d and f block elements

Transition element: Those elements whose atom or simplest ion have partially filled d-orbital (i.e. d-
orbital containing 1 to 9 electrons) are called transition elements.

There are 4 series of transition element.

(1) 3d series (Sc-Zn)
(2) 4d series (Y-Cd)
(3) 5d series (La-Hg)
(4) 6d series (Ac-Uub)

Sc Ti V Cr Mn Fe Co Ni Cu Zn

3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d10 4s1 3d10 4s2
Ag Cd
4d10 5s1 4d10 5s2
Au Hg
5d10 6s1 5d10 6s2

Cu (29) : [Ar] 3d104s1

Cu+ (28) : [Ar] 3d104s0 E0 Cu+/Cu = 0.52V

Cu2+ (27) : [Ar] 3d94s0 (More stable) E0 Cu2+/Cu = 0.34V

Zn (30) : [Ar] 3d104s2

Zn2+ (28) : [Ar] 3d104s0

175
Q1. Explain why Zn, Cd, Hg are not regarded as transition element?
Ans. Zn (30) : [Ar] 3d104S2
Zn2+ (28) : [Ar] 3d104S0

Because neither their atom nor the simplest ion have partially filled d-orbital. Hence, these are not
regarded as transition element.

Q2. Silver atom has completely filled d- orbitals (4 d10) in its ground state. How can you say that
it is a transition elements.
Ans. The outer electronic configuration of Ag ( Z= 47) is 4d105s1. In addition to +1, it shows an
oxidation state of +2 (e.g., AgO and AgF2 exist). In +2 oxidation state, the configuration is 4d9, i.e.,
the d-subshell is incompletely filled. Hence, it is a transition elements.
Atomic radii

Sc Ti V Cr Mn Fe Co Ni Cu Zn
(pm) 162 147 134 127 126 126 125 124 124 138

Q3. Explain why atomic size in 3d-series first decreases then remains almost constant in the
middle and in the end finally increases.
Ans. In the beginning, atomic radii decreases with the increase in atomic number as the nuclear
charge increases whereas the shielding effect of d electron is small. After midway, as the electron
enter the last but one (penultimate) shell, the added d electron shields the outermost electron. Hence
with increase in d electrons, screening effect increases. This counter balances the increased nuclear
charge due to increase in atomic number. As a result, the atomic radii remain practically almost same
after Cr. But at the end of the period there is a slight increase in atomic radii due to electron-electron
repulsion between added electrons in d- orbital.

Melting and boiling points

Q4. Explain the melting point of transition element rises to a maximum and then falls as atomic
number increases.

Ans. The strength of metallic bond depends upon the number of unpaired electrons in d and s orbital .
Greater the no. of unpaired electrons, stronger is the metallic bonding. In a particular series, the
metallic strength increases up to middle with increasing numbered of unpaired electrons i.e. up to d5
configuration.
After Cr, the no. of unpaired electrons goes on decreasing. Accordingly the melting point decreases
after Cr because of increasing pairing of electrons.
176
Q5. Explain Manganese, Technetium, have exceptionally low melting points?
Ans. Manganese, Technetium have exactly half-filled d-orbital, as a result in each case the
electronic configuration is stable i.e. electrons are held tightly by nucleus so that delocalization is less
and metallic bond is much weaker than that preceding element.

Q6. Explain why Zn, Cd and Hg have low melting points?

Ans. Zn, Cd and Hg have no unpaired electron. Hence they have weakest metallic bond resulting in
low melting point.

Q7. Why do the transition elements exhibit higher enthalpies of atomization (sublimation) ?

Ans.Because of having large no. of unpaired e- in their atoms, they have stronger interatomic
interaction and nce stronger bonding between atoms.

Ionization enthalpy
Thermodynamic stability of Transition Element can be evaluated in terms of magnitude of ionization
energies of metal. Smaller the I.E. stabler is its compound.

