d-BLOCK ELEMENTS & f-BLOCK ELEMENTS

Total number of Questions in d-Block Elements & f-Block Elements are :

In Chapter Examples ...........................................................................10

Solved Examples ................................................................................26

Total no. of questions .......................................................................36

1. INTRODUCTION
(i) The elements lying between s- & p - block
element of the periodic table are collectively
known as transition or transitional elements.
(ii) Their properties are transitional between the
highly electropositive s- block element to least
electropositive p - block elements.
(iii) In d-block elements, the last differentiating
electron is accommodated to the penultimate
shell, expanding it from 8 to 18 electrons.
(iv) The general electronic configuration of transition
element is (n–1) d1–10 ns0, 1 or 2
(v) These elements either in their atomic state or
in any of their common oxidation state have
partly filled ( n– 1) d- orbitals of ( n– 1) th main
shell.
(vi) The configuration clearly show that strictly,
according to the definition of d- block elements,
Cu, Ag & Au should be excluded from d- block
element.Since these elements, both in their
atomic state
[With configuration ( n– 1) d10 ns1] & in their +1
oxidation state [ with configuration ( n– 1) d10],
do not have partly filled ( n–1) d- orbitals.
(vii) Similarly Zn, Cd & Hg which both in their atomic
state [ ( n– 1) d10 ns2] & in + 2 oxidation state
[ (n– 1) d10 ] do not contain partly filled ( n– 1) d
orbitals should be excluded from d- block
elements..
(viii) Yet, in order to maintain a rational classification
of the elements; these elements (viz. Cu, Ag,
Au, Zn, Cd & Hg) are also generally studied
with d- block elements.
(ix) There are four complete rows ( called series) of
ten elements each corresponding to the filling
of 3d, 4d, 5d & 6d orbitals respectively.
(x) The irregularities in the observed configuration
of Cr (3d5 4s1 instead of 3d4 4s2), Cu (3d104s1),
Mo ( 4d5 4s1),Pd ([Kr] 4d10 5s0) , Au( [Xe] 4f 14
5d10 4s1), Ag ( [Kr] 4d10 5s1)] are explained on
the basis of the concept that half- filled and
completely filled d- orbitals are relatively more
stable than other d- orbitals.
Note : (a) For explaining the irregularities found in the
observed electronic configurations, one has
to consider the net effect of so many other
factors such as.
(i) Nuclear electronic attraction
(ii) Screening effect
(iii) Inter- electronic repulsion
(iv) The exchange energy force etc.
(b) All these factors play an important part
together in determining the final stability of
an atoms.
(c) It is not easy to explain why W unlike Cr
(3d5 4s1) & Mo ( 4d5 5s1) should have
idealised electronic configuration ( 4f 14 5d4
6s2)
2. GENERAL CHARACTERISTICS
(i) The properties of d-block elements of any given
period are not so much different from one
another as those of the same period of non
transition elements.
(ii) It is due to the fact that, in transition series,
there is no change in number of electrons of
outermost shell and only change occur in ( n–
1) d electron from member to member in a
period.
2.1 Metallic Character
(i) All the transition elements are metals, since
the number of electrons in the outermost shell
is very small being equal to 2.
(ii) They are hard, malleable and ductile, except
Hg which is liquid and soft.
(iii) They exhibit all the three types of structures.
Face Centred Cubic ( fcc), Hexagonal Close
packed (hcp) and Body Centred Cubic ( bcc).
(iv) Covalent and Metallic bonding both exist in the
atom of transition metals.
(v) The presence of unfilled d- subshell favour
covalent bonding, and metallic bonding is due
to possession of one or two electron in
outermost energy shell.
(vi) These metals are good conductors of heat and
electricity.
2.2 Melting and Boiling Points
(i) The transition elements have very high melting
& boiling points as compared to those of s & p
block elements.
(ii) The high melting and boiling point of transition
metals are attributed to the stronger force that
bind their atoms together.
(iii) As the number of d- electron increases the
number of covalent bond between the atoms are
expected to increase up to Cr- Mo- W family
where each of the d- orbital has only unpaired
electrons and the opportunity for covalent
sharing is greatest.
(iv) Inspite of presence of five unpaired electrons in
Mn, the unexpected low melting and boiling is
due to its complex structure it is unable to form
metallic and covalent bonds.
(v) The absence of unpaired electron [ ( n– 1) d10
4s2] in Zn, Cd, & Hg is responsible for its low
melting & boiling point.

Cr
2000 V 1900
Ti 1710
Melting Point t/ºC

1530
1672
1500 Sc Fe 1495
Ni
1397 Co 1455
Mn Cu
1244 1083
1000

420
500
Zn
IA IIA IIIB IVB V B VIBVIIBVIII IA IIB

Graphic representation m.p. of 3d - series elements

2.3 Atomic and Ionic Radii

Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic Radii (Aº) 1.44 1.32 1.22 1.18 1.14 1.17 1.16 1.15 1.27 1.25
Ionic radii (Aº)
for M2+ 0.95 0.90 0.88 0.74 0.80 0.76 0.74 0.72 0.69 0.74
for M3+ 0.81 0.68 0.73 0.69 0.66 0.64 0.63 0.62 - -
Metallic
radii (Aº) 1.62 1.47 1.34 1.27 1.26 1.26 1.25 1.24 1.28 1.38
(i) The value of these radii decreases generally, on atomic radii do not alter much on moving from
moving from left to right in the period. Cr to Cu.
(ii) This is due to the fact that an increase in the (vi) The radii of M2+ ions, although some what
nuclear charge tends to attract the electron smaller than that of Ca2+ ion ( = 0.99 Aº) are
cloud inwards. comparable with it.
(iii) The radii for the elements from Cr to Cu are (vii) Thus Mo oxides of transition element should be
however very close to one another. similar to CaO in many ways, although some
(iv) The simultaneous addition of electron of 3d- what less basic and less soluble in water.
level exercises the reverse effect by screening (viii) Similarly the Hydration energy of M 2+ ion
the outer 4s - electron from the inward pull [Ti2+  Cu2+] are between 446 KCal to 597 KCal
of the nucleus. is some what greater than that of Ca2+ ion
(v) As a result of these two opposing effects, the [ 395 K cal].
 (ix) The radii of M3+ ion are slightly greater than that
of Ga3+ ion ( = 0.62 Aº)
(x) M2O3 oxides of transitional element should be
similar to but slightly less acidic ( more basic)
than Ga2O3.
(xi) The hydration energies of M3+ ion
( Sc3+  Fe3+ - 947 K Cal to 1072 K Cal] is
less than that of Ge3+ ion ( 1124 K cal).
2.4 Ionisation Potential
(i) The first ionisation potential of transitional
elements lie between those of s & p block
elements.
(ii) The first ionization potential of all the transition
elements lie between 6 to 10 ev.
(iii) In case of transition elements the addition of
the extra electron in the ( n– 1) d provides a
screening effect which shields the outer ns
electron from the inward pull of positive nucleus.
(iv) Thus the effect of increasing nuclear charge &
the shielding effect created due to the expansion
of ( n– 1) d orbital oppose each other.
(v) On account of these counter affects, the
ionisation potentials increases rather slowly on
the moving in a period of the first transition series.
(vi) The IE1 for the first four 3d - block elements (
Sc, Ti, V & Cr) differ only slightly from one
another.
(vii) Similarly the value of Fe, Co, Ni & Cu also are
fairly close to one another.
(viii) The value of IE1 for Zn is considerably higher,
due to the extra stability of 3d10,4s2 level which
is completely filled in Zn atom.
(ix) The IE2 are seen to increase more or less
regularly with increase of atomic number.
(x) IE2 value for Cr & Cu are higher due to the
configuration of Cr+ & Cu+ ion are extra stable
3d5 and 3d10 levels.
(xi) In vertical columns, the ionisation potential
decrease from first member to the second
member in most of the cases as expected,
(xii) However the third member (5d series) has higher
value than second member ( 4d- series) due to
lanthanide contraction.

Ionisation Sc Ti V Cr Mn Fe Co Ni Cu Zn
Potential (ev.)
IE1 6.56 6.83 6.74 7.43 7.43 7.90 7.86 7.63 7.72 9.39
IE2 12.91 13.69 14.26 16.95 15.69 16.21 17.08 18.21 20.34 18.00
IE3 24.79 27.52 29.35 31.0 23.34 30.69 33.54 35.21 36.88 39.78

Lay out :
 2.5 Oxidation State (ii) This unique property is due to the fact that the
energy levels of 3d, 4d and 5d orbitals are fairly
(i) One of the most important property that close to those of 4s, 5s and 6s respectively.
distinguishes transition element from s & p block
element is that they show variable oxidation (iii) Therefore, in addition to ns electron, variable
states. number of ( n– 1) d electron are also lost in
getting various oxidation states.

