THE D AND F BLOCK

ELEMENTS

CHAPTER – 8

THE D AND F BLOCK ELEMENTS

have partly or incompletely filled (n-1)d orbital in their
elementary states.
D-block elements:
The d-block elements are called transition metals (belonging
to group 3 to 12) and have valence electrons in the d-orbitals.
Its standard electronic configuration is (n-1) d1-10 ns1-2 where
(n-1) represents the front shell (last but only one).
Definition: initially they were named ‘transition elements’
because their properties were found to be transitional
between s and p block elements.
However, IUPAC definition is as follows,
Transition metals are metals which have incomplete d
subshell either which have one or more unpaired d electrons
in their ground state or in their common oxidation state can
be called transition elements.
Introduction to d-Block Elements
The d-block elements are defined as the elements from Note
periodic table in which, last electron enters into the ‘d-orbital’
of the penultimate shell i.e. (n-1)d orbital. Where ‘n’ is the last group-12 elements i.e., Zn, Cd and Hg have completely
shell.
filled d-orbital both in their ground state and in their
The d-block elements are also called transition elements,
oxidation state thus they are not considered transition
because their properties are intermediate between the
properties of highly electropositive s-block elements and elements but nonetheless are studied under d-block.
highly electronegative p-block elements. Transition elements
A lot of elements do not possess unpaired electrons in their According to Classical or earlier concept reduction is a
ground state but definition helps identify them as transition process which involves the addition of hydrogen or any
elements. Eg. – Copper electropositive element or the removal of oxygen or any
electronegative element.
Electronic configuration of is: 1s2 2s2 2p6 3s2 3p6 4s1 3d10. As
we can see, it has a completely filled d-orbital in its ground According to electronic concept reduction is defined as the
state but in its common oxidation state i.e., +2, process in which an atom or ion gains one or more electrons.
Electronic configuration of Cu2+ is: 1s2 2s2 2p6 3s2 3p6 4s0 3d9 Why are d-Block elements called transition elements?
and it has an unpaired electron thus it can be called a The position of d-block elements are in between s−block and
transition element. A similar case is observed for silver. p−block elements in periodic table. These d-block elements
are called transition elements because they exhibit
The possession of unpaired d and f electrons makes transition transitional behaviour between s− and p−elements.
elements different from s and p block elements and hence
there study is carried out separately. Their properties are transitional between highly reactive
metallic elements of s−block which are typically ionic
Some important concepts compounds and elements of p−block which are large -
Enthalpy of Atomisation: covalent.
Enthalpy of atomization, ΔaH0, is the change in enthalpy F-Block Elements:
when one mole of bonds is completely broken to obtain atoms The elements of f block are lanthanides and actinides and are
in the gas phase. For example: atomization of methane called genetic mutations due to their placement in the
molecule. periodic table due to the activation of electrons. The orbitals
CH4 (g) → C (g) + 4H (g) ΔaH0= 1665.0 kJ mol-1 of the electron shell are filled with “n-2.” There are a high
For diatomic molecules, the enthalpy of atomization is equal number of fourteen electrons that can reside in orbitals.
to the enthalpy of bond dissociation. For example: the Lanthanoids:
atomization of dihydrogen molecule. The 14 elements that immediately follow lanthanum, namely,
H2 (g) → 2H (g); ΔaH0= 435.0 kJ mol-1 Cerium (58) to Lutetium (71) are called lanthanoids. They
belong to the first series of inner-transition elements.
Metallic Bonding: Lanthanum (57) has similar properties. Therefore, they
Metallic bonding is a type of chemical bonding that arises called as lanthanoids.
from the electrostatic attractive force between conduction
Actinoids:
electrons (in the form of an electron cloud of delocalized The 14 elements immediately after actinium (89), with
electrons) and positively charged metal ions. atomic numbers 90 (Thorium) to 103 (Lawrencium) are
Lanthanoid contraction: called actinoids. They are in the second phase of inner-
Lanthanides are the rare earth elements of the modern transition elements. Actinium (89) has similar features.
periodic table, i.e. the elements with atomic numbers from 58 Therefore, they called as actinoids.
to 71, following the element Lanthanum.
Why are f-block elements called inner transition
The atomic size or the ionic radii of tri positive lanthanide elements?
ions decrease steadily from La to Lu due to increasing nuclear F block elements are called inner transition elements because
charge and electrons entering the inner (n-2) f orbital. This the last electron enters the anti-penultimate shell, which is
gradual decrease in the size with an increasing atomic inner to the penultimate shell in which the last electron of d-
number is called lanthanoid contraction. Lanthanoid block elements enters.
contraction is also known as lanthanide contraction Electronic Configuration d-Block Elements
General electronic configuration of four series of d-block
Standard Electrode Potential:
elements are given below.
Under standard conditions, the standard electrode potential
3d series:[Ar] 3d1-10 4S1-2
occurs in an electrochemical cell say the temperature = 298K, 4d series :[Kr] 4d1-10 5S0-2
pressure = 1atm, concentration = 1M. The symbol ‘E ocell’ 5d series :[Xe] 5d1-10 6S2
represents the standard electrode potential of a cell. 6d series :[Rn] 6d1-10 7S2
Oxidation and Reduction: Abnormal Electronic Configuration of Chromium And Copper
According to Classical or earlier concept oxidation is a among d Block Elements
process which involves the addition of oxygen or any Chromium(24Cr) has electronic configuration
electronegative element or the removal of hydrogen or any (Expected):[Ar] 3d4 4S2
electropositive element. (Observed):[Ar] 3d5 4s1
Copper (29Cu) has electronic configuration
According to electronic concept oxidation is defined as the (Expected):[Ar] 3d9 4s1
process in which an atom or ion loses one or more electrons. (Observed):[Ar] 3d10 4s1
 Four Transition series
Explanation 1. 3d - Transition series. Transition elements with an
atomic number 21 (Sc) to 30 (Zn) and with an
due to more stability of half –filled and
incomplete 3d orbital are called the first series of
completely filled orbital. mutations.

Physical Properties
The transition metals are hard and tough. They have low
volatility but Zn, Cd and Hg are an exception.
They have high melting and boiling points due to the greater
quantity of electrons from (n-1) d along with the ns electrons
metallic

2. 4d - Transition series. It contains elements with an

atomic number 39 (Y) to 48 (Cd) and has an incomplete
4d orbital. It is called the second version of the version.
Metals possessing high boiling point are noble in their
The metals belonging to second and third series have greater
enthalpies of atomisation than the elements belonging to first
series.