Q8. How would you account for the irregular variation of ionization enthalpies (first and
second) in first series of the transition elements?
Ans. Irregular variation of first ionization enthalpy. As we move from left to right along the first
transition series, as effective nuclear charge increases, it is expected in general that the first ionization
enthalpy should show an increasing trend. However, the trend is irregular because removal of the
electron alters the relative energies of 4s and 3d orbitals. Thus, there is a reorganization energy
accompanying ionization. This results into the release of exchange energy which increases as the
number of electrons increases in the dn configuration and also from the transference of s-electrons into
d-orbitals. Cr has low first ionization energy because loss of one electron gives stable electronic
configuration (3d5). Zn has very high ionization energy because energy electron has to be removed
from 4s orbital of the stable configuration (3d10 4s2).

Irregularities of second ionization enthalpy. After the loss of one electron, the removal of second
electron becomes difficult. Hence, second ionization enthalpies are much higher and in general
increases from left to right. However, Cr and Cu show much higher values because the second
electron has to be removed from the stable configurations of Cr+(3d5) and Cu +(3d10 )

177
Oxidation state

Sc Ti V Cr Mn Fe Co Ni Cu Zn
(3d14s2) +2 +2 +2 +2 +2 +2 +2 +1
+2 +2

+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
Q9. Explain briefly how +2 state becomes more and more stable in the first half of the first row
transition elements with increasing atomic number.
A: Except scandium (which shows an oxidation state of +3), all other first row transition elements
show an oxidation state of +2. This is due to loss of two 4s electrons.

In the first half, as we move from Ti2+ to Mn2+, the electronic configuration changes from 3d2 to 3d5,
i.e. more and more of d-orbitals are half-filled imparting greater and greater stability to +2 state.

Q10. To What extent do the electronic configurations decide the stability of oxidation states in
the first series of transition elements? Illustrate your answer with example.
Ans. In a transition series, the oxidation states which lead to noble gas or exactly half-filled or
completely filled d-orbitals are more stable. For example, Mn (Z = 25) has electronic configuration
[Ar] 3d5 4 s2. It shows oxidation states + 2 to + 7 but Mn (II) is most stable because of half-filled
configuration [Ar] 3d5. Similarly Sc3+ is more stable then Sc+ and Fe3+ is more stable than Fe2+ due to
half filled it d-orbitals.

In solution stability of compound depends upon electrode potential rather than ionization energy.
Electrode potential values depend upon factors such as:

(1) Energy of sublimation

(2) Ionization energy
(3)Hydration energy

ΔHT
M(s) M+ (aq) +e-

ΔHsub ΔHhyd

M(g) M+ (g) +e-

I.E.
ΔHT = ΔHsub + I.E. + ΔHhyd

The electrode potential are a measure of ΔHT. The lower the electrode potential more stable is the
oxidation state of transition element in aqueous solution.

178
Q11. For the first row transition metals the E0 values are

E0 V Cr Mn Fe Co Ni Cu Zn
(M2+/M) -1.19 -0.91 -1.18 -0.44 -0.28 -0.23 +0.34 -0.76
Explain the irregularity in the above values.

Ans. The E0(M2+/M) values are not regular which can be explained from the irregular variation of
ionization energies (IE1+IIE2) and also the sublimation energies which are relatively much less for
manganese and vanadium.
Q12. Explain as to why the E0 value for Mn3+/Mn2+ couple is much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+ ?
Ans. Much larger third ionization energy of Mn (where the required change is 3d5 to 3d4 ) is mainly
responsible for this. This also explains why the +3 state of Mn is of little importance.

Mn2+ Mn3+ + e-
(3d5) (3d4)

Cr2+ Cr3+ + e-
(3d4) (3d3)

Fe2+ Fe3+ + e-
(3d6) (3d5)
179
Q13. Which is a stronger reducing agent Cr2+ or Fe2+ and why?