Different oxidation states exhibited by ‘Transitional Metals’

III B IV B VB VI B VII B VIII IB II B
Elements of 3d- series ( Period 4)

Sc21 Ti22 V23 Cr24 Mn25 Fe26 Co27 Ni28 Cu29 Zn30
+1 +1
+ 2* + 2* +2 +2 (+ 2) (+ 2) (+ 2) (+ 2) (+ 2) (+ 2)
(+ 3) +3 +3 (+ 3) + 3* (+ 3) (+ 3) +3
(+ 4) +4 (+ 4) (+ 4) + 4* + 4* + 4*
(+ 5) + 5* + 5* + 5* + 5*
(+ 6) +6 (+ 6)
(+ 7)

Note : I - Most stable oxidation states are in
brackets.
II - Very rare oxidation states are shown by *.
(iv) All the transition elements with exception of Cr,
Cu, Ag, Au & Hg (which have a minimum
oxidation state of +1) exhibit a minimum
oxidation state of + 2.
(v) Each of the elements in groups II B to VII B can
show maximum oxidation state equal to its
group number. Example Cr in group VI B show
maximum oxidation state equal to + 6 in Cr2O72–
ion.
(vi) Most of the elements of VIII group show a
maximum oxidation state equal to + 6.
(vii) However, Ru (RuO 4) & Os (OsO 4) have a
maximum oxidation state equal to + 8 which is
the highest oxidation state shown by any
element.
 (viii) There is an increase in number of oxidation states (b) On the other hand VF5 is formed because
in going from left to right in a period. V5+ ion unable to oxidize highly
(ix) Maximum number of oxidation state is reached electronegative & small anion F–.
somewhere in the middle of a series. (c) Similarly highly electronegative and
small O2–ion formed oxides eg. VO43–,
2.6 Relative stability of various oxidation states CrO42– & MnO4– etc.
(iv) All transition elements in their lower
(i) The relative stabilities of various oxidation states oxidation state like to form ionic compounds.
of 3d- series element can be correlated with Whereas in their higher oxidation state they
the extra stability of 3dº, 3d5 & 3d10 configuration generally formed covalent compound.
to some extent. Example-
Example - +2 +3 +4 +5 +6 +7
Ti4+ ( 3dº) is more stable than Ti 3+ ( 3d1) TiCl2 TiCl3 TiCl4
Mn2+ ( 3d5) is more stable than Mn3+ ( 3d4). VCl2 VCl3 VCl4 VOCl3
(ii) The higher oxidation state of 4d and 5d series (Ionic, Less ionic
element are generally more stable than those
basic) Amphoteric Covalent & Acidic,
of the element of 3d series.
(Strong Lewis acid)
Example -
TiO Ti2O3 TiO2
(a) MoviO42–,TcviiO4–(4d- series element) & Wvi VO V2O3 V2O5
O42–, ReviiO4– ( 5d - series elements) are
CrO Cr2O3 CrO3
more stable and in which the transition
MnO Mn2O3 MnO2 MnO3 Mn2O7
element concerned show their maximum
oxidation state.
(b) Crvi O 42– & Mnvii O4– ( 3d - series) are Ionic Less Ionic Acidic
strong oxidizing agents. (Basic) (Amphoteric) (Covalent)
(iii) Strongly reducing states probably do not form Increasing order of chloride compound & oxides,
fluorides or oxides, but may well form the heavier hydrolysis & Reactivity 
halides. Conversely, strong oxidizing state form
oxides & fluoride, but not Bromide and Iodide. (v) Transition metals also form compounds in low
Example - oxidation state (1,0).
(a) V react with halogens to form VF5, VCl4, (vi) Such compounds are expected to be unstable
VBr3, but doesn’t form VBr5 or VI5 because except in case where vacant d- orbitals are used
in + 5 oxidation state V is strong oxidizing for accepting lone- pair from  bonding ligand
agent thus convert Br– & I– to Br2 & I 2 e.g. Ni (CO4) [Ag(CN)2]– [Ag (NH3)2]+
respectively, So VBr3 & VI3 are formed but
not VBr5 & VI5.

bond
Vacant p orbital in CO

bond 
M C O 

bonding ligand
bond

(Fully filled d- orbitals) (collateral) ( back bonding)

 (vii) When an element exists in more than one in the substance may be greater than or less
oxidation state, Eº data provide a clue to relative than H.
stabilities of different state w.r.t. oxidation. (ii) If the field in substance is greater than H, the
Example- substance is paramagnetic.
Cr2+ is unstable in water w.r.t. oxidation whereas
(iii) The paramagnetic substance, allow the
Cr3+ is stable in water.
magnetic lines of force to pass through them
Fe2+ is unstable in aerated water ( and change
rather than vacuum and show increase in weight.
to Fe3+ ) w.r.t. oxidation ( Air is basic in nature).
(iv) Thus paramagnetic substance attract line of
Note : In acidic medium lower oxidation state are force and it is free to move thus a paramagnetic
stable whereas in basic medium these metals material will move from a weaker to a stronger
show higher oxidation state. part of the field.
(v) Paramagnetism arises as a result of unpaired
(viii) Pd, Cu, Ag & Au behave as typical transition electron spin in the atom.
elements because of their most common (vi) If the field of substance is less than H , the
oxidation state Ag (II) , Cu (II) (d9), Pd (II) & substance is diamagnetic.
Ag(III) (d8 ) configuration ( incomplete d- level).
(vii) Diamagnetic material tend to repel line of force
(ix) However Zn (II), Cd( II), & Hg (II) have d10 and alien themselves perpendicular to the
configuration because of this these element do magnetic field.
not show the characteristic properties of
(viii) It is harder for magnetic line of force to travel
transition elements.
through diamagnetic substance than through a
vacuum and show a slight decrease in weight.
Examples
based on Oxidation State (ix) Such material will tend to move from a stronger
to weaker part of the field.
Ex.1 Chromium forms most stable compound in the (x) The diamagnetism arises as a result of paired
following oxidation state- electrons. i.e. all electrons spin mutually cancel
(A) Cr(I) (B) Cr (II) each other.
(C) Cr (III) (D) Cr(V)
(xi) The paramagnetic effect is much larger than
Sol. Chromium f orms most stable chromic
diamagnetic effect.
compounds in + 3 state. So answer is (C).
Ans.[C] (xii) Ferromagnetism is a special type of
paramagnetism in which permanent magnetic
Ex.2 In which of the following complexes the oxidation moment is acquired by the substance due to
number of metal is zero- the presence of unpaired electrons. It is shown
(A) [Pt(NH3)2Cl2] (B) [Cr(CO)6] by Fe, Co & Ni.
(C) [Cr(NH3)3Cl3] (D) [Cr(en)2Cl2]
(xiii) Transition metals & many of their compounds
Sol. In [(CrCO)6], the O.N. of chromium is zero.
show paramagnetic behaviour where there are
x + 6 x 0 = 0 or x = 0 Ans.[B]
unpaired electrons.
Ex.3 In which compound Mn will not show +2 (xiv)The magnetic moment arise from the spin and
oxidation state - orbital motions in ions or molecules.
(A) [Mn (H2O)6]+2 (B) MnCl2
(xv) Magnetic moment of substance with N unpaired
(C) [MnCl4]– (D) MnO
Ans.[C] electrons is   N (N 2) Bohr Magneton (B.M.)
Sol. The oxidation state of Mn in [MnCl4]– is : Note : (a) Paramagnetism varies inversely with
x–4=–1 temperature and independent of H.
x=+3 (b) Diamagnetism is Independent of
temperature & H.
2.7 Magnetic Properties
(c) For normal paramagnetic and diamagnetic
(i) When a substance is placed in magnetic field substance  ,  g ,  M are constants,
of strength H, The intensity of the magnetic field independent of field strength.
 Variation of Magnetic moment of 3d- series

Ions Outer Number of Magnetic Moment  B.M.

with most unpaired
configuration configuration electron

Sc3+ 3dº 0 0
Ti3+, V4+ 3d1 1 1.75
Ti2+, V3+ 3d2 2 2.86
V2+, Cr3+ 3d3 3 3.86
Cr3+, Mn3+ 3d4 4 4.80
Mn2+, Fe3+ 3d5 5 5.95
Fe2+,Co3+ 3d6 4 5.0 – 5.5
Co2+ 3d7 3 4.0 – 5.2
Ni2+ 3d8 2 2.9 – 3.4
Cu2+ 3d9 1 1.4– 2.2
Zn2+ 3d10 0 0

Examples
Magnetic Properties (ii) The colour of the compound of transition metals
based on
may be attributed to the presence of incom plete
Ex.4 Which of the following transition metal ions is (n – 1) d- subshell.
diamagnetic- (iii) In case of free metal ion all the five d- orbitals
(A) Co2+ (B) Ni2+ are assumed to be degenerated i.e. they have
(C) Cu2+ (D) Zn2+ the same energy.
Sol. All the electrons are paired in Zn2+ .So it is
(iv) The degeneracy of the five d- orbital is removed
diamagnetic. under the influence of the ligands.
Ans.[D]
Ex.5 Which pair of ions is colourless- (v) The separation of five d- orbital of the metal into
(A) Mn2+, Zn2+ (B) Fe3+, Cu+ sets having different energies viz.
2+ 3+
(C) Zn ,Sc (D) Ti2+,Cu2+ (a) t2g level ( i.e. dxy, dyz & dzx orbital lie between
Sol. In choice (C) both the ions have all the electrons the path of approaching ligand) triply degenerate
paired so their ions will be colourless . and is of lower energy.
Ans.[C] (b) e g level which is doubly degenerate
Ex.6 Zero magnetic moment will be shown by the ( i.e. dz2 & d x 2  y 2 orbital lie in the path of
compound -
approaching ligands) & is of higher energy.
(A) [Cr(NH3)6]+3 (B) [Ag(CN2)]–1
(C) [Fe(CN6)] –3
(D) [CoF6]3– (c) This phenomenon is known as crystal field
Sol. Oxidation Number of Ag in [Ag(CN)2]– is H. Its splitting or energy level splitting ( CFT).
configuration is (Kr) 5d10 .That the magnetic (vi) In such case transition metal ion absorbs light
moment is zero . Ans.[B] at specific wave length in visible part of
electromagnetic spectrum ( 4000– 7000 Aº) may
2.8 Formation of coloured Ions under go d-d transition .