3. 5d - Transition series. Transition elements with

atomic numbers 57 (La), 72 (Hf) to 80 (Hg) and with an
incomplete orbital 5d are called the third
transformation series.
 Ionic radii - In the first row of transition elements ionic radii
decreases with the increase in the number of atoms. The
amount of ionic radii also depends on the oxidation state of
the metals. As the oxidation state increases ionic radii
decrease and as the oxidation state decreases ionic radii
4. 6d - Transition series. Transition elements have an increase.
atomic number 89 (Ac), 104 (Rf) to 112 (Uub) and have
an incomplete 6d orbital. It is called the fourth Melting point: generally, transition metals have a high
revolution series. melting and boiling point because of strong metallic bonds
that they form using the ns and (n – 1)d electrons.
Common features of transition elements
In a row, generally increases from the first element to the
Metallic Character - element with d^5 electronic configuration and then falls
All the transition metals have high thermal as well as regularly from there to last.
electrical conductivity and having very high melting and The reason attributed to this is that because the d5
boiling points compared to those of representative elements configuration forms the strongest metallic bonding, melting
due to their closed-packed structure. point becomes very high.
On-going across the period melting points first increase, Metals with very high enthalpy of atomisation tend to be
attain maximum value and then steadily decreases as atomic noble in their reactions.
number.
Exception: Mn and Tc’s melting point is less than the
The strength of metallic bond depends upon the number of previous element in their respective period despite having a
unpaired electrons, it increases up to middle i.e., up to (n-1)d5 d^5 configuration. This is because these elements have a
hence accordingly melting and boiling points also increases. stable half-filled configuration due to which these electrons
After (n-1) d5 configuration, the electrons start pairing, do not participate in bonding, thus the atom-atom attraction
hence metallic strength, melting and boiling points decreases of these metals is weaker and hence its easier to break their
with increase in atomic number. metallic bonds leading to a low melting point and hence the
metals preceeding these (Cr and Mo) have the highest melting
Atomic radii points.
The atomic radii of the elements of 3d-series decreases as the
atomic number increases. Lanthanoid Contraction - The continuous depletion of the
atomic and ionic radiation of the transition metals as the
The atomic radii increase from 3d to 4d, the atomic radii of number of atoms increases. This is due to filling of 4f orbital
the 4d and 5d transition series are very close due to before 5d orbitals. This size limit is normal. This is called
lanthanoid contraction. For example, Zirconium and lanthanoid contraction. It is because of the lanthanoid array
Hafnium. that the atom of the second-line radio of genetic mutations is
This decrease in the metallic radius due to increase in the almost identical to that of the third-line mutation gene.
atomic mass leads to an increase in the density of elements. Ionization enthalpy - Transition elements have small size
Consequently the density increases from titanium to copper. which results in high ionization energy.
They exhibit less electro positivity than the s-block elements Pressure of hydrogen gas = 1 bar
due to their ionization potentials lying between S and P block
Concentration of hydrogen ion in the solution = 1 molar
elements.
Ecell = Ecathode – Eanode
They form covalent compounds.
Ecell = Ecathode – 0 = Ecathode
The d-block elements exhibit an increase in the ionization
potentials from left to right due to the screening effect of the The measured Emf of the cell:
new electrons added into the (n-1) d subshell. Pt| H2 (1 bar)| H+ (1M) || Cu2+ (1M)| Cu is 0.34 V.
The first transition series exhibit an increase in the second The positive value of the standard electrode potential
ionisation energies with the increase in atomic number due signifies the easy reduction of Cu2+ ions than H+ ions.
to stable electronic configuration. T he measured Emf of the cell
Ionization energy decreases down the group. Pt| H2 (1 bar)| H+ (1M) || Zn2+ (1M)| Zn is -0.76 V.
Ionization energy increases across the period. The negative value of the standard electrode potential
signifies that the hydrogen ions oxidizes the zinc (or it can be
Oxidation state - The transition metal exhibit variable
said that zinc can reduce hydrogen ions).
oxidation states and form compounds showing more than
one (variable) oxidation states because energies levels of ns An electrode with standard electrode potential greater than
and (n-1)d are nearly similar. The oxidation state of 3d series zero is stable in its reduced form compared to hydrogen gas.
is from +2 to +7 (except Cr and Cu).
Whereas an electrode with negative standard electrode
The lowest oxidation states of these elements are +1 or +2 potential is less stable in its reduced form compared to
which is due to their 4s electrons. hydrogen gas.
As the number of unpaired electrons in 3d orbital increases This decreases the standard electrode potential which in turn
the number of oxidation state also increases form Sc to Mn decreases the oxidizing power of the specific electrode on the
and after that electrons starts pairing in 3d orbital hence left and increases the reducing power of the electrode to the
oxidation states decreases form Fe to Zn. right of the reaction.
The highest oxidation state of transition elements is +8 which Magnetic Properties - Due to presence of unpaired electrons
shown by Os and Ru. in the (n-1)d orbital, most of the transition metal ions and
their compounds are paramagnetic i.e. they are attracted by
Standard hydrogen electrode
magnetic field.
The electrode is connected to a standard hydrogen electrode
(SHE) to constitute a cell The transition element and their ions having all electrons
paired are diamagnetic i.e. they are repelled by magnetic
It consists of a platinum electrode coated with a layer of
field.
platinum black.
Metals like Fe, Co and Ni possess very high paramagnetic and
H+(aq) + e- → ½ H2 (g)
acquire permanent magnetic moment hence, they are
ferromagnetic.
Alnico is an alloy of Al(12%), Ni(20%),Co(50%) and
remaining Fe(18%). It is used to make permanent magnets.
Bohr magneton (B.M) is unit of magnetic moment:
1B.M = eh/4πmec
The effective magnetic moment µeff, of a paramagnetic
substance is given by ‘spin only’ formula.

Where n is the number of unpaired electrons.

Catalytic Properties - Many transition metals are used as
The electrode is immersed in an acidic solution and the pure catalysts which influence the rate of chemical reaction.
hydrogen gas is bubbled through it.
A catalytic substance is capable of forming an unstable
The concentration of the reduced form and the oxidized form intermediate compound which readily decomposes yielding
of hydrogen is sustained at unity with following conditions: the products and regenerating the catalyst.
A+B + C —–> [A-B-C] —–> A-B + C
(a) V2O5 is used in the contact process for the manufacture
(reactant) (catalyst) (intermediate) (product)
of H2SO4.
(catalyst)
(b) Fe is used in Haber’s process for the manufacture of
The commonly used transition metals as a catalyst are Fe, Co, NH3.
Pt, Cr, Mn etc. (c) Ni is used in the hydrogenation of oils.
(d) FeSO4 is used in the oxidation of Benzene with H2O2.
Example (e) Cu is used in the dehydrogenation of alcohols.
(f) TiCl4 is used as a catalyst in Vinyl polymerisation.
(g) Pt is used in Ostwald’s process of nitric acid.
MnO2 acts as a catalyst for decomposition of
Formation of coloured compounds - Most of the
KClO3 to O2.
compounds of transition metals are coloured in their solid or
In manufacture of ammonia, Fe with Mo is solution form. Colour of the compound of the transition
used as catalyst. metals may be attributed to the presence of incomplete (n-
Nickel acts as a catalyst in hydrogenation of 1)d orbital and the number of unpaired electrons.

oils to fats. Transition metal ions with no unpaired electrons are

colourless because there is possibility of d-d transition. e.g.
Transition metals and their compounds
Sc+3(3d0), Ti+4(3d0), Cu+(3d10). Ions with unpaired electrons
exhibiting catalytic properties in various are coloured i.e. ions with electronic configuration 3d1 to 3d9
processes are given below. are coloured.

In general, the colour of transition ions can be related to –

• Presence of unpaired d electrons.
• d-d transition.
• Nature of groups i.e. ligands linked to metal ions.
• Geometry of the complexes formed by the metal ion

Formation of complexes - The cations of transition metals The structure of these complex ions is linear, square, planar,
have great tendency to form complexes with several tetrahedral, octahedral depending upon nature of
molecules or ions called ligands. hybridization of metal ions.
The bonds involved in the formation of complexes are The weak ligand like CO, NO forms complexes only when
coordinate and hence the complexes are called coordinate transition metals are in zero due to the availability of vacant
complexes. orbitals in the donor atom of the ligand in addition to lone
pair.
The highly electronegative and basic ligand like F -, Cl- can In the molten state, transition metals are miscible with one
form complexes with transition metals even though there are another, which forms solid alloy on cooling.
in high oxidation states due to the presence of small, highly
Transition metals can form alloy with non-transition metals
charged or neutral ligands with lone pair of electrons that can
such as brass (Cu-Zn) and bronze (Cu-Sn).
form strong sigma bond by donating a lone pair of electrons.
Transition metals have the following physical
In a transition series the stability of complexes increases with
characteristics:
the rise in atomic number.
• They are good heat and electricity conductors.
The transition metal atom reveals multiple oxidation state; • They can be hammered or bent easily.
the higher valent ion forms more stable complexes. • They have high melting points (but mercury is a liquid at
room temperature)
A few examples are: [Fe (CN)6]3–
• They are usually strong and durable.
• They have high density.
Non-stoichiometric Compounds
The compounds in which the there is no conformity in
chemical composition with the ideal chemical formula are
called non-stoichiometric compounds.
These compounds are formed due to variable valency in
transition metals and also due to the defects arising in solid
state.
The compounds formed with O, S, Se, Te, Fe, Zn etc. are the
examples of such compounds.

Preparation of potassium dichromate (K2Cr2O7):

Formation of Interstitial Compounds - Transition elements Prepared by a combination of chromate ore (FeCr 2O4) and
in combination with small atoms like H, B, C, N etc. leads to sodium carbonate over air:
the formation of interstitial compounds that are non- Potassium dichromate, (K2Cr2O7) is an orange-ish inorganic
stoichiometric in composition. chemical reagent. In different laboratory or industry it is
E.g.: TiH1.3, VH0.5 basically used as an oxidizing agent usually for alcohols.
The interstitial compounds so formed are chemically inert It can be prepared through the following process:
having higher melting points as compared to pure metals.
These compounds are hard and tough and keep metallic At first the fusion of chromite ore FeCr2O4 with sodium or
conductivity. potassium carbonate in the presence of access of air.
4FeCr2O4 + 8Na2CO3 + 7O2 --> 8Na2CrO4 + 2FeO3 + 8CO2
Solution of sodium chromate is first filtered and then
acidified with a solution of sulfuric acid which results in an
orange sodium dichromate solution Na2Cr2O7.2H2O can be
crystallized.
2Na2CrO4 + 2H+ --> Na2Cr2O7 + 2Na+ + H2O
Sodium dichromate is more soluble than potassium
dichromate and therefore it is fused with KCl that leads to the
formation of orange crystals of potassium dichromate.

