exist between certain pairs
of diagonally adjacent elements in the second and third periods (first 20
elements) of the periodic table. These pairs (lithium (Li) and
magnesium (Mg), beryllium (Be) and aluminium (Al), boron (B) and
silicon (Si), etc. For examples: Lithium resembles with Mg It is due to
similarities in properties such as electronegativity, I.E, atomic size,
charge/ radius etc. .On moving from left to right across the period the
electronegativity increases while moving down the group
electronegativity decreases. Therefore on moving diagonally the two
opposing tendencies almost cancel out and electronegativity values
remain almost same. Thus diagonal pair have similar properties.

Ionisation Enthalpy The energy required to remove an electron

from isolated gaseous atom in its ground state to form a gaseous
cation is called Ionisation energy
X (g) X+ (g) +e-

The energy required to remove second electron from resulting cation

to form divalent cation in gaseous state is called second ionisation
energy and so on .It is expressed in KJ/mol

X+ (g) X++ (g) +e-

Thus ionisation energy gives the ease with which electron can be
removed from an atom, Smaller the value of I.E the easier it is to
remove the electron from an atom.

Factors affecting the Ionisation energy

Size of atom: Ionisation enthalpy is depends upon the distance

between electron and nucleus is size of an atom .The attractive force
between nucleus and electron is inversely proportional to distance.
As the atomic size increases outermost electrons is less tightly held
by nucleus as a result it becomes easier to remove the electrons
.Therefore I .E decreases with increase in atomic size.

Charge on nucleus: The attractive force increases between the

nucleus and electron with the increase in nuclear charge .Therefore
with the increase in nuclear charge it becomes more difficult to
remove an electron and ionisation enthalpy increases.

Screening effect: In multi electron atom the outermost electron are

shielded or screened from nucleus by inner electrons. This is known
as shielding effect .As a result outermost electron does the feel the
full charge of nucleus. If the number of electrons in the inner shell is
large the screening effect will be large .As a result nuclear –electron
attraction will be less consequently I.E will decrease.

Penetration effect of electron: In multi-electron system ,the electron

in S orbital have maximum probability of being near the nucleus and
this probability goes on decreasing in case of p ,d and f orbitals .In
other words S electron are more penetrating towards nucleus than p
,d or f electrons. If penetration power is more, electron are closer to
nucleus and will be held firmly .Consequently I.E will be high. Thus
for a same shell, IE would be more to remove s electron than energy
required to remove p or d or f electrons

Electronic arrangements: It has been observed that certain electronic

configuration are more stable than others. Half-filled and completely
filled shell have extra stability associated with them .Consequently it
is difficult to remove electron from these stable configuration and I.E
is high. Noble gas have stable configuration so have high I.E Be, Mg
have higher I.E s orbital is completely filled ., N,P have half-filled
configuration so have high I.E

Variation of I.E in periodic table:

In general the I.E increases with the increase in atomic number along
a period. It is because along a period nuclear charge increases ,
atomic size decrease so valence electron are more and more tightly
held by nucleus . Therefore more and more energy is required to
remove electrons.

However there are some irregularities due to half- filled and full
filled electronic configuration which have extra stability .

Down the group : With in a group there is a gradual decrease in

I.E . It is due to increase in atomic size, shielding effect , as well as
nuclear charge but increase in shielding effect and atomic size is
much more than nuclear charge as a result electron are less tightly
held by nucleus so can easily be removed.

Successive I.E

The energies required to remove subsequent electrons from the

atom in the gaseous state are known as successive I.E it can be
representative as

I.E1

M (g) M+ + e-
I.E2

M +(g) M++ + e-
I.E3
M ++
(g ) M+++ + e-

Successive I.E are higher than I.E. It is due to fact that after removal of first
electron the atom changes into cation which has same nuclear charge but less
electrons. so remaining electrons are held more tightly by nucleus .Electronic
configuration has great effect on successive I.E for examples First I.E of Li is
lower than Be but second I.E is very high due to extra stability .