(i) Unlike the cation, anions and oxyanions of the eg

representative elements (all of which are
colourless), the transition metal ions and their h
 
oxyanions such as CrO42– (yellow) Cr2O72–
(Orange) and MnO4– (Purple) are generally t2g
coloured.
 (vii) The transmitted light is coloured with the
complementary coloured.
A - Factors affecting the colour of complex.
The colour of a transition metal complex depend
on-
(i) The magnitude of energy difference between the
two d- levels (  0 ),
(ii) An increase in the magnitude of  0 decreases
the wave length (  ) of the light absorbed by
the complexes.
(iii) Thus with a decrease in the  the colour of
complex changes from Red  Violet.

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation
Potential value
(v) for M  - 1.60 1.20 0.91 1.18 0.44 0.28 0.25 0.34 0.76
M2++ 2e–
M  M3+ +
3 e– 2.10 - - 0.74 - - - - - -

2.9 Standard Oxidation potentials & Reducing
properties
(i) The oxidation potential value of the member of
first transition series are as follows.
(ii) The irregular trend is due to the variation in
Ionization energies, sublimation energies and
the hydration energies of the divalent ion of the
member of the transition series.
(iii) The value of standard oxidation potential reveal
that the value for any element except Cu is higher
than that of standard hydrogen electrode ( taken
as zero.).
(iv) It is therefore expected that these metals,
except Cu, would evolve H2 gas from acid
solution
M + 2H+  M2+ + H2  gas
(v) In actual practice the rate at which most of the
metal react with acid is very slow.
(vi) Some of the metals get protected from further
attack of the acid due to the formation of a thin
protective layer of their oxide, which prevent the
acid to come in further contact with metals.
(viii) The poor reducing capacity of the transition metal
is due to high heats of vaporization, high
ionization potential and low heat of hydration of
their ions.
2.10 Tendency to form Complex Compounds
(i) The cation of the transition metals have a great
tendency to form complex with ligands (NH3, H2O,
CN–, Cl– etc.)
(ii) These ligands possess invariably lone pairs of
electrons which they donate to the transition
metal cations in the formation of complex
compounds.
(iii) This tendency of the transition metal cation to
form the complex is due to the following reasons:
(a) These transition metals cations are relatively
very small in size & have high positive density
which make it easy for transition metals to
accepts the lone pairs of electrons from the
ligands.

(a) Although E 0ox of Cr is high, it get coated
with its non reactive oxide (Cr2O3) which
make the Cr metal so unreactive that it can
be used as a protective non oxidizing
metals.
(vii) Inspite of the fact that metals of first transition
series, except Cu, have high value of E 0ox
, these
are not good reducing agent as the metal of IA,
IIA & IIIA groups.
(b) The transition metals cation have vacant ( n– 1)
d- orbital which are of approximately the right
type of energy to accept lone pair of electrons.
(c) The transition metals are capable of showing
several oxidation states.
(iv) The structure commonly found in such complex
are linear ( i.e. co- ordination number, C.N.= 2),
square planer ( C.N.= 4) , tetrahedral (CN= 4)
or octahedral (C.N.= 6).
 (v) Cobalt form more complex than any other (ii) V2O5 - Convert SO2 to SO3 in the contact
elements process for making H2SO4.
Co3+ + 6NH3  [Co(NH3)6]3+ (iii) MnO2 - Used as a catalyst to decompose
Fe2+ + 6CN–  [Fe(CN)6]4– KClO3 to give O2.
Co3+ + 6H2O  [Co ( H2O)6 ]3+ (iv) Fe - promoted iron is used in Haber- Bosch
(vi) Coordination number (CN) : The number of process for making NH3.
monodentate ligand attached to central metal (v) FeCl3 - Used for making CCl4 from CS2 & Cl2.
ion is called the coordination number. (vi) FeSO4 & H2O2 - Used as Fenton's reagent for
Metal ion Ligand C.N. Complex ion oxidizing alcohol to aldehyde.
(vii) Pt.- used as a catalyst in the manufacture
Ag+ NH3 2 [Ag(NH3)2]+ of H2SO4.
Ni+2 CN– 4 Ni(CN)4]–2 (viii) Ni - used as a catalyst in the hydrogenation
Cu2+ NH3 4 [Cu(NH3)4]+2 of oils.
Fe+2 CN– 6 [Fe(CN)6]–4
(ix) PdCl2 - Wocker process for converting C2H4 +
H2O + PdCl2 to CH3CHO + 2HCl + Pd.
Charge on complex:
(x) Pt/ PtO- Adams catalyst, used for reduction.
(i) [Cr(C2O4)3]x O. N. of Cr = (+3)
+ 3 +3 x (–2) = x (b) In some cases the transition metals with their
–3 = x variable valency may form unstable intermediate
compounds.
(ii) [Co(NH3)2Cl4]x O.N. of Co = (+3)
 x =+ 3 + 2x 0 + 4x (–1) = – 1 (c) In other cases the transition metal provide a
(iii) [Hg(CN)4]x O.N. of Hg = [+2] suitable reaction surface.
x= + 2 + 4x (–1) = –2 (d) Enzymes are catalyst that enhance the rate of
specific reactions. Some enzymes require the
(VII) Oxidation number of metal in the complex presence of metal ions as cofactors and these
ion : are called metalloenzymes.
(i) [PtCl6]–2 charge on complex = O.N. of
2.13 Nonstoichiometry
metal + charge on ligand – 2 = x + 6 x ( – 1) or
(i) The transition elements sometimes form
x=+4
nonstoichiometric compounds.
 O.N. of platinum = + 4
(ii) These are the compounds of indefinite structure
(ii) [Co (NH3)6]Cl6 ; +3=x+6x0 & proportion.
or x = + 3  O.N. of Cobalt = + 3. (iii) For example, Iron (II), Oxide FeO should be
_____
written as a bar over the formula FeO to indicate
2.11 Formation of interstitial compounds
the ratio of Fe & O atom is not exactly 1:1
(i) Small non metallic atom such as H,B,C,N etc.
are able to occupy interstitial space of the lattice (Fe0.94O & Fe0.84O), V Se ( VSe0.98  VSe1.2),
of the d- block elements to form combinations
(iv) V2Se 3 (VSe1.2  VSe1.6) & V2 Se 4 ( VSe1.6
which are termed interstitial compounds.
 VSe2)
(ii) These are non-stoichiometric in nature and do
(v) Non stoichiometry is shown particularly among
not follow the common rule of valency.
transition metal compounds of the group 16
(iii) These interstitial compounds have similar elements (O,S,Se,Te).
chemical properties as the parent metal but differ (vi) It is mostly due to the variable valency of
appreciably in their physical properties such as transition elements.
density, hardness and conductivity. (vii) Sometimes nonstoichiometry is caused by
defect in the solid structure.
2.12 Catalytic properties
(a) Many transition metals & their compounds have 2.14 Alloy formation
catalytic properties. Some common examples (i) Transition metals form a large number of alloys.
are- (ii) d- block elements are quite similar in atomic
(i) TiCl3 - Used as Ziegler - Natta catalyst in the size, the atom of one metal can substitute the
production of polyethene. atoms of other metal in its crystal lattices.
 (iii) Thus, on cooling a mixture solution of two or Ex.9 Which of the following has maximum number of
more transition metals, smooth solid, alloys are unpaired electrons?
formed. (A) Fe2+ (B) Fe3+
(iv) Alloy containing mercury as one of the (C) Co3+ (D) Co2+
constituent elements are called amalgams. Ans.[B]
(v) The purpose of making alloy is to develop some Sol. 4s 3d
useful properties which are absent in constituent
element Fe2+