Alloy Formation - The transition metals can form large Na2Cr2O7 + 2KCl --> K2Cr2O7 + 2NaCl
number of alloys among themselves having high melting 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
points.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + H2O + Na2SO4 It oxidizes iodides to iodine.
Cr2O7 2- + 14H+ + 6I- --> 2Cr 3+ + 7H2O + 3I2
Sodium Sodium
It oxidizes ferrous salts to ferric salts.
Chromate Dichromate Cr2O7 2- + 14H+ + 6 Fe2+ --> 2Cr 3++ 7H2O + 6Fe3+
It oxidizes stannous salts to stannic salts.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Cr2O7 2- + 14H+ + 3Sn 2+ --> 2Cr 3+ + 7H2O + 3Sn 4+
Potassium Dichromate exists as orange red crystals and is It oxidizes H2S to sulphur.
soluble in water. Cr2O7 2- + 8H+ + 3H2S --> 2Cr 3+ + 7H2O + 3S
Action of Alkali Effect of pH on chromate and dichromate ions: Chromates
Alkali (KoH) reacts with potassium dichromate to give yellow and dichromates are converted into aqueous solution
coloured solution of potassium chromate. depending on the pH of the solution. The oxidation status of
K2Cr2O7 + 2KOH → 2K2CrO4 + H2O. chromium in chromate and dichromate is similar.
Properties of potassium dichromate 2CrO42- + 2H+ → Cr2O72- + H2O
Oxidizing Properties
Cr2O72- + 2OH- → 2CrO42- + H2O
Potassium Dichromate is good oxidizing agent in acidic
Potassium dichromate acts as a strong oxidizing agent in an
medium. Potassium dichromate (oxidation number of Cr =
acidic environment.
+6) is reduced to chromium sulphate (oxidation number of Cr
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
= +3)
Uses of Potassium Dichromate
Cr2 O72- + 14H+ + 6e– → 2Cr3+ + 7H2O.
• It is used as an oxidizing agent.
By gaining six electrons dichromate ions acts as an oxidizing • Used in a dyeing.
agent. • In manufacture of lead chromate and chrome alum.
• Used in the detect ion of chloride ion.
• In the tanning of leather.
• In manufacture of pigments and inks.

Preparation of potassium permanganate (KMnO4):

A. Potassium permanganate is prepared by the combination of MnO 4 with alkali metal hydroxide (KOH) in the presence of O 2
or an oxidizing agent similar to KNO3. It produces a dark green K2MnO4 that gets oxidation and reduces the neutral or acidic
solution to give permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
4H+ + 3MnO42- → 2MnO4- + MnO2 + 2H2O
B. Commercially prepared by alkaline oxidative fusion of MnO2 followed by electrolytic oxidation of manganite (VI).

C. In the laboratory, Mn +2 salt can be oxygenated with peroxodisulphate ions to permanganate ions:
In acidic medium: MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
In neutral or faintly basic medium: MnO4- + 3e- + 2H2O → MnO2 + 4OH-
Properties of KMnO4 2KMnO4 → K2MnO4 + MnO2 + O2
It is crystalline solid having deep purple colour. It is soluble At red heat, it further decomposes to K2MnO3 and oxygen.
in water at room temperature. Heated solid KMnO4 gives KOH, MnO and water vapour in
When heated it decomposes giving oxygen at 473K. current of H2.
Uses of KMnO4 Europium (Eu) as well as ytterbium (Yb) attains 4f 7 and 4f14
• It is used as – respectively in +2 oxidation state.
• Disinfectant. Chemical Reactivity of Lanthanoids
• An oxidizing agent.
• Baeyer’s reagent. Earlier members of lanthanoids are quite reactive, behaves
• For detecting halides in qualitative analysis. like calcium but as atomic number increases, they behaves
more like aluminium.
F-block Elements
Elements whose f orbital getting filled up by electrons are Lanthanoids forms carbides, hydrides, oxides, nitrides,
called f block elements. These elements have electrons, (1 to halides, etc.
14) in the f orbital, (0 to 1) in the d orbital of the penultimate Carbides-
energy level and in the outermost’s orbital. Ln + C → Lanthanoid Carbide
There are two series in the f block corresponding to the filling Hydrides-
up of 4f and 5f orbitals. The elements are 4f series of Ce to Lu 2Ln + 3H2 → 2LnH3
and 5f series of Th to Lw. There are 14 elements filling up the Oxides-
‘f’ orbital in each series. 2Ln + 3O2 → 2Ln2O3
Lanthanides: Nitrides-
2Ln + N2 → 2LnN
Halides-
2Ln + 6HCl → 2LnCl3 + 3H2
Sulphides-
2Ln + 3S → Ln2S3
Lanthanoid Contraction
The gradual decrease in atomic and ionic size of lanthanoids
with increases in atomic number is called lanthanoid
contraction.
As we move along the lanthanoid series, the atomic number
gradually increases by one or we can say number of electrons
and protons increases by one.
The electronic Configuration of lanthanoid is [Xe] 4fn+1 5d° 6s2 Addition of electrons to the same shell increases the effective
or [Xe] 4fn 5d1 6s2 with their valence shell electronic nuclear charge.
configuration as 4f1−14 6s2. Increase in atomic number also increases the number of
They exhibit the oxidation state of +3, +2 and +4. electrons in the 4f orbital having poor shielding effect due to
The initial members of this series are somewhat reactive which the effective nuclear charge upon the outer electrons
towards calcium which resembles their behaviour to that of also increases.
aluminium with the gradual increasing atomic number.
On application of gentle heat Lanthanides combine with Therefore the size of lanthanoids steadily decreases with the
hydrogen. increase in the atomic number and phenomenon is called
lanthanoid
Heating them with carbon leads to the formation of carbides
and halides (in presence of halogens while burning). As a result of lanthanoid contraction there is a similarity in
the properties of second and third transition series.
Reaction of Lanthanides with dilute acids releases hydrogen
gas.
They form basic alkaline earth metal oxides and hydroxides
like N2O3 and M(OH)3.
Oxidation States of Lanthanoids
The common oxidation state of all lanthanoids is +3. It is Effects of Lanthanoid Contraction
characteristics of series. Decrease in Basicity
Due to lanthanoid contraction the size of the tri-positive
Lanthanum, gadolinium and lutetium shows only +3 lanthanoid ion (M3+) regularly decreases with increase in
oxidation state by losing two 6s and one 5d electrons giving atomic number i.e. from La3+ to La3+. It results into decrease
stable outer electronic configuration 4f0,4f7 and 4f14 of basic from La3+ to Lu3+.
respectively.
Ionic Radii of the Post Lanthanoids
In +4 oxidation state cerium, terbium attains 4f0 and 4f7 The elements which follow the lanthanoids in the third
respectively. transition series are known as post lanthanoid. As a result of
lanthanoid contraction the atomic radii (size) of the elements Some elements exhibit +2 oxidation states in their complexes
which follow lanthanum (Hf, Ta, W, etc) are similar to that of in solutions. For example, Samarium (Sm), Europium (Eu),
the elements of 4d series. Since Zr-Hf, Nb-Ta, Mo-W and Tc- Thulium (Tm) and Ytterbium (Yb) show +2 oxidation state.
Re have almost identical sizes, similar number of valence Some elements exhibit +4 oxidation states due to high
electrons and similar properties these pairs of elements are stability of empty, half-filled or fully filled f-subshells.
called chemical twins. Praseodymium (Pr), Neodymium (Nd), Terbium (Tb) and
Oxidation States of lanthanoids Dysprosium (Dy) exhibits +4 oxidation state in their oxides.
The elements belonging to lanthanide series exhibit an Cerium (Ce) shows both +3 as well as +4 state.
oxidation state of +3. For example, Praseodymium (Pr) shows
+3 oxidation state.
Actinides Series

