D and F Block

D Block: Elements in the group 3 to 12 in which the d orbitals are progressively filled in 4 long
periods is known as D block. It lies in the middle of the periodic table between the p block and s
block.
Transitional Elements: The elements having partially filled d orbitals in their most common
oxidation state or ground state. General Formula (n-1)d¹`¹⁰ns.
•Pd has exceptional general configuration 4d¹⁰5s⁰.
•Cr,Cu has exceptional configuration because half filled and fully filled orbitals are more stable
than partially filled. Cr: 3d⁵4s¹ ; Cu: 3d¹⁰4s¹
Non transitional elements: General Formula (n-1)3¹⁰d ns². Some examples are Zn,Hg,Cd,Cn.
These elements are non transitional because they don't have partially filled d orbitals in their
most common oxidation state as well as ground state.

General Properties of D Block Elements

1.Physical Properties: Transitional elements displays typical metallic properties such as,
•High tensile strength.
•Ductility & Malleability.
•High thermal and electrical conductivity.
•Lusture and high density.

They exhibit metallic character due to their relatively low ionization enthalpy and number of
vacant orbitals in the outermost shell.

Transition metals (except Zn,Hg,Cd) are very hard. Have high MP and BP and high enthalpy of
atomisation.
The hardness and high MP is due presence of unpaired es thus stronger is the bonding which
implies higher enthalpy of atomisation.

Cr,Mo,W are hard and have high enthalpy of atomisation whereas Zn,Hg,Cd are soft and has
low enthalpy due to no dd overlapping because of the absence of unpaired es.

NOTE: 2nd & 3rd series have high enthalpy of atomisation than first.

2.Atomic and Ionic Radii:

Along a Period: In a given series, shows progressive decrease in radius with increase in
atomic number up to the middle and remains constant for a while then increases towards the
end.
•Decreasing sizes due to increase in nuclear charge which increases the effective nuclear
attraction.

•As the number of the electron increases, the shielding effect also increases which neutralizes
the effect of increasing nuclear charge. Thus atomic radius remains almost constant after
chromium.
•Towards the end of the series there is increased electron electron repulsion between and
electrons in the same subshell which exceeds the attraction force due to increased nuclear
charge. Show electron cloud expense and size increases.

Along a Group: Atomic radius increases but the elements of 3rd transition series have nearly
the same radius as second transition series. Reason being lanthanoid contraction

Lanthanoid Contraction: Steady decrease in ionic and atomic size of lanthanide elements with
increase in atomic radius.
The nuclear charge increases by one unit on moving from left to right in lanthanide series. The
number of e-s in 4f orbitals also increases. However, 4f electrons do not shield each other very
well so effective nuclear charge increases and size decreases. (STUDY ITS CONSEQUENCES
FROM NOTES)

3.Density: The decrease in metallic radius with increase in atomic number results in the
increase in the density of elements. Thus, from titanium to copper there is a significant increase
in density.

4.Ionization Enthalpy: There is an increase in ionization enthalpy from left to right due to
increase in nuclear charge but the increase isn't regular.
•IE1 of D block elements are higher than S block but lower than P block.
•The IE1 of the third transition series is higher than those of the second transition series because
of poor shielding effect of 4f orbitals.
•The IE1 of Cr and Cu is low due to removal of 1e-s gives stable electronic config while IE2 is
very high because removal of 1 more electron disturbs stable config.
•The IE2of Mn and Zn are lower than the IE1 because after removal of 1 more e-s they attain
stable electronic config.

5.M.P and B.P: In a given series, MP& BP increase upto middle and then decreases.
REASON: As no of unpaired es increases, metallic bond strength increases hence MP increase.
But in transition series no of unpaired es increases upto middle and then decreases.

•It rises upto max value upto Cr, shows slight dip at Mn. Then slight increases upto Fe & Co and
then decreases.
•High MP is due to strong metallic bond formed due to d-d overlapping of half filled orbitals.
•Cr,Mo,W has max MP and BP
•Zn,Cd,Hg has low MP and BP (absence of es)
•Mn & Tc have low MP because of stable electronic config (d⁵). Thus es are tightly held by the
nucleus and it reduces delocalisation of es, resulting in weak metallic bonding.
•The 2nd & 3rd transition series have higher MP than 1st. (Strong bond formation).
6.Electrode Potential:The E° values of transition series generally increases from left to right
along a period due to increase in sum of IE1 and IE2. Thus in 3d series, value becomes less and
less -ve. Some expectations are;

•The E°(Cu²+/Cu) is +ve, while the Eº values of all the other 3d transition elements are -ve.
Reson Cu has a high value of atomization enthalpy and low hydration enthalpy.