Li Be
I st I.E 520 899
2nd I.E 7298 1758
Electron Affinity
Electron affinity or electron gain enthalpy is enthalpy change (energy released)
when an electron is added to an isolated gaseous atom to form a gaseous
anion
A (g) + e- A-(g) + energy
It is represented by Kj /mol
It may be exothermic or endothermic. For many element it is exothermic eg.
Group 17 elements have very high negative electron gain enthalpy because
they have tendency to acquire electros .On other hand noble gases have large
positive electron gain enthalpy because they have no tendency to accept the
electron .On other hand noble gases have large positive electron gain enthalpy
because they have no tendency to accept the electron. The magnitude of the
electron gain enthalpy measures the ability of an atom to hold an additional
electron. If atom has more tendency to accept electron large amount of energy
will be released. Consequently electron gain enthalpy would be negative .If an
atom has less tendency to hold electron small amount of energy is released.
Factor affecting the electron gain enthalpy
Nuclear charge
The electron gain enthalpy becomes more negative as nuclear charge
increases. This is due to greater attraction for incoming electron.
The size of the atom: With the increase in the size of the atom,-the distance
between the nucleus and the incoming electron increases and this results in
lesser attraction .Consequently electron gain enthalpy becomes less negative
with increase in size of the atom of the element.
Electronic configuration: The element having stable electronic configuration of
half- filled and completely filled valence shells show very small tendency to
accept additional electron and thus electron gain enthalpies are less negative.
Shielding effect: Electronic energy state, lying between nucleus and outermost
state hinder the nuclear attraction for incoming electron. Therefore, greater the
number of inner lying state, less will be the electron affinity.
Periodic variation: In general electron gain enthalpies becomes more negative
from left to right in a period and becomes less negative as we go from top to
bottom in a group.
On moving down the group atomic size and nuclear charge increases. Effect in
increase in size is more than nuclear charge so additional electron feels less
attraction by large atom so it goes on decreasing from top to bottom.
Along a period atomic size decrease and nuclear charge increase .Both of these
factors result greater attraction for incoming electron. Therefore electron
affinity becomes more negative.
Some important features:
Halogen s have the highest electron gain enthalpy. It is due to fact that
halogen have ns2np5 electronic configuration and have only one electron less
than stable noble gas so they have strong tendency to accept additional
electron.
Electron gain enthalpy for noble gas are positive .while Be, Mg ,N and P are
almost zero .I t is because noble gases have ns2np6 stable electronic
configuration so they have absolutely no tendency to take an additional
electron. Thus energy is required to force the electron in their atom and
therefore electron affinity is positive. Similarly Be , Mg have 2s 2 electronic
configuration which has extra stability and N, P have half- filled p orbital (np3 )
So configuration shows little tendency to gain any electron so E.A is almost
zero.
Electron gain enthalpies of fluorine is less than chlorine. It is due to the very
small size of F atom .As a consequence of small size there are strong inter-
nuclear repulsion in relatively compact 2p sub shell of fluorine and thus the
incoming electron does not feel much attraction.
Successive Electron Gain Enthalpies
The second and higher electron gain enthalpies are also possible .However the
second electron is added to negatively charged ion and addition is opposed by
repulsion. So energy has to be supplied to force the electron into anion.
O +e → O-- + ∆H=-141kj/mol
O- + e → O -- -∆ H =+788kj/mole
Electronegativity:

The relative tendency of a bonded atom in a molecule to attract the

shared electron pair towards itself is called electronegativity.
In other words, electronegativity is a measure of the ability of an
atom in a molecule to draw bonding electrons to itself. The greater
an atom’s electronegativity, the greater is its ability to attract
electrons towards itself.
Electronegativity is fundamentally different from electron affinity bec
ause of  the 
tendency of an isolated gaseous atom to attract the electron.  While
 electronegativity represents the tendency of a bonded atom to
attract the shared electron pair.
An atom’s electronegativity in a molecule is related to its energy of ioni
zation and its affinity with electrons, which are properties of isolated 
atoms.
Generally small atoms are more electronegative. The atoms with
nearly filled shells of electrons have higher electronegativity than
those with less than half-filled or scarcely filled.
 Halogens, for example, are the elements with almost filled shells and 
therefore the most electronegative, whereas alkali metals are the ele
ments that are  barely filled and the least electronegative.

