Chapter 4- The d and f block elements

D - BLOCK ELEMENTS OR TRANSITION ELEMENTS An element which has incompletely filled d-orbital in
its atom or at least one of its ions.

GENERAL ELECTRONIC CONFIGURATION. : (n - 1)d 1-10 ns 1-2

POSITION IN PERIODIC TABLE: Placed in 4 horizontal rows b/w s and p block elements, and are
classified into four series.( Gp 3 to Gp 12)

First transition series (3d series): From Sc(21) to Zn(30) Have incomplete penultimate 3d orbitals

Sc-21 Ti-22 V-23 Cr-24 Mn-25 Co-27 Ni-28 Cu-29 Zn-

30
3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d74s2 3d84s2 3d104s1 3d104s2

Second transition series(4d series): From Yttrium(39) to Cd (48) Have incomplete penultimate d-orbital
Third transition series(5d series): From La(57) and hafnium(72) to Hg(80) Have incomplete
penultimate 5d orbital
Fourth transition series (6d series): Incomplete penultimate 6d orbital

Ques 1: Why are Zn, Cd, Hg not considered as transition elements?

is because the penultimate d-orbital of these orbital [(n-1)d10ns2] as well as the ions M2+
[(n-1)d10ns0] are fully filled with e- and according to the definition cannot be considered as transition
elements.

Ques 2: On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30)
is not?
Solution: Scandium atom in its ground state (3d1) has incompletely filled 3d orbitals, so, it is regarded as a
transition element. On the other hand, zinc atom has completely filled d orbitals (3d10) in its ground state
as well as in its oxidised state, hence it is not regarded as a transition element.

Ques 3: Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it
is a transition element?
Solution: For an element to be termed as a transition element, it should have partially filled d orbitals in its
atom or in commonly found oxidation states. Silver can exhibit +2 oxidation state (3d9) in which it has
partially filled d-orbitals. Due to this reason, we can say that silver is a transition element.

Ques 4: Name the transition elements which do not have partially filled d- orbitals in their atoms or in
commonly found oxidation states.
Solution: The last member of each of the transition series i.e. Zinc (Zn), Cadmium (Cd) and Mercury
(Hg) are the transition elements which do not have partially filled d- orbitals in their atom as well as
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simple ions (having oxidation state of +2). Therefore, these elements do not possess characteristic
properties of transition elements and hence, generally not regarded as transition elements.

Ques 5: Write down the electronic configuration of:

(i)
Cr3+ (ii) Ni2+ (iii) Mn2+ (iv) Fe3+ (v) Cu+ (vi) Zn2+

Solution:
(i) Cr3+ : 1s2 2s2 2p6 3s2 3p6 3d3 Note – Remove electrons from 4s first and then from 3d.
(ii) Ni2+: 1s2 2s2 2p6 3s2 3p6 3d8
(iii) Mn2+: 1s2 2s2 2p6 3s2 3p6 3d5
(iv) Fe3+:1s2 2s2 2p6 3s2 3p6 3d5
(v) Cu+: 1s2 2s2 2p6 3s2 3p6 3d10
(vi) Zn2+ : 1s2 2s2 2p6 3s2 3p6 3d10

GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS:

1.Typically metallic- high tensile strength, ductility, malleability, high thermal and electrical conductivity and
metallic lustre.
2.All have typical metallic structures at normal temp except Zn, Hg, Cd and Mn
3. Hard and low volatility ( except Zn, Hg and Cd).
4. High densities.
5.Electropositive nature.
6.Form coloured compounds
7.Variable Oxidation States and paramagnetic behaviour.
8.Tendency to form complexes and used as catalysts.

PHYSICAL PROPERTIES
1) ATOMIC RADII and IONIC RADII:
Intermediate as that of s and p block elements (in a period smaller than s block but larger than p block
members)

The curves in Fig. show an increase in

atomic radii from the first (3d) to the
second (4d) series of the elements but the
radii of the third (5d) series are virtually
the same as those of the corresponding
members of the second series.

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 • Normally the size of 5d series > 4d series > 3d series but the size of 5d series is comparable to 4d series
because of the intervention of the 4f electrons before the 5d electrons which will cause very less shielding
and increases nuclear attraction and hence reduces the size of 5d series. This filling of 4f before 5d orbital
results in a regular decrease in atomic radii called Lanthanoid contraction which essentially
compensates for the expected increase in atomic size with increasing atomic number.