•The E° values for Mn and Zn are more negative than expected because they have either
half-filled and fully-filled configurations.

•Ni have more negative E values than expected because of smaller ionic radius which result in
highest (-ve) enthalpy of hydration. Thus Ni²+ is more stable than Ni.

7.Oxidation State: Transition elements exhibit variable oxidation states[expect Zn(+2) &
Sc(+3)], because d and s es have compareable energy so s and d electrons also participate in
chemical reaction. Oxidation State generally increases up to the middle and then decreases.

•Mn[7] has highest and max no of variable oxdn state in 3d series while those of d block 8+ is
maximum.
•Only Cu has +1 oxdn state.
•Oxdn state of Zn is +2(no d electrons are involved).
•Transition elements exhibit 0 oxdn state in metal carbonyls
Eg Ni(CO4) ; Fe(CO5)

8.Magnetic Property: Measure of number of unpaired electrons when a magnetic field is

supplied. Types of magnetic field
a. Diamagnetic: They are repelled by magnetic field and all electrons are paired.
b. Paramagnetism: They are attracted by magnetic field and all electrons are unpaired.

•As number of unpaired electrons increases paramagnetism increases(In transition series no of

unpaired es increases upto middle and decreases). d⁵ config has max no of unpaired es thus
maximum paramagnetic nature.
•To calculate Magnetic Moment we use Spin-Only Formula.
[ μ0=√n(n+2) ] where n is no of unpaired es

•Most of the transition metal ions are paramagnetic in nature. Transition metal ions having
3d⁰and 3d¹⁰ configuration exhibit diamagnetic nature.

9.Coloured Complexes: they form coloured ions due to the presence of unpaired es in d
orbitals which undergo d-d transition and exhibit color.

•d-block metals having fully paired es are colorless, whereas those having unpaired es are
coloured in nature.
•Transition metal compounds are mostly coloured in their solid or in solution states.
Q.Why anhydrous CuSO4 is colorless but hydrated CuSO4 is blue in color?
Due to absence of water(which acts as ligand), d-d transition is not possible in CuSO4. Thus it
doesn't exhibit color.

10.Formation of Complex Compounds: They have high tendency to form complexes

because of their
●​ Small Size
●​ High Nuclear Charge(shows variable oxdn state)
●​ Availability of vacant d orbitals.

11.Catalytic Properties: they act catalyst due to

●​ Ability to show variable oxdn states
●​ Ability to form complexes
●​ Large surface area of d block elements.
Eg: Fe(3+) catalyses the reaction b/w iodide & persulphate.

12.Formation Of Interstitial Compounds: Small non metallic atom such as H, B, C, N etc

are able to occupy interstitial space of the lattice of the d-block elements to form combinations
which are termed interstitial compounds.
Eg TiC, TiH1.7, VH0.56
These Interstitial compounds have similar chemical properties as parent atom but different
physical properties.

Steel and Cast Iron are hard because of formation of Interstitial compounds with carbon

Characteristics
They have high MP, higher than those of pure metals.
They are chemically inert.
Interstitial compounds are neither ionic nor covalent.
They are non-stoichiometry in nature and do not follow the common rule of valency.

13.Alloy Formation: Due to similiar atomic d block elements readily form alloys. The alloys
formed are
●​ Hard
●​ High MP
Cr, W, Mo and Mn are used for the production of a variety of steels and stainless steel.
Alloys of Transition elements with non transition elements are; Brass(Cu-Zn) Bronze(Cu-Tin).
Important Questions
Q. Explain why Cu+ ion is not stable in aqueous solutions?
Because it undergoes disproportion reaction.

Q. Which is a stronger reducing agent Cr²+ or Fe2+ and why?

Cr2+ is a stronger reducing agent than Fe2+ because it has a greater reduction potential and
can more easily lose electrons

Q.Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Both oxide and fluoride ions are highly electronegative because of high oxidizing power and
they have a very small size. Due to these properties, they are able to oxidize the metal to its
highest oxidation state.