The series of fourteen elements 90Th to 103Lr which follows actinium (89Ac) and in which last electrons are progressively filled
in 5f orbital in pre-penultimate shell are called actinoid series or 5f series.
The elements which are synthetically or artificially prepared by man having atomic number higher than uranium (z=92) are
called as trans-uranic elements (Np-93 to Uno-118).
Position of Actinoids frequency of light is absorbed, the f-f electron transition
The actinoids belongs to third group of the periodic table in produces a visible colour.
the seventh period.
Ionization of Actinides
Actinoids are placed at the bottom of the periodic table below
The actinides have lower ionization enthalpies than
the lanthanoid series because it interrupts fourth transition
lanthanides because 5f electrons are more effectively
series of d-block elements.
shielded from nuclear charge than 4f.
Electronic Configuration The general electronic
Formation of Complexes
configuration of 5f elements is represented as 5f1-14 6d0-1
Actinides are better complexing agents than lanthanides due
7s2.
to the smaller size but higher nuclear charge. They can form
The electronic configuration of actinoids is not definite.
Pπ – complexes as well.
Actinium and thorium does not contain any 4f electron.
Degree of complexion decreases in the order M 4+ > MO22+ >
Oxidation state in Actinoids M3+ > MO22+.
In general the oxidation state of these elements is +3 (similar
Chemical Reactivity of Actinides
to lanthanides).
Because of the lower ionization energy, actinides are
They also exhibit +4 oxidation states.
electropositive than lanthanides and most reactive. They
Some of the elements also exhibit higher oxidation states.
react with hot water. React with oxidizing agents and form a
The oxidation state initially rises to the middle of the series
passive coating. Form halides and hydrides. Actinides are
(+4 for Th to +5, +6 and +7 for Pa, V and Np) and then
strong reducing agents.
descends in the succeeding elements.
Properties of Lanthanides
Actinide Contraction
• Lanthanides are soft metals with a silvery white colour.
The atomic size/ ionic radii of tri positive actinides ions
decrease steadily from Th to Lw due to increasing nuclear • Their colour dulls and their brightness reduces rapidly
charge and electrons entering the inner (n-2) f orbital. when exposed to air.
• They have melting points ranging from 1000K to 1200K
This gradual decrease in the size with an increasing atomic (Except Samarium, 1623K).
number is called actinide contraction like lanthanide • Lanthanides are good conductors of heat and electricity.
contraction. Because of the very poor shielding by 5f • They are non-radioactive in nature except Promethium
electrons, contraction is larger along the period. • A decrease in atomic and ionic radii from lanthanum to
Formation of Coloured Ions lutetium is observed. This is called the lanthanoid
Actinides like lanthanides ions have electrons in f-orbital and contraction.
also empty orbitals like the d-block elements. When a
Properties of Actinoids:
• They all have radiation.
• Actinides are very electropositive.
• Metals decompose easily in air. Q. What is the significance of formation of
• Actinides are very dense metals with different properties. coloured ions by transition metals?
• Reacts with boiling water or purifying acid to release
hydrogen gas. Sol. Coloured compounds of transition
• Actinide iron is usually soft. elements are associated with partially
Difference between Lanthanides and Actinides filled (n-1)d orbitals. The transition
• Lanthanoids are involved in the filling of 4f- orbitals
whereas actinoids are involved in the filling of 5f- undergoes electronic unpaired d-
orbitals. The binding energy of 4f electrons is electrons undergo an electronic transition
comparatively less than that of 5f-electrons. The
shielding effect of 5f-electrons is less effective as from one -d- orbital to another. During this
compared to that of 4f-electrons. d-d transition process, the electrons
• The paramagnetic properties of lanthanoids can be easily
explained but this explanation is difficult in the case of absorb certain energy from the radiation
actinoids. and emit the remainder of energy as
• Lanthanides are non-radioactive in nature except
promethium whereas all actinide series elements are coloured light. The colour of the ion is
radioactive. complementary to the colour absorbed by
• Lanthanides do not have a tendency to form oxo-cations,
but several oxo-cations of actinide series exist. The it. Hence, the coloured ion is formed due to
compounds formed by lanthanides are less basic on the d-d transition which falls in the visible
other hand the compounds of actinides are highly basic.
region for all transition elements.
Uses of Lanthanides:
It is used as a catalyst in the manufacture of petroleum and
synthetic products.
Thoria and Ceria are used in lamps, magnets, lasers, motion Q. Why do d-block element form complexes?
picture projectors, and X-ray intensify screens. Sol. The d-block elements are smaller in size and have
Alloys of Lanthanides are used in the instrumental steels,
stainless steel, and heat resistance. high electropositive density and they consist of
It is used for the metallothermic reaction. (n-1)d free orbitals to accept the free electrons
Ceria salts are used in lead storage batteries.
from the ligand and it forms complexes easily.

Q. Actinoid contraction is greater from

element to element than lanthanoid Mischmetal: Mischmetal is an alloy of rare earth elements
with iron and traces of S, C, Ca and Al. The composition is 50%
contraction. Why?
cerium and 25% lanthanum, with small amounts of
Sol. In actinoids, 5f orbitals are filled having neodymium and praseodymium. It improves workability of
poorer shielding effect than 4f orbitals (in steel. It is used in the ferrocerium "flint" ignition device of
lanthanoids) due to which the effective many lighters and torches.
nuclear charge experienced by the electrons It is also used in the preparation of rare earth elements.
in valence shells of actinoids is more than
what is experienced by lanthanoids. Question For You
Therefore, the size of contraction in actinoids Why F-block elements are placed separately?
is greater as compared to that in lanthanoids. Are all F-block elements radioactive?
They are termed as inner transition elements
Why are F-block elements called inner transition
due to their occurence inside the series of
elements?
transition elements.
The d-block consisting of group 3-12 occupies the large Transition metals react with a number of non-metals like
middle section of the periodic table. In these elements are oxygen, nitrogen, sulphur etc. to form binary compounds. The
filled in d-orbitals. The f-block is at the bottom and the first transition series is generally formed from the reaction of
electrons are filled in 4f and 5f orbitals. metals with oxygen at high temperatures. These oxides
dissolved in acids and bases to form oxometallic salts.
All the transition elements exhibit typical metallic properties
Potassium dichromate and potassium permanganate are
such as high tensile strength, ductility, malleability, thermal
common examples. Potassium dichromate is prepared from
and electrical conductivity. Their melting and boiling points
the chromite ore by fusion with alkali in presence of air and
are high because the elements were go into the (n-1) d
acidifying the extract. Pyrolusite ore is used for the
subshell resulting into strong interatomic bonding. The
preparation of potassium permanganate. Both are strong
maxima of all the properties will occur at the middle of each
oxidising agent.
series which indicates that one unpaired electron per d
orbital is particularly a favourable configuration for strong The two series of inner transition elements lanthanoids and
interatomic interaction. actinoids are called the f- block elements. With the successive
filling of the inner orbitals 4f, there is a gradual decrease in
Successive ionisation enthalpies do not increase as gradually
the atomic and ionic size of these metals. Lanthanum and all
as in the group elements with increasing atomic number.
the lanthanoids are rather soft white metals. They react easily
Hence, the loss of variable number of electrons form (n-1) d
with water to give solutions giving +3 ions. The principal
orbitals is not energetically unfavourable. The transition
oxidation state is +3, although+4, +2 oxidation states are also
elements exhibit certain different characteristics because of
exhibited by some occassionally. The chemistry of the
involvement of (n-1)d subshell. Thus, in addition to variable
actinoids is more complex in view of their ability to exist in
oxidation state, they exhibit paramagnetic behaviour,
different oxidation states. Furthermore, many of the actinoids
catalytic properties and tendency for the formation of
elements are radioactive which make the study of these
coloured ions, interstitial compounds and complexes.
elements rather difficult.
Transition elements varies in their chemical behaviour also.
There are many useful applications of the d and f-block
Many of them are sufficiently electropositive and remaining
elements and their compounds.
are noble. With the exception of copper, all the first transition
elements are relatively reactive.
 QUESTIONS FOR PRACTICE
Q1. In which of the following pairs, both the ions are Q11. The oxidation state of Cr in final product formed by
coloured in aqueous solutions? reaction of KI and acidified dichromate solution is
(a) Sc3+, Ti (b) Sc3+, CO2+ (a) +4 (b) +6
(c) Ni , Cu
2+ + (d) Ni2+, Ti3+ (c) +2 (d) +3
Q2. The number of moles of KMnO4 that will be needed to Q12. KMnO4 gets reduced to
react with one mole of SO32- in acidic solution. (a) K2MnO4 in neutral medium
(a) 1 (b) 3/5 (b) MnO2 in acidic medium
(c) 4/5 (d) 2/5 (c) Mn2+ in alkaline medium
Q3. The correct order of decreasing second ionisation (d) MnO2 in neutral medium
enthalpy of Ti(22), V(23), Cr(24) Mn(25) Q13. The electronic configuration of Cu(II) is 3d9 whereas
(a) V > Mn > Cr > Ti
that of Cu(I) is 3d10. Which of the following is correct?
(b) Mn > Cr > Ti > V
[NCERT Exemplar]
(c) Ti > V > Cr > Mn
(a) Cu(II) is more stable
(d) Cr > Mn > V > Ti
(b) Cu(II) is less stable
Q4. Which of the following pairs has the same ionic size? (c) Cu(I) and Cu(II) are equally stable
(a) Zr4+, Hf4+ (b) Zn2+, Hf4+ (d) Stability of Cu(I) and Cu(II) depends on nature of
(c) Fe , Ni
2+ 2+ (d) Zr4+, Ti4+ copper salts
Q5. Acidified K2Cr2O7 solution turns green when S02 gas is Q14. Generally transition elements form coloured salts due
passed through it due to formation of to the presence of unpaired electrons. Which of the
(a) Cr2(SO4)3 (b) CrO42- following compounds will be coloured in solid state?
(c) Cr2(SO3)3 (d) CrSO4 (a) Ag2SO4 (b) CuF2
Q6. The stability of Mn2+ , Fe2+, Cr2+, Co2+ is in order of (At (c) ZnF2 (d) Cu2Cl2
No. of Mn = 25, Fe = 26, Cr = 24, Co = 27)
Q15. On addition of small amount of KMnO4 to concentrated
(a) Mn2+ > Fe2+ > Cr2+ > Co2+
H2SO4, a green oily compound is obtained which is
(b) Fe2+ > Mn2+ > Co2+> Cr2+
highly explosive in nature. Identify the compound from
(c) Co2+> Mn2+ > Fe2+ > Cr2+
the following.
(d) Cr2+ > Mn2+ > Co2+> Fe2+
(a) Mn2O7 (b) MnO2
Q7. Which of the following lanthanoid ion is diamagnetic? (c) MnSO4 (c) Mn2O3
(At No. of Ce = 58, Sm = 62, Eu = 63 Yb = 70)
Q16. Anomalous electronic configuration in the 3d series
(a) Eu2+ (b) Yb2+
(c) Ce 2+ (d) Sm2+ are of
(a) Cr and Fe (b) Cu and Zn
Q8. Magnetic moment of 2.83 BM is given by which of the (c) Fe and Cu (d) Cr and Cu
following ion? Q17. Which of the following are d-block elements but not
(a) Ti3+ (b) Ni2+ regarded as transition elements?
(c) Cr3+ (d) Mn2+ (a) Cu, Ag, Au
Q9. KMnO4 is not acidified by HCl instead of H2SO4 because (b) Zn, Cd, Hg
(a) H2SO4 is stronger acid than HCl (c) Fe, Co, Ni
(b) HCl is oxidised to Cl2 by KMnO4 (d) Ru, Rh, Pd
(c) H2SO4 is dibasic acid
Q18. CuSO4.5H2O is blue is colour because
(d) rate is faster in presence of H2SO4
(a) It contains water of crystallization.
Q10. Out of Mn2O7 V2O3, V2O5, CrO, Cr2O3, the basic oxides (b) SO42- ions absorb red light.
are (c) Cu2+ ions absorb orange red light.
(a) Mn2O7, V2O3 (b) V2O3, V2O5 (d) Cu2+ ions absorb all colours except red from the
(c) V2O5, CrO (d) V2O3 and CrO white light.
Q19. Transition elements form alloys easily because they (c) Yb (d) Ho.
have
Q28. The anomalous electronic configuration in 3d-series
(a) Same atomic number
shown by______
(b) Same electronic configuration
(a) Cr, Cu (b) Sc, Cr
(c) Nearly same atomic size (c) Cr, Zn (d) Cr, Mn
(d) None of the above
Q29. Which element is having lowest melting and boiling
Q20. Which one of the following characteristics of the point.
transition metals is associated with higher catalytic (a) Ti (b) Cu
activity? (c) Zn (d) Mn
(a) High enthalpy of atomisation
(b) Paramagnetic behaviour Q30. In 1st transition series which has low melting point
(c) Colour of hydrate ions (a) V (b) Mn
(d) Variable oxidation states (c) Cu (d) Zn

