Transition elements (or d-block elements) : Transition elements are the elements

which lie inbetween s and p block elements in the long form of periodic table.
They are called d-block elements as the last electron enters in the d-orbital.
General electronic configuration : (1-1)d "ns
Transition series : d-block consists of four transition series,
1 Transition series or 3d series ,Sc-
0Zn
2nd Transition series or 4d series 9Y - 48Cd
3rd Transition series or 5d series La, ,Hf -
soHg
4th Transition series or 6d series ggAc, 10gRf
-u2Cn
General properties of the transition elements:
Property Trends and Explanations
Melting and High due to involvement of greater number of electrons from
boiling points (n-1)d in addition to ns electrons in the interatomic metallic
bonding (greater the number of valence electrons, stronger is
the resultant bonding).
Enthalpiesof High due to strong interatomic interactions.
atomisation
Atomic and ionic Decrease in the series with increase in atomic number
sizes because of increased nuclear charge and ineffective
shielding effect of d-electrons.
Increase down the group but radii of third series are
virtually the same as those of the corresponding members
of secondseries due to lanthanoid contraction.
Ionisation Jonisation enthalpy increases from left to right in a series.
enthalpies The first ionisation enthalpies of Zn, Cd, Hg are very high
because of fully filled configurations.
Cr and Cu show unusually high values of second ionisation
enthalpies due to disruption of d and d°configurations
of M ion respectively while that of Zn is low as it leads to
stable d'" configuration.
 Third jonisation enthalpy of Mn is very high due to disruption of d configuration
while that of Fe is very small as it leads to d configuration.
Oxidation states
Alltransition elements except the first and last member ofeach series show variahla
oxidation states because difference of energy in the (n-1)d and ns orbitals is ve
little and electrons from both the orbitals can be used for bond formation.
Highest oxidation state of transition metals are found in fluorides and oxides and +.
ability of oxygen to stabilise high oxidation states exceeds that of fluorine due to ite
ability to form multiple bonds.
The compounds in +2 and +3 oxidation states are mostly ionic.
The highest oxidation state is equal to total number of s- and d-electrons. Maximum
oxidation state increases from Scto Mn and then decreases to Zn.
M²*/M standard EM'M do not show regular trend because of irregularities in ionisation enthalpies
electrode and enthalpy of atomisation.
potential The general trend towards less negative E values across the series is related to
increase in sum of first and second ionisation enthalpies.
E for Mn, Niand Zn are more negative due to stable configurations of Mn"(d)
and Zn (d) and high negative enthalpy of hydration in case of Ni.
Cuhas positive E value due to its low hydration enthalpy.
MIM EN shows the varying trends.
standard Thevalues are high for Zn and Mn due tostability of d and d configurations
electrode while the values are low for Fe and Sc due to extra stability of Fe*(d) andSe* (a).
potential Low value for Vis due to stability of half filled t, configuration in V*.
Magnetic Transition metal ions and their compounds are paramagnetic due to presence of
properties unpaired electrons in the (n-1)d-orbitals.
Paramagnetism increases with increase in the no. of unpaired electrons fromn l to 5.
Those transition elements which have no unpaired electrons are diamagnetic.
Magnetic moment is determined by the number of unpaired electrons and is
calculated by using the formula, =ynn+2) ; where n is the no. of unpaired
electrons and uis the magnetic moment in units of Bohr magneton (BM),
Formation of Transition metal compounds are coloured both in solid state and aqueous solution
coloured ions because of incompletely filled d-orbitals which split into two sets- one with lower energy
and one with higher energy in the presence of the anions (Crystal field splitting). Hence,
d-d transitions of unpaired electrons are responsible for colour.
Formation Transition metals form a large number of complexes due to
of complex High nuclear charge and small size i.e. charge/size ratio is large.
compounds Availability of empty d- orbitals to accept lone pair of electrons donated by ligands.
