You’re on the right track now • .

CHAPTER - 4
D & F BLOCK ELEMENTS

• In the periodic table, element of group 3 - Second transition series or 4d-series Yt-
12 constitute the d block element trium (39Y) to Cadmium (48Cd).
(TRANSITION ELEMENT) Third transition series or 5d-series Lan-
• Two horizontal rows at the bottom of the thanum (57La) to Mercury (80Hg). Exclud-
periodic table (LANTHANOIDS & AC- ing 58Ce to 71Lu.
TINOIDS). constitute f block elements Fourth transition series or 6-d series Ac-
(INNER TRANSITION ELEMENTS) tinium (89Ac) to Copernicium (112Cn) ex-
• In transition elements d orbitals are succes- cluding 90Th to 103Lr.
sively filled with general outer electronic • General electronic configuration of outer
configuration (n-1)d1-10 ns 1-2 orbitals of these elements is (n-1)d1-10 ns1-2
TRANSITION ELEMENTS except for Pd where its electronic configu-
ration is 4d105s0. The (n-1) stands for the
• These elements which have partially filled inner d orbitals.
d – subshells in their ground state or any of
its oxidation states are called Transition Half and completely filled sets of orbitals
elements are relatively more stable.

Exception: General Properties of Transition Ele-

ments
• Zn, Cd, Hg does not have partially filled d
orbitals hence they are not regarded as • These are all metals and are good conduc-
transition elements. But they show some tor of heat and electricity.
resemblance to transition elements and are • They do not show vertical similarity as
called Pseudo- transition elements. other elements of periodic table. They
• Cr: 3d54s1 instead of 3d44s2 show similarities in properties.

Cu: 3d104s1 instead of 3d94s2 • They exhibit more than one oxidation
states.
Note:
• They show property of catalysis.
(i) Half and completely filled sets of or-
bitals are relatively more stable. • They form complex compounds.

(ii) There is less difference in energy be- • They form coloured complexes.
tween 3d and 4s subshell. • They show paramagnetism.
• There are mainly four series of the • They form interstitial compounds.
transition metals:
• They form many types of alloys.
First transition series or 3d-series Scan-
dium (21Sc) to Zinc (30Zn). • Generally, all the elements are strong, high
melting and boiling point and hard.

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 There is no substitute for hard work • .

Atomic And Ionic Radii • Thus Cr, Mo, W having maximum no of

unpaired electrons and are very hard met-
• The atomic radii decrease from left to right als, Zn, Cd and Hg are not so hard metals
with increase in atomicnumber but the de- due to the absence of unpaired d electrons.
crease in atomic size is small after mid-
way. Note:

• This is due to the increased screening ef- • Transition elements exhibit higher en-
fect of the electrons inthe (n-1) d orbital thalpies of atomization because of large
resulting in the cancellation of effective no. of unpaired electrons resulting in
nuclear charge. stronger bonding between the atoms.

• There is a slight increase in the atomic ra- • Energy required to convert metallic crystal
dii at the end of the series. Thisis due to into individual atom is known as enthalpy
the repulsion of electrons in the same sub- of atomization. In transition metals, it first
shell exceeding the effect of increased nu- increases to maximum in the middle of
clear charge. each series and then decreases.

Note: Melting And Boiling Point

• Atomic radii of Zr and Hf are 160pm and Melting point and boiling point of d- block ele-
159 pm respectively and have similar ments are very high due to strong metallic
physical and chemical properties due to bonding due to overlapping of (n-1)d orbitals
Lanthanide contraction.
• Covalent bonding by the unpaired elec-
(Filling of 4f orbital before 5d robtal) trons causes the increase in melting point
and boiling point.
• In the case of group 11 & 12 elements, the
d-orbital is full with ten e– and shield the • Melting and boiling point increase up to
electrons present in the higher s-orbital. So group 6 and then decrease
group 11 & 12 elements like Cu & Zn have
• Among metals Tungsten has the highest
bigger size than its earlier elements in the
melting points
block.
Metallic Character • Zn, Cd and Hg have comparatively low
melting point.
• d - Block elements have low ionization
energy and hence they easily form cations. Ionisation Enthalpies
Also these metals have large no of oxida- Ionization energy is the energy needed to re-
tion states. move the valence e– from the atom/ion and is
directly related to the force of attraction on the
• They are malleable and ductile, form alloys
e-.
andare good conductors of heat and elec-
tricity Hence, larger the nuclear charge and smaller
the radii of the electron, larger will be the ioni-
• Metallic strength increases up to middle of
zation energy (IE).
the periodic table due to the increase in the
unpaired electrons. • In a transition series, the ionization en-
thalpies increase with increase in atomic