Factors Affecting the Magnitude of Electronegativity

 Atomic Size. The smaller the size of an atom, greater is its

tendency to attract towards itself the shared pair of electrons .Thus
smaller atoms have greater Electronegativity values than the larger
atoms.
 Number of inner shells. The atom with greater number of
Inner shells has less value of electronegativity than the atom with
smaller number of inner shells, For
example, the electronegative values of halogens decrease from F to i
odine as the  number of inner shells increases from F to I.
  Charge on the ion (i.e., Oxidation state). Electro-negativity is
a variable quantity. It varies with the change in the oxidation state of
the element. The element in higher oxidation state has more value of
electronegativity than in the lower oxidation state. Thus the value of
electronegativity of Fe3+ is higher than that of Fe2+
  Type of hybridization. The magnitude of electronegativity of
an atom also depends on the type of hybridization which the atom
undergoes in the formation of different bonds in the molecule. The
magnitude of electronegativity increases as the s character in hybrid
orbitals increases.
  Ionisation energy and electron affinity
  The atoms of the elements that have higher values of ionizatio
n power and resistance to the electrons also have higher electronega
tive values.
  Nature of atoms to which the atom is bonded. Since
electro-negativity of an atom is not the property of isolated atom, it
depends on the number and nature of the atoms to which the atom
is bonded. Therefore the electro-negativity value of an atom is not
constant. For example, electro-negativity value of P atom in PCl 3
molecule is different from that in PF5 molecule in which the number
and nature of the atom both to which P atom is bonded change. ‘
 Periodic variation
 Electro-negativity increases from left to right in a period in the
periodic table since nuclear charge increases and atomic radius
decreases which cause electro-negativity to increase across a
period.
 With some exceptions (especially within transition metals),
electro-negativity decreases in going down a group due to successive
appearance of inner shells and increase in atomic radius with
increase in atomic number. The addition of extra inner shells in
larger atoms screen the shared pair from the nucleus and thus the
electron pair is attracted less by the atoms in the combined state.

Electronegativity and Nature of bond.

Non-metallic elements have tendency to gain electron so it is directly

related to the nom metallic properties of the elements.
Electronegativity is inversely proportional to metallic character. So
increase in electronegativity along a period metallic character
decreases and decreases the electronegativity metallic character
increases has highest value of electronegativity 4 and Ce has 0.7
( the most metallic element) .Elements with electronegativity 2 or
greater are non -metals and less than 2 metals .

The magnitude of electronegativity difference reflect the degree of

polarity .Greater the difference in electro negativities of the atoms
forming the bond greater will be the polarity of the molecule. When
electronegativity difference increases polarity of the molecule
increases and dipole moment of the molecule is also more.

Electronegativity of atom involved in a molecule predict the nature of

chemical bond . If the difference in electronegativity of two atoms is
large the bond is highly polar. In a extreme case electrons are
transferred and ionic bond is formed. So ionic bond is the extreme
Observed dipole moment/
case of covalent bond. Greater the electronegativity greater is the
ionic character .When electronegativities
Dipole moment difference
for ionic between two
atoms is 1.7 then the bond is 50% ionic and 50% covalent. If the
electronegativities difference is more than 1.7 the bond is
predominately ionic and if less than 1.7 bond is mainly covalent.

% of Ionic character = x 100

Differences between electron gain enthalpy and

electronegativity

.
Transition Elements:

The elements in the periodic table are classified as S,P,D,and F

block elements .The S and P block elements are called
representative elements .The d block elements are called
Transition elements because they exhibit transitional behaviour
between highly reactive ionic compound forming S block
elements in one side and covalent compound forming p block
elements on other side.