Catalytic
properties
Transition metals show catalytic properties due to their ability to adopt multiple
oxidation states and to form complexes.
Formation Transition elements have empty spaces in their lattices in which small atoms like H, C,
of interstitial Bor N can be accommodated, hence they form interstitial compounds like TiC, Mn,N,
compounds Fe,H, etc.
Alloy formation Transition metals form alloys easily because
They have similar atomic sizes.
In crystal lattice one metal can easily replace the other, giving solid solution and
smooth alloys.
Compounds of transition elements :
Oxides :They form oxides with oxidation states +l to +7 and their ionic character decreases whereas
acidic character increases as oxidation state increases.
e.g.; MnO Mn,0, Mn,O, MnO, Mn,O,
Basic Acidic
lonic Amphoteric
Covalent
 Potassiumn dichromate (K,Cr,0.):
Preparation:It is obtained by fusion of chromite ore (FeCr,0,) through the following steps:
4FeCr,0,+8Na,CO,+ 70, ’ 8Na,Cr0, + 2Fe,O, + 8CO,
2Na,CrO, + H,SO, > Na,Cr.0- + Na,SO, + H,0
Na.Cr,0, + 2KCl -> K,Cr,0. + 2NaCI
Properties:
Orange crystals and are moderately soluble in cold water but readily soluble in hot water.
In aqueous solution, dichromate ion (Cr,0)andchromate ion (Cro,) exist as follows:
Cr,0 + H,02Cr0; +2H*
(Orange) (Yellow)
In alkaline medium,equilibrium shifts in forward direction and solution is yellow.
In acidic medium, the equilibrium shifts in backwarddirection andcolour is orange.
It is astrong oxidising agent in acidic medium,
Cr,0 + 14H + 6e ’ 2Cr* + 7H,0
It oxidises I to l, H,Sto S, Sn* to Sn,Fe to Fe*, etc.
Chromyl chloride test : Ametal chloride on heating with solid K,Cr,0, and conc. H,SO, gives red
vapours of chromylchloride (CrO,C,).
K,Cr,0, +4KCI + 6H,SO,> 2Cr0,CI, + 6KHSO, + 3H,0
) Potassium permanganate (KMn0):
Preparation: t is prepared from pyrolusite ore (MnO,) through the following steps :
2MnO, + 4KOH + O, ’ 2K,Mn0, + 2H,0
K,MnO, can be converted to KMnO, by two methods:
Electrochemical oxidation :
At anode : MnO ’ MnO,+e
Green Purple
At cathode: 2H* + 2e > H,
In acidic or neutral medium, manganate ion disproportionates to give permanganate.
3MnO +4H* ’ 2MnO, +MnO, +2H,0
Properties:
Dark purple (almost black) crystals and sparingly soluble in water.
Strong oxidising agent in alkaline and acidic medium.
In acidic medium,
MnO, + 8H + 5e ’ Mn + 4H,0
ItInoxidises I to I, Fe* to Fe*, C,of to CO, S to S, so to SO, NO; to NO;, etc.
neutral or faintly alkaline medium,
MnO, +2H,0 + 3e ’ MnO, + 40H
Itoxidises I to IO3,S,o to SO, Mn" to MnO, etc.
Volumetric titrations involving KMnO4 are carried out only in the presence of dil. H,SO, but not in
the nresence of HCl or HNO, because HCI is oxidised to Cl, and HNO, is itself a
strong oxidising agent
and partlyoxidises the reducing agent. FH,sO, does not give any oxygen of its own to oxidise the reducing
agent.
Inner transition elements (or f-Block elements) :
º Lanthanoids :The elements withatomic numbers 58to071 i.e. cerium to
after lanthanum, Z = 57) are called lanthanoids. lutetium (which come immediately
Actinoids The elements with atomic numbers 90 to 103 i.e. thorium to lawrencium
Immediately after actinium, Z= 89) are called actinojds. (which come
They are called f-block elements because last electron enters into f-orbital.