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Whatever you are, be a good one • .
number. (General trend) (i) The multiple oxidation state of transi-
tion elements is due to the availability
• But the value of ΔiH depends heavily on
of d electrons for bond formation.
the electronic configuration. Atoms or ions
with half-filled and fully filledd- orbitals Oxidation states of the first transition
show higher ionization enthalpies. series

• IE of s - block < I.E of d - block < I.E of p

block
Example:

• 1st ΔiH of Zn is high due to completely

filled d orbital

• 2nd ΔiH of Cr > Mn because Cr + has d5 con- (i) Common oxidation state of 1st series
figuration and Mn+ has 3d5 4s1configuration is +2 ( except Sc+3)
• 3rd ΔiH of Mn is high because Mn2+ has 3d5 (ii) +2 and +3 oxidation states are mostly
configuration. ionic, but higher oxidation states are
covalent
Standard Electrode Potential
(iii) Within the same group maximum oxi-
• The general trend towards less negative E dation state increases with atomic
values across the series is related to the number
general increase in the sum of the first and
second ionization enthalpies. Eg: Fe 2+ and Fe3+
But, Ruthenium [Ru] and Osmium
•
[Os] in the same group +4, +6, +8
by its hydration enthalpy
and hence Cu shows a positive E0 value. (+8 is the maximum oxidation state
The +ve E0 value of Cu accounts for its shown by transition elements)
inability to liberate H2 from acids
(iv) Low oxidation states such as +1and
• Only oxidizing acids (HNO3 and and 0 are also found in some transi-
conc.H2SO4) react with Cu. tion elements

Oxidation State Eg: [Ni (CO4)]Ni (0) & [Fe (CO) 5]

Fe (0)
• Transition element show variable oxidation
states because of the small difference be- Magnetic Properties
tween the energies of electrons in the ‘ns’ Materials are classified by their interaction
and (n-1) d orbitals .Thus electrons from ns with the magnetic field as
and (n-1) d orbitals can be used for com-
pound formation. • Diamagnetic:- if repelled

• Variable oxidation state is also related to • Paramagnetic:- if attracted

their electronicconfiguration.
• Ferromagnetic:- if it can retain the larger
magnetic nature even in the absence of

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Be better than yesterday • .
magnetic field. pear complementary blue green.
⇒ Paired e– s cause diamagnetism, unpaired  Hydrated Co2+ ions absorb radiation in the
e- results in paramagnetism and aligned blue green region and therefore appear in
together unpaired e-s produce ferromag- red in sunlight.
netism.  Colours of the ions varies with its O.S. The
d block elements and their ions exhibit Cr+6 as in potassium dichromate (K2Cr2O7)
this behaviour depending on the unpaired yellow in colour. Whereas Cr+3 and Cr+2
e-s. are generally green & blue respectively.

⇒ Unpaired e-s contribute to orbital magnetic  Colour of the compound is dependent on

moment and spin magnetic moment. the complexing or coordinating group also.

However for 3d series the orbital angular For Ex. Cu+2 shows light blue colour in the
moment is negligible and the approximate presence of water as ligand but the deep
spin only magnetic moment is given by blue colour in the NH3 as the ligand.
the formula-  Transition metals ions which have-