The elements which have partially filled d – orbitals in their

neutral atom or in their common ion are called Transition
elements.Thus outer electronic congiguration of transition
elements is (n-1) d1-10 ns1-2 where n is outermost shell and n-1
stands for penultimate shell . There are four transition series
3d, 4d, 5d,and 6d .The first transition series consist of 10
elements starting from scandium (21) to Zinc ( at no. 30) .These
are lie in 4th period of periodic table

Second series yttrium (39) ………..Cd P( 48)

Third series Lanthanum ( 57) …………….72 Hafnium

4th series is incomplete 89…………………….104

Properties of Transition Elements:

 All transition elements are metals .These elements show

high tensile strength ,ductility, malleability ,high thermal
and electrical conductivity and possess metallic lusture.
 These are hard (except mercury) with high melting and
boiling point.
 They form alloys among themselves and with other metals.
 Many of them are electropositive and dissolve in minerals
acid.
 They exhibit variable valencies and their ions or compound
are coloured in one or all oxidation state
 d- subshell is partially filled so they are paramagnetic
  Thet have valence electron both in outermost and second
outermost shell.
 [ Zn, Cd and Hg are the end of first three series ( 3rd, 4th and
5th) .Their electronic configuration are represented by
general formula (n-1) d10 ns2 .Since d orbitals are
completely filled hence these do not show the general
characteristics of transition elements .Therefore they are
metals not considered as transition elements ] these are
volatile metals.
 Transition elements have strong bonding between the
atoms so atoms are tightly held which increased nuclear
charge which drawn the electrons in to give a high density.
 Many transition metals and their compound are
extensively used as a catalyst in automobiles industry as
antipollution in exhaust gases.
 Transition metals ion can form large number of coordinate
compound in solution either with water or any other
molecules or ions. They have shall highly charged metal ion
with vacant d- orbital to receive lone pair of electrons

General characteristics of Transition elements

Some physical and Chemical characteristics of of transition

elements ( d- block elements) are given below

Electronic Configuration:

The electronic configuration of these elements is (n-1) d 1–10ns 1–2.

The (n–1) remains for the inward d orbitals which may have one to
ten electrons and the peripheral ns orbital may have one or two
electrons. They consist of an inner core of electrons having
noble gas configuration.
The half- filled and completely filled d- orbitals gain extra
stability so such configuration are favoured wherever
possible

Atomic Size: The atomic radii of d block elements in any

series decreases with increase in the atomic number .The
decrease in size is however not regular .The variation with in
a series is very small .The atomic radii tend to reach
minimum near at the middle of the series increase slightly
towards the end of the series.

Along a series nuclear charge increase gradually . The

additional electron goes to same penultimate shell .The
increased nuclear charge tends to reduce atomic radii. At
the beginning due to less number of electrons in a d-
subshell increased nuclear charge predominates and size
decreases but when d- electrons are increased shielding
effect increases and atomic size increases so at the middle
atomic size tends to minimum .The atomic size goes on
increasing while going down the group .This is due to
introduction of an additional shell .But size of 4th and 5th
series elements is nearly equal due to lanthanide
contraction

The ionic radii follow the same trend as atomic radii.

Ionisation enthalpies:

The ionisation enthalpies of these elements are high and in

most of the cases lie between those s and p block elements.
This is because transition elements are less electropositive
than S block elements . They have smaller atomic radii and
higher nuclear charge than alkali metals .

The ionisation enthalpies in any transition series increases

with atomic number however it is not smooth as S and P
block elements. Higher the value of second I.E of Cu and Cr
other than neighbouring element is due to extra stability of
full filled and half filled electronic configuration. .3rd I.E for
Cu , Ni ,Zn is much higher shows that oxidation number
greater than two is much difficult . 3rd I.E is quite high and
there is a break between Mn2+ and Fe2+ .

It is because the ionisation enthalpy increase due to

increase in nuclear charge with atomic number at the
beginning of the series. Gradually the shielding effect of
added electrons also increase which tends to decrease
attraction by nucleus lead gradually decreaing I.E. But
shielding power of electrons present in the d- orbitals is
relatively very less in comparisition to s and p orbitals . So
value of I.E increase. The first I.E of 5d series of element are
much higher than those of 3d and 4d series.

Metallic character:
All the transition elements except Zn ,Hg And Cd are harder
and are less volatile. The transition elements are good
conductor of heat and electricity . They are malleable and
ductile and form alloys with other metals . They exhibit all
three types of structure face centered cubic (fcc) hexagonal
closed packed ( hcp) and body centred cubic ( bcc) .