Q21. The property which is not characteristic of transition Q31. The lowest density d-block element is______
metals is (a) Copper (b) Nickel
(a) Variable oxidation states. (c) Sc (d) Zinc
(b) Tendency to form complexes. Q32. Which one of the following metals is used as a catalyst
(c) Formation of coloured compounds. in the Haber’s process?
(d) Natural radioactivity. (a) Tungsten (b) Molybdenum
(c) Chromium (d) iron containing Mo.
Q22. Which of the following is incorrect for KMnO4 to be
Q33. When manganese dioxide is fused with KOH in air. It
used as an oxidising agent?
gives
(a) HCl cannot be used because some KMnO4 is
(a) potassium permanganate
consumed in the reaction.
(b) potassium manganate
(b) Nitric acid is not used for the above purpose
(c) manganese hydroxide
because it itself acts as a self-oxidising agent and
(d) Mn3O4.
will react with the reducing agent.
(c) The equivalent weight of KMnO4 in basic Q34. Which metal has lowest melting point?
medium is 158. (a) Cs (b) Na
(d) The number of electrons involved in oxidation of (c) Hg (d) Sn
KMnO4 in acidic medium is 3. Q35. Which is the first man-made element?
Q23. Transition metals, despite high E° oxidation, are poor (a) Sc (b) Os
reducing agents. The incorrect reason is (c) Tc (d) Zr
(a) High heat of vaporization.
(b) High ionization energies. Q36. Which transition metal can show highest oxidation
(c) Low heats of hydration. state?
(d) Complex forming nature. (a) Sc (b) Ti
(c) Os (d) Zn
Q24. Which of the following has magnetic moment value of
5.9? Q37. In KMnO4 oxidation number of Mn is
(a) Fe2+ (b) Fe3+ (a) +2 (b) + 4
(c) Ni2+ (d) Cu2+ (c) + 6 (d) + 7