• Completely filled d-orbitals having no

vacant d-orbitals having no vacant d-
orbitals for excitation of electrons are
Where, S - total spin
colourless.
n - no. of unpaired e-
Cu2+(3d10), Zn2+(3d10), cd+2(4d10), Mg2+
(UNIT): BM - Bohr magneton (5d10) and Zn, cd & Hg are colourless.
Colour • Transition metal ions which have com-
pletely empty d-orbitals without d-e-s
• The transition elements exhibit color, when
are also colourless.
lights of some frequencyare absorbed and
electrons from a lower d-orbital become Sc3+(3d0) & Ti4+(3d0) ions are colour-
excited to a higher energy d-orbital. This less.
frequency generally lies in the visible re-
Formation Of Complex Compounds
gion and they exhibit color corresponding
to the light absorbed. • The transition elements (metals) form large
no of complex compounds due to the
d-d Transition
smaller size of the metal ions, their high
One way is the excitation of an e– to a higher ionic charges and the availability of d or-
energy level. bitals for bond formation.
In transition elements ions, the presence of d-e– Eg: [Fe (CN) 6]3- & [Fe (CN) 6]4-
and empty d-orbital shall result in colour for-
mation due to valence e– excitation and d e–
Catalytic Properties
excitation. This is called d-d transition. Transition metals and their compounds
Example: shows catalytic activity because of their
ability to adopt multiple oxidation state and
[Cu(H2O)6]2+ ions absorb red radiation and ap- to form complexes.
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Education is the key to success • .
Bronze (copper -tin)

• Ferrous alloys (with Cr, V, W, Mo & Mn)

form varieties of steel.
• Fe in Haber process
TOPIC - 1
• Ni in catalytic, hydrogenation
Objective Type Questions
They take the reaction through a path of low
activation energy by: 1. Electronic configuration of a transition
element X in +3 oxidation state is 3d5.
• Providing a large surface area for absorp- What is its atomic number?
tion and allowing sufficient time to react.
(a) 25 (b) 26
• May interact with the reactants through
their empty orbitals. (c) 27 (d) 24

• May actively interact by redox reaction 2. The electronic configuration of Cu (II) is

through their multiple oxidation state. 3d9whereas that of Cu (I) is 3d10. Which
of the following is correct?
Formation Of Interstitial Compounds
(a) Cu (II) is more stable
• Interstitial compounds are those which are
(b) Cu (II) is less stable
formed when small atoms like H, C or N
are trapped inside the crystal lattice of met- (c) Cu (I) and Cu (II) are equally stable
als.
(d) Stability of Cu (I) and Cu (II) de-
• Eg: TiC, Mn4N, Fe3H, VH0.56 and TiH1.7 pends copper salts

Properties of Interstitial Compounds 3. Metallic radii of some transition elements

are given below. Which of these elements
• They have high melting points, higher than will have highest density?
pure metal.

• They are very hard some borides approach Element Fe Co Ni Cu

Diamond in hardness.