Due to low I.E and partially filled or vacant orbitals make

these elements metallic in character. The presence of
unfilled d- orbitals favour covalent bonding. Metallic
bonding in these elements is indicated by conducting nature
of these metals. Therefore it appears that their exist in
covalent and metallic bonding for transition elements.

Metallic character:

All the transition elements except Zn ,Hg And Cd are harder

and are less volatile. The transition elements are good
conductor of heat and electricity . They are malleable and
ductile and form alloys with other metals . They exhibit all
three types of structure face centered cubic (fcc) hexagonal
closed packed ( hcp) and body centred cubic ( bcc) .

Due to low I.E and partially filled or vacant orbitals make

these elements metallic in character. The presence of
unfilled d- orbitals favour covalent bonding. Metallic
bonding in these elements is indicated by conducting nature
of these metals. Therefore it appears that their exist in
covalent and metallic bonding for transition elements.

Tendency to the formation of complex compound:

An electrically charged species in which a metal atom or
simple cation is coordinated to two or more anions or
neutral molecules and which retains its identity in solution
is called a complex ion. Transition metals and their ions
show strong tendency for complex formation . It is due to

i) small size and high nuclear charge of

transition metal cation so it makes easy to
accept lone pair of electrons from ligands.
ii) ii) the availability of vacant inner d orbitals
of suitable energy.
iii) iii) They are capable of showing several
oxidation state.

The cation of transition elements form complex ion with

certain molecule containing one more lone pair of electrons
like H2O, NO, NH3, CO etc with anions like F- , Cl- ,CN- etc. eg.
[Fe(CN)6]4- [Cu( NH3)4]2+ Ni(CO)4 .The structure of
complexes are linear (C.N=2) square planner (C.N=4)
octahedral (C.N=6)

Since the electropositive character increases on moving

down the group ,the member of 1st transition series from
more stable complex with ligand containing nitrogen and
oxygen. Second series with form with sulphur, phosphorous
. Complex formation is due to lone pair of electron donated
by ligands (ligands are neutral molecule or ions having lone
pair of electrons and can form coordinate covalent bond
with transition metal atom or ions having vacant d orbitals.)
Complexes of +3 oxidation state are more stable than +2
oxidation state

Variable oxidation state:

Most of the transition elements exhibit several oxidation
state ie they show variable valencies in their compounds.
These elements show variable oxidation state because their valence
electrons in two different sets of orbitals, that is (n-1)d and ns. The
energy difference between these orbitals is very less, so both the energy
levels can be used for bond formation. Thus, transition
elements have variable oxidation states. The elements which
show the largest no. of oxidation state occur in the middle
of the series eg. Mn shows oxidation state from +2 to +7.
Oxidation state of first 3d series is

The outermost electronic configuration of the transition

element is (n-1) d1-10 ns2. Since the energy level of (n-1) d
and ns orbitals are quite close to each other . Hence both
the ns and (n-1)d electrons are available for bonding
purposes so no. of oxidation state shown by these elements
depends upon the no. of d electron it has. For example Sc
show O.S +2 ( only s electrons are lost) and +3 when d
electrons are also lost.. The highest oxidation state is given
by the total no. of ns and (n-1)d electrons. The stability of
different oxidation state depends upon the electronic
configuration, nature of bonding, lattice energy, etc.The
highest oxidation state is +8 showing by Ru, Os

Conclusion:

The variable oxidation state shown by transition elements

are due to the participation of outer ns and inner ( n-1)d
electron in bonding.

Except Sc the most common O.S shown by element of 1 St

transition series is +2. This O.S is arises from the loss of two
4s electrons. This means d orbitals are more stable than S
orbitals.

The highest O.S are observed in fluorides and oxides .The

highest O.S is + 8 shown by Ru , Os

Transition element in +2 and +3 oxidation state form mostly

ionic bond in higher oxidation state these elements form
essentially covalent bonds

With in group the maximum O,S increases with atomic

number eg Fe shows +3 but Ru shows +4,+6,+8

They also form compounds in low O.S such as +1and zero eg

Ni(CO)4 has zero S.O

Formation of Coloured Ions

Most of the compounds of transition elements are coloured
in solid state and in solution due to presence of unpaired
electrons in d orbitals.