Examples
based on General Characteristics Fe3+

Ex.7 The oxidation number is changed in which of Co2+

the following case-
(A) SO2 gas is passed into Cr2O72–/H+ Co3+
(B) Aqueous solution of CrO42– is acidified  Fe3+ has maximum number ( = 5) of unpaired
(C) CrO2Cl2 is dissolved in NaOH electrons.
(D) Cr2O72– solution is made alkaline
Ans. [A] Ex.10 The atomic number of Potassium is 19 & that
of Manganese is 25. Although the colour of
Sol. MnO4– is dark violet yet the K+ is colourless.
(1) Cr2O72– + SO2 + 2H+  2Cr3+ + 3SO42– + H2O This is due to the fact that
+6 +4 +3 + 6 (change) (A) Mn is a transition element; while K+ is not
(2) 2CrO42– + 2H+  Cr2O72– + H2O ( No change) (B) [MnO4]– is negatively charged; while K+ has
+6 +6 a positive charge.
(3) CrO2Cl2 + 2 NaOH  Na2CrO4 ( No change) (C) The effective atomic number of Mn in [ MnO4]
–
+6 +6 is 26; while for K+, the atomic number is
(4) Cr2O72– + 2OH–  2CrO42– + H2O ( No change) 18.
+6 +6 (D) The Mn in a high positive oxidation state
allow charge transfer transitions.
Ex.8 Match the underlined atom in column A with Ans [D]
oxidation number in column B. –
Sol. In MnO4 the oxidation state of Mn is + 7 (dº
A B configuration) , expected to be colourless but
 MnO4– is coloured due to transfer of charge from
(a) [ Fe(CN)5 NO ]2– (I) 0 Oxygen to Manganese.
(b) [Ag(CN)2]– (II) 3
(c) [Cr (en)3]3+ (III) 1 3. COMPOUNDS OF TRANSITION ELEMENTS
(d) Ni (CO)4 (IV) 2
a b c d
3.1 Potassium Dichromate (K2Cr2O7)
(A) (I) (II) (III) (IV)
(B) (II) (III) (IV) (I)
(C) (IV) (III) (II) (I) 3.1.1 Preparation :
(D) (II) (III) (I) (IV) (i) It is prepared from Chromite ore (FeCr2O4).
(ii) The preparation of K2Cr2O7 from chromite ore
Ans.[C]
 involve the following steps:
Sol. (a) [Fe(CN)5 N O]2–  Fe + ( – 1) x 5 + 1
(A) Conversion of Chromite ore to Sodium
=–2
Chromate :
Fe = + 2
(b) [Ag(CN)2]–  Ag + (–1) x 2 = – 1 (i) The Chromite ore is fused with Sodium
Ag = + 1 hydroxide or Sodium Carbonate in the
(c) [Cr(en)3]3+  Cr + 0 = + 3 presence of air.
Cr = + 3 4FeCr2O4 + 16 NaOH + 7O2 
(d) Ni(CO)4  Ni + 0 = 0 ( zero)
Chromite ore (Air)
 8Na2CrO4 +2Fe2O3 + 8 H2O (c)
Sod. Chromite
OR 2Cr2O42– + 2H+ 2 H CrO4–
4 FeCr2O4 + 8 Na2CO3 + 7O2 
8 Na2CrO4 + 2Fe2O3 + 8 CO2 Chromate Hydrogen
(Yellow) chromate
Sod.Chromite
Cr2O72– + H2O
Sod. Chromite is extracted with water & ferric
Dichromate
oxide is left behind.
( orange)
(B) Conversion of Sodium chromate to Thus in alkaline solution, chromate ions are
Sodium dichromate : present while in acidic solution, dichromate ions
(i) The Sod. chromite is acidified with dilute are present.
H2SO4 giving its dichromate (v) Chromyl Chloride Test :
(a) This is the test of Chloride
2 Na2CrO4 + H2SO4 
K2Cr2O7 + 2H2SO4  2 KHSO4 + 2 CrO3
(dil.)
+ H2O
Na2Cr2O7 + Na2SO4 + H2O NaCl + H2SO4  NaHSO4 + HCl] × 4
Sod. dichromate CrO3 + 2HCl  CrO2Cl2 + H2O ] × 2
(ii) On concentration, the less soluble sulphate
crystallises and is filtered out. The resulting K 2 Cr 2 O 7 + 6H 2 SO 4 + 4NaCl 
solution contains Sod. dichromate. 2 KHSO4 + 4 NaHSO4 + 2CrO2Cl2 + 3H2O
(C) Conversion of Sod. dichromate to Pot. Chromyl chloride
(b) When Chromyl Chloride vapours are passed
dichromate :
through NaOH solution, yellow coloured
(i) Hot concentrated solution of Na2Cr2O7
solution is obtained.
with KCl in equimolar proportion 4 NaOH + CrO2Cl2  Na2CrO4 + 2 NaCl + 2H2O
Na2Cr2O7 + 2 KCl  K2Cr2O7 + 2 NaCl Chromyl Yellow solution
Sod.dichromate Pot.dichromate Chloride (Sod. Chromate)
(vi) Action with HCl :
3.1.2 Properties : K2Cr2O7 + 14 HCl  2 KCl + 2CrCl3 + 7H2O
(i) It is orange- red crystalline compound having + 3Cl2 
melting point 670 K. Chlorine
(ii) It is moderately soluble in cold water but (vii)Oxidising character :
(A) The dichromates act. as powerful oxidizing
readily soluble in hot water.
agent in acidic medium.
(iii) Action of Heat : K2Cr2O7 + 4 H2SO4  K2SO4 + Cr2 (SO4)3
+ 4 H2O + 3 [O]
4K2Cr2O7  4 K2CrO4 + 2Cr2O3 + 3O2 
Nascent oxygen
Pot.dichromate Pot. chromate Chromic acid (B) In term of electronic concept, the Cr2O72–
(iv) Action with Alkalies : ion take up electron in Acidic medium and
(a) K2Cr2O7 + 2 KOH  2K2CrO4 + H2O hence acts as an oxidizing agent
Cr2O72– + 14 H+ + 6e–  2Cr3+ + 7H2O
Pot. dichromate Pot.chromate
(+ 6) (+3)
or Cr2O72– + 2 OH  2CrO42– +H2O
–

(b) 2K2CrO4 + H2SO4  Note : Both Na2Cr2O7 & K2Cr2O7 are oxidizing agents
but K 2 Cr 2 O 7 is pref erred since it is not
K2Cr2O7 + K2SO4 + H2O
hygroscopic and can be used as primary
or 2CrO42– + 2H+ Cr2O72– + H2O standard.
 (C) Some oxidizing reactions of K2Cr2O7 are: Note :
(a) It liberate I2 from KI K2Cr2O7+ H2SO4 + 3SO4  K2SO4 + Cr2(SO4)3 + H2O
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2
( SO4)3 + 4 H2O + 3O
2 KI + H2SO 4 + O  K2SO 4 + H2O K2SO4. Cr2 (SO4)3. 24H2O
+ I2 ] × 3 (Chrome alum)
K2 Cr2O7 + 6 KI + 7H2SO4  4 K2SO4 (f) Similarly, it oxidises, chlorides to
+ Cr2(SO4)3 + 7 H2O + 3I2 (Iodine) chlorine, nitrites to nitrates, arsenites to
arsenates thiosulphate to sulphate and
or Cr2O72– + 14 H+ + 6e–  2 Cr3+ + 7H2O sulphur (S2O32– + O  SO42– + S), HBr
6I–  3 I2 + 6e– to Br2, H to 2.
Cr2O7 + 14H + 6I  2Cr3+ + 3I2 + 7H2O
2– + – (g) It oxidises ethyl alcohol to acetaldehyde
(b) It oxidises ferrous salts to ferric salts. and acetic acid
K2Cr2O7 + 4H2SO4  K2SO4 K 2 Cr 2 O 7 + 4H 2 SO 4  K 2 SO 4
+ Cr2 (SO4)3 + 4H2O+ 3(O) + Cr2(SO4)3 + 4H2O + 3 [O]
2 FeSO 4 + H 2SO 4 + O  Fe 2(SO 4 ) 3 CH3CH2OH + [O]  CH3CHO + H2O
+ H2O ] ×3 Ethyl Alcohol
CH3CHO + O  CH3COOH
K2Cr2O7 + 7H2SO4 + 6FeSO4 
Acetaldehyde
3Fe2(SO4)3 + K2SO4 + Cr2(SO4)3 + 7H2O
or 6Fe2+ + Cr2O72– + 14 H+  6Fe3+ + 2Cr3+ 3.1.3 Structure of Chromate and dichromate ions :
+ 7H2O
(c) It oxidises hydrogen sulphide to sulphur
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3
+ 4H2O + 3 [O]
H2S + O  H2O + S ] x 3