• They retain metallic conductivity. Metallic

• They are chemically inert. radii/ 126 125 125 128
pm
Alloy Formation
Transition Metals Form A Large No. Of Al- (a) Fe (b) Ni
loys (c) Co (d) Cu
• Alloys are homogeneous solid solutions in 4. The magnetic nature of elements depends
which the atom of onemetal are distributed on the presence of unpaired electrons.
randomly among the atoms of other,[ met- Identify the configuration of transition
als should have comparable radii (15% of element, which shows highest magnetic
each other)] moment.
Eg: Brass (copper- zinc)
th
12 Chemistry Winner’s Coaching Centre D & F Block Elements
 Respect your parents, world will respect you • .
(a) 3rd7 (b) 3rd5 11. Predict which of the following will be col-
oured in aqueous solution?
(c) 3rd8 (d) 3rd2
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+.
5. Generally, transition elements form col-
Give reasons for each.
oured salts due to the presence of un-
paired electrons. Which of the following 12. Account for the following:
compounds will be coloured in solid
Zn, Cd, Hg are considered as d-block ele-
state?
ments but not as transition elements.
(a) Ag2SO4 (b) CuF2
13. Which transition metal of 3d series does
(c) ZnF2 (d) Cu2Cl2 not show variable oxidation states?
6. Interstitial compounds are formed when 14. Why do transition metals and their com-
small atoms are trapped inside the crystal pounds show catalytic activity?
lattice of metals. Which of the following
15. Why are melting points of transition met-
is not the characteristic property of inter-
als high?
stitial compounds?
16. Why is Cu2+ ion coloured while Zn2+ ion
(a) They have high melting points in
is colourless in aqueous solution?
comparison to pure metals
17. Account for the following:
(b) They are very hard
Copper (I) compounds are white whereas
(c) They retain metallic conductivity
Copper (II) compounds are coloured.
(d) The are chemically very reactive
18. Give reason and select one atom/ion
Short Answer Questions (2 Marks) which will exhibit asked property:
7. What are the transition elements? Write (i) Sc3+ or Cr3+ (exhibit diamagnetic be-
the two characteristics of the transition haviour)
elements.
(ii) Cr or Cu (high melting and boiling
8. Explain the following observations: point)
(i) Copper atom has completely filled d 19. Out of Cu+ and Cu2+, which ion is unsta-
orbitals (3d10) in its ground state, yet ble in aqueous solution and why?
it is regarded as a transition element.
Short Answer Questions (3 Marks)
(ii) Cr2+ is a stronger reducing agent than
Fe2+ in aqueous solutions. 20. Why do transition elements show variable
oxidation states?
9. Explain why Cu+ ion is not stable in aque-
ous solution? (i) Name the element showing maximum
number of oxidation states among the
OR first series of transition metals from
Explain why Cu (I) ion is not known in Sc (Z = 21) to Zn (Z = 30).
aqueous solution? (ii) Name the element which shows only
10. Calculate the ‘spin only’ magnetic mo- +3 oxidation state.
ment of M2+ (aq) ion. (Z = 27)
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 A minute is not as minute as it seems to be • .
21. Give reasons for the following. 26. Account the following:
(i) Mn+3 is a good oxidizing agent. (i) Transition metals form large number
of complex compounds.
(ii) The lowest oxide of transition metal
row of transition metals (3d –series).
is basic whereas the highest oxide is
(iii) Although F is more electronegative amphoteric or acidic.
than O, the highest fluoride of Mn is
(iii) E0 value for the Mn3+ / Mn2+ couple
MnF4, whereas the highest fluoride is
is highly positive (+1.57 V) as com-
Mn2O7.
pared to Cr3+ / Cr2+.
22. How would you account for the follow-
27.
ing?
(i) Of the d4 species, Cr2+ is strongly re- Cr Mn Fe Co Ni Cu
ducing agent while manganese (III) is E0
2+
strongly oxidizing agent. (M /M)
-0.91 -1.18 -0.44 -0.28 -0.25 +0.34
(ii) Cobalt (II) is stable in aqueous solu-
tion but in the presence of complex- For the given data of E0 values, answer
ing regents, it is easily oxidised. the following questions.
(iii) The d1 configuration is very unstable
in ions.
23. Give reasons: positive?

(a) Eo value for Mn3+ /Mn2+ couple is

much more positive than that for as compared to other elements?
Fe3+ /Fe2+.
(iii) Which is a stronger reducing agent
(b) Iron has higher enthalpy of atomiza- Cr2+ or Fe2+? Give reason?
tion than that of copper.
Long Answer Questions (5 Marks)
(c) Sc3+ is colourless in aqueous solution
whereas Ti3+ is colured. 28. Explain giving reasons.
24. The halides of transition elements become (i) The enthalpies of atomization of the
more covalent with increasing oxidation transition metals are high.
state of the metal Why?
(ii) Transition metals and many of their
25. Following ions are given: compounds show paramagnetic be-
haviour.
Cu+, Cr2+, Cu2+, Fe2+, Fe3+, Mn3+ identify
the ion which is (iii) The transition metals generally from
coloured compounds.
(i) A strong reducing agent.
(iv) Transition metals and their many
(ii) Unstable in aqueous solution.
compounds act as good catalyst.
(iii) A strong oxidizing agent.

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 You are good enough, respect yourself • .
29. Account for the following. 2. Acidification Of Sodium Chromate To
Sodium Dichromate
(i) Mn2+ is more stable than Fe2+ to-
wards oxidation to +3 state. • The yellow solution of sodium chromate is
(ii) The enthalpy of atomization is low- filtered and acidified with sulphuric acid to
est for Zn in 3d– series of the transi- give a solution of orange sodium dichro-
tion elements. mate.