General electronic configuration: (n-2)f
General characteristics of lanthanoids :
Atomic and Jonic radii: The atomic and ioniCradii decrease steadily on going from La to Lu.
 Oxidation states : Most common oxidation state of lanthanoids is +3. Some elements exhibit +2
oxidation states due to extra stability of empty, half-filled or filled f-subshell. e.g., Ce* acts as arn and+4
agent and gets reduced to Ce". Eu", Yb act as strong reducing agents and get oxidised to Eu+ and Y oxidisinp
Action of air:All the lanthanoids are silvery white soft metals and tarnish readily in moist air. They bu"
in oxygen of air and form oxides (Ln,0, type).
Coloured ions: They form coloured ions due to f-f transitions of unpaired electrons. La and I ,3+
are
colourless ions due to empty (4f) or fully (4f") orbitals.
Magnetic properties : La", Lu" are diamagnetic while trivalent ions of the rest of lanthanoids are
paramagnetic.
Reducing agents : They readily lose electrons and are good reducing agents.
Electropositive character : Highly electropositive because of low transition energies.
Alloy formation : They form alloys easily with other metals especially iron.
Tendency to form complexes : Lanthanoids do not have much tendency to form complexes due to low
charge density because of their large size. The tendency toform complexes and their stability increases
with increasing atomic number.
Lanthanoid contraction : In lanthanoid series, with increasing atomic number, there is progresSsive
decrease in atomic/ionic radii (M²* ions) from La to Lu".
Reason : Due to addition of new electrons into f-subshell and imperfect shielding of one electron by
another in the f-orbitals, there is greater effect of increased nuclear charge than screening efect hence
contraction in size.
Consequences : Their separation is difficult, they have small differences in properties and 4d and 5d
transition series have almost same atomic radii (Zr and Hf have similar properties due to same size).
Uses of lanthanoids : Used in making misch metal, an alloy of a lanthanoid metal (- 95%) with iron (~ 5%)
and traces of S, C, Caand Al. It is used to make tracer bullets, shells and lighter flints.
General characteristics of actinoids :
lonic radii :Like lanthanoids, ionic radi decrease regularly across the series. Actinoid contraction is
greater due to poor sheilding effect of the 5f-electrons. Further, Sf-orbitals extend in space beyond 6s and
6p-orbitals whereas 4f-orbitals are burried deep.
Oxidation states :Like lanthanoids, most common is+3. They also show oxidation state of +4, +5, +6
and +7, e.g., in Th, Pa, Uand Np respectively. They show alarge number of oxidation states because of very
small energy gap between 5f, 6d and 7s subshells.
Action of air, alkalies and acids : Like lanthanoids they are also silvery white metals, tarnish rapidly in air
forming oxide coating and are not attacked by alkalies and are les reactive towards acids.
Coloured ions : Are coloured due to ff transition except Ac (5f"), Cm*(5f') and Th**(5f") which are
colourless.
Magnetic properties : They are strongly paramagnetic.
Density : All actinoids except thorium and americium have high densities.
Melting and boiling points : High melting and boiling points however there is no regular trend with rise
in atomic number.
Ionisation energy:They have low ionisation energies.
Reducing agents: Al actionoids are strong reducing agents.
Electropositive character : Highly electropositive metals.
Uses of actinoids : Thorium is used in atomic reactor and treatment of cancer. U and Pu are used as fuel in
nuclear reactor.
Difference between lanthanoids and actinoids :
Lanthanoids Actinoids
They show +2 and +4 oxidation states in few cases They show higher oxidation states of +4, +5, +6 and
besides +3. +7 besides +3.
Except promethium, they are non-radioactive. Allactinoids are radioactive.
They do not form oxO-cations. They form oxo-cations like UO, PuO%*, UO, etc.
|The compounds of lanthanoids are less basic. Actinoid compounds are more basic.
They have less tendencyof complex formation. They have greater tendency of complex formation.