• Trend-In a transition series the atomic radii decrease initially and then varies irregularly becoming almost
constant.
• In First transition series the atomic radii decrease from Sc to Cr and then is almost constant up to copper
but the last element Zn has larger radii than copper.
• Reason: With increase in atomic no. the e- are added in the penultimate d-orbital that increases the nuclear
charge and thereby decreases the atomic radii. But the increased no. of e- in penultimate shell increases the
shielding effect (inner e- shield outer e- from nuclear attraction) due to which outer e- tend to be away from
nucleus i.e. e- cloud expands resulting in the increase in atomic radii. Thus with increase in nuclear charge,
the nuclear attraction as well as the shielding effect increases. But as the shielding effect counterbalances
the increased attraction there is small decrease in atomic radii.
• Zn has larger atomic radii than Cu-Due to greater screening effect in Zn (3d104s2) than Cu(3d104s1)

IONIC RADII – it follows the same trend

• The ionic radii decreases with the increase in the OS.
• For same OS the ionic radii generally decreases with the increase in the nuclear charge.
• For Eg. Fe3+ < Fe2+ and Cu+ > Cu2+

2) IONISATION ENTHALPY:
• Higher than s-block elements but lower than p-block elements.
• I.E of elements of 3d series increase irregularly with increase in atomic no.

Reason:
1) With increase in atomic number the nuclear charge increases, but due to greater shielding effect
caused by inner d e- & little variation in their atomic sizes result in marginal & irregular increase
in first I.E of transition elements.
2) The removal of one electron alters the relative energies of 4s and 3d orbitals. There is thus, a
reorganisation energy accompanying ionisation with the transference of s electrons into d orbitals and from
some gains in exchange energy as the number of d- electrons increases.
3) Elements have high IE because of half and full filled d-orbitals.
Irst I.E of Zn(fully filled 4s) > Cu (half filled 4s) and IInd I.E of Cr> Mn (half filled)
IE1 < IE2 < IE3 for the same element . Magnitude of IE2 and IE3 is much higher.

Down the group : First I.E of 5d elements is higher than 3d or 4d elements.

Reason: 5d elements have higher at no than 3d or 4d elements. With increase in the no of protons, nuclear
charge increase,but the poor shielding effect of 4f e- results in lanthanoid contraction which increases attractive
forces further.

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 Example 1: The first ionisation enthalpy value of zinc shows a higher increase while the second
ionisation enthalpy value drops off in the otherwise increasing regular trend in 3d series.
Explain.
Solution: Zinc has fully filled configuration; (Ar) 3d10 4s2. The first ionisation enthalpy represents the
removal of 4s electron while second ionisation enthalpy consists of the removal of an electron which allows
the production of the stable d 10 configuration. So the second ionisation enthalpy value drop off.

Example 2: Why the second and third ionization enthalpies of manganese and iron show anomalous dip
in the values across the period?
Solution: Manganese and iron attain stable half filled configuration (3d5) in +2 and +3 oxidation states
respectively. So they show anomalous dip in the values across the period.

Example 3: IE1 of Cr is low and that of Zn is high. Why?

Solution: Cr (3d5 4s1) and Zn (3d10 4s2) . Electrons to be removed from completely filled s orbital is higher than that of
half filled orbital.

Example 4: IE2 of Cr and Cu is exceptionally high . Why?

Solution: After losing an electron they attain extra stability of half filled and completely filled orbitals
Cr (3d5 4s0) and Cu (3d10 4s0). Removal of 2nd electron requires high energy.

Example 5: IE3 of Mn and Zn is exceptionally high . Why?

Solution : Mn2+(3d5 4s0) and Zn2+ (3d10 4s0) . Very stable configuration to shed the third electron.

3) METALLIC CHARACTER: They are metals and show all properties of metals.
Reasons :
• They have low I.E, due to which they lose e- to form cations and therefore show all metallic properties.
• They have incompletely filled d-orbital, so sideways overlapping result in the formation of strong
interatomic metallic bond that increase the strength of metallic bonding in them. Greater the number of
unpaired e- greater is the extent of metallic bonding due to d-d overlapping.
• Cr, Mo, W have high M.P and B.P and are hard whereas Zn. Cd, Hg are soft metals volatile with low
M.P and B.P
• Cr, Mo, W have max. no. of unpaired e- and so strong intermetallic bonding whereas Zn, Cd, Hg have
fully filled d-orbital and so weak intermetallic bonding.

4) MELTING & BOILING POINT:

• High M.P & B.P- They have incompletely filled d-orbital, so sideways overlapping result in the
formation of strong interatomic metallic bond that increase the strength of metallic bonding in them.

• M.P increase to a max in the middle of series & then fall

Reason:
1) Due to closed-packed structure of atoms, the attractive forces are
stronger (metallic bond), hence high M.P & B.P
2) They have unpaired e- present in d-orbital that causes strong
intermetallic bonding. The presence of this additional covalent
bonding due to d-d overlapping causes increase in M.P.

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 • Mn and Tc show a dip in the curve unexpectedly due to Half filled extra stability of Mn and Tc
due to which they do not interact with Surrounding atoms & so metallic bond is weak & M.P is Low.
Electrons are too tightly held and do not delocalize.
• Zn, Cd, Hg are soft and volatile metals. They have low m.p as they do not have unpaired electron for
metallic bonding.
• Cr(3d54s1) is hard and Hg(5d106s1) is liquid at room temperature( melts at -38oC )

5) FORMATION OF COLOURED COMPOUNDS

Due to incompletely filled d-subshell. The e- can be excited from one energy level to another within d-
subshell known as d-d transition. When the energy req for these transitions is within the visible range of light
then the compound is coloured.
• Cu (II) is blue but Cu(I) is white.
• Compounds of Zn2+, Cd2+, Hg2+ (d10) & Sc3+(d0) all are white/ colourless as they do not have
vacant d-orbitals for d-d transitions.