(iii) Identify the metal in MO3F and justi- 2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na++
fy your answer. H2O

(iv) The Eo value for the Mn3+ / Mn2+ 3. Conversion Of Sodium Dichromate To
couple is much more positive than Potassium Dichromate
that for Cr3+ /Cr2+ couple. • Prepared by treating the solution of sodium
(v) Transition metals from a large num- dichromate with potassium chloride.
ber of complexes. Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
30. Write down the number of 3d– electron in Properties:
each of the following ions; Ti2+, V2+, Cr3+,
Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+. The chromate and dichromate ion are intercon-
Indicate how would you expect the five vertible in aqueous solution depending upon
3d– orbitals to be occupied for these hy- pH of the solution. Chromate on acidification
drated ions (octahedral)? gives dichromate and the dichromate ion n
treating with alkali gives Chromate.
Some Important Compounds Of
2CrO4 2- + 2H+ → Cr2O7 2- + H2O
Transition Elements
Cr2O7 2- + 2OH- → 2CrO4 2- + H2O
Oxides and Oxoanions Of Metals:
The oxidation state of Chromium in chromate
• Except ‘Scandium’ all other metals form
oxides of the formula MO and they are and Dichromate is +6.
ionic. (when M is a transition metal) The structures of chromate ion, CrO42- and the
POTASSIUM DICHROMATE [K2Cr2O7] dichromate ion, Cr2O72-
• Potassium dichromate generally prepared whereas the dichro-
from chromite ore[FeCr2O4]. This prepa- mate ion consists of two tetrahedral sharing
ration involve three steps one corner with Cr–O–Cr bond angle of 126°.
1. Conversion Of Chromite Ore to Sodium
Chromate
• Chromite ore is first used with sodium car-
bonate in presence of air to form sodium
chromate.
4FeCr2O4+8Na2CO3+7O2 → 8Na2CrO4 +
2Fe2O3 + 8CO2

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Hard work beats talent when talent doesn't work • .

Sodium and potassium dichromate are strong (ii) Commercially it is prepared by the alka-
oxidizing agents. The sodium salt has a greater line oxidative fusion of MnO2 followed by
solubility in water and is extensively used as the electrolytic oxidation of manganate
an oxidizing agent in organic chemistry. Potas- (Vl).
sium dichromate is used as a primary standard
in volumetric analysis.
Oxidising Property
In acidic solution, the oxidising action can be
represented as
Cr2O72- + 14 H+ + 6e- → 2Cr3+ + 7H2O

Acidified potassium dichromate will oxidise

(iii) In the laboratory, a manganese (II) ion
1. Iodides to iodine salt is oxidised by peroxodisulphate to
permanganate.
6I- → 3I2 + 6e-
2. sulphides to sulphur
3H2S → 6H+ + 3S + 6e- Properties:
3. tin (II) to tin (IV) Potassium permaganate forms dark purple
crystals which are isostructural with those of
3Sn2+ → 3Sn4+ + 6e-
KClO4, when heated it decomposes and liber-
4. Iron (II) salts to iron (III) ates O2.
6Fe2+ → 6Fe3+ + 6e- 2KMnO4 → K2MnO4 + MnO2 + O2
Uses:
Used as oxidizing agent, disinfectant, in volu-
metric analysis, for tanning of leather and in
chromyl chloride test.
Potassium Permagnate (KMnO4)
Potassium permagnate is commercially pre-
pared from MnO2.The preparation involves
two steps, • The magnate and permagnate ions are tet-
rahedral.
(i) MnO2 is fused with KOH to form potassi-
um magnate (K2MnO4). • The green magnate is paramagnetic with
one unpaired electron but the permanga-
K2MnO4 is electrolytically oxidized to po-
nate is diamagnetic
tassium permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + Oxidising property
2H2O KMnO4 is a good oxidising agent, in acidic,
2- +
3MnO + 4H → 2MnO + MnO + 2H2O - basic, and neutral media. The oxidising action
in acidic medium is due to the reaction;
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Don't blame distraction, improve your focus • .