In an isolated atom or ion of transition elements all the five

d orbitals are of equal energy said to be degenerate. Under
the influence of the combing anions or electron rich
molecule the five d orbitals split into two level of different
energies. The difference between two energy level depends
upon the nature of combing ions but corresponds to the
energy associated with radiation of visible region. This
phenomenon is known as crystal field splitting

The transition elements in elemental form or in ionic form

have one or more unpaired electron. When visible light falls
on the sample the electron from lower energy level get
promoted into higher energy level due to adsorption of light
of characteristics wave length. This wave length of absorbed
light depend upon the energy difference between two
levels. Rest of the light is transmitted, the transmitted light
has a colour complementary to the absorbed colour.
Therefore the compound or solution appears to be a
complementary colour.

The colour of transition metal complexes are due to

transition of unpaired electron from one energy level to
another energy level i.e from one d orbital to another d
called d-d transition. [Cu (H2O)6]2-

Absorb red radiation and appear blue green, a

complementary colour.Co2+ absorb blue green a so appears
red in sunlight.

The transition metal ion which have completely filled d-

orbitals are colourless as there are no vacant d orbital to
permit the promotion of the electron. Therefore Zn 2+ Cd2+
and Hg 2+ are colourless. Transition metals which have
completely empty d orbitals are also colourless eg Sc3+ Ti4+
ions are colourless. No d-d transition is possible in them so
no light is absorbed. Colour due to 3d series ion is as
Factor affecting the colour of complexes

Change in the no. of d- electrons

Field strength of the ligand

Geometry of complex

Magnetic properties

On basis of behaviour in a magnetic field ,the substances

are classified as paramagnetic ,diamagnetic and
ferromagnetic. Most of the transition metals and their
compound show paramagnetism . These substances
which are attracted by the applied magnetic field are
called paramagnetic .The maximum paramagnetism is
seen around middle of the series .Paramagnetism is due
to presence of unpaired electron in atom or ions or
molecules. As the number of unpaired electron increases
the paramagnetic character also increases. The magnetic
moment of any transition element or its compound is given
by
μs = n(n+2)BM

where n is the no of unpaired electron and BM is Bohr

magneton.

In a d orbitals belonging to a particular energy level , there

can be a maximum five unpaired electron in d5 cases.
Therefore paramagnetism in any transition series first
increase and reaches to maximum value for d5 case and
then decrease thereafter.

Those substances which are repelled by applied magnetic

field are diamagnetic .For diamagnetic ꭎ = 0

Those substances which are very strongly attracted by

applied magnetic field are ferromagnetic .

Catalytic properties:

Most of the transition elements act as good catalyst,

because of

Presence of vacant d orbitals

The tendency to exhibit variable oxidation state

The tendency to form reaction intermediate with reactant

The presence of defect in their lattice

Pt ( a general catalyst), Fe Haber process),

Ni( Hydrogenation), V2O5 ( Contact process) are important
catalyst .

The surface of solid catalyst provides sites for absorption

of reacting molecule which causes the weakening of
certain bonds in reacting molecule and facilitates the
reaction . These elements can form unstable intermediate
compound with suitable reactant path for lower activation
energy , Therefore increase the rate of reaction . The
intermediate compound decomposes readily to give a final
products.

Reactant + transition element unstable intermediate

product + transition metal

Alloy formation: A homogenous solid mixture of metal with

one or more metals or non-metals is called an alloy.
Transition metals form alloy among themselves. The alloy
of transition metals are hard and high melting as
compared to host metal.

Steel = Fe + C

Bronze = Cu+ Tin

Brass= Cu+ Zn

The atomic radii of transition elements in any series are

not much different from each other. As a result they can
very easily replaces other in the lattice and form a solid
solution.

Chemical reactivity:

The d- block elements have lesser tendency to react as

compared to S block elements. Thus low reactivity of
element is due to

High ionisation enthalpies

Low enthalpy of hydration of their ion

High enthalpy of sublimation