Formation of Coloured Ions: In the compounds of

transition metals, an electron from a lower
energy d orbital is excited to a higher energy d
orbital on absorption of light. The energy of
excitation corresponds to the frequency of light
absorbed. This frequency generally lies in the visible
region. The colour observed corresponds to the
complementary colour of the light absorbed. The
frequency of the light absorbed is determined by the
nature of the ligand.

6) FORMATION OF COMPLEXES :
Transition metals forms the large number of complexes because -
(i) Smalller sizes of metal ions.
(ii) High ionic charges
(iii) Availability of d-orbitals for bond formation.

Examples are: [FeF6]3-, [Fe (CN)6]3-, [Cu (NH3)4]2+, [PtCl4]2-, [Fe(CN)6]3- etc. In [FeF6]3 Fe3+- central metal ion
and F-- ligand that surround octahedrally around metal ion.

7) FORMATION OF INTERSTITIAL COMPOUNDS :

Interstitial compounds are those which are formed when small atoms like H, C or N are trapped inside the
crystal lattices of metals. They are usually non stoichiometric and are neither typically ionic nor covalent, for
example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc. The formulas quoted do not, of course, correspond to any
normal oxidation state of the metal. Because of the nature of their composition, these compounds are referred to
as interstitial compounds.
The principal physical and chemical characteristics of these compounds are as follows:
• They have high melting points, higher than those of pure metals.
• They are very hard, some borides approach diamond in hardness.
• They retain metallic conductivity.
• They are chemically inert.

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8) MAGNETIC PROPERTIES:
) ) a) Diamagnetic- repelled by magnetic field- no unpaired e-
b) Paramagnetic- attracted by magnetic field- unpaired e-.
* Greater the no of unpaired e-, greater is the paramagnetic behaviour
Magnetic moment (µ) = √ n(n+2) ,( n= number of unpaired electrons ) (spin only formula)

Example 1: Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.
Solution: With atomic number 25(3d54s2), the divalent ion in aqueous solution will have d5 configuration
(five unpaired electrons). The magnetic moment, μ is μ=√5(5+2) =5.92 BM

Example 2: Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
Solution: The electronic configuration of the M2+ ion (Z = 27) would be 3d74s2.Unpaired electrons i.e. it has

three unpaired electrons n = 3, therefore its spin only magnetic moment is μ= √3(3+2)=3.87BM (BM =
Bohr Magneton)

9) CATALYTIC PROPERTIES: Transition elements are good catalysts.

Reason:
1) Due to partly filled d-orbital they can form unstable intermediate products with the reactants.
2)They have large surface areas to adsorb reactants and lowers its activation energy.
3) show multiple oxidation states.
Some examples are-
In H2SO4 Preparation- Vanadium(V) oxide (in Contact Process), NH3 Preparation- divided iron
(in Haber’s Process), and nickel (in Catalytic Hydrogenation) .

Catalysts at a solid surface involve the formation of bonds between reactant molecules and atoms of
the surface of the catalyst (first row transition metals utilise 3d and 4s electrons for bonding). This has the effect
of increasing the concentration of the reactants at the catalyst surface and also weakening of the bonds in the
reacting molecules (the activation energy is lowering).
For example, iron(III) catalyses the reaction between iodide and persulphate ions.
2I- + S2O82- Fe3+ I2 + 2SO42-
An explanation to this catalytic activity can be given as :
2Fe3+ + 2I- 2Fe2+ + I2
2+
2Fe + S2O8 2- 2Fe3+ + 2SO42-

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10) ALLOY FORMATION :
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly
among the atoms of the other. These are formed because of their similar radii and having property of
metallic bonds.
➢ The best known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are
used for the production of a variety of steels and stainless steel.
➢ brass (copper-zinc) and bronze (copper- tin)

Example 1: What is meant by ‘disproportionation’ of an oxidation state? Give an example.

Solution: 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.
+6 +7 +4
2-
3MnO4 + 4H + -
2MnO4 + MnO2 + 2H2O
Manganate ion permanganate ion

11) OXIDATION STATES:

• They show variable oxidation states in compounds.

Reason : Because of the availability of vacant d-orbitals and having incomplete filling of d-orbitals.
• In the first transition series, the max. oxidation state shown by elements increases from Sc(3d14s2)
to Mn(3d54s2) due to increase in no. of unpaired e- and then decreases Zn(3d104s2). This irregularity
can be explained due to electronic configuration. As there are max no of unpaired e- in the middle.