Cr2+ Cr3+ + e-
(3d4) (3d3)

Fe2+ Fe3+ + e-
(3d6) (3d5)
In a medium like water d3 is more stable than d5. Hence, Cr2+ is a stronger reducing agent than Fe2+

Q14. The E0 (M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this?
Ans. Copper has high enthalpy of atomization (i.e., energy absorbed) and low enthalpy of hydration
(i.e. energy released). Hence, E0 (Cu2+/Cu) is positive.
The high energy required to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.

Q15 Explain why Cu+ ion is not stable in aqueous solution?

Ans. Cu2+ (aq) is much more stable than Cu+ (aq). This is because although second ionization
enthalpy of copper is large but Δhyd H for Cu2+(aq) is much more negative than that for Cu+(aq) and
hence it more than compensates for the second ionization enthalpy of copper. Therefore, many copper
(I) compounds are unstable in aqueous solution and undergo disproportionation as follows:
Cu+ + Cu+ Cu2+ + Cu

Q.16 Why do transition element show variable oxidation states?

Ans. In transition element the energies of (n-1)d orbital and ns orbital are very close. Hence, electrons
from both orbitals can participate in bonding.

Q17. The highest oxidation state is exhibited in oxo- anions of metal. Why?
Ans. Oxo- anions have highest oxidation state eg. Cr in Cr2O72- & Mn in MnO4-. This is due to
combination of metal with oxygen which is highly electronegative & oxidising agent.

Q18. The lowest oxidation state of transition metal is basic, the highest is acidic. Why?
Ans. In low oxidation state of metal some of the valence electrons of the metal atom are not involved
in bonding. Hence it can donate electrons & behave as base.
In higher oxidation state, the valence electrons are involved in bonding and not available, hence it can
accept electrons and behave as acid.

Q19. Transition Elements exhibit higher oxidation state in oxides & fluorides.
Ans. Because Oxygen and Fluorine are highly electronegative elements, small in size hence
strongest oxidizing agent.

Q20. Compare the stability of +2 oxidation state for the elements of the first transition series.
Ans. In general, the stability of +2 oxidation state in first transition series decreases from left to right
due to increase in the sum of first and second ionisation energies. However Mn2+( is more stable due
to half filled d-orbitals (3d5) and Zn2+( is more stable due to completely filled d-orbitals (3d10).

Q21. Which metal in the first transition series exhibits +1 oxidation state most frequently and
why?
Ans: Copper has the electronic configuration 3d104s1. It can lose one electron from 4s orbital to give
stable 3d10 configuration. Hence it shows +1 oxidation state.
(i) due to proper shielding by 5 f electrons.
180
Q22. How would you account for the following?
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents,
it is easily oxidized.
(iii)The d1 configuration is very unstable in ions.
(i) Cr2+(3d4) is reducing as it involves change from 3d4 to 3d3, the latter is more stable
configuration (t32g).
Mn3+ to Mn2+ is from 3d4 to 3d5 again 3d5 is an extra stable configuration. Hence, Cr2+ acts as strong
reducing agent whereas Mn3+ acts as oxidizing agent.

(ii)Due to Crystal field stabilization energy, which more than compensates the third ionization
energy.
5Co3+(3d6) has greater tendency to from coordination complexes than Co2+(3d7). Hence, in the
presence of ligands, Co2+(3d7) changes to Co3+(3d6) , i.e. is easily oxidized.

(iii) The hydration or lattice energy more than compensates the ionization enthalpy in removing
electron from d1. The ions with d1 configuration have the tendency to lose the only electron present in
d-subshell to acquire stable d0 configuration.
Note
The relative stability of diff. oxidation state can be observed from their electrode potential.

Cu+ (aq) + e- Cu (s) E0 Cu+/Cu = 0.52V

Cu2+ (aq) + 2e- Cu (s) E0 Cu2+/Cu =0.34V

Thus, Cu+ is reduced more easily and hence is less stable than Cu2+
or, the one which has lower value of reduction potential is more stable oxidation state.

