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d & f – block elements By Govind Ahuja

The elements that lie in between S-block and P-block are the d-block elements. These
elements are called transition elements as they show transitional properties between s and p-
block elements. These elements contain partially filled d-orbitals and hence they are called as
d-block elements. The general electronic configuration of d-block elements is (n-1)d1-10 ns1-2.

he elements belonging to d-block are metals. The d-block elements are classified into four
transition series. These 4 series corresponds the filling of 3d, 4d, 5d and 6d orbitals.

Electronic Configuration
The general electronic configuration of d-block elements is (n-1) d1-10ns1-2. All the d-block
elements except zinc, cadmium and mercury have partially filled d-orbitals. But, zinc,
cadmium and mercury have completely filled d-orbitals and they exhibit common oxidation
state. So, they do not come under transition elements but are studied along with d-block
elements. In all the other transition elements the last electron enters the (n-1)d orbital which is
called the penultimate shell. The electronic configurations of 4 transition series are given
below
Characteristics of Transition Metals
All the transition metals except Zn, cd and Hg exhibit several physical and chemical
properties. Some of their properties are discussed below:

Variable oxidation states

By the study of electronic configuration of transition metals it is understood that variable
oxidation state can be formed as there are both ns and (n-1)d electrons in bonding. The
participation of ns electrons in bonding leads to +2 oxidation state which is a lower oxidation
state. The participation of (n-1)d electrons in bonding leads to higher oxidation states like +3,
+4, +5, +6 etc. These oxidation states depend upon the nature of combination of transition
metals with other elements. The oxidation state increases with atomic number. This increase is
related to groups. The most common oxidation state of the elements of first transition series is
+2. Ionic bonds are formed in lower oxidation state transition elements whereas covalent
bonds are formed in higher oxidation states.
The highest oxidation states are observed in fluorides and oxides. The highest oxidation state shown by any
transition element (by Ru and Os) is 8.
The transition elements in the + 2 and + 3 oxidation states mostly form ionic bonds.

Magnetic properties
By the study if electronic configuration of transition metals it is understood that they generally
contain one or more unpaired electrons in the (n-1)d orbital. Due to these unpaired electrons
they behave as paramagnetic substances. These substances are attracted by the magnetic field.
The transition elements that contain paired electrons behave as diamagnetic substances. These
substances are repelled by the magnetic field. The paramagnetic character increases as the
number of unpaired electrons increases.

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d & f – block elements By Govind Ahuja

The paramagnetism first increase in any transition element series, and then decreases. ( think ?? )
A substance which is attracted by magnetic field is called paramagnetic substance.
The substances which are repelled by magnetic field are called diamagnetic substances.
The magnetic moment of any transition element or its compound/ion is given by

(assuming no contribution from the orbital magnetic moment),

 s  4SS  1 BM  n n  2 BM

Where, S is the total spin (n x s) : n is the number of unpaired electrons and s is equal to ½ (representing the spin
of an unpaired electron). The paramagnetism is described in Bohr Magneton (BM) units.

Formation of colored compounds

Most of the transition elements form colored compounds both in solid state as well as in
aqueous solution. It is already studied that the transition metals have incomplete d-orbital. The
electrons are to be promoted from a lower energy level to a higher energy level. Some amount
of energy is required for this process and the radiations of light are observed in the visible
region. The compounds absorb a particular color from the radiation and the remaining ones are
emitted.
For e.g., Cu2+ are bluish green in color due to absorption of red light wavelength.
As Zn has completely filled d-orbitals it cannot absorb radiation and hence Zn2+ salts are
white.

Formation of complexes
Transition metals form many complex ions. They are the electrically charged complexes with
a metal ion in the center which is surrounded and linked by a number of neutral molecules or
negative ions. These neutral molecules or negative ions are called as ligands. As the
transitions metals are small in size they form large number of complexes.