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

The common O.S is +2

• Sc+2 is unknown due to high IE1+ IE2 values.
• The highest O.S shown by Osmium (+8) in OsO4 & elements with high O.S occur in middle and
increases down the group.
• The high O.S is shown in oxides and flourides (Like O and F)
• Greater the no of unpaired e- greater is the no of O.Ss.
• In group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI) because of inert pair effect.. Thus
Cr(VI) in the form of dichromate in acidic medium is a strong oxidising agent, whereas MoO3 ( +6) and
WO3 (+6) are not.
• The compounds of transition elements in lower O.S(+2, +3) are mostly ionic.
• Higher the oxidation state, lower the ionic character and higher the acidic character.
• Transition metals exhibit O.S of +1 and 0 in carbonyl and nitrosyls (Ni (CO)4 and Fe(CO)5 in complexes
where ligand has π-accepting character in addition to σ bonding. (bonding in Metal Carbonyls)

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 • Out of d4 species, Cr(II) is strongly reducing but Mn(III) strongly oxidizing
Reason: As Cr(II)[3d44s0] loses an e- easily to form stable 3d3(t2g) configuration but Mn(III)
accepts e- to have 3d5 configuration.
Cr+2 Cr+3 + e- Mn+3 + e- Mn+2
4 3 4
3d 3d 3d 3d5
(stable t2g)

In general, halides occur in high O.S.

• Highest O.S with F in halides due to greater electronegativity of F. For ex TiX4, VF5, CrF6 etc.
• Mn forms Mn+7 in MnO3F but with O.
• After Mn high O.S declines.
• The tendency of F to stabilize the highest O.S is due to its higher lattice enthalpy as in the case of CoF3,
or higher bond enthalpy terms for the higher covalent compounds, e.g., VF5 and CrF6
• Flourides are unstable in low oxidation state.

• All Cu halides are known except the iodide- because Cu+2 oxidises I- to I2 Cuperous ion- Cu+ cupric-
Cu2+
2Cu+2 + 4I-  Cu2I2 (cuprous iodide) + I2 (Disproportionation Reaction)
• Cu(I) compounds are unstable in aq soln –because Cu in +2 O.S are more stable than +1 O.S due to
the large –ve hydration enthalpy of Cu+2 than Cu+1which is much more compensates for larger energy
required to remove second electron.

• High O.S occurs in oxides because of ability of O to stabilize the O.S due to its small size ,high
electronegativity and ability to form multiple bonds.
Oxocations (VO2+, TiO2+) are stable

Example 1: Explain why Cu+ ion is not stable in aqueous solutions?

Solution: Cu+ in aqueous solution undergoes disproportionation as follows:
2 Cu+ (aq) → Cu2+ (aq) + Cu (s)

Example2: Name a transition element which does not exhibit variable oxidation states.
Solution: Scandium (Z = 21) does not exhibit variable oxidation states.

Example 3: Which transition metal of the 3d series exhibits the largest number of oxidation states and
why?
Solution: Manganese (Z=25) exhibits the largest number of oxidation states because it has maximum
number of electrons ns and (n-1)d electrons available for the bond formation. It exhibits all oxidation
states from +2 to +7.

Example 4: How would you account for the increasing oxidising power in the series
VO2+ <Cr2O72– < MnO4 – ?
Solution: This is due to the increasing stability of the lower species; V5+ <Cr6+ <Mn7+ to which they are
reduced. V5+ to v4+ , Cr+6 to Cr+3 , Mn7+ to Mn2+

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TRENDS IN M2+/M STANDARDS

Trends in the M2+ /M Standard Electrode

Potentials: Given Table contains the
thermochemical parameters related to the
transformation of the solid metal atoms to M2+
ions in solution and their standard electrode
potentials. The observed values of E° and those
calculated using the data are compared in Fig. 2.

In solution, the stability of an O.S depends upon Electrode potential E0

which in turn depend upon
(i) ∆sub H - ehthalpy of sublimation
(ii) ∆hyd H – enthalpy of hydration (ii) ∆iH – enthalpy of ionization
(iii) M(s) ∆totalH M2+(aq) [∆totalH = ∆iH (1+2) + ∆sub H + ∆hyd H]
(+ve) (+ve) (-ve)
∆subH ∆hydH
∆iH(1+2)
M(g) M2+(g)
Born Haber Cycle

* Smaller the value of ∆totalH in aqueous soln, greater will be the stability of O.S because E0 value are a
measure of ∆totalH and Lower the reduction potential value, greater is the stability of O.S

For First transition series-

*No regular trend observed due to irregular I.E1 + I.E2 values and ∆subH or ∆aH. In general the
value becomes less negative.
* Zn has more –ve Eo value than expected despite low ∆aH and large ∆hydH b’coz of high ∆iH due to fully-
filled(3d10)stable electronic config.
* (Mn, Zn) Eo values are more –ve- than expected due to stability of half-filled(3d5) or fully filled(3d10)
electronic configuration.
* Ni has more –ve Eo value –Due to high ∆hydH of Ni2+.