Q25. Which of the following actinoids show oxidation states Q38. When KMnO4 acts as oxidising agent in alkaline
upto +7? medium, the oxidation number of Mn decreases by
(a) Am (b) Pu (a) 1 (b) 2
(c) 3 (d) 5.
(c) U (d) Np
Q39. Ag+ ion is isoelectric with
Q26. General electronic configuration of actionoids is (n –
(a) Au3+ (b) Cd2+
2)f1 – 14 (n – 1)d0 – 2 ns².Which of the following actinoids
(c) Zn2+ (d) Pd2+
have one electron in 6d orbital?
(a) U (Atomic no. 92) (b) Np (Atomic no. 93) Q40. The transition element with lowest atomic number is
(c) Pu (Atomic no. 94) (d) Am (Atomic no. 95) (a) Scandium (b) Titanium
(c) Zinc (d) Lanthanum
Q27. Which of the following lanthanoids show +2 oxidation
state besides the characteristic oxidation state +3 of Q41. Which of the following oxides is amphoteric in nature?
lanthanoids? (a) CaO (b) CO2
(a) Ce (b) Eu (c) SiO2 (d) SnO2
Q42. The equivalent mass of K2Cr2O7, when it acts as Reason: Cuprous ion (Cu+) is colourless whereas
oxidising agent in acidic medium, is equal to cupric ion (Cu++) is blue in the aqueous solution.
(a) M (b) M/2 (a) If both Assertion and Reason are correct and the
(c) M/6 (d) M/5 Reason is a correct explanation of the Assertion.
Q43. Rutile is an ore of (b) If both Assertion and Reason are correct but
(a) Scandium (b) Titanium Reason is not a correct explanation of the
(c) Manganese (d) Chromium Assertion.
Q44. If two compounds have the same crystal structure and (c) If the Assertion is correct but Reason is incorrect.
analogous formula, they are called (d) If both the Assertion and Reason are incorrect.
(a) Isomers (b) Isotopes (e) Assertion is incorrect but Reason is correct
(c) Isobars (d) Isomorphous.
Q3. Assertion: Transition metals show variable valency.
Q45. Which of the following would be diamagnetic? Reason: Transition metals have a large energy
(a) Cu2+ (b) Ni2+ difference between the ns2 and (n – 1)d electrons.
(c) Cd2+ (d) Ti3+. (a) If both Assertion and Reason are correct and the
Q46. Which of the following would be paramagnetic? Reason is a correct explanation of the Assertion.
(a) Zn2+ (b) Cu+ (b) If both Assertion and Reason are correct but
(c) Ag+ (d) Ni2+ Reason is not a correct explanation of the
Assertion.
Q47. Which of the following is not an actinide?
(c) If the Assertion is correct but Reason is
(a) curium (b) californium.
(c) uranium (d) terbium. incorrect.
(d) If both the Assertion and Reason are incorrect.
Q48. Least paramagnetic property is shown by (e) Assertion is incorrect but Reason is correct
(a) Fe (b) Mn Q4. Assertion: Transition metals are good catalysts.
(c) Ni (d) Cu
Reason: V2O5 or Pt is used in the preparation of H2SO4
Q49. Vanadium (III) oxide is a strong by contact process.
(a) Drying agent (b) Oxidizing agent (a) If both Assertion and Reason are correct and the
(c) Reducing agent (d) Witting agent Reason is a correct explanation of the Assertion.
(e) Precipiting agent. (b) If both Assertion and Reason are correct but
Q50. The value of’spin only’ magnetic moment for one of the Reason is not a correct explanation of the
following configurations is 2.84 BM. The correct one is Assertion.
(a) d4 (in strong ligand field) (c) If the Assertion is correct but Reason is incorrect.
(b) d4 (in weak ligand field) (d) If both the Assertion and Reason are incorrect.
(c) d³ (in weak as well as strong fields) (e) Assertion is incorrect but Reason is correct.
(d) d5 (in strong ligand field)
TRUE/FALSE
ASSERTION AND REASONING
Q1. Interstitial compounds have high melting points,
Q1. Assertion: Magnetic moment values of actinides are higher than those of pure metals.
lesser than the theoretically predicted values. (a) True
Reason: Actinide elements are strongly paramagnetic (b) False
(a) If both Assertion and Reason are correct and the
Reason is a correct explanation of the Assertion. Q2. Permangnate titrations in presence of hydrochloric
(b) If both Assertion and Reason are correct but acid are unsatisfactory.
Reason is not a correct explanation of the (a) True
Assertion. (b) False
(c) If the Assertion is correct but Reason is
incorrect. Q3. KMnO4 does not act as an oxidising agent in strong
(d) If both the Assertion and Reason are incorrect. alkaline medium.
Q2. Assertion: Cuprous ion (Cu+) has unpaired electrons (a) True
while cupric ion (Cu++) does not. (b) False
 QUESTIONS FOR PRACTICE
Q1. Transition metals are generally coloured because Q12. What is the colour of KMnO4?
(a) they absorb electromagnetic radiations (a) Colourless (b) Green
(b) their penultimate d-subshells are fully filled (c) Purple (d) Blue
(c) of d-d transition
(d) none of the above Q13. Which property of actinoids cannot be explained?
(a) Acidic (b) Radioactive
Q2. Paramagnetism is common in (c) Oxidation (d) Magnetic
(a) s-block elements (b) p-block elements
(c) d-block elements (d) any of them Q14. Actinoids are mostly attacked by which acid?
(a) Hydrochloric acid (b) Nitric acid
Q3. Transition elements exhibit variable valency because
(c) Sulphuric acid (d) Boric acid
they release electrons from
(a) ns orbitals (b) np orbitals Q15. Which of the following is amphoteric?
(c) (n-1)d orbitals (d) (n-1)d & ns orbitals (a) CrO (b) Cr2O3
Q4. In industrial processes, transition elements and their (c) CrO5 (d) CrO3
oxides are used as
Q16. What happens to the atomic size of the lanthanides
(a) Surfactants (b) Insecticides
with increase in atomic number?
(c) Catalyst (d) any of them
(a) The radius remains unchanged
Q5. What is the nature of the transition elements? (b) The radius decreases
(a) Varies from element to element (c) The radius increases
(b) Metallic (d) The radius first increases and then decreases
(c) Non-metallic
(d) Metalloid Q17. Which of the following is not a consequence of
lanthanide contraction?
Q6. How many series’ of transition elements are present in
(a) The atomic radii of 4d and 5d series is similar
the periodic table?
(b) From La+3 to Lu+3, the ionic radii changes from
(a) One (b) Two
106 pm to 85 pm
(c) Three (d) Four
(c) As the size of the lanthanide ions decreases the
Q7. Which of the following element belongs to the second basic strength increases
transition series of the periodic table? (d) The basic character of oxides and hydroxides
(a) Nb (b) Ni decreases with increase in atomic number
(c) Au (d) La
Q18. Which of the following is not a property of lanthanides?
Q8. Which of the following element belongs to the third
(a) The melting point of the metal ranges from 500-
transition series of the periodic table?
1000K
(a) Tc (b) Sc
(b) They are soft metals with white silvery color
(c) Re (d) Rh
(c) They tarnish rapidly by air
Q9. Which of the following element is not a transition (d) The hardness of the metals increases with
element? increase in the atomic number
(a) Fe (b) Mn Q19. Which of the following is the correct order of
(c) Zn (d) Ag arrangement of the first five lanthanides according to
Q10. Which of the following is used as a nuclear fuel? atomic number?
(a) Uranium (b) Cobalt (a) La, Ce, Pr, Pm, Nd
(c) Zinc (d) Iron (b) La, Ce, Pr, Nd, Pm
(c) La, Pr, Ce, Pm, Nd
Q11. What is the end product formed when KMnO4 reacts
(d) La, Pr, Ce, Nd, Pm
with HCl?
(a) Dense white fumes (b) Brown fumes Q20. Which is the last element of lanthanides?
(c) Dark green gas (d) Greenish yellow gas (a) Ytterbium (b) Lutetium
(c) Thulium (d) Erbium
Q21. What is the nature of the transition elements? (c) Ferric chloride
(a) Varies from element to element (d) Ferrous sulphate
(b) Metallic
Q30. Which compound is used in Ultra-violet calibration?
(c) Non-metallic
(a) Hg2Cl2
(d) Metalloid
(b) HgCl2
Q22. Why there is an increase in the atomic radius of (c) K2Cr2O7
transition elements at the end of the period? (d) KMnO4
(a) Increased electron-electron repulsions
(b) Decreased electron-electron repulsions
ASSERTION AND REASONING
(c) Increase in nuclear charge
(d) Increase in atomic mass
Q1. Assertion: Transition metals are efficient catalysts.
Q23. Why the atomic radii of the second and third transition Reason: Transition metals usually contain incomplete
series are almost same? d-orbitals and provide larger surface area for
(a) Actinoid contraction adsorption.
(b) Radioactive nature Transition metals are efficient catalysts.
(c) Lanthanoid contraction (a) If both Assertion and Reason are correct and the
(d) Filled d-orbital Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but
Q24. Group VIB of transition elements contains
Reason is not a correct explanation of the
(a) Zn Cd Hg
Assertion.
(b) Fe Ru Os
(c) If the Assertion is correct but Reason is incorrect.
(c) Cr Mo W
(d) If both the Assertion and Reason are incorrect.
(d) Mn Te Re
(e) Assertion is incorrect but Reason is correct
Q25. What is the formula of hematite?
Q2. Assertion: In transition elements, the ns orbital is
(a) Fe3O4
filled up first and (n-1)d afterwards. During ionization,
(b) FeSO4.7H2O
ns electrons are lost prior to (n-1)d electrons.
(c) Fe2O3
Reason: The effective nuclear charge felt by (n-1) d
(d) FeCl3
electrons is higher as compared to that by ns electrons.
Q26. Which of the following is Baeyer’s reagent? (a) If both Assertion and Reason are correct and the
(a) Acidified KMnO4 Reason is a correct explanation of the Assertion.
(b) Alkaline KMnO4 (b) If both Assertion and Reason are correct but
(c) Acidified K2Cr2O7 Reason is not a correct explanation of the
(d) Aqueous KMnO4 Assertion.
(c) If the Assertion is correct but Reason is incorrect.
Q27. Which of the following metal is used as a thermometric (d) If both the Assertion and Reason are incorrect.
liquid? (e) Assertion is incorrect but Reason is correct
(a) Iron
(b) Copper Q3. Assertion: It is not possible to obtain anhydrous ZnCl2
(c) Mercury by heating ZnCI2.2H2O.
(d) Potassium Reason: ZnCI2.2H2O. undergoes hydrolysis to produce
Q28. Which of the following test does AgCl not answer? Zn(OH)2 and HCI.
(a) Chromyl chloride test (a) If both Assertion and Reason are correct and the
(b) Baeyer’s test Reason is a correct explanation of the Assertion.
(c) Alkaline test (b) If both Assertion and Reason are correct but
(d) Acidic test Reason is not a correct explanation of the
Assertion.
Q29. Which compound forms double salt with sulpahtes of (c) If the Assertion is correct but Reason is incorrect.
alkali metals? (d) If both the Assertion and Reason are incorrect.
(a) Ferric oxide (e) Assertion is incorrect but Reason is correct
(b) Silver nitrate
Q4. Assertion: Copper metal gets readily corroded in an (c) If the Assertion is correct but Reason is incorrect.
acidic aqueous solution. (d) If both the Assertion and Reason are incorrect.
Reason: Free energy change for this process is (e) Assertion is incorrect but Reason is correct.
negative.
(a) If both Assertion and Reason are correct and the TRUE/FALSE
Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Q1. Mn2+ compounds more stable than Fe2+ towards
Reason is not a correct explanation of the oxidation to their +3 states.
Assertion. (a) True (b) False
(c) If the Assertion is correct but Reason is incorrect.
Q2. Titanium and copper both in the first series of
(d) If both the Assertion and Reason are incorrect.
transition metal exhibits +1 oxidation state most
(e) Assertion is incorrect but Reason is correct
frequently
Q5. Assertion: Promethium is a man-made element. (a) True (b) False
Reason: It is radioactive and has been prepared by
Q3. Elements belonging to the d -block of the periodic table
artificial means.
are transition elements.
(a) If both Assertion and Reason are correct and the
(a) True (b) False
Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Q4. The second transition series involves the filling of 3d -
Reason is not a correct explanation of the subshell.
Assertion. (a) True (b) False
 SOLUTION FOR PRACTICE QUESTIONS
S1. (d) Ni2+, Ti3+ are coloured due to presence of The electronic configuration of mercury is [Xe]
unpaired electrons. 5d10 6s2.
S2. (d) 2 MnO4– + 5SO32- + 16H+ → 2Mn2+ + 5SO42+ + S18. (a) Anhydrous CuSO4 is white in colour due to the
8H2O absence of water molecules. When we make the
5 moles of SO32- needs 2 moles of KMnO4 solution of CuSO4 water molecules will attach to
1 mole of SO32- needs 2/5 moles of KMnO4 CuSO4 molecule making CuSO4.Two of the
orbitals interact with the water molecules and
S3. (d) ∵ Cr+(4s°3d5), Mn+ 4s13d5, V+(4s13d3), Ti+4s13d2
raises in energy. The energy difference is
S4. (a) Zr4+, Hf have similar size due to lanthanoid equivalent of the wavelength of blue light.
contraction.
The blue colour of the CuSO4 is because of Cu(II),
S5. (a) It is due to formation of chromium sulphate. which means it had lost two electrons; it gives
the copper a 2+ charge.
S6. (a) Mn2+(3d5) is most stable, Fe2+(3d6), Cr2+(3d4
Co2+(3d1) Due to the arrangement of d-orbitals, there is a
splitting effect. There are 5 d orbitals that can
S7. (b) Yb2+(4f14) does not have unpaired election,
interact with other orbitals. Two of the orbitals
therefore, diamagnetic.
interact with the water molecules and raises in
S8. b Ni2+ has 2 unpaired electrons. energy. The energy difference is equivalent of
the wavelength of blue light. When the copper
S9. (b) 2KMnO4 + 16 HCl → 2KCl + 2MnCl2 + 5Cl2 + 2H2O
absorbs photons, it releases energy from the
S10. (d) V2O3 and CrO are basic oxides due to lower, upper-level energy orbitals back to the lower
oxidation states. orbitals, giving blue light.
S11. (d) Cr3+ is formed. S19. (c)
S12. (a) S20. (d) Due to large surface area and variable oxidation
state, d-block element shows catalytic activities.
S13. (a) Cu(II) is more stable due to higher hydration
S21. (d)
energy.
S22. (c),(d) Statement(a) HCl cannot be used because some
S14. (b) CUF2 is coloured due to presence of unpaired
KMnO4 is consumed in the reaction. Is Correct as
electron in d-orbital.
it reacts with KMnO4 to get oxidized and follows
S15. (a) It is due to formation of Mn2O7. up with the liberation of Cl2 gas.
Statement(b) Nitric acid is not used for the
S16. (d) Cromium(Cr) and copper(Cu) are the exceptions
above purpose because it itself acts as a self-
of 3-d transition series which show anomalous
oxidizing agent and will react with the reducing
electonic configuration.Cr and Cu attain extra
agent. Is Correct as it is a very strong oxidizing
stability of half-filled and full-filled electronic
agent which reduces the KMnO4.
configuration by changing the expected pattern
of electronic configuration. Statement(c) The equivalent weight of KMnO4 in
The electronic configuration of Cr and Cu is the basic medium is 158. This is Incorrect as the
[Ar]3d5 4s1 and [Ar]3d10 4s1 respectively. equivalent weight of KMnO4 in the basic medium
In both cases, an electron from the 4s orbital is 52.66gm/equivalent.
jumps to 3d subshell as it is more stable due to
statement(d) The number of electrons involved
half-filled and full-filled stable configuration.
in the oxidation of KMnO4 in an acidic medium is
S17. (b) Transition elements are characterized by 3. This is Incorrect as the number of electrons
partially filled(n-1) d subshells. involved in the oxidation of KMnO4 in an acidic
Zn, Cd and Hg are not regarded as transition medium is 5.
elements as they have completely filled(n-1)d
S23. (d)
subshell.
The electronic configuration of zinc is [Ar] 3d10
4s2. S24. (b)
The electronic configuration of cadmium is [Kr] n(n + 2) = 5.9 × 5.9 = 34.8
4d10 5s2. n2 + 2n = 34.8
 and addition of extra electrons in inner orbital
and then increase in Zinc due to interelectronic
repulsion in completely filled d-and s-orbitals.
After solving, Consequently densities increase from Sc to Cu
n = -2 + 12/2 or n = -2 – 12/2 and then decreases in Zn.
n = 10/2 or n = -14/2
S32. (d) The catalyst used in Haber’s process in a metal
n = 5 or n = -7
catalyst. Usually, iron is widely used as a catalyst
The negative value is discarded as the number of
in this process. Iron has been preferred because
electrons cannot be negative.
it helps to achieve an acceptable yield of a
∴n=5 product in a much faster time.
Fe3+ ion(with valence shell electronic S33. (b) When blackish coloured compound MnO2 is
configuration 3d5 4s0 has magnetic moment 5.90 fused with KOH in presence of air, produces a
B.M. It has 5 unpaired electrons. dark green coloured compound potassium
manganate.
S25. (b),(d) As we move from left to right in a row of
MnO2 + 4KOH + O2 → 2K2MnO4 + H2O
actinoid, oxidation state first increases than
reaches maximum(in middle of row) and then S34. (c) The melting points of the alkali metals as a group
decreases so Np, Pu will show +7 oxidation are lower than those of any other non-gaseous
state. group of the periodic table, ranging between 179
S26. (a),(b) Actinoids are element 89 to 103 and fill their °C(354 °F) for lithium and 28.5 °C(83.3 °F) for
5f shell. They are typical metals and radioactive cesium. Among the metallic elements, only
also. Eg−Th,U,Pu. mercury has a lower melting point(−38.9 °C, or
−38.02 °F) than cesium.
S35. (c) Generally man-made elements are radioactive in
nature and to gain stability they emit radiation
to get a stable nucleus. The emitted radiation
may contain alpha, beta and gamma particles.
Technetium is the first man-made element.
S36. (c) Highest oxidation state(+8) is shown by Os.