Catalytic Property
Q23. Transition element acts as catalyst. Explain?
Ans.The catalytic property of transition element are due to the presence of unpaired electrons in their
incomplete d-orbital. These elements exhibit multiple oxidation state and tendency of complex
formation and these possess the capacity of absorb and re-emit wide range of energies. This makes
the required energy of activation available.
In some cases, transition elements may form intermediate compounds with one of reactants and thus
provide a new path at lower activation energy.
E.g. Iron (III) catalyse the reaction as:

It proceeds as:

Q24. Most of transition metal compounds are coloured both in solid state and aqueous solution.
Explain?
Ans. The colour is due to the presence of incomplete d-subshell. Further, when anions approach
transition metals ion, their d- orbitals do not remain degenerate. They split into two sets eg and t2g,
thus the electron can jump from lower energy d-orbital to higher d-orbital by absorbing energy from
visible light and re-emit the complimentary colour of light absorbed.
181
Q25. Which of the following compounds are coloured in aq. Solution.
(a) CuSO4 (b) ScCl3 (c) [Ti(H2O)6]3+ (d)[Sc(H2O)6]3+ (e) FeCl3
Ans. (1) CuSO4
Cu (29) = [Ar] 3d104s1
Cu2+ (27) = [Ar] 3d94s0 (coloured)

(2)ScCl3
x+3(-1) =0 Sc(21) = [Ar] 3d14s2
x=3 Sc3+(18) = [Ar] 3d04s0 (colourless)

(3) [Ti(H2O)6]3+
Ti(22) = [Ar] 3d24s2
Ti3+(19) = [Ar] 3d14s0 (coloured)
182
 (2) FeCl3
Fe(26) = [Ar] 3d64s2
Fe3+(23) = [Ar] 3d54s0 (coloured)

Q26. Are the following compound coloured or colourless. Explain giving proper reason.
(a) CrO2Cl2 (orange)
(b) KMnO4 (purple)

Ans. (a) CrO2Cl2

X+2(-2) +2(-1) =0 X=6

Cr (24) = [Ar] 3d54s1

Cr6+ (18) = [Ar] 3d04s0

(b) KMnO4
X+1+4(-2)=0, X=7
Mn (25) = [Ar] 3d54s2
Mn7+ (18) = [Ar] 3d04s0
The colour in these compound arises due to charge/ electron transfer spectra and not from d-d
transition.

Magnetic Property
Q27. Transition metals and many of their compounds show paramagnetic behaviour, why?
Ans: Due to the presence of unpaired e- in (n-1) d orbital most of the transition metal ions are
paramagnetic in nature the effective magnetic moment is calculated as
µ eff =√n(n+2)
where n is number of unpaired e- in d- orbital. It is expressed in Bohr Magneton.

Q28. Which is more paramagnetic Mn 2+ or Cr3+Find the magnetic moment in each case?
Ans. Mn (25) = [Ar] 3d54s2
Mn2+ (23) = [Ar] 3d54s0

[Ar] 5 unpaired e- in d- orbital

µ eff =√n(n+2)
=√5(7)
==√35=5.92 B.M
Cr (24) = [Ar] 3d54s1
Cr3+ (21) = [Ar] 3d34s0

= [Ar]
µ eff =√3(3+2)
=√15 B.M.
Mn2+ is more paramagnetic.

Try Yourself. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).

Formation of complex compounds

Q29. Transition element forms large no. of complex. Explain?
Ans. Transition element forms a large no. of complex due to comparatively smaller sizes of metal
ions, their high ionic charges and the availability of d-orbitals for bond formation.

183
Formation of interstitial compounds
Transition metal forms a large no. of interstitial compounds in which small atom such as H, C, B, N
occupy the empty space (interstitial site) in their lattices. Eg: TiC, Mn4H, Fe3H etc.

Properties of interstitial compounds

(1) They have high melting point., higher than those of pure metals.
(2) They are chemically inert.