NOTE: Cr and Zn have very high and low enthalpy of atomization respectively among d-block
elements.

Important Compounds of Transition Elements

Oxides of Metals The oxides of transition elements are generally formed by the reaction of
metals with O2 at
high temperature. All the metals except Sc form metal oxide which are ionic.

Potassium dichromate K2Cr22O7

It's an acidic compound in which Cr is present in +6 oxdn state. Its used in Leather Industry.

Preparation: Prepared from Chromite Ore.(FeCr2O4 )

Chromite ore is fused with Na2CO3 in excess air.

The yellow soln of sodium chromate is filtered and acidified to give sodium dichromate.

By mixing a hot con. soln of sodium dichromate and KCl and on cooling orange crystals
separate out.
Structure

The oxdn state of Cr in chromate and dichromate is the same +6.

Potassium Permanganate (Refer Notes)

F Block Elements OR Inner Transition Elements

F block: elements in which electrons enter in the f-subshell are called F block elements.The 2
series of f block are lanthanoids and actinoids.
General Config
[ (n-2)f¹-¹⁴ (n-1)d⁰-¹ ns² ]

Lanthanoids: The 14 elements after lanthanum in which 4f orbitals are progressively filled are
called Lanthanoids. They comprises of rare elements thus called Rare Earth.
General Configuration 4f¹-¹⁴ 5d⁰-¹ 6s²
•Promethium is a radioactive element.

General Properties of D Block Elements

Atomic and Ionic Radii: In lanthanide series, with increasing atomic number, there is a
progressive decrease in the atomic radii as well as ionic radii La to Lu. This is due to lanthanide
contraction happening due to poor shielding effect of 4f orbitals.

Check Consequence of Lanthanoid Contraction From Notes

Oxidation State:
•Most common oxdn state is +3. However only Cerium (Ce) exhibit higher oxidation state +4.

Praseodymium (Pr),Terbium (Tb), Nd,Dy exhibit +4 but in oxides.

•Oxidation state +2 and +4 occur specifically
when they lead to,
●​ Inert gas configuration e.g Ce⁴+(4f⁰)
●​ Half filled f orbital e.g Eu²+, Tb4+ (4f⁷)
●​ Fully filled f orbital e.g. Yb²+ (4f¹⁴)

•Lower oxidation state act as reducing agent (Eu2+, Yb2+) and higher oxidation state act as
oxidizing agent (Ce4+, Tb4+).
•Eu²+ is stable because of half filled config, but it's strong oxidizing agent thus changing to Eu³+.

•The E⁰ value for Ce4+/ Ce3+ is + 1.74 V which suggests that it can oxidize water. However, the
reaction rate is very slow and hence Ce(IV) is a good analytical reagent.

Refer Notes For

•General Properties
•Magnetic Property
•Formation of Coloured Compounds.

Alloy Formation: Lanthanoids forms alloys.The best use of lanthanoids is for production of
alloy steels for plates and pipes. Eg of alloy formed is MischMetal. It consists of a lanthanoid
metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
Misch metal is used in Mg-based alloy to produce bullets, shells etcoids

Actinides: The elements in which the last electron enters

5f-orbitals of (n–2)th main are known as actinides or actinoids.
General configuration of actinides may be
given as 5f1–14 6d0–1, 7s².

Oxdn State
•The actinoids show in general + 3 oxidation state.
• Actinoids show a variety of oxidation state. It is because of a small energy difference between
5f, 6d and 7s subshells.
•The element in the first half of the series frequently exhibit higher oxidation states. For example
the maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and
Np but decreases in succeeding
elements.
•The actinoids exhibit a large number of oxidation states than the corresponding members in the
lanthanoid series.

Atomic Radii:
In actinoid series size of atom or ions gradually decreases. It is considered as actinoids
contraction (similar to lanthanoid contraction). Due to poor shielding by 5f-electrons.

General characteristics & comparison with lanthanoids

•Instead of having same color (silver) all actinoid metals display the variety of structures, this
variety is due to irregularities in metallic radii which are far greater than in lanthanoids.
•The actinoids are highly reactive metals.
•The magnetic properties of the actinoids are more complex than those of the lanthanoids.
•Actinoids compound or their ions are coloured most probably due to f-f transition.
•Actinide contraction is greater than lanthanoid contraction due to poor shielding by 5f-electrons
in actinides than that of 4f-electrons in the lanthanoids.