* Cu has +ve E0 value- least reactive –it cannot liberate H2 from acid- because high energy is required to
convert Cu to Cu+2 is not balanced by its ∆hydH.
The unique behaviour of Cu, having a positive Eo, accounts for its inability to liberate H2 from acids.
Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids being reduced. The high
energy to transform Cu(s) to Cu2+ (aq) { Δa H(M) +ΔiH1 +ΔiH2} is not balanced by its hydration
enthalpy{ΔhydHO (M2+)}. Hence The stability of Cu2+ (aq) rather than Cu+ (aq) is due to the much more
negative ΔhydH° of Cu2+ (aq) than Cu+, which more than compensates for the second ionisation enthalpy of
Cu.

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* Varying trends are observed-Except Cu and Zn all show +3 O.S. [M3+ + e-  M2+]

Ti V Cr Mn Fe Co
Eo -0.37 -0.26 -0.41 +1.57 0.77 +1.92
M3+/M2+

• Sc has a low Eo value because Sc+3 has stable noble gas configuration.( 4s0 3d0)
• Zn has highest value as it is difficult to remove e- from 3d10.
• Mn has high value –Mn+2(3d5) is stable…. So Mn+3 is unstable.
• Fe has low value indicating extra stability of Fe+3(3d5) than Fe +2(3d6)
• V has a low value due to stability of V+2. (half-filled t2g level)- 4s0 3d3 ** E0 for Mn3+/Mn2+ is more +ve
than Cr+3/Cr+2 or Fe+3/Fe+2? Much large I.E3 (3d5-3d4) +3 state has little relevance.

Example 1: Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Solution Cr2++ is reducing as its configuration changes from d4 to d3, the latter having a half filled t2g level
(details will be discussed in chapter of coordination chemistry). On the other hand, the change from Mn3+ to
Mn2+ results in the half-filled (d5) configuration which has extra stability.

Example 2: The EO (M2+/M) value for copper is positive (+0.34V). What is possible reason for this?
Solution: The EO (M2+/M) value for copper is positive (+0.34V) because the sum of first and second ionisation
enthalpies for copper is very large due to exceptionally high second ionisation enthalpy which is not
compensated by the hydration enthalpy (ΔhydH0) of Cu2+ ion.

Example 3: Cu+ has fully filled d10 configuration, but +2 is the common oxidation state for Cu(aq.).
Explain.
Solution: The hydration energy of Cu2+ is more negative than Cu+ and more than compensates the
second ionization enthalpy of copper. So though Cu+ has fully filled d10 configuration, copper exists as
Cu2+in aqueous solution.

RELATIVE STABILITY OF O.S

• Lower the magnitude of I.E of element, more stable is the O.S
Element E1 + E2 KJ/mole E3 + E4KJ/mole Total
Ni 2.49 8.80 11.24
Pt 2.66 6.70 9.36

Shows Ni(II) is stable than Pt(II), but Pt(IV) is more stable than Ni(IV)
• Lower the reduction electrode potential value, greater the stability of O.S
Cu 2+ + 2e- Cu (E0red = +0.34V)
Cu + + e- Cu (E0red = +0.52V)
So Cu2+ is more stable than Cu+

CHEMICAL REACTIVITY OF TRANSITION ELEMENTS

• Less reactive due to their high I.E, high heats of sublimation & low heats of hydration. Ex: They may
remain inactive also as most of them form a protective inert & sticky oxide layer with conc. Acid & are not
further attacked by it
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 • Weak reducing agents- Due to their moderate electrode potential values
• Out of Cr2+ and Cr+3, Cr3+ is more stable in aqueous solutions
Reason -As it has smaller size & high charge density so is hydrated to a greater extent

Assignment

Q1 Which gives coloured aq soln – Co2+, Sc+3, Cr+3 ? how will they respond to magnetic
field.?
Q2 Out Of Ag+, Co+2,Ti4+, which forms coloured solution?
Q3 Which will show greater O.S- Zr, Ti, V, Ni, Mn?
Q4 K2PtCl6 is known but Ni compounds are not known?
Q5 Eo values for Co+2 & Co+3are -0.28V and 1.8V –Which will be a better reducing agent
in water?
Q6 How would you account for inc. Oxidising power of – VO2+<Cr2O72-
<MnO4-
Q7 Based on data arrange Fe+2, Mn+2, & Cr+2 in inc order of stability of +2 O.S
Q8 Cr+2 is reducing but Mn3+ oxidising although both have d4 configuration. Why?
[ Hint - Cr+2(3d4) → Cr+3(3d3-stable half-filled t2g configuration)
& Mn3+(3d4) + e- → Mn2+ (3d5- stable half-filled configuration)]
Q9 Why isCu2+ is more stable than Cu+?
[Hint- ∆hydH is more -ve which more than compensates for I.E2 of Cu2+]
Q10 Consider the E0 values in 1M acidic solutions Fe2+/Fe = -0.4V, Fe3+/Fe2+ = 0.8V,
Mn2+/Mn = -1.2V, Mn3+/Mn2+ = +1.5V
a) Comment on the relative stability of +2 & +3 O.S of Fe & Mn
b) Which of them may be more easily oxidized to +2 Oxidation states.