Electrode potential and low reactivity

The electrode potential is a measure of the total enthalpy change (HT) when a solid metal, M
is brought into aqueous medium in the form of M+ (aq).

The total enthalpy change depends on sublimation energy, ionization energy and hydration
energy of the metal.

The stability of the oxidation state of metal depends on the electrode potential. When electrode
potential is less the stability is more.

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d & f – block elements By Govind Ahuja

Metallic Character All the transition elements are metals. The presence of unfilled d-orbitals favour covalent
bonding; Metallic bonding in these metals is indicated by the conducting nature of these metals. Therefore, it
appears that there exists covalent and metallic bonding in transition elements.

Melting and Boiling Points Atoms of the transition elements are closely packed and held together by strong
metallic bonds which have appreciable covalent character.
This leads to high melting and boiling points of the transition elements.
NOTE: The low melting points of Zn, Cd, and Hg may be due to the absence of unpaired d-electrons in their
atoms. Lowest m.p. : mercury, highest m.p. tungsten

Catalytic Properties Most of the transition metals and their compounds particularly oxides have good
catalytic properties. Platinum, iron, vanadium pent oxide, nickel, etc., are important catalysts.
Vanadium pentoxide (V2 O5) is used in the Contact process for the manufacture of sulphuric acid,

Explanation :The presence of vacant d-orbitals.

(a) The tendency to exhibit variable oxidation states.
(b) The tendency to form reaction intermediates with reactants.
(c) The presence of defects in their crystal lattices.

Why are Zinc, Cadmium and Mercury not considered as the Transition Elements
Zinc cadmium and mercury are the end-members of the first three series, 3d, 4d and 5d series of the transition
elements. Their electronic configurations are represented by the general formula (n-1) d10 ns2. Since, these
metals d-orbitals are completely filled, hence these do not exhibit the general characteristic properties of the
transition elements. Therefore, these metals are not considered as transition elements.

Characteristics of the transition elements

(i) All transition elements are metals.
(ii) These elements are hard, high melting, and high boiling metals.
(iii) These elements form alloys among themselves and with other metals.
(iv) Many of the transition elements are sufficiently electropositive and get dissolved in minerals acids.
(v) With very few exceptions, these elements exhibit variable valencies and their ions and compounds are
coloured in one or all the oxidation states.
(vi) Because of the partially filled shells these elements form paramagnetic compounds.

Atomic Radii The atomic radii and atomic volumes of d-block elements in any series decrease with increase in
the atomic number. The decrease however, is not regular. The atomic radii tend to reach minimum near at the
middle of the series, and increase slightly towards the end of the series.

Q. The sums of first and second ionization enthalpies and those of third and fourth ionization enthalpies of
nickel and platinum are:IE1 + IE2 (KJ mol-1) IE3 + IE4 (KJ mol-1) [Ni 2.49 8.80] [Pt 2.66 6.70]
Based on this information, write:
(a) The most common oxidation state for Ni and Pt and mention why they are common?
(b) Name the metal (Ni or Pt) which can easily form compounds in +4 oxidation state and why?
Ans.(a) The most common oxidation state of Ni is +2 and of Pt is +4 because these have lower I.E.
(b) Platinum because the sum of first four ionization enthalpies for Pt is lower than that for Ni.

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d & f – block elements By Govind Ahuja

Q. Why does AgNO3 produces a black stain on the skin?

Ans. In the presence of organic matter (skin) and light, AgNO3 decomposes to give a black stain
of metallic silver. 2AgNO3 2Ag + 2 NO2 + O2

Q. Why is KMnO4 solution used to clean surgical instruments in hospitals?

Ans. Because of the germicidal action of KMnO4

Q. K2 PtCl6 known but Ni compound is not known. State a reason for it.
Ans. This is because Pt4+ is more stable than Ni4+ as the sum of four I.E. of Pt is les than that of Ni.