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O zinc oxide catalyses the oxidation :
A few important oxidising reactions of
KMnO4 are given below :
Note:
1. In acid solutions:
Permanganate titrations in presence of hydro-
(a) Iodine is liberated from potassium io- chloric acid areunsatisfactory since hydrochlo-
dide: ric acid is oxidised to chlorine.
10I- + 2MnO4- + 16H+ → 2Mn2+ + Uses:
8H2O + 5I2
Used as oxidising agent in acidic, basic and
(b) Fe2+ ion (green) is converted to Fe3+ Neutral medium
(yellow):
Used as a primary standard in volumetric anal-
5Fe2+ MnO– 4 + 8H+ → Mn2+ + 4H2O ysis.
+ 5Fe3+
Used for bleaching wool, cotton and other fi-
(c) Oxalate ion or oxalic acid is oxidised bres.
at 333 K:
For decolourisation of oils
TOPIC - 2
(d) Hydrogen sulphide is oxidised, suphur
Objective Type Questions (1 Marks)
being precipitated:
1. Which of the following reactions are dis-
proportionation reactions?
i) Cu+ → Cu2 + Cu
(e) Sulphurous acid or sulphite is oxidized
to a sulphate or sulphuric acid:

(f) Nitrite is oxidised to nitrate

(a) (i)
(b) (i), (ii) and (iii)
2. In neutral of failntly alkaline solutions:
(c) (ii), (iii) and (iv)
(a) A notable reaction is the oxidation of
iodide to iodate: (d) (i) and (iv)
2. When acidified K2Cr2O7 solution is added
to Sn2+ salt then Sn2+ changes to
(b) Thiosulphate is oxidised almost quan-
(a) Sn (b) Sn3+
titatively to sulphate:
(c) Sn4+ (d) Sn+

(c) Manganous salt is oxidised to

MnO2:the presence of zinc sulphate or
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Value yourself to fight for happiness • .

3. When KMnO4 solution is added to oxalic (a) Both (A) and (R) are correct, (R) is
acid solution, the decolourisation is slow the correct explanation of (A).
in the beginning but becomes instantane-
(b) Both (A) and (R) are correct, (R) is
ous after some time because
not the correct explanation of (A).
(a) CO2 is formed as the product
(c) (A) is correct; (R) is incorrect.
(b) reaction is exotherm
(d) (A) is incorrect; (R) is correct.
–
(c) MnO4 catalyses the reaction
7. Assertion (A) First ionization enthalpy of
(d) Mn2+ acts as autocatalyst Cr is lower than that of Zn.
4. On addition of small amount of KMnO4 to Reason (R) Ionization enthalpy of Cr is
concentrated H2SO4, a green oily com- lower than Zn due to the stability of d5-
pound is obtained which is highly explo- electron configuration.
sive in nature.
8. Assertion (A) Cr2+ is reducing, while
Identify the compound from the follow- Mn3+ is oxidising even both have d4 con-
ing. figuration.
(a) Mn2O7 (b) MnO2 Reason (R) Configuration of Cu changes
from d3 to d4.
(c) MnSO4 (d) Mn2
9. Assertion (A) KMnO4 oxidises oxalic
5. KMnO4 acts as an oxidising agent in alka-
acid to CO2 and itself changes to Mn2+
line medium. When alkaline KMnO4 is
ion.
treated with KI, iodide ion is oxidised
to…….. Reason (R) KMnO4 acts as an oxidisiong
agent.
(a) I2 (b) IO-
10. Assertion (A) The highest oxidation state
(c) IO3- (d) IO4-
of Osmium is +8.
6. KMnO4 acts as an oxidizing agent in acid-
Reason (R) Osmium is a 5d– series ele-
ic medium. The number of moles of
ment.
KMnO4 that will be needed to react with
one mole of sulphide ions in acidic solu- 11. Assertion (A) Transition metals are good
tion is catalysts.
Reason (R) V2O5 or Pt is used on the
preparation of H2SO4 by contact process.
Short Answer Questions (2 Marks)
12. Describe the oxidising action of potassi-
Assertion and Reasoning um dichromate and write the ionic equa-
tions for its reaction with (i) iodide (ii)
Directions: In the following questions. an As-
iron (II) solution and (iii) H2S.
sertion (A) is followed by a corresponding
Reason (R) Use the following keys to choose 13. Explain why does colour of KMnO4 dis-
the appropriate answer. appear when oxalic acid is added to its
solution in acidic medium?
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Patience is waiting with good attitude • .