So, U and Np have one electron in 6d orbital. S37. (d) KMnO4 dissociates as K+ and MnO4-. Thus we
will now calculate the oxidation number of Mn
S27. (b),(c) Europium and Ytterbium have this Let us suppose it has an oxidation state of X.
characteristic oxidation which is an exception
Thus the equation is-
from the characteristic +3 oxidation exhibited in
+1+ X − 8 = 0
general by the Lanthanoids.
Thus the value of X is +7
S28. (a) The equation has been written in that manner
S29. (c) Melting points of metals are attributed to the because KMnO4 has an overall oxidation number
involvement of number of electrons from(n-1) d of 0. K has an oxidation number of +1 and O has
in addition to the ns electrons in the interatomic an oxidation number of −2. Thus four oxygen
metallic bonding. Unpaired electron per d orbital atoms will have an oxidation number of −8
is particularly favourable for strong interatomic Oxidation numbers on both the sides should be
interaction. Zn has no unpaired electron hence it balanced and hence we get the value to be +7.
has lowest melting and boiling point.
S38. (d) When KMnO4 acts as oxidizing agent in acidic
S30. (d) Zinc(Zn) has the minimum melting point among medium, the oxidation number of manganese
3d-series of transition metals. Vanadium(V) has decreases from +7 to +2.
the maximum melting point. The reason for least Thus, the oxidation number decreases by 5.
melting point for zinc is absence of unpaired d-
electrons. S39. (b) The species which contain the same number of
electrons are called isoelectronic species.
S31. (c) (a)=8.95 ,(b)=8.95,(C )=3.0 ,(d) =7.14 The number of electrons in Ag+ is 47-1 = 46
Across the period atomic volume decrease upto The number of electrons in Au+3 is 79-3 = 76
copper due poor shielding of d-orbital electrons The number of electrons in Zn+2 is 30-2 = 28
 The number of electrons in Cd+2 is 48-2 = 46. have high reduction potential. It has a low heat
Hence Cd+2 is isoelectronic with Ag+ as they of sublimation and low ionisation potential.
contain the same number of electrons.
S50. (a) Spin magnetic moment = √𝑛(𝑛 + 2)B.M.
S40. (a) Scandium is the first transition metal. Where, n = number of unpaired electrons.
S41. (d) CaO is basic, CO2 is acidic, SiO2 is weakly acidic. Given, √𝑛(𝑛 + 2) = 2.84
SnO2 is amphoteric. or, n(n + 2) = 8.0656
or, n = 2
S42. (c) An equivalent weight of a solution is defined as
In an octahedral complex, for a d4 configuration
the molecular weight of the solute divided by the
in a strong filed ligand, number of unpaired
valence of the solute. Equivalent weight is used
electrons = 2
for predicting the mass of a substance that reacts
with one atom of hydrogen in an acid-base
analysis like in titration.
The equivalent weight of K2Cr2O7 = 49 g/mol
In the solution, K2Cr2O7 gives the following ions,
K2Cr2O7 + 14H+ + 6e– → 2K+ + 2Cr3+ + 7H2O
ASSERTION AND REASONING
The chemical equivalent is 6 because six
electrons participate in the chemical reaction.
Formula to calculate equivalent weight is S1. (b) The magnetic moments are lesser than the fact
Equivalent weight(Z) = molecular weight / that 5f electrons of actinides are less effectively
chemical equivalent shielded which results in quenching of orbitals
Z = M/6 contribution.
Actinide elements are strongly paramagnetic
S43. (b) Rutile is a mineral compared primarily of due to the presence of unpaired electrons.
titanium dioxide, TiO2. S2. (d) Cu+ →[Ar]3d10 is diamagnetic because it has no
S44. (d) Compounds with identical crystal structures and unpaired electrons and is colourless.
analogous chemical formula are called Cu2+ →[Ar]3d9 is paramagnetic because it has
isomorphous. one unpaired electron and is coloured.