Q. Why are the ionization energies of 5d elements are greater than 3d elements?
Ans. In the 5d series, after lanthanum (Z = 57), there is lanthanide contraction. As a result, in each group the
atomic size of 5d elements is small and its nuclear charge is large.
Hence the ionization energies of 5d elements are larger than 3d elements.

Q. (a) Of the ions Ag+, Co2+ and Ti4+, which ones will be coloured in aqueous solutions.
(b) If each one of above species is in turn placed in a magnetic field, how will it respond and why?
Ans.(a) Of the ions Ag+ (4d10), Co2+ (3d7) and Ti4+ (3s23p6), Co2+ will be coloured in aqueous solution because it
contains unpaired electrons in d-sub shell. (b) Co2+ will be attracted by the magnetic field and is paramagnetic.

Q. What is the basic difference in three varieties of iron? Ans. These differ in their carbon content.
Q.What is the role of limestone in the blast furnace? Ans. Basic flux.
Q. What are the constituents of Bordeaux mixture? Ans. Copper sulphate and slaked lime

Q. Give example and suggest reaction for the following features of the transition metal chemistry
(a) The lowest oxide of transition metal is basic, the highest is acidic
(b) A transition metal exhibits higher oxidation states in oxide and fluorides.
(c) The highest oxidation state exhibited in oxoanions in metal.
(d) Write the different oxide of chromium and mention basic and acidic oxides.

Ans. (a) As the oxidation state of transition element in oxide increases, the charge density on the metal also
increases, thus the increase of the polarization of the anion charge cloud by the metal will take place. Because of
this, covalent characters of the oxides increase with the increase in oxidation state. Hence the oxides in lower
oxidation states are ionic and dissolve in water whi8le the oxides in higher oxidation state are covalent and acidic

(b) Because oxygen and fluorine are most electronegative elements so the transition metals are oxidized to their
higher oxidation states with oxygen and fluorine.

(c) Because the highest oxidation state of metal in oxoanions is stabilized by O2- ion, therefore, the metal shows
highest oxidation state in oxoanions.
Example: Cr2O72- (dichromate) and MnO4- (permanganate) have the highest oxidation states of metal i.e., Cr (VI)
and Mn (VII).

(d) Oxides of Cr Oxidation state of Cr Nature of the oxide

CrO +2 Basic
Cr2O3 +3 Amphoteric
CrO2 +4
CrO3 +6 Acidic

Q.What is meant by disproportion? Give two examples of disproportion reaction in aqueous solution.
Ans. Disproportion reactions are those in which one oxidation state decomposes, forming some ions in higher
oxidation state and some in lower oxidation state. Disproportion occurs when a given oxidation state is stronger
oxidizing agent than the next highest oxidation state.

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d & f – block elements By Govind Ahuja

Examples: 3CrO42- + 8H+ 2CrO42- + 3Cr3+ + 4H2O

(oxi. State = 5) (oxi. State = 6) (oxi. State = 3)

Q. How would you account for the following

(a) Of the d4 species, Cr2+ is strongly reducing while Mn3+ is strongly oxidizing.
(b) Cobalt (II) is stable in aqueous solution but in presence of complexing reagent, it is easily oxidized.

Ans. (a) It can explained on the basis of Eo values of Cr3+/Cr2+ (-0.4 V) and Mn3+ (+ 1.5 V). On the basis values,
it is clear that Cr2+ has a great tendency to oxidize into Cr3+, thus it acts as reducing agent.
Cr2+ (aq) Cr2+ (aq) + e- while Mn2+ has a great tendency to reduce into Mn 2+
Thus it acts as an oxidizing agent. Mn3+ (aq) + e- Mn2+ (aq)

(b) It can be explained on the basis of crystal field theory. In water Co2+ is more stable than Co3+ ion because
[Co(H2O)6]2+ complex (formed with water) is more stable than [Co(H2O)6]3+ due to having higher value of crystal
field stabilizing energy.