Alloy formation
Q30. Transition elements form a large no. of alloys. Explain?
Ans. Transition metals have similar atomic sizes due to which atoms of one metal can easily take a
position in the crystal lattice of other. Transition metals are therefore miscible with each other in
molten state and forms alloy on cooling.

Q31.What is meant by ‘disproportionation’ of an oxidation state. Give an Example.

Ans. When a particular oxidation state becomes less stable relative to other oxidation states, one
lower, one higher, it is said to undergo disproportionation.
For example, manganese (VI) becomes unstable relative to manganese (VII) and manganese (IV) in
acidic solution.

3MnVIO42- + 4H+ 2MnVIIO4- + Mn IVO2 + 2H2O

Cu+ + Cu+ Cu2+ + Cu

Q 32: Transition elements have high enthalpy of hydration. Explain why.

Ans.(1) Because of small size of cation.
(2)Large positive charge, thus when they are added to water, they are surrounded by large
number of polar molecules and thus release large amt. of energy.

Potassium dichromate (K2Cr2O7)

K2Cr2O7 is obtained by fusion of chromite ore (FeCr2O4) with sodium or potassium carbonate in free
access of air.
4FeCr2O4+8Na2CO3+7O2 8Na2CrO4+4Fe2O3+8CO2

The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution
from which orange sodium dichromate Na2Cr2O7.2H2O can be crystallized.

2Na2CrO4+2H+ Na2Cr2O7+2Na++H2O
184
Sodium dichromate is more soluble than potassium dichromate. The latter is prepared by treating the
solution of sodium dichromate with potassium chloride.
 Na2Cr2O7+2KCl K2Cr2O7+2NaCl

Q.33Write the equation for chromate and dichromate ion in acidic and basic medium.

2CrO42-+2H+ 2Cr2O72-+H2O
(yellow) (orange)

Cr2O72-+2OH- 2CrO42-+H2O
(orange) (yellow)

Q.34: Draw structure for chromate and dichromate ions?

Oxidising Properties:

K2Cr2O7 act as oxidizing agent in acidic solution.

Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O

It oxidizes

2I- I2 + 2e- ( Iodide to iodine)

H2S 2H++ 2e- +S (H2S to sulphur)

Sn2+ Sn4+ + 2e- ( Stannous salt to stannic)

Fe2+ Fe3+ + e- ( Ferrous to Ferric)

SO2 + 2H2O H2SO4 +2e- +2H+ ( Sulphur dioxide to sulphuric acid)

C2O42- 2CO2 + 2e- ( Oxalate ion to carbon dioxide)

185
Q.35 Give equation showing oxidation iron(ii), H2S and SO2 by potassium dichromate in acidic
solution.(Try yourself)

Potassium Permanganate (KMnO4)

(1) KMnO4 is prepared by fusion (melting) of MnO2, with an alkali metal hydroxide and an
oxidizing agent like KNO3. (KNO3 KNO2 + O )
This produces the dark green K2MnO4 which disproportionates in a neutral or acidic solution
to give permanganate.

2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O

(Black) (Dark green)

3 MnO42- + 4H+ 2 MnO4- + MnO2 + 2H2O

(Dark green) (Purple)

(2)Commercially it is prepared by alkaline oxidative fusion of MnO2 followed by electrolytic

oxidation of manganate (VI)

MnO2 fused with KOH, oxidised with air or KNO3 MnO42-

(Black) (Dark green)

MnO42- electrolytic oxidation MnO4-

(Manganate) in alkaline solution (Purple), permanganate

Oxidising property of KMnO4

Alkaline solution : MnO-4 + 2H2O + 3e- MnO2 + 4OH- (E0=1.23V)

Acidic solution : MnO-4 + 8H+ + 5e- Mn2+ + 4H2O (E0=1.515V)

It oxidizes

2I- I2 + 2e- ( Iodide to iodine)

H2S 2H++ 2e- +S (H2S to sulphur)

Sn2+ Sn4+ + 2e- (Stannous salt to stannic)

Fe2+ Fe3+ + e- (Ferrous to Ferric)

SO2+2H2O H2SO4 + 2e- + 2H+ (Sulphur dioxide to sulphuric acid)

C2O42- 2CO2 + 2e- (Oxalate ion to carbon dioxide)

Uses of KMnO4

(1) It is used as an oxidant both in the laboratory and in industry.