K2Cr2O7 + 4H2SO4 + H2S  K2SO4

+ Cr2(SO4)3 + 3S + 7 H2O
Sulphur
or H2S + Cr2O72– + 8H+  2Cr3+ + 3S
+ 7H2O
(d) It oxidises sulphites to sulphates
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 (SO4)3
3.1.4 Uses : Potassium dichromate is used :
+ 4H2O + 3(O)
Na2SO3 + O  Na2SO4 ] x 3 (i) As a volumetric reagent in laboratory for the
estimation of ferrous ions, iodide ions etc.
3 Na2SO3 + K2Cr2O7 + 4H2SO4 
(ii) For the preparation of chrome yellow (PbCrO4),
Sod.Sulphite
Chrome red (PbCrO 4.PbO), Zinc yellow
K2SO4 + Cr2 (SO4)3 + 3Na2SO4 + 4H2O
Sod.Sulphate (ZnCrO 4 ),Gugrets green
–
or 3SO 3 2– + Cr 2 O 7 2– + 8H +  3SO 4 2– (Cr2O3. 2H2O), chromic acid (CrO3 orange), K3
+ 2 Cr3+ + 4H2O [CrO8] (Red brown).
(e) SO2 is oxidised to H2SO4 (iii) In organic chemistry as oxidising agents.
K 2 Cr 2 O 7 + 4H 2 SO 4  K 2 SO 4 (iv) In photography for hardening gelatine films.
+ Cr2 (SO4)3 + 4H2O + 3[O] Note : (a) Cr2O72+ 2H+ + 4H2O2  2CrO (O2) + 5H2O
SO2+ (O) + H2O  H2SO4 ] x 3

K2Cr2O7 + H2SO4 + 3SO2  K2SO4 +

Cr2(SO4)3 + H2O
or Cr2O72– + 3SO2 + 2H+ 
2Cr3+ + 3SO42– + H2O Chromic peroxide
 (b) In alkaline solution with 30% H2O2, a red- (C) Action of heat
brown compound K3CrO8 is formed. It is 
2KMnO4  K2MnO4 + MnO2 + O2 
tetraperoxo species [Cr(O 2)4] 3– & thus
contain Cr (v) ion. Pot.Manganate
(c) In ammoniacal solution (NH3)3CrO4, a (D) Action of alkalies :
dark red- brown compound with Cr(IV) 4 KMnO4 + 4KOH  4K2MnO4 + 2H2O + O2 
ion is formed. Pot.Manganate
3.2 Potassium Permanganate (KMnO4) : (E) Oxidising character :
Potassium permanganate act as an oxidizing
3.2.1 Preparation : agent in neutral, alkaline and acidic solutions.
` Potassium Permanganate is prepared from (a) In Neutral Medium : MnO2 is formed
mineral pyrolusite ( MnO2). 2KMnO4 + H2O  2KOH + 2MnO2 + 3O
The preparation involves the following steps. MnO4– + 2H2O + 3e–  MnO2 + 4 OH–
(A) Conversion of Pyrolusite ore to Potassium +7 +4
Manganate Important reactions of Neutral KMnO4
(a) The pyrolusite ( MnO2) is fused with caustic (i) It oxidises H2S to S
potash (KOH) or potassium carbonate in 2KMnO4 + H2O  2KOH + 2MnO2 + 3O
presence of air to give a green mass due to H2S + O  H2O + S ] x 3
the formation of potassium manganate.
 2 KMnO4 + 3H2S  2KOH + 2 MnO2 + 3S
2 MnO2 + 4 KOH + O2 
+ 2H2O
2K2MnO4 + 2H2O (ii) It oxidises manganese sulphate to
Pot. Manganate (Green mass) manganese dioxide.

2 MnO2 + 2K2CO3 + O2  2KMnO4 + 3MnSO4 + 2H2O  5 MnO2
2K2MnO4 + 2CO2 + K2SO4 + 2H2SO4
Pot. Manganate ( Green Mass) or MnO 4– + 3Mn 2+ + 2H 2O  5 MnO 2
(B) Oxidation of Potassium Manganate to + 4H+
Potassium permanganate : (iii) It oxidises sodium thiosulphate to
(a) The fused mass is extracted with water and sulphate and Sulphur
the solution is green (MnO42–). The solution 2KMnO4 + 3Na2S2O3 + H2O 
is treated with Cl2 or ozone (O3) or CO2 to
2MnO2 + 3Na2SO4 + 2 KOH + 3S
oxidize K2MnO4 to KMnO4.
2K2MnO4 + Cl2  2KCl + 2KMnO4 or 2MnO4– + 3S2O32– + H2O 
2K 2 MnO 4 + O 3 + H 2 O  2KMnO 4 2MnO2 + 3SO42– 3S + 2OH–
+ 2KOH + O2 (b) Alkaline medium :
2K 2 MnO 4 + 2CO 2  2K 2 CO 3
(i) 2KMnO4 + 2KOH  K2MnO4 + H2O + O
+ 2MnO2  + 2KMnO4
2K2MnO4 + 2H2O  2MnO2 + 4KOH
Purple
+ 2O
(b) MnO42– can be oxidized to MnO4–
electrochemically at anode. alkaline
2KMnO4– + H2O  
K2MnO4 2K+ + MnO42–
2 MnO2 + 2KOH + 3O
At anode : MnO42–  MnO4– + e–
Green Purple or 2MnO4– + 2H2O + 3e–  MnO2 + 4OH–
At cathode : 2H+ + e–  2H  H2 (ii) Equivalent weight of KMnO4 in alkaline or
neutral solution
3.2.2 Properties : 2 MnO4– + 2H2O + 3e–  MnO2 + 4OH–
(A) It is a dark violet crystalline solid having a molecular weight
metallic lustre. It has M.P. 523 K.  Equivalent weight =
3
(B) It is fairly soluble in water giving a purple solution. 158
= = 52.6
3
 Important reactions of alkaline KMnO4 : (iii) It oxidises H2S to Sulphur
2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
(i) It oxidises iodides to iodates in alkaline medium + 3H2O + 5 [O]
alkaline
2KMnO4 + H2O   2MnO2 + 2KOH + 3[O] H2S + O  H2O + S ] x 5
KI + 3[O]  KIO3
2KMnO4 + 3H2SO4 + 5H2S 
or 2KMnO4 + KI + H2O  2MnO2 + 2KOH + KIO3 2MnSO4 + K2SO4 + 8H2O + 5S.
2MnO4– + I– + H2O  2 MnO2 + IO3— + 2OH–
(ii) Oxidises ethylene to ethylene glycol : (iv) It oxidises sulphur dioxide to sulphuric acid
CH2 2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
CH 2  OH
|| + H2O + O  | + 3H2O + 5 [O]
CH2 CH 2  OH SO2 + H2O + O  H2SO4 ] x 5
Ethylene Glycol 2KMnO4 + 5SO2 + 2H2O 
In alkaline medium it is called Bayer' s Reagent K2SO4 + 2MnSO4 + 2H2SO4
or 2MnO4 + 5 SO2 + 2H2O  5 SO42–
–

Note : (a) KMnO4 + 3H2SO4  + 2Mn2+ + 4H+

(Conc.)
K+ + MnO3+ + 3HSO4– + H3O+ (v) It oxidises nitrites to nitrates
(Green) 2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
(b) 2KMnO4 + H2SO4   + 3H2O + 5[O]
KNO2 + O  KNO3 ] x 5
Excess Conc.
Mn2O7 + K2SO4 + H2O 2KMnO4 + 3H2SO4 + 5KNO2 
(Explosive oil) K2SO4 + 2MnSO4 + 5KNO3 + 3H2O
(c) Acidic solution :
2KMnO4 + 3H2SO4  K2SO4 or 2 MnO4– + 5NO2– + 6H+  2Mn2+ + 5NO3–
+ 2MnSO4 + 3H2O + 5O + 3H2O
or 2 MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
Equivalent weight ( acidic solution) (vi) It oxidises oxalates or oxalic acid to carbon
molecular weight 158 dioxide
= = = 31.6 2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
5 5
+ 3H2O + 5O
Some of the important reactions of acidified
KMnO4 are - COOH
(i) It oxidises acidified ferrous salt to ferric salts. | + O  2CO2 + H2O ] x 5
2KMnO4 + 3H2SO4  K2SO 4 + 2MnSO4 + COOH
3H2O + 5[O] 2KMnO4 + 5C2H2O4 + 3H2SO4 
2FeSO4 + H2SO4 + [O]  Fe2 (SO4)3 K2SO4 + 2MnSO4 + 10 CO2 + 8H2O
+ H2O ] × 5
2KMnO4 + 10 FeSO4 + 8H2SO4  2MnSO4 +
K2SO4 + 5Fe2(SO4)3 + 8H2O
or 2MnO4– + 10Fe2+ + 16H+ 
2 Mn2+ + 10Fe3+ + 8H2O

(ii) It oxidises acidified KI to I2

2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
+3H2O + 5 [O]
2KI + H2SO4 + O  K2SO4 + H2O + I2 ] x 5