11
Oxides and Oxoanions of Metals
These oxides are generally formed by the reaction of metals with oxygen at high temperatures. All the
metals except scandium form MO oxides which are ionic. The highest oxidation number in the oxides,
coincides with the group number and is attained in Sc2O3 to Mn2O7 . Beyond group 7, no higher oxides
of iron above Fe2O3 are known.
In the case of Mn, Mn2O7 is a covalent green oil.
Even CrO3 and V2O5 have low melting points. In these higher oxides, the acidic character is
predominant.
Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7 .
V2O5 is, however, amphoteric though mainly acidic which reacts with alkalies as well as acids to give
VO4 3- and VO4 + respectively. The well characterised CrO is basic but Cr2O3 is amphoteric.

Potassium dichromate (K2Cr2O7 )

Preparation: From Chromite ore (FeCr2O4 )
• 4 FeCr2O4 + 8 Na2CO3+ 7O2 8 Na2CrO4+ 2 Fe2O3+ CO2 (chromite ore)
• 2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O • Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
• Orange crystals of K2Cr2O7 are obtained on crystallisation.

❖ Physical Properties:
•Orange-red coloured crystalline compound.
•Moderately soluble in cold water but freely soluble in hot water.
•It melts at 398°C.
• K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric estimation because Na2Cr2O7
is hygroscopic in nature but K2Cr2O7 is not.

Effect of pH on Potassium dichromate

• Cr2O7 2- + 2 OH- → 2 CrO4 2- + H2O (pH >7)
(Orange) (Yellow)
• 2 CrO4 + 2 H → Cr2O7 2- + H2O (pH <7)
2- +

(Yellow) (orange)

Oxidising nature of Potassium dichromate

Powerful oxidising agent in acidic medium (dil. H2SO4 )
Cr2O7 2- + 14H+ + 6e- → 2Cr3+ + 7H2O (E° = 1.33 V)
It shows following redox reactions;
• 6Fe2+ + Cr2O7 2- + 14 H+ → 6Fe3+ + 2Cr3+ + 7H2O
• 6I- + Cr2O7 2- + 14 H+ → 3I2 + 2Cr3+ + 7H2O
• 3Sn2+ + Cr2O7 2- + 14 H+ → 3Sn4+ + 2Cr3+ + 7H2O
• 3H2S + Cr2O7 2- + 14 H+ → 3S + 2Cr3+ + 7H2O
• Note: Oxidation state of Cr changes from +6 to +3
Uses Of Potassium Dichromate
• Used as a primary standard in volumetric analysis for the estimation of reducing agents such as oxalic
acid, ferrous ions, iodide ions, etc.
• For tanning of leather, calico printing, photography etc.
•As a cleansing agent for glass ware in the form of chromic acid.

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 Potassium permanganate (KMnO4)

Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an oxidising
agent like KNO3. This produces the dark green K2MnO4 which disproportionates in a neutral or acidic
solution to give permanganate.

Preparation: From pyrolusite ore (MnO2)

• 2MnO2 + 4KOH + O2 → 2K2MnO4 (dark green) + 2H2O (K2MnO4 → 2K+ + MnO42- )
• 3MnO4 2- + 4H+ → 2MnO4- + 2H2O + MnO2
Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (Vl)

In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

2Mn2+ + 5S2O82- + 8H2O → 2MnO4- + 10SO4 2- + 16H+

❖ Physical Properties:
•It is purple coloured crystalline compound which are isostructural with those of KClO4.
•Sparingly soluble in water at room temperature (6.4 g/100 g of water at 293 K), but when heated it
decomposes at 513 K.

•Effect of heating •2KMnO4 → K2MnO4 + MnO2 + O2

It has two physical properties of considerable interest: its intense colour and its weak temperature
dependent paramagnetism.
The π-bonding takes place by overlap of p orbitals of oxygen with d orbitals of manganese.

•Effect of pH
MnO4 – (OH-) = MnO42- (H+)

• Oxidising nature of potassium permanganate

• KMnO4 shows strong oxidising nature.
• It shows different oxidising nature in different medium.
❖ Acidic medium: MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O
❖ Neutral or faintly alkaline medium: MnO4 - + 2H2O + 3e- → MnO2 + 4OH-
❖ Strongly alkaline medium: MnO4- + e-→ MnO42-

Oxidising nature of KMnO4 • In acidic medium (presence of dil. H2SO4):

In acid solutions:
(a) Iodine is liberated from potassium iodide :
10I-+ 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5Fe2+ + MnO4- + 8H+ ——> Mn2+ + 4H2O + 5Fe3+
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42- + 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 10CO2

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 Oxalic acid is oxidised to CO2 (This reaction is slow at room temperature, but is rapid at 60°C. Mn(II)
ions produced catalyse the reaction; thus the reaction is autocatalytic)