(2) It is used as bleaching agent for wood, cotton, silk and other textiles and for decolourisation of
oils.

186
Lanthanoids
Q.36: What are inner transition elements?
Ans: The f-block elements, i.e. in which the last e- enters into f-subshell are called inner transition
elements. These include lanthanoids (58-71) & actinoids(90-103).

Q37.What is lanthanoid contraction?

In lanthanoid series, with increasing atomic no. there is a progressive decrease in the atomic as well
as ionic radii of trivalent ions from La3+ to Lu3+. This regular decrease (contraction) in the atomic and
ionic radii with increasing atomic no. is known as lanthanoid contraction.
187
Q38.Explain the cause of lanthanoid contraction?
As we move along the lanthanoid series the nuclear charge increases by one unit at each successive
element. The new electron is added into the same subshell (4f). As a result, the attraction on the
electron by the nucleus increases and this tends to decrease the size. Further, as the new electron is
added into the same subshell, there is imperfect shielding of one electron by another in this subshell
due to the shapes of these f-orbitals. This, imperfect shielding is unable to counter balance the effect
of the increased nuclear charge. Hence, the net result is a contraction in size from La3+ to Lu3+ ion
though the decrease is very small.

Q39. What are the consequences of lanthanoid contraction.

(1) Difficulty in separation of lanthanoids: Since the change in ionic radii in lanthanoid is very
small their chemical properties are similar. This makes separation of elements in the pure
states difficult. However, lanthanoid contraction results in slight difference in the size of
lanthanoids which results in the difference in properties like solubilities, complex formation,
hydration etc. These differences enable the separation of individual lanthanoid elements by
ion exchange methods.

(2) Similarity in size of elements belonging to same group of second & third transition series
: Due to lanthanoid contraction, the atomic size of elements belonging to same group of
second & third transition series are almost same. Eg. Zr(160pm), Nb(146 pm)
Hf(159 pm), Ta(146pm)
(3) Effect on basic strength of hydroxides: As the size of the lanthanoid ions decreases from
La3+ to Lu3+, the covalent character of hydroxide increases and hence basic strength decreases.
Thus, La(OH)3 is more basic than Lu(OH)3 .

Q40.Give two uses of Lanthanoids

Mischmetal- It consist of lanthanoid metal (95%), Fe (5%) and traces of S, C, Ca & Al.
(1) The maximum of mischmetall is used in making magnesium based alloy (i.e. Mg mixed with
about 3% mischmetal to increase strength of Mg). It is a pyrophoric alloy (alloy which emits
spark when struck, i.e. takes up fire easily) and is used in making bullets, shells & lighter
flint.

(2)Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.

188
Q41.What are Pyrophoric alloys.
 Alloy which emits spark when struck, i.e. takes up fire easily are called pyrophoric alloys. Ex:
mischmetal-

Colour
Most of the trivalent metal ions are coloured both in solid state & aqueous solution. This is due to
partly filled f-orbitals which permit f-f transition.

Q.42. Why Sm2+, Eu2+, Yb2+ ions in solutions are good reducing agents but an aqueous solution
of Ce4+ is a good oxidizing agent.

Sm2+ Sm3+ + e- Ce4+ +e- Ce3+

Eu2+ Eu3+ +e-
2+
Yb Yb3+ +e-
The most stable oxidation state of lanthanoids is +3, Hence, ions in +2 state tend to change in +3 by
loss of electron & those in +4 state tend to change in +3 by gain of electron.