2KMn
+ 6K2SO4 + 8H2O + 5I2
or 2MnO4– + 10I– + 16H+  2Mn2+ + 8H2O + 5I2
 f-BLOCK ELEMENTS
1. INTRODUCTION
(i) Those elements in which the differentiating
electron enters in (n – 2) f-orbital are called
f-block elements.
(ii) Elements hav ing three outer shells
incomplete are known as inner transition or
f-block elements, i.e., they have configura-
tion (n – 2)s2p6d10 f 1–14 , (n – 1)s2p6d0–1,
ns2
(iii) There are two series of f-block elements
corresponding to the filling of 4f and
5f-orbitals.
2. Lanthanoid Series
(a) The dif f erentiating electrons occupy
4f-subshell and thus these elements have
three outermost shell not filled to the capac-
ity. These are called lanthanoids, lanthanones
or rare earths.
0 2 6 1 2 from lanthanum to lutetium as lanthanoids.
57La : .................4f , 5s 5p 5d , 6s
1 2 6 1 2
58Ce : .................4f , 5s 5p 5d , 6s
: lanthanoids.
71Lu : ...............4f 14, 5s2 5p6 5d1, 6s2
The name rare earth was given because
for many years, the pure compounds of these
elements were difficult to obtain as well as
these were originally obtained as earths (ox-
ides) fron relatively rare minerals. Now the
term rare earth is usually not used for them
because many of these elements are not rare
and substantial deposits of these elements
hav e been f ound in India, USA and
Russia.
(b) Strictly speaking, the f irst member
lanthanum (configuration 4f 0, 5d1 , 6s2 ) and
lutetium (configuration 4f 14 , 5d1 , 6s2) have
no partially filled 4f-orbitals in their ground
state, should not be included in lanthanoid
series, but because these resemble closely
in their nature with other thirteen elements
and thus for all practical purposes, they are
included in lanthanoids.
(c) Thus the 4f-series includes fifteen elments
The name lanthanoids has been derived from
lanthanum which is the prototype of
(d) Some of the properties of lanthanoids are
listed in table given below :

Some properties of Lanthanoids

Element Symbol Atomic number Outer configuration Oxidation states M3+ radius (pm)

Lanthanum La 57 [Xe] 5d1, 6s2 +3 106

Cerium Ce 58 [Xe] 4f2, 6s2 +3, +4 103
Praseodymium Pr 59 [Xe] 4f3, 6s2 +3, +4 101
Neodymium Nd 60 [Xe] 4f4, 6s2 +2, +3, +4 100
Promethium Pm 61 [Xe] 4f5, 6s2 +3 98
Samarium Sm 62 [Xe] 4f6, 6s2 +2, +3 96
Europium Eu 63 [Xe] 4f7, 6s2 +2, +3 95
Gadolinium Gd 64 [Xe] 4f7, 5d1, 6s2 +3 94
Terbium Tb 65 [Xe] 4f9, 6s2 +3, +4 92
Dysprosium Dy 66 [Xe] 4f10, 6s2 +3, +4 91
Holmium Ho 67 [Xe] 4f11, 6s2 +3 89
Erbium Er 68 [Xe] 4f12, 6s2 +3 88
Thulium Tm 69 [Xe] 4f13, 6s2 +2, +3 87
Ytterbium Yb 70 [Xe] 4f14, 6s2 +2, +3 86
Lutetium Lu 71 [Xe] 4f14, 5d1, 6s2 +3 85
 configuration for lanthanoids as
shown in table is [Xe] 4f 0–14 , 5d0–1 , 6s2
where [Xe] stands for xenon core. In these
elements, the number of electrons in the
outermost and penultimate subshell
remains the same and therefore all these
elements resemble closely in their chemical
nature. Their great chemical similarity is re-
sponsible for the problems of their separation
Note : The existence of lanthanoids in oxidation state
from each other from mineral monazite sand,
in which these elements are found collec-
tively. Owing to their similar chemical nature,
these elements are grouped together at one
place in the periodic table.
The electronic configuration of the
elements with completely filled (f 14) and half-
filled (f 7) f-orbitals is relatively more stable.
However, extra stability has been noticed in
europium (4f 7 , 6s2) and gadolinium (4f 7, 5d1,
(h) Ionisation enegry and electropositive na-
6s2). Also, note that only 57La, 64Gd and
71Lu possess a single electron in 5d-orbitals
and rest all lanthanoids do not have 5d-elec-
tron
(F) Physical state : (i) All are silvery white
metals having tensile strength and are good
conductor of heat and electricity.
(ii) Lanthanoids hav e higher density
values (ranging in between 6.77 to 9.74
g/cm3) increasing with increase in atomic
number.
(iii) These possess high m.pt., however, no
regularity is noticed with increase in
atomic number.
(iv) These form alloys with other metals
especially with iron.
(g) Oxidation state : The most common and
stable oxidation state of lanthanoids is +3.
Some elements exhibit +2 oxidation state
also, e.g., Sm2+, Eu2+ , Tm2+ and Yb2+ exist
in aqueous solution, however, they possess
the tendency to attain stable +3 oxidation
state and therefore are good reducing agent.
The +3 oxidation state is most stable in
lanthanum, gadolinium and lutetium as they
attain empty, half-filled and completely filled
4f-subshell, respectively. Some elements also
exhibit +4 oxidation state e.g., Pr4+, Ce4+,
Tb4+, and Dy4+ exist in aqueous solution.
However, these also possess the tendency
to attain +3 oxidation state and, therefore,
are good oxidant.
Thus elements in +2 oxidation state act
as reducing agent and in +4 oxidation state
act as oxidising agent.
Ce4+ + Fe2+  Ce3+ + Fe3+
Oxidant
Sm2+ + 2H2O  2Sm 3+ + 2OH– + H2
Reductant
of +2 and +4 is due to the fact that empty,
half f illed or completely f illed
f-subshells provide lower energy levels and
the ions get stabilized. For example, Ce and
Tb show +4 oxidation state by
attaining stable f 0 and f 7 configuration
respectively whereas Eu and Yb show +2
oxidation state by attaining stable f 7 and f 14
configuration, respectively.
ture : Lanthanoids have low values of first
and second ionisation energy (IE1 and IE2)
which are closer to alkaline earth metals
specially to calcium. On account of fairly low
ionisation enegry and large atomic size,
lanthanoids are strong electropositive ele-
ments.
(i) Coloured cations and paramagnetism :
Most of the lanthanoid ions are coloured
and exhibit paramagnetic nature due to
partially filled f-orbitals. The unpaired
electrons inv olv e f -f transition in
lanthanoid ion which is responsible for
the colour in solid as well as
solution state. Also, the number of
unpaired electrons giv es rise to
paramagnetism in them.
(j) Atomic-ionic radii and lanthanoid con-
traction : Ionic radii of M 3+ ions in
lanthanoids series show a regular change
in the size of ions with increase in atomic
number. This regular decrease in the size
of lanthanide ions (M3+) with the increase
in atomic number is known as lanthanoid
contraction.
Cause of lanthanoid contraction: The
lanthanoid contraction along the lanthanoid
series has been explained in terms of poor
shielding or secreening effect of f-subshell of
pre-penultimate subshell. On moving along
the lanthanoid series, the nuclear charge
increases due to increase in number of pro-
tons as well as one electron increases in f-
subshell of pre-penultimate shell. Recall that
shielding effect is poor in case of pre-
penultimate shell as well as it
becomes very less effective if shielding is by
f-subshell as they are more diffused. The
shielding order is s > p > d > f.
Evidently, the increase in nuclear charge
due to increase in number of proton with
increase in atomic number predominates over
decrease in nuclear charge due to shielding
effect and thus valence shells are pulled more
effectively towards nucleus to show a de-
crease in atomic size.

Atomic and ionic radii (pm) of lanthanum and lanthanoids

Element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Atomic radii (Ln) 187 183 182 181 181 180 199 180 178 177 176 175 174 173 –
3+
Ionic radii (Ln ) 106 103 101 99 98 96 95 94 92 91 89 88 87 86 –