(d) Hydrogen sulphide is oxidised, sulphur being precipitated:

H2S —> 2H+ + S2-
5S2- + 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 5S
(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:
5SO32-+ 2MnO4-+ 6H+ ——> 2Mn2+ + 3H2O + 5SO42-
(f) Nitrite is oxidised to nitrate:
5NO2- + 2MnO4- + 6H+ ——> 2Mn2+ + 5NO3- + 3H2O
(g) SO2 is oxidised to H2SO4
(SO2 + 2H2O → SO42- + 4H+ +2e-) x 5
(MnO4- + 8H+ + 5e- → Mn2+ + 4H2O) x 2
5SO2 + 2MnO4- + 2H2O → 5SO42- + 2Mn2+ + 4H+

Oxidising nature of KMnO4 In slightly alkaline & neutral medium :

In slightly alkaline medium KMnO4 is reduced to MnO2 (MnO4- to MnO2 )
(a) A notable reaction is the oxidation of iodide to iodate:
2 MnO4- + I- + H2O → 2 MnO2 + IO3- + 2 OH-
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8 MnO4-+ 3 S2O32- + H2O → 8 MnO2 + 6 SO42- + 2OH-
Point to be noted: Permanganometric titrations in the presence of HCl are unsatisfactory as HCl is
oxidised to chlorine by KMnO4

Uses of KMnO4
• Used as an oxidising agent in laboratory and industry.
• Alkaline potassium permanganate is called Baeyer's reagent. This reagent is used in organic chemistry
for testing unsaturation.
• KMnO4 is used in the manufacture of saccharin, benzoic acid, acetaldehyde,etc.
• KMnO4 is used as a reagent in qualitative analysis and as primary standard in quantitative analysis.
• KMnO4 is used as an antiseptic

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Note: KMnO4 (Mn7+) has d0 in Mn and
yet it is coloured because of charge
transfer from oxygen to metal atom.

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 f-block(inner transition elements)
(n-2)f1-14(n-1)d0 or 1 ns2 ( n=6 for lanthanoids and n=7 for Actinoids)

The f-block of the periodic table of the elements consists of those elements (sometimes referred to as the
inner transition elements) for which, in the atomic ground state, the highest-energy electrons occupy f-
orbitals. Unlike the other blocks, the conventional divisions of the f-block follow periods of similar
atomic number rather than groups of similar electron configuration. Thus, the f-block is divided into the
lanthanoid series and the actinoid series.

• Inner transition elements(f -Block elements): • They are present in separate block in the periodic table.
• Last electron enters in pre-penultimate f-subshell, so they are known as f-block elements. •
Lanthanoids: last electron enters one of the 4f orbital. Cerium(at. No. 58) to Lutetium(at. No.71) •
Actinoids: last electron enters one of the 5f orbital. Thorium (at.no.90)to lutetium(at. No.103) • They are
also known as ‘inner transition elements’..

f-block
Period f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 d1
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
6
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
7
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
139 140 141 142 143 144 145 146 147 148 149 150 151 152 153
8
Ute Uqn Uqu Uqb Uqt Uqq Uqp Uqh Uqs Uqo Uqe Upn Upu Upb Upt

LANTHANOIDS

Electronic Configuration: All lanthanoids have electronic configuration with 6s2 common
but with variable occupancy of 4f level in their atoms . ( 6s2, 5d0-1, 4f1-14) However, the electronic
configuration of all the tri-positive ions (the most stable oxidation state of all the lanthanoids)
is of the form 4fn (n = 1 to 14 with increasing atomic number).

Atomic and Ionic sizes: The overall decrease in atomic and ionic radii from lanthanum to
lutetium (the lanthanoid contraction) is a unique feature in the chemistry of the lanthanoids.
It has far reaching consequences in the chemistry of the third transition series of the elements.
The decrease in atomic radii (derived from the structures of metals) is not quite regular while
decrease in ionic radii (M3+) is regular

The shielding of one 4f electron by another is less than one d electron by another with the increase in
nuclear charge along the series. There is fairly regular decrease in the sizes with increasing atomic
number. (lanthanoid contraction)

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 Lanthanoid contraction : In Lanthanoid series, with increasing atomic number, there is progressive
decrease in atomic/ionic radii due to poor shielding effect of 4f-orbitals.
❖ Reason : Due to addition of new electrons into (n-2) f-subshell which shows more poor shielding
effect.
❖ Consequences :
• Their separation is difficult as they have small difference in size.
• Basic strength of hydroxide decreases from left to right.
(La(OH)3 is more basic than Lu(OH)3 )
• 4d and 5d transition series have almost same atomic radii. (Zr and Hf have similar properties due to
similar size
Oxidation States: The possible stable oxidation states of the lanthanoids are tabulated in In the
lanthanoids, La(III) and Ln(III) compounds are predominant species.(+3 OS most stable)
However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained.
This irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty,
half-filled or filled f subshell. Thus,
• the formation of CeIV is favoured by its noble gas configuration, but it is a strong oxidant
reverting to the common +3 state. The E° value for Ce4+/Ce3+ is + 1.74 V which suggests
that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a
good analytical reagent.
• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is formed by losing
the two s electrons and its f7 configuration accounts for the formation of this ion.
However, Eu2+ is a strong reducing agent changing to the common +3 state.
• Similarly Yb2+ which has f14 configuration is a reductant which has f14 configuration is a
reductant.
• TbIV has half-filled f-orbitals and is an oxidant.
• The behaviour of samarium is very much like europium, exhibiting both +2 and +3
oxidation states.

