d BLOCK ELEMENT

1. A transition element is defined as the one which has incompletely filled d orbitals in its ground
state or in their common oxidation state.
2. Zn, Cd & Hg are not regarded as transition metals.
They have d10 configuration in their ground state as well as in their common oxidation states.
3. On what ground can you that Sc (Z=21) is a transition element but Zn (Z=30) is not?
On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state
(3d1), 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 oxidized state, hence it is not regarded as a
transition element.
4. Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that
it is a transition element
In general, the electronic configuration of outer orbitals of these elements is
(n-1) d 1-10 ns 1-2 except for Pd where its electronic configuration is 4d105s0.
5. With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic structures at
normal temperatures.
6. The transition metals are very hard and have low volatility.
Exception - Zn, Cd and Hg
7. Their melting and boiling points are high.
a. The high melting points of these metals are attributed to the involvement of greater number
of electrons from (n-1)d in addition to the ns electrons in the interatomic metallic bonding.
b. W has the highest melting point amongst transition elements.
c. Mn & Tc have abnormally low melting points.
8. They have high enthalpies of atomisation.
a. Because of greater number of valence electrons in their atoms they have stronger
interatomic interaction, stronger is the resultant bonding.
b. In 3d series, element with lowest enthalpy of atomisation Zn.
c. In 3d series, element with highest enthalpy of atomisation V.
d. Metals of the second and third series have greater enthalpies of atomisation than the
corresponding elements of the first series due to the occurrence of much more frequent
metal – metal bonding in compounds of the heavy transition metals.
9. Why do the transition elements exhibit higher enthalpies of atomization?
Because of the large number of unpaired electrons in their atoms they have
stronger interatomic interaction and hence stronger bonding between atoms resulting in
higher enthalpies of atomisation.
10. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest,
i.e., 126 kJ mol–1. Why?
11. They have high densities
a. density increases down the group.
b. The lightest transition metal is Sc.

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c. Heaviest & densest transition metals are Os(22.59g/ml) & Ir (22.61g/ml).

d. Order in 3d – Cu>Ni≈Co>Fe>Mn>Cr>Zn>V>Ti>Sc.
12. Atomic and ionic size
a. Order of atomic radii - Sc > Ti > Mn = Zn >V > Cr > Cu > Fe > Co = Ni
b. Order of ionic radii (M2+) - Mn = Cr >V > Fe > Zn > Co >Cu > Ni
c. Order of ionic radii (M3+) - Sc > Ti > Mn = Fe >V > Cr > Co > Ni
d. Order - first (3d) < second (4d) series≈ third (5d) series (corresponding members of the
second series). Exception – Sc < Y < La.
13. Lanthanoid contraction - the filling of 4f before 5d orbital results in a regular decrease in
atomic radii called lanthanoid contraction.
a. Reason- the imperfect shielding of one electron by another in the same set of orbitals.
However, the shielding of one 4f electron by another is less than that of one d electron by
another, and as the nuclear charge increases along the series, there is fairly regular decrease
in the size of the entire 4f n orbitals.
b. Consequence of lanthanoid contraction-
• Second and the third d series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm)
• The second and the third d series have very similar physical and chemical
properties.
14. IONIZATION ENTHALPIES
a. First - Zn>Fe>Co>Cu>Ni>Mn>Cr>V>Ti>Sc
b. Second - Cu>Ni>Zn>Co>Cr>Fe>Mn>V>Ti>Sc
c. Third- Zn>Cu>Ni>Mn>Co>Cr>Fe>V>Ti>Sc
d. The irregular trend in the first ionisation enthalpy of the metals of 3d series, though of little
chemical significance, can be accounted for by considering that the removal of one electron
alters the relative energies of 4s and 3d orbitals
e. The trend of steady increase in second and third ionisation enthalpy breaks for the formation
of Mn2+ and Fe3+ respectively. In both cases, ions have d5 configuration.
f. First ionisation enthalpy of Zn is lower because there is no change in the d configuration
and gives stable configuration.
g. First ionisation enthalpy of Cr is higher because electron is lost from Stable filled 4s
orbital.
h. Ionisation enthalpy of Mn+ is lower than Cr+ -Since Mn+ has 3d54s1 configuration and
configuration of Cr+ is d5.
i. Second ionization enthalpy of Cu (Cu+ has 3d10 configuration) is more than that of Zn
(Zn+ has 3d10 4s1)
j. Third ionization enthalpy of Zn is very high due to d10 (Zn2+) configuration.
k. Third ionisation enthalpy of Fe is lower than that of Mn. Since Fe2+ has d6 configuration
and Mn2+ has 3d5 configuration.
15. Oxidation states
a. Except Sc, the most common oxidation state of the 3d series is +2.
b. The highest oxidation state shown by any transition metal is +8.
c. Ti (IV) is more stable than Ti (III) and Ti(II).
d.Mo (VI) and W(VI) are found to be more stable than Cr (VI).