(i) It is ev ident f rom table that in

going from La3+ to Lu3+, the ionic radii C a se El e m e n t S e ri e s A to m ic ra d iu s
change from 106 pm to 85 pm in steps
showing an average decrease of about 2 2 Ti 3d 132pm
1.4 pm (21 pm for 15 elements). I 4 0 Zr 4d } Largedifference
160pm
72 H f
5d } Almostsame
(ii) This small average decrease in atomic 159pm
size is responsible for a small decrease
in electronegativ ity and standard 23V 3d 122 pm
} Large difference
oxidation potential along the lanthanoid II 4 1N b 4d 146 pm
5d } same
series. 7 3 Ta 146 pm
M(g)  M3+ (aq.) + 3e 24 C r 3d 130 pm
} Large difference
(iii) The basic character of oxides and III 42 M o 4d 139 pm
5d } same
hydroxides decreases from La(OH)3 to 74 W 140 pm
Lu(OH)3. Due to smaller size of Lu, the
Lu–OH bond acquires more covalent (v) Lanthanoids hav e similar chemical
character.
properties and it is, therefore, difficult to
(iv) It is influence of lanthanoid contraction separate them from each other. However,
which is responsible for the the closer due to lanthanoid contraction, their
values of atomic radii for Zr–Hf, Nb–Ta ability to form complexes, varies slightly.
and Mo–W pairs of elements, the This slight v ariation is utilised to
members of 4th-5th d-series of a subse-
separate lanthanides by ion-exchange
quent group. Here the usual increase in
method.
size on moving down the group from 4d-
(k) Chemical reactivity : These are very
series to 5d-series is cancelled by the
decrease in size due to lanthanoid reactiv e metals like alkaline earth
contraction. This is the reason that metals, however, they show very little
members of 4d and 5d-series of a group difference in their chemical reactivity. On
resemble more closely in comparison to strong heating with H2 and carbon, these form
3d-members. salt like non-stoichiometic hydrides and
carbides. These burn in oxygen to give
sesquioxides M2O 3 (except Ce which gives
CeO3). These ionic oxides react with water
to form insoluble hydroxides. The oxides and
hydroxides being strong base react with CO2
to form carbonates (M2CO 3). On burning in
sulphur these f orm sulphides (M 2 S 3 ).
 Common reactions of lanthanoids have been
summarized below :
(I) Uses of lanthanoids : Lanthanoids are com-
monly used as :
(i) Pyrophoric alloys, known as
Misch metals, contain lanthanoids about 90-
95% (Ce 40.5%, lanthanum and neodymium
44%), iron 4.5%, calcium, carbon and silicon
about 10.5% are used in cigarette and gas
lighters, flame throwing tanks, toys, tanks
and tracer bullets as well as in shells.
(ii) Any alloy containing 30% Misch metals and
1% Zr are used for making parts of jet en-
gines.
(iii) Cerium salts are commonly used as catalyst
in petroleum cracking (cerium phosphate),
volumetric analysis and as oxidising agent
(ceric sulphate), in dying cotton, in lead
accumulators etc.
(iv) Oxides of praseodymium (Pr2O3) and neody-
mium (Nd2O4) are used in the preparation of
coloured glasses and standard filters.
(v) Oxides of cerium and thorium are used in
the preparation of gas lamp mantles.
(vi) Cerium oxide is used to prepare sun glasses
as cerium cuts off heat and ultraviolet light.
3. Actionoids Series
(i) The dif f erentiating electron occupies
5f-subshell and thus these elements also
have three outermost shells not filled to their
capacity as well as. These are called
actinoids or actionons.
:...........5f0, 6s26p66d1,7s2
89Ac
90Th :...........5f1, 6s26p66d1,7s2
: :
103Lw :...........5f14, 6s26p66d1,7s2
(ii) The numbers of actionoid series are
radioactive and majority of them are not found
in nature. The elements from atomic number
93 and onwards are called transuranic ele-
ments and have been prepared by artificial
means using nuclear reactions. G.T. Seaburg
has maximum contribution in the discoveries
of these elements.
(iii) The name actinoid is deriv ed f rom
actinium, the first member of the series.
(iv) Thus the 5f -series includes f if teen
elements from actinium to lawrencium.
(v) Some of the properties of actionoids are listed
below in table.
 Som e prope rtie s of a ctinoids
Ele me nt Sym bol Atomic num be r Configura tion Ox ida tion sta te s
1 2
Actinium Ac 89 [Rn] 6d , 7s +3
2 2
Thorium Th 90 [Rn] 6d , 7s +3,+4
2 1 2
Protactinium Pa 91 [Rn] 5f , 6d , 7s +3, +4, +5
Uranium U 92 [Rn] 5f3 , 6d1, 7s 2 +3, +4, +5, +6
4 1 2
Neptunium Np 93 [Rn] 5f , 6d , 7s +3, +4, +5, +6, +7
6 2
Plutonium Pu 94 [Rn] 5f , 7s +3, +4, +5, +6, +7
7 2
Am ericium Am 95 [Rn] 5f , 7s +2,+3, +4, +5, +6
7 1 2
Curium Cm 96 [Rn] 5f , 6d , 7s +3,+4
8 1 2
Berkelium Bk 97 [Rn] 5f , 6d , 7s +3,+4
Californium Cf 98 [Rn] 5f10, 7s 2 +2,+3
11 2
Einsteinium Es 99 [Rn] 5f , 7s +2,+3
12 2
Fermium Fm 100 [Rn] 5f , 7s +2,+3
13 2
Mendelevium Md 101 [Rn] 5f , 7s +2,+3
14 2
Nobelium No 102 [Rn] 5f , 7s +2,+3
Lawrencium Lr 103 [Rn] 5f14, 6d1 , 7s 2 +3

(vi) The electronic configuration of actinoids is

[Rn] 5f 0–14, 6d0–2, 7s2 where [Rn] stands for (viii) Actinoids show a range of oxidation states
radon core. Like lanthanoids, these are placed which is due to comparable
together because of similar chemical nature. energies of 5f, 6d and 7s-orbitals. The gen-
eral oxidation state of actinoids is + 3; the
(vii) Like lanthanoids contraction, these too show
elements in the first half of the series show
actinoid contraction due to poor shielding
higher oxidation states.
effect of 5f-subshells. It is, therefore, atomic
size of actinoids too decrease gradually from
Ac to Lw.

Positive oxidation states of actinium and actinoids

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
3 3 3 3 3 3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4 4
5 5 5 5 5
6 6 6 6
7 7