14. Complete the following equations. agent. Identify compound (A) and (B).
Write chemical reactions involved.
23. Describe the preparation of potassium di-
chromate from chromite ore. What is the
effect of the increasing pH on a solution
of potassium dichromate?
24.(i) Give reasons for the following:
What can you assert about the nature
(a) Compounds of transition elements
of KMnO4 and K2Cr2O7?
are generally coloured.
16. Complete and balance the following
(b) MnO is basic while Mn2O7 is acid-
chemical equations:
ic.
(ii) Calculate the magnetic moment of a
divalent ion in aqueous medium if its
17. Write the formula of an oxoanion of chro-
atomic number is 26.
mium (Cr) in which it shows the oxidation
state equl to its group number. 25. Complete the following chemical equa-
tions.
18. Write the formula of an oxoanion of man-
ganese (Mn) in which it shows the oxida-
tion state equal to its group number.
19. Write the balanced ionic equations show-
ing the oxidizing action of acidified di-
chromate (Cr2O72-) solution with (i) iron
(II) and (ii) tin (II) ion. 26. When orange solution containing Cr2O72-
ion. Is treated with an alkali, a yellow so-
20. Complete the balance the following chem-
lution is formed and when H+ ions are
ical equations:
added to yellow solution, an orange solu-
(i) Fe2+ + MnO4- + H+ → tion is obtained. Explain, why does this
(ii) MnO4- + H2O + I- → happen?

21. Complete the following equation: 27. How do you prepare:

(i) 2MnO4- + 16H+ + 5S2- → (i) K2MnO4 from MnO2?

(ii) Na2Cr2O7 from Na2CrO4?
Long Answer Questions
Short Answer Questions (3 Marks) 28. Describe the preparation of potassium
permanganate. How does the acidified
22. Mixed oxide of iron and chromium is
permanganate solution react with (i) iron
fused with sodium carbonate in free ac-
(II) ions, (ii) SO2 and (iii) oxalic acid?
cess of air to form a yellow coloured com-
pound (A). On acidification, the com- Write the ionic equations for the reac-
pound (A) forms an orange coloured com- tions.
pound (B), which is a strong oxidizing
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Sometimes you win, sometimes you learn • .

29.(i) Name a compound of is also includes with them. Similarly Actinium

(89Ac) is included along with the actinides be-
(a) Transition metal which is used in
cause of its close resemblance with them.
the manufacture of sulphuric acid.
(b) Transition metal that is used in The Lanthanoids or Lanthanides
Haber’s process for the manufac- The 14 elements after Lanthanum of the 6th
ture of ammonia. period are called lanthanides or lanthanoids or
Rare earths. They include elements from 58Ce
(c) Transition metal that have light
to 71Lu. General electronic configuration of
sensitive properties and act as val-
lanthanoids are 6s2 5d0-1 4f1-14. In these ele-
uable source in photographic in-
ments, last electron enters into the 4f orbital
dustry. till Yb(4f14).
(ii) Write the equations which are involved Atomic and Ionic radii - Lanthanide
in the oxidation of hydrogen sulphide
contraction
to sulphur by potassium permanganate
solution. In Lanthanides, the atomic and ionic radii de-
crease regularly from Lanthanum to lutetium.
30. When chromite ore is fused with sodium
This regular decrease in atomic and ionic radii
carbonate in free access of air and the
along the lanthanide series (though very slight-
product is dissolved in water, a yellow
ly) is called lanthanide contraction.
solution of compound (A) is obtained. On
acidifying the yellow solution with sul- Reason: In lanthanides, as the atomic number
phuric acid, compound (B) is crystalised increases, the nuclear charge increases one by
out. When compound (B) is treated with one and the electrons are added to the antipe-
KCl, orange crystals of compound (C) nultimate f subshell. Due to the diffused shape,
crystallise out. Identify (A), (B) and (C) f orbitals have poor shielding effect. So the
and write the reactions involved. nucleus can attract the most electrons strongly
and as a result, the radii decreases.
31. When MnO2 is fused with KOH in the
presence of KNO3 as an oxidizing agent, Consequences:
it gives a dark green compound (A). Com-
pound (A) disproportionate in acidic solu- (i) Due to Lanthanide Contraction, the 2nd
tion to give purple compound (B). An al- and 3rd row transition series elements have
kaline solution of compound (B) oxidises similar radii.
KI to compound (C) whereas an acidified
(ii) Lanthanides have similar physical proper-
solution of compound (B) oxidises KI to
ties and they occur together in nature. So
(D). Identify (A), (B), (C) and (D).
their isolation is difficult
The Inner Transition Elements (iii) The basic character of their hydroxides
The elements in which the last electron enters decreases from lanthanum to lutetium i.e.
the antipenultimate f- subshell are called f- La (OH) 3 is more basic than Lu (OH) 3.
block elements. They include lanthanides of 6th
Oxidation number
period and actinides of 7th period. They are also
called inner transition elements. Since lantha- In Lanthanoids, the most common oxidation
num (57La) closely resemblances lanthanides, it state is +3.However, +2 and + 4 ions in solu-