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Thus Cr (VI) in the form of dichromate in acidic medium is a

strong oxidising agent, whereas MoO3 and WO3 are not.
e. The only oxidation state of Zn is +2.
f. Most common oxidation state of V is +5, Cr is +3 & +6, Mn is +2 &+7,
Fe is +2&+3,Co is +2&+3,Ni is +2 and Cu is +2.
g. The element which gives the greatest number of oxidation state is Mn
16. Which of the 3d series of the transition metals exhibits the largest number of oxidation
states?
Mn
17. Transition element which does not exhibit variable oxidation states.
Scandium (Z = 21).
18. 3d series element which does not show variable oxidation state
Sc & Zn
19. Trends in the M 2+/M standard electrode potential
a. Cu is the only metal in 3d series which have positive Eo value.
The high energy to transform Cu to Cu2+ is not balanced by its hydration enthalpy.
b. The general trend towards less negative Eo values across the series is due to the general
increase in the sum of the first and second ionization entalpies.
c. The value of Eo for Mn, Ni and Zn are more negative than expected from the trend. This is
due to the greater stability of half-filled d subshell in Mn2+ and filled d subshell in Zn2+ &
highest negative enthalpy of hydration in Ni2+.
20. Trends in the M 3+/M2+ standard electrode potential
a. Low value for Sc indicates the stability of Sc3+ which has a noble gas configuration.
b. The highest value for Zn is due to the removal of an electron from the stable d10
configuration of Zn2+.
c. The high value for Mn shows that Mn2+( d5)is stable.
d. Comparatively low value for Fe shows the extra stability of Fe3+(d5)
e. Comparatively low value for V shows the extra stability of V2+(half-filled t2g level))
21. Why is the EO value for the Mn3+/Mn2+ couple much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+? Explain.
Much larger third ionisation energy of Mn (where the required change is d 5 to d 4)
22. Trends in stability of higher oxidation states.
a. The highest oxidation numbers are achieved in TiX4 (F→I), VF5 & CrF6
b. The +7 oxidation state for Mn is not shown by simple halides but MnO3F is known.
c. Beyond Mn no metal has a tri halide except FeX3 and CoX3
d. The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice
energy (ex- CoF3) or higher bond enthalpy terms for the higher covalent compounds (VF5 &
CrF6).
e. VX5 (X→ Cl to I) undergo hydrolysis to form oxohalides VOX3
f. Fluorides are not stable in their low oxidation state Ex- TiX2, CuX
VX2 (X=Cl →I).
g. Cu(II) halides are known except the iodide. Cu2+ oxidises I- to I2

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h. Oxygen stabilizes the highest oxidation states more than fluorine. This is due to the ability of
oxygen to form multiple bonds with the metal atoms. Thus, highest oxidation state of Mn in
fluorides is MnF4 whereas the highest oxidation state is Mn2O7.

i. [MO4]n- is tetrahedral ( M= V(V), Cr(VI), Mn(V), Mn(VI), Mn(VII) )

j. The highest oxidation state in the oxides is same as that of group number upto group 7
(Sc2O3 to Mn2O7).
k. Beyond group 7, the maximum oxidation state is +3 (Fe2O3) although ferrates are formed in
alkaline media, but they readily decompose to Fe2O3 &O2.
l. Higher oxidation state is also found in oxocations and oxoanions.
V(V) in VO2+, V(IV) in VO2+ & Ti(IV) in TiO2+
m. Cu(I) compounds are unstable in aqueous solution and undergo disproportionation.