(ix) All these elements are strong reducing agents
and are very reactive metals. Actinoids are
radioactive and, therefore, it is difficult to
study their chemical nature. However, rela-
tively more stable isotopes of these elements
beyond uranium have been discovered and
the chemistry of these elements has been
studied to an extent by using radiotracer tech-
niques.
Like lanthanoids, they react with oxygen, halo-
gens, hydrogens, sulphur and acids.
(x) Difficulties in studying chemical nature of
actinoids : The chemical nature of actinoids
(beyond uranium) has not been studied to a
greater extent due to following reasons :
(a) All the radioactive and the radioactive
decay gives out extremely energetic
particles which may break bond and
disrupt crystal structure
(b) The breaking up of bonds by emitted
particles due to higher energy
associated with them also develops the
process of self oxidation and it is
therefore difficult to decide the more
stable oxidation state.
(xi) Uses of actinoids : Only U, Th and Pu mem-
bers of this series have found application in
nuclear reactions undergoing nuclear fission
to produce nuclear power and nuclear bomb.
 SOLVED EXAMPLES
Ex.1 The aqueous solution of the following salts will Ex.5 A metal ion from the first transition series has a
be coloured in the case of- magnetic moment (calculated) of 2.83 BM. How
(A) Zn (NO3)2 (B) Li NO3 many unpaired electrons are expected to be
present in the ion?
(C) Co(NO3)2 (D) Mg(NO3)2 (A) 1 (B) 2
Ans. [C] (C) 3 (D) 4
Sol. The aqueous solution of Co(NO3)2 will be pink Ans. [B]
Sol. A metal ion from the first transition series has a
coloured. The colour is due to the presence of
magnetic moment (calculated) of 2.83 BM. The
unpaired d-electrons which absorb light from the
no. of unpaired electrons are expected to be
visible part and thus move to high energy levels.
present in the ion are 2
Ex.2 Rusting of iron in moist air involves-
 = n ( n  2) = 2 ( 2  2 )
(A) Loss of electrons by iron
(B) Gain of electrons by iron = 2. 2 = 2 x 1.414 = 2.828 B.M
(C) Neither gain nor loss of electrons
= 2.83 B.M
(D) Hydration of iron
Ans. [A] Ex.6 Out of the compounds K2SO4, MgCl2, FeSO4,
Sol. Rusting of iron in moist air involves the loss of
electrons by iron. The oxidation of iron to ferrous NiCl2 and ZnO which of the following pair will
ion takes place and a brown deposit takes place show paramagnetism-
on the surface of iron. (A) K2SO4, MgCl2 (B) ZnO, MgCl2
Fe Fe+2 +2e (C) K2SO4, ZnCl2 (D) FeSO4, NiCl2
Rusting is an electrochemical process. Ans.[D]
Ex.3 Which of the following statements is correct? Sol. The pair which shows paramagnetism is FeSO4
(A) Iron belongs to third transition series of the
and NiCl2. It consist of Fe+2 and Ni+2 ions which
periodic table
have got unpaired electrons. Their electronic
(B) Iron belongs to f-block of the periodic table
configs. are as given below.
(C) Iron belongs to first transition series
(D) Iron belongs to group VIII of the periodic table Fe26
Ans. [C]
Sol. The correct statement is that iron belongs to first  4 unpaired electrons
transition series of elements . It is called 3d
series. The members of this series are
Sc Ti V Cr Mn Fe Co Ni Cu Zn Fe+2
The electronic confine of Fe26 is 3d6 . 4s2  4 unpaired electrons
Ex.4 Zn and Hg do not show variable valency like
d-block elements because- Ni28
(A) They are soft
(B) Their d-shells are complete  2 unpaired electrons
(C) They have only two electrons in the outermost
subshell
(D) Their d-shells are incomplete Ni+2
Ans. [B]
Sol. Zn and Hg do not show variable valency like d-  2 unpaired electrons
block elements because their d-shell are
complete their electronic confign are Ex.7 Variable valency is generally shown by-
Zn 30 3d10 . 4s2 (A) s-block elements
(B) p-block elements
Hg48 4d10. 5s2 (C) Transition elements
The variable valency is shown by those elements (D) All elements in periodic table
which have got incompletely filled 'd'orbitals Ans. [C]
Sol. One of the most striking features of the transition
elements, is that they exhibit variable valency.
The variable valency occurs to some extent in
the p-block elements also. In this case the
valency changes usually in units of two. Some
example are SnCl2, SnCl4, PCl3, PCl5 etc. But
in transition elements the valency changes in
one unit e.g Cu+, Cu+2, Fe+2 , Fe+3 etc.
Ex.8 The common oxidation states of gold are-
(A) 1,2 and 3 (B) 1, 3
(C) 2 and 3 (D) 3 , 4
Ans.[ 2]
Sol. The common oxdiation states of gold are +1 and
+3. The +3 state is more stable. This is
explained on the basis that +1 ion gets
disproportionate.
3 Au+1  Au+3 + 2Au
Ex.9 Protective coating of iron with tin-
(A) Is not as durable as a coating with Zn as
in galvanized iron.
(B) More durable than a coating with Zn.
(C) Is as much durable as a coating with Zn
(D) When partly removed the rusting is in no
way acceleration
Ans. [A]
Sol. Tin coating of iron is not as durable as a coating
with Zn. More over when a small area of tin
coating is damages the exposed iron surface
becomes more susceptible to further corrosion,
than an unprotected iron piece. This is because
iron is above tin in the activity series and is
therefore more electropositive than tin. iron
therefore, easily releases electrons and rusting
is hastened.
Ex.10 The d-block elements easily form alloys because-
(A) Their d-block are only partly filled
(B) They have very widely differing atomic
sizes.
(C) They are very similar in their atomic sizes
(D) They are highly electronegative in character
Ans.[C]
Sol. In the case of the transition metals the atomic
radii have values which are very close, that is
they are of very similar size. Hence the atom of
an element in a crystal lattice can easily be
replaced by a metal atom of another transition
elements. This makes metals form alloys very
easily.
Ex.11 The ions of d- block elements are mostly
paramagnetic-
(A) Because their d-orbitals are complete
(B) Because they have mostly paired electrons
(C) Because they have mostly unpaired
electrons
(D) Because they form coloured ions.
Ans. [C]
Sol. All atomic and molecular species which contains
one or more unpaired electrons are paramagnetic.
Most of the ions of transition elements have
unpaired electrons. Hence they are all
paramagnetic. Some ions of d - block elements
with no unpaired electrons are Sc+3,Ti+4, Zn+2
and Cu+1. These ions are not paramagnetic and
they are also without colour.
Ex.12 Silver jewelry can be made to retain its silvery
white appearance by-
(A) Coating the silver with a film of oxide by
dipping the silver in conc. HNO3
(B) Coating with a film of the insoluble chloride
by dipping the silver in conc. HNO3
(C) Plating with Palladium
(D) Plating with gold
Ans.[ 3]
Sol. Silver jewelry easily gets blackened when
exposed to sulphur compounds. In order to
prevent this blackening of silver jewelry, it is
coated with Pd.
Ex.13 The order of stability of complexes of ion Cu+2 ,
Ni+2 , Mn+2 and Fe+2 decreases in the order -
(A) Cu+2 > Ni+2 > Fe+2 > Mn+2
(B) Mn+2 > Ni+2 > Cu +2 > Fe+2
(C) Ni +2 > Cu +2 > Fe+2 > Mn+2
(D) Fe +2 > Ni +2 > Cu+2 > Mn+2
Ans. [A]
Sol. The order of stability of the complexes of some
of the ions carrying the same charge but differing
in ionic radii decrease as the ionic radii increase.
ion Cu+2 , Ni+2 , Fe+2 , Mn+2
Ionic radii 0.69 0.78 0.83 0.91
+2
The complexes of Cu are most stable while
Mn+2 is least stable.
Ex.14 Wilkinson's catalyst used as a homogenous Sol. The process of depositing a thin uniform layer of
catalyst in the hydrogenation of alkene contains- silver on clean glass surface is called silvering of
(A) Fe (B) Al (C) Rh (D) Co mirror. The thin film is protected by coating of red
Ans. [C] and turpentine mixture.
Sol. Wilkinson's catalyst contains Rh. The formula is 2AgNO3 + 2NH4OH ——
(Ph3P)3 RhCl. It is used as homogeneous Ag2O + 2NH4NO3 + H2O
Ag2O + HCHO —— 2Ag + HCOOH.
catalyst in the hydrogenation of alkenes.
Ex.20 Which compound is deliquescent –
Ex.15 Which of the following is the softest metals-
(A) Hg2Cl2 (B) HgCl2 (C) ZnCl2 (D) CdCl2
(A) Sc (B) Zn (C) Ti (D) V
Ans. [C]
Ans. [B]
Sol. ZnCl2 is white deliquescent solid, exceedingly
Sol. The softest metal is Zn, while remaining all other
soluble in water. 330g of anhydrous salt is
metal are comparatively harder metals.
soluble in 100g water at 10°C.
Ex.16 In which of the following transition metal ions d-
d transition is possible- Ex.21 An element which is highly toxic for plants and
animals is –
(A) Cu+ (B) Zn+2 (C) Ti+3 (D) Sc+3 (A) Au (B) Mn (C) Hg (D) Ca
Ans. [C] Ans. [C]
Sol. +3
The d-d transition is possible in Ti because it Sol. HgCl2 is dangerous poison; the antidote being
white of an egg which is coagulated by the salt
has got 3d1 configuration , hence one electron
in the system and is eliminated by the system
can easily go from one orbital to another in with salts absorbed in it, also Hg itself is very
degenerate levels. poisonous.
Ex.17 Which of the following cuprous compounds is Ex.22 The elements which exhibit both vertical and
not stable- horizontal similarities are –
(A) CuCl2 (B) Cu2 (CNS)2 (A) Inert gas elements
(C) Cu2Cl2 (D) Cu2SO4 (B) Representative elements
(C) Rare elements
Ans. [D]
(D) Transition elements
Sol. The compound Cu2SO4 is not stable because Ans. [D]
Cu is stabilized only in Cu+2 state in its Sol. It is a characteristic of transition elements.
Vertical relationship is due to similar electronic
compounds with SO4-2 ions hence Cu2SO4 is configuration in a gp and horizontal relationship
not stable while CuSO4 is stable. due to shielding effect being more predominant
in last five elements in a period.
Ex.18 A developer used in photography is –
(A) A weak acid Ex.23 Transition metals and their oxides are used in
(B) A weak base industrial processes as –
(A) Detergents (B) Insecticides
(C) A mild reducing agent (C) Catalysts (D) None
(D) An oxidizing agent Ans. [C]
Ans. [C] Sol. Transition metals and their compounds are very
Sol. A developer is a weak reducing agent, e.g., good catalyst, e.g., CuCl2 in Deacon process,
Ferrous oxalate; the parts affected by light on Ni in hydrogenation of oils.
photographic plate are reduced to the maximum
extent whereas part not affected by light remains Ex.24 Zinc gives H2 gas with H2SO4 and conc. HCl
unaffected. but no with conc. HNO3 because –
(A) NO3– ion is reduced in preference to
Ex.19 Preparation of looking mirrors involves the use of – hydronium ion
(A) Red lead (B) conc. HNO3 is a weaker acid than conc.
(B) Ammoniacal silver nitrate H2SO4 and conc.HCl
(C) Ammoniacal AgNO3 + red lead (C) conc. HNO3 acts as a reducing agent
(D) Ammoniacal AgNO3 + red lead + HCHO (D) Zinc is more reactive than H2
Ans. [D] Ans. [A]
 Ex.26 A metal gives two chlorides 'A' and 'B' gives
Sol. Zn H2SO 4 
 ZnSO 4  H2 
conc. black precipitate with NH4OH and 'B' gives
white. With KI 'B' gives a red precipitate,
Zn 2HCl 
 ZnCl2  H2  soluble in excess of Kl. 'A ' and 'B' are respec-
conc.
tively –
Zn 4HNO 3 
 Zn(NO 3 )2  2NO 2  2H 2O
conc.
(A) HgCl2 and Hg2Cl2
(B) Hg2Cl2 and HgCl2
NO3– ion is reduced to NO 2 in preference
(C) HgCl2 and HgCl
to H3O+ ion. (D) None of these
Ans. [B]
Ex.25 A blue solution of copper sulphate becomes
darker when treated with excess of ammonia. Sol. ‘A’ is Hg2Cl2 and ‘B’ is HgCl2.
This is because – Hg2Cl 2 + 2NH4OH –
(A) ammonia molecules replace water
NH2
molecules in the solution Hg + Hg + NH4Cl + 2H2O
(B) ammonia is stronger ligand than water Cl
(C) ammonia forms a stable complex ion Black
[Cu(NH3)4]2+ with Cu2+ ions
(D) All are correct HgCl2 + 2NH4OH –
Ans. [D] NH2
Sol. [Cu(H2O)4]SO4. H2O + 4NH4OH – Hg + NH4Cl + 2H2O
Cl
Blue soln. [Cu(NH3)4]SO4 + 9H2O
White
Dark blue soln.
HgCl2 + 2KI – HgI2 + 2KCl
Red
HgI2 + 2KI – K2Hgl 4
Soluble