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General Characteristics:
1.Physical State: All the lanthanoids are silvery white soft metals
and tarnish rapidly in air. The hardness increases with increasing atomic number, samarium
being steel hard. Their melting points vary between 1000 to 1200 K but samarium melts at
1623 K. They have typical metallic structure and are good conductors of heat and electricity.
Density and other properties change smoothly except for Eu and Yb and occasionally for Sm
and Tm.

2.Colour & Magnetic Property: Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be attributed to the excitation of f
electrons on absorption of light in the visible region. Neither La3+ nor Lu3+ ion shows any
colour but the rest do so. However, absorption bands are narrow, probably because of the
excitation within f level. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f14
type (Yb2+ and Lu2+) are all paramagnetic. The orbital motions of the electrons in lanthanoids
are not quenched, so both spin and orbital angular momentum contribute towards μ. This is in
contrast to metal ions of the first transition series where ‘spin only’ formula is used.

3.Ionisation Enthalpy: The first ionisation enthalpies of the lanthanoids are around 600 kJ mol-1, the
second about 1200 kJ mol-1 comparable with those of calcium. A detailed discussion of
the variation of the third ionisation enthalpies indicates that the exchange enthalpy
considerations (as in 3d orbitals of the first transition series), appear to impart a certain
degree of stability to empty, half-filled and completely filled orbitals f level. This is indicated
from the abnormally low value of the third ionisation enthalpy of lanthanum, gadolinium and
lutetium.

4. Some chemical reactions of lanthanoids are

Uses: The best single use of the lanthanoids is for the production of alloy steels for plates and
pipes. A well known alloy is mischmetal which consists of a lanthanoid metal (~ 95%) and
iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in Mg-based
alloy to produce bullets, shell and lighter flint. Mixed oxides of lanthanoids are employed as
catalysts in petroleum cracking. Some individual Ln oxides are used as phosphors in
television screens and similar fluorescing surfaces.

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ACTINOIDS
The actinoids include the fourteen elements from Th to Lr. The names, symbols and some properties of
these elements are given in Table below

The actinoids are radioactive elements and the earlier members have relatively long half-lives, the latter
ones have half-life values ranging from a day to 3 minutes for lawrencium (Z =103). The latter members
could be prepared only in nanogram quantities. These facts render their study more difficult.

ELECTRONIC CONFIGURATION: 7s2, 6d0-1, 5f1-14

The fourteen electrons are formally added to 5f, though not in thorium (Z = 90) but from Pa onwards
the 5f orbitals are complete at element 103. The irregularities in the electronic configurations of the
actinoids, like those in the lanthanoids are related to the stabilities of the f 0 , f 7 and f 14 occupancies of
the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f7 7s2 and [Rn] 5f7 6d1 7s2.

IONIC SIZES
There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as
the actinoid contraction (like lanthanoid contraction). The contraction is, however, greater from element
to element in this series resulting from poor shielding by 5f electrons. There is a greater range of
oxidation states, which is in part attributed to the fact that the 5f, 6d and 7s levels are of comparable
energies.

OXIDATION STATES
The actinoids show in general +3 oxidation state.
The elements, 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.

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The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state.
However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states among the
actinoids is so uneven and so different for the former and later elements, it is unsatisfactory to review
their chemistry in terms of oxidation states.

GENERAL CHARECTERSTICS OF ACTINOIDS

• The actinoid metals are all silvery in appearance but display a variety of structures.
• Its metallic radii are far greater than in lanthanoids.
• The actinoids are highly reactive metals, especially when finely divided
• The magnetic properties of the actinoids are more complex than those of the lanthanoids.
Although the variation in the magnetic susceptibility of the actinoids with the number of
unpaired 5 f electrons is roughly parallel to the corresponding results for the lanthanoids, the
latter have higher values.
• Ionisation enthalpies of the early actinoids, though not accurately known, but are lower than for
the early lanthanoids. This is quite reasonable since it is to be expected that when 5f orbitals are
beginning to be occupied, they will penetrate less into the inner core of electrons. The 5f
electrons, will therefore, be more effectively shielded from the nuclear charge than the 4f
electrons of the corresponding lanthanoids. Because the outer electrons are less firmly held, they
are available for bonding in the actinoids.

Example: Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
Answer: Cerium (Z = 58)

Example: Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Answer: Actinoid contraction is, however, greater from element to element in this series resulting from poor
shielding by 5f electrons.