n. Stability of Cu2+(aq) more than Cu+(aq) is due to more negative hydration enthalpy of
Cu2+ than Cu+, which more than compensates for the second ionization enthalpy of Cu.
23. How would you account for the increasing oxidizing power in the series VO2 + < Cr2O7 2–
< MnO4 – ?
This is due to the increasing stability of the lower species to which they are reduced.
o
24. Chemical Reactivity and E Values
a. The Eo values for M2+/M indicate a decreasing tendency to form divalent cations across the
series.
b. Metals of the 3d series are relatively more reactive and are oxidised by 1M H+
Exception – i) Cu ii) Ti & V are passive to dilute non oxidising acids at room temperature.
c. Mn3+ & Co3+ ions are the strongest oxidizing agents in aqueous solution. (based on the Eo)
d. Mn3+ & Co3+ ions are the strongest oxidizing agents in aqueous solution. (based on the Eo)
e. Ti2+,V2+& Cr2+ ions are the strong reducing agents in aqueous solution.(based on the Eo
values) & liberate H2 from a dilute acid.

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

Cr2+ .
E0(Cr3+/Cr2+) is -ve whereas E0(Fe3+/Fe2+) is +ve. Thus Cr2+ is easily oxidised to Cr3+ but
Fe2+cannot be easily oxidised to Fe3+.
26. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Cr2+ is reducing as its configuration changes from d 4 to d 3 , the latter having a half-filled
t2g level . On the other hand, the change from Mn to Mn results in the half-filled (d 5)
3+ 2+

configuration which has extra stability.

27. Magnetic properties

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a. Diamagnetic substances are repelled by the applied field due to the absence of unpaired
electrons.
b. Paramagnetic substances are attracted by the applied field.
• It is due to the presence of unpaired electrons.
• For the compounds of the 3d series, the contribution of the orbital angular
momentum is effectively quenched & hence is of no significance.
• Spin magnetic moment
n = number of unpaired electrons.
d0 d1 d2 d3 d4 d5
0 1.73 2.84 3.87 4.9 5.92 μ(BM)
10 9 8 7
d d d d d6

c. Ferromagnetic Substances are very strongly attracted by the applied field.

28. Catalytic properties of transition metals & their compounds
Ex- Vanadium (V) oxide in contact process.
Finely divided iron in Haber’s process.
Nickel in catalytic hydrogenation.
• Catalytic activity is due to their ability to adopt multiple oxidation states and to form
complexes.
Ex- Fe (III) catalyses the reaction between iodide and persulphate ions.

29. Formation of colored ions

a. Colour observed corresponds to the complementary colour of the light absorbed.
b. Colour is due to d-d transition.
c. Transition metal ions having d0 & d10 configuration are colourless.
Ex- Cu+ (d10), Zn2+(d10), Cd2+(d10), Hg2+(d10),Sc3+(d0) Ti4+(d0)
d. Colour of 3d series ions in water

ION COLOUR
Ti3+ purple
V4+ Cr2+ Cu2+ Co3+ blue
V3+ Fe2+ Ni2+ green
V2+ Cr3+ Mn3+ violet
Mn2+ Co2+ pink
Fe3+ yellow

30. Formation of complex compounds

The great tendency of transition metal ions to form complexes is due to their (i) Small size
(ii) high charge (iii) availability of d orbitals for bond formation.

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31. Formation of interstitial compounds