Q.43 Ce3+ can be easily oxidized to Ce4+, Explain why?

Ans: Ce(58)= [Xe] 4f15d16s2
Ce3+ = [Xe] 4f1
Ce4+ = [Xe]
Ce3+ having configuration [Xe] 4f15d06s0 can easily loose an electron to acquire noble gas
configuration of Xe.

Chemical properties of lanthanum.

Actinoids

90 Thorium Th=[Rn]5f06d27s2 Th4+=[Rn]

Q44. Define actinoid contraction. Why actinoid contraction is greater from elements to element
than lanthanoid contraction?
Ans: The actinoids show actinoid contraction due to poor shielding effect of 5f electrons. As a result,
the radii of the atoms or ions of these metals decrease regularly across the series. The contraction is
greater from element to element in this series due to poorer sheilding by 5f electrons. This is because
5f orbitals extent in space beyond 6s and 6p orbitals whereas 4f orbitals are buried deep inside the
atom.

189
Q45.Compare the chemistry of actinoids with that of lanthanoids with special reference to
(i) Electronic configuration (ii) oxidation state
(ii) Atomic and ionic sizes

Ans: (i) Electronic configuration. The general electronic configuration of lanthanoids is

[Xe ]54 4f1-14 5d 0-1 6s2 whereas that of actinoids is [Rn ]86 5f1-14 6d0-1 7s2.Thus, lanthanoids belong to
4f-series whereas actinoids belong to 5f series.

Oxidation states. Lanthanoids show limited oxidation stated (+2, +3, +4) out of which +3 is most
common. This is because of large energy gap between 4f, 5d and 6s subshells.
On the other hand, actinoids show a large number of oxidation stated because of small energy gap
between 5f, 6d, and 7s subshells.

(iii)Atomic and ionic sizes. Both show decrease in size of their atoms or ions in +3 oxidation state.
In lanthanoids the decrease is called lanthanoid contraction whereas in actinoids, it is called actinoid
contraction. However, the contraction is greater from element to element in actinoids due to poorer
shielding by 5f electrons.

Lanthanoids{[Xe]4f1-145d0-16s2} Actinoids{[Rn] 5f1-146d0-17s2}

(1) Besides +3 O.S, they show +2 & +4
O.S only in few cases.
(2) They have less tendency towards
complex formation.
(3) Do not form oxocation
(4) Except promethium, they are non
radioactive.
(1) Besides+3 O.S, they show higher O.S of .
+4,+5,+6,+7 also
(2) They have greater tendency towards complex
formation.
(3) Form oxocations e.g. UO22+, PuO22+ & UO+
(4) They are radioactive.

Q46. The chemistry of the actinoid elements is not so smooth as that of the lanthanoids.
Justify this statement by giving some examples from the oxidation state of these elements.
Ans: Lanthanoids show limited number of oxidation state, viz, + 2, + 3 and + 4 (out of which + 3
is most common). This is because of large energy gap between 4f, 5d and 6s subshells.
The dominant oxidation state of actinoids is also + 3 but they show a number of other oxidation
states also. For example, uranium (Z=92) and plutonium (Z = 94), show + 3, + 4, + 5 and + 6,
neptunium (Z = 93) shows + 3, +4, + 5 and + 7, etc. This is because of the small energy difference
between. 5f, 6d and 7s orbitals of the subshell.

Q47.Name the members of the lanthanoid series which exhibit +4 oxidation state and those
which exhibit +2 oxidation state. Try to co-relate this type of behaviour with the electronic
configuration of these elements

Sol: +4oxidationstate: 58Ce, 59Pr, 65Tb

+2oxidationstate: 60Nd, 62Sm, 63Eu, 69Tm, 70Yb.
In general +2 oxidation state is exhibited by the elements with configuration 5d06s2 so that two
electrons may be easily lost. Similarly +4 oxidation state is shown by the elements which after
losing four electrons acquire configuration either close to 4f0 or 4f7.
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