S45. (c) S3. (c) The assertion is correct but the reason is false.
Transition metals show variable valency due to
S46. (d) Zn2+: [Ar]18 3d10, Ag+: [Kr]36 4d10 very small difference between the ns and(n−1)d
Cu+: [Ar]18 3d10, Ni2+: [Ar]18 3d8 electrons.
As such Ni2+ has two unpaired electrons and is
paramagnetic. S4. (b) Due to larger surface area and variable valencies
to form intermediate, transition metals are used
S47. (d) The valence electrons of the terbium element as good catalysts. V2O5 or Pt is used in the
enter into 4f-orbital so the terbium is not an preparation of H2SO4 by contact process.
actinide. It is a lanthanide. Nowadays V2O5 is used as catalyst in place of Pt
S48. (d) Paramagnetic property is dependent on the because Pt is a costly metal and poisoned by
number of unpaired electron. compound of arsenic.
Element which has least number of unpaired
electron will be less paramagnetic. TRUE/FALSE
Electronic configuration of given elements is as
follows: S1. (a) Interstitial compounds have high melting points,
Fe = [Ar] 3d6 4s2 higher than those of pure metals due to strong
Mn = [Ar] 3d5 4s2 interatomic forces.
Ni = [Ar] 3d8 4s2 S2. (a) Permangnate titrations in presence of
Cu = [Ar] 3d10 4s1 hydrochloric acid are unsatisfactory because in
Number of unpaired electrons in Fe, Mn, Ni, Cu is that case hydrochloric acid is oxidised to
4, 5, 2, 1. Therefore, Cu shows least chlorine.
paramagnetic property.
S3. (b) In strong alkaline medium, it act as oxidising
S49. (c) Vanadium(III) oxide is a strong reducing agent agent. The reaction occurs as:
because vanadium is electropositive metal and MnO4- + e- → MnO42-
 SOLUTION FOR PRACTICE QUESTIONS
S1. (c) Coloured compound of transition elements is [Ar] 3d^10. Thus, both the element and its only
associated with partially filled(n-1)d orbitals. known stable ion have completely filled d-
The transition metal ions containing unpaired d- orbitals. Also, the metal does not exhibit any
electrons undergoes electronic transition from variable valency or multiple oxidation states in
one d-orbital to another. During this d-d compound formation.
transition process the electrons absorb certain S10. (a) Uranium(atomic no. 92, symbol-U) is used as
energy from the radiation and emit the nuclear fuel. Its salts are used in the glass
remainder of energy as coloured light. The industry(for imparting green colour), textile
colour of ion is complementary of the colour industry, ceramic industry and in medicines.
absorbed by it. Hence, coloured ion is formed Natural uranium has three major isotopes.
due to d-d transition which falls in visible region
S11. (d) Potassium permanganate(KMnO4) reacts with
for all transition elements.
hydrochloric acid(HCl) to form potassium
S2. (c) d-block elements are often paramagnetic owing chloride, manganese chloride, chlorine and
to the presence of unpaired d-electrons. water. Here, one of the products formed,
S3. (d) The ability of the transition metals to exhibit chlorine, is a greenish yellow gas. It has a
variable valency is generally attributed to the pungent smell and is toxic.
availability of more electrons in the(n−1)d
S12. (a) The physical state of potassium
orbitals which are closer to the outermost ns
permanganate(KMnO4) is an odourless solid,
orbital in energy levels.
and they look like dark purple or bronze-
S4. (c) Transition metals have variable oxidation states coloured crystals. If we dissolve these crystals in
as they have high number of unpaired valence water, then the solution becomes purple in
electrons. This property is used as catalysing the colour.
reactions
S13. (d) Their magnetic properties cannot be explained
S5. (b) Because they are all metals, the transition easily, as they are more complex. The 5f bands
elements are often called the transition metals. formed due to 5f-5f wave function overlap or to
As a group, they display typical metallic hybridisation with s, p or d electrons. As a result
properties and are less reactive than the metals of the band formation, a wide variety of magnetic
in group 1 and group 2 of the periodic table. phenomena may occur.
S6. (d) Unlike s or p block elements which are usually S14. (a) Actinoids are highly reactive metals especially in
discussed as columns or groups, d-block the finely divided state. All these metals are
elements are better discussed by classifying attacked by hydrochloric acid but the effect of
them into horizontal series. In the periodic table, nitric acid is very small due to the formation of a
there are four main transition series of elements protective oxide layer on their surface.
corresponding to filling of 3d, 4d, 5d and 6d
S15. (b) Chromium(atomic no.24, symbol-Cr) forms
sublevels in the 4^th, 5^th, 6^th and 7^th
many oxides. Some of its common oxidation
periods.
states are +2, +3 and +6. Chromium(III)
S7. (a) The second transition series or 4d series oxide(green in colour) is amphoteric, i.e., it can
corresponding to the filling of 4d sublevel react as both acid and base. Its formula is Cr2O3.
consists of the following 10 elements of the 5^th
S16. (b) The gradual decrease in the atomic and ionic
period: Y(Atomic No. = 39), Zr, Nb, Mo, Tc, Ru,
radii of the lanthanides with an increase in
Rh, Pd, Ag and Cd(Atomic No. = 48).
atomic number is called lanthanide contraction.
S8. (c) The third transition series or 5d series It occurs due to the poor shielding effect of the 4f
corresponding to the filling of 5d sublevel electrons.
consists of the following 10 elements of the 6^th S17. (c) The small average decreases in the atomic size is
period: La(Atomic No. = 57); Hf(Atomic No. = responsible for a small decrease in
72), Ta, W, Re, Os, Ir, Pt, Au and Hg(Atomic No. = electronegativity and S.O.P of lanthanides. As the
80). size of the lanthanide ions decreases the
covalent character of M—OH bond increases and
S9. (c) All transition elements are d-block elements, but
hence basic strength decreases.
all d-block elements are not transition elements.
Zinc has the electronic configuration [Ar] S18. (a) All lanthanides are soft metals with silvery white
3d104s2, and the configuration of the Zn2+ ion is colour. They tarnish rapidly by air. With increase
 in atomic number, the harness of these metals S30. (c)
also increases. The melting points of the
lanthanides ranges from 1000 to 1200K but ASSERTION AND REASONING
samarium melts at 1623K.
S1. (a) A Catalyst is a substance which accelerates the
S19. (b) The first five elements of Lanthanides are:
rate of a chemical reaction without undergoing
Lanthanum(La) – 57
any change in its chemical composition or mass
Cerium(Ce) – 58
during the reaction. A catalyst accelerates the
Praseodymium(Pr) – 59
rate of a reaction by lowering the activation
Neodymium(Nd) – 60
energy. Transition metals are efficient catalysts.
Promethium(Pm) – 61
For example, Ni, Pd and Pt are used for the
S20. (b) The atomic numbers of Erbium, Thulium, hydrogenation of alkenes.
Ytterbium and Lutetium is 68, 69, 70 and 71 Transition metals usually contain incomplete d-
respectfully. So the last element of lanthanide orbitals(so that they can show variable valency)
series is Lutetium with electronic configuration and provide a larger surface area for adsorption.
[Xe]4f145d16s2. Hence, both Assertion and Reason are correct
and Reason is the correct explanation for
S21. (b) Because they are all metals, the transition
Assertion.
elements are often called the transition metals.
As a group, they display typical metallic S2. (a)
properties and are less reactive than the metals S3. (a)
in group 1 and group 2 of the periodic table. S4. (d) Copper corrodes at negligible rate in unpolluted
S22. (a) Near the end of the period, the increased air, water and non-oxidising acids. Pure copper
electron-electron repulsions between added and the high copper alloys can be considered to
electrons in the same orbitals are greater than exhibit similar resistance to most Corrosive
the attractive forces due to increased nuclear environments. They possess excellent resistance
charge. This result in the expansion of the to atmospheric environments.(corrosion is a
electron cloud and therefore, increases the spontaneous process for which free energy
atomic size. change must be negative.
S5. (a) Promethium is a man-made element because it
S23. (c) In the atoms of the second transition series, the has been prepared by artificial me
number of shells increases and so, their atomic
radii is greater than that of the first transition TRUE/FALSE
series. The atomic radii of the second and third
transition series are almost same due to
S1. (a) It is because Mn2+ has 3d5 configuration which
lanthanoid contraction.
has extra stability.
S24. (c)
S2. (b) Not Titanium but copper, because with +1
S25. (c) oxidation state an extra stable configuration
S26. (b) Alkaline KMnO4 is called Baeyer’s reagent. 3d10 results.
Baeyer’s reagent is an alkaline solution of cold S3. (a) Elements belonging to the d-block of the
potassium permanganate, which is a powerful periodic table are transition elements. The d-
oxidant making this a redox reaction. Reaction block of the periodic table, includes groups 3 to
with double or triple bond in an organic material 12. The boiling points and the melting points of
causes the colour to fade from purplish-pink to transition elements are high, due to the
brown. It is a syn addition reaction. delocalized d-electrons in metallic bonding and
S27. (c) Mercury is the only liquid metal at room these elements form coloured compounds and
temperature. It has a high coefficient of ions due to the d-d transition of metals.
expansion and boiling point. This helps use to S4. (b) The second transition series involves the filling
identify even the slightest change in of 4d− subshell not the 3d− subshell. This series
temperature of the surroundings. contains the elements which have an atomic
S28. (a) number from39 to 48 and Y, Zr, Nb, Mo, Tc, Ru,
Rh, Pd, Ag, and Cd. All of these elements involve
S29. (d)
the filling of the 4d subshell.