Q. Decide giving reason which one of the following pair has the property indicated:
(I) Fe or Cu has higher melting point, (II) Co2+ or Ni2+ has lower magnetic moment.
Ans. (I) Fe has higher melting point than Cu, because iron has for unpaired electrons in d-sub shell (3d6 4s2),
therefore, the metallic bonds and covalent bonds in iron are stronger in Fe but in Cu no d-electron is unpaired and
only one 4s 1 electron is responsible for metallic bon.
Ans (II) Co2+ and Ni2+ have 3d7 4s0 and 3d8 4s0 configuration respectively, hence 3 unpaired electrons are present
in Co2+ and 2 unpaired electrons are present in Ni2+. Therefore, Ni2+ has lower magnetic moment, because it
depends upon number of unpaired electrons

Q. Discuss the chromyl chloride test.

Ans. Chromyl chloride test is used to detect the presence to chloride ions. When any chloride salt is heated with
solid K2Cr2O7 and conc. H2SO4, orange coloured vapours of chromyl chloride are formed.

f block elts
The elements which in their elemental or ionic form have party filled f-orbitals are called f-block elements. As
the f-orbitals lie inner to the penultimate (second outermost) shell, therefore, these elements having partially
filled f-orbitals are also known as inner-transition elements.
There are two series of inner-transition elements, each having 14 elements.
 The elements in which 4f-orbitals are progressively filled are called lanthanides.
 The elements in which 5f orbitals are progressively filled are termed actinides.

Q. Why do the d-block elements exhibit a larger number of oxidation states than the f-block elements?
Ans. Because the energy of ns-electrons and (n - 1) d-electrons can take part in bond formation in transition
elements. In f-block elements last electron goes to the f-orbitals of second outer most shell, thus the difference
between the energy of ns-electron and (n - 2) f-electrons increases.
Due to this reason all the (n - 2) f-electrons cannot take part in bond formation.

Lanthanides
The fourteen elements after lanthanum (atomic number 58-71) are called lanthanides or lanthanous. The general
electronic configuration of lanthanides is 4f1-14 5d0-1 6s2.

 Oxidation states. Lanthanides in aqueous solution and in the solid state exhibit oxidation states
of + 2 , + 3 and + 4. The trivalent state (+3) being more stable.
 Magnetic properties. Trivalent ion of lanthanides (except La3+ and Lu3+) are paramagnetic.

Q.Why do Zr and Hf exhibit similar properties?

Ans. Due to lanthanoid contraction, Hf and Zr have almost similar size and therefore, their properties are similar

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d & f – block elements By Govind Ahuja

Q. Among the lanthanides. Ce (III) can be easily oxidized to Ce (IV). (At. No. of Ce = 58)
Ans. Ce (III) has the electronic configuration: 4f 1 5do 6so. It can be easily oxidised because it can readily lose an
electron to acquire the stable 4f o configuration and form Ce (IV)

Actinides.
The fourteen elements (atomic number 90-103) after actinium are called actinides. These are also called second
series of inner-transition elements. The general electronic configuration of actinides is 5f 1-14 6d 0-1 7s2.

 Oxidation states. Actinides show variable oxidation states. The oxidation state 3+ is the most common.
 Coloured ions / salts. Most M3+, M4+ ions of actinides are coloured. Ions having 0, 1 and 7 electrons
in f-subhells are colourless. The ions having 2, 3, 4, 5 and 6 electrons in the f-orbitals are coloured.
 Misch metal. The alloy containing 94-95% a rare earth element, iron up to 5% and traces of sulphur,
carbon, calcium and aluminium is called misch metal.
 Pyrophoric alloys. A typical composition of a pyrophoric alloy is cerium 40.5% , lanthanum +
neodymium 44% iron 4.5% aluminium 0.5% and the remainder calcium, silicon and carbon. The
pyrophroic alloys containing rare earth metals are used in the preparation of ignition devices, e.g., tracer
bullets and shells and flints for lighters.

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