a. Interstitial compounds are those which are formed when small atoms like H, C or N are
trapped inside the crystal lattices of metals.
b. They are usually nonstoichiometric
c. neither typically ionic nor covalent
d. Example- TiC, Mn4N, Fe3H, VH0 .56 and TiH1.7, etc.
e. Physical and chemical properties of these compounds are
• 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.
32. Alloy formation
a. An alloy is a blend of metals prepared by mixing the components.
b. Alloys may be homogeneous solid solutions in which the atoms of one metal are
distributed randomly among the atoms of the other.
c. Because of similar radii and other characteristics of transition metals, alloys are readily
formed by these metals.
d. The alloys so formed are hard and have often high melting points.
e. Ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are used for
the production of a variety of steels and stainless steel.
f. Alloys of transition metals with non-transition metals such as brass (copper-zinc) and
bronze (copper-tin).
33. Oxides and Oxoanions of Metals
a. As the oxidation number of a metal increases, ionic character decreases.
b. Mn2O7 is a covalent green oil, acidic & gives HMnO4
c. CrO3 has low melting points, acidic & gives H2CrO4 and H2Cr2O7.
d. V2O5 has low melting points, amphoteric though mainly acidic & it gives
VO4 3– as well as VO2 + salts.
e. V2O3 is basic, V2O4 is less basic and V2O5 is amphoteric.
f. V2O4 dissolves in acids to give VO2+ salts.
g. V2O5 reacts with alkalies as well as acids to give VO43− and VO4+ resp.
h. The well characterised CrO is basic, but Cr2O3 is amphoteric.
34. Potassium dichromate
a. Preparation –
• Chromite ore (FeCr2O4) is fused with sodium or potassium carbonate in excess of air.

• 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
crystallised

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• Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.

Orange crystals of potassium dichromate crystallise out

b. Uses- used in leather industry and as an oxidant for preparation of many azo compounds.
c. Properties
• The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution.

• In acidic solution, it acts as an oxidizing agent.

• Acidified potassium dichromate will oxidise iodides to iodine sulphides to sulphur,

tin(II) to tin(IV) and iron(II) salts to iron(III).

d. Structure

Tetrahedral Two tetrahedral units

Diamagnetic Diamagnetic
Yellow Orange
35.Potassium permanganate
a. Preparation-
• MnO2 is fused 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

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• Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the

electrolytic oxidation of manganate (Vl).

• In the laboratory, manganese (II) ion salt is oxidised by peroxodisulphate to

permanganate.

b. Properties
• It decomposes at 513 K.

• It acts as oxidising agents

Permanganate at [H+ ] = 1 should oxidise water but in practice the reaction is extremely
slow unless either manganese(ll) ions are present or the temperature is raised.
In acid solutions
(i) Iodine is liberated from potassium iodide

(ii) Fe2+ ion (green) is converted to Fe3+ (yellow)

(iii)Oxalate ion or oxalic acid is oxidised at 333 K

(iv) Hydrogen sulphide is oxidised, sulphur being precipitated

(v) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid

(vi) Nitrite is oxidised to nitrate.

In neutral or faintly alkaline solutions

(i) oxidation of iodide to iodate

(ii) Thiosulphate is oxidised almost quantitatively to sulphate.

(iii) Manganous salt is oxidised to MnO2 ; the presence of zinc sulphate or

zinc oxide catalyses the oxidation:

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c. Structure

Paramagnetic Diamagnetic
d. Uses
• As analytical reagent
• Potassium permanganate is used as an oxidant in preparative organic chemistry.
• Used for bleaching wool, cotton, silk and other textile fibers and for the decolorization
of oils are also dependent on its strong oxidizing power.
e. Applications of d Block Elements
a) Iron and steel are the most important construction materials.
Their production is based on the reduction of iron oxides, the removal of impurities
and the addition of C& alloying metals such as Cr, Mn & Ni.
b) Some compounds are manufactured for special purposes such as TiO for the pigment
industry and MnO2 for use in dry battery cells.
c) The battery industry also requires Zn and Ni/Cd.
d) The elements of Group 11 are still worthy of being called the coinage metals, although
Ag and Au are restricted to collection items and the contemporary UK ‘copper’ coins are
copper-coated steel. The ‘silver’ UK coins are a Cu/Ni alloy.
e) Many of the metals and/or their compounds are essential catalysts in the chemical
industry. Example-

• V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.

• TiCl4 with A1(CH3)3 forms the basis of the Ziegler catalysts used manufacture
polyethylene (polythene).
• Iron catalysts are used in the Haber process for the production of ammonia from N2/H2
mixtures.
• Nickel catalysts enable the hydrogenation of fats to proceed.
• In the Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2 .
• Nickel complexes are useful in the polymerisation of alkynes and other organic
compounds such as benzene.
• The photographic industry relies on the special light-sensitive properties of AgBr