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Learning is never done with errors and defeats • .

tion or in solid compounds are also obtained. • A well-known alloy is mischmetal which
This irregularity arises from the extra stability consists of a lanthanoids (~ 95%) and iron
of empty, half-filled or filled state but only in (~ 5%) and traces of S, C, Ca andAl.
oxides MO2.
• Mixed oxides of lanthanoids are employed
Eu and Yb shows +2 oxidation state because of as catalysts inpetroleum cracking.
the stable f7 or f14configuration. Sm also shows
+2 oxidation state. • Some individual Ln oxides are used as
phosphors in televisionscreens and similar
General properties of Lanthanoids fluorescing surfaces.
All Lanthanoids are silvery white soft metals The Actinides
and tarnish rapidly in air. Their hardness in-
creases with increasing atomic number. They The 14 elements after the Actinium in the 7th
have typical metallic structure and are good period of modernperiodic table are called Acti-
conductors of heat and electricity. Most of nides or Actinoids. Last e– filled in 5f orbital.
Lanthanoids ions are coloured both in solid Include elements from Thorium (90Th) and
states and in aqueous solutions. Lawrencium (103Lr).Most of them are artificial-
Colour of these ions is due the presence of f ly prepared and are short lived. They are radio-
electrons. But La3+ or Lu3+ ion are colourless. active.
The lanthanide ions other than the f0 type (La3+ General electronic configuration: 5f1-14 6d0-1
and Ce4+) and f14 type (Yb2+ and Lu3+) are all 7s2
paramagnetic. The paramagnetism rises to
maximum in Neodymium. The elements after Uranium are called Trans
Uranium elements.
Lanthanoids are highly dense metals and have
high melting point. They form alloys with oth- Atomic and Ionic radii:
er metals especially Fe. The first ionisation en-
thalpies of lanthanoids are around 600 kJ mol In Actinoid series, the atomic and ionic radii
-1
, the second about 1200 KJ mol-1 decreases regularly from left to right. This is
known as actinoid contraction.
Oxidation state:
Common oxidation state of Actinides is
+3.The elements in the first half of the series
show higher oxidation states. The maximum
oxidation states increases from +4 in Th to +5,
+6 and +7 in Pa, U and Np but decreases in
succeeding elements. The Actinoids resemble
the lanthanoids in having more compounds in
+3 state than in the +4 state.
Similarities between Lanthanoids and Ac-
Uses of Lanthanides: tinoids

• Production of alloy steels for plates and There are some similarities between lantha-
pipes. noids and actinoids, which are:

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Knowledge increases by sharing • .

(i) Both exhibit +3 oxidation state predomi- Chemical reactivity

nantly.
Tendency to Less More
(ii) Both are electropositive and have high
form com-
reactivity.
plexes
(iii) Like lanthanoid contraction, there is actin-
oid contraction also. Radioactivity Except pro- These are
(iv) They show ion exchange behavior. methium, radioactive
these are non substances.
(v) In both series, f-orbitals are being progres- -radioactive
sively filled. substances.
Difference between lanthanoids and actin-
oids Basic char- These are These are
acter less basic. more basic.
Property Lanthanoids Actinoids
Oxidation They show In addition to Applications of f-Block Elements
states mainly +3 +3 oxidation (i) Lanthanoids are used as catalyst in petro-
oxidation state, actinoids leum cracking.
state. +2 and also show
(ii) Lanthanoids are used in producing alloys.
+4 oxidation higher oxida-
states also tion states like (iii) Oxides of lanthanoids are used to produce
exist. +4, +5, +6 and red colour on television screen.
+7. (iv) Actinoids are used in nuclear reactors for
the production of electricity.
Binding en- Binding en- Binding ener-
ergies ergies of 4f gies of 5f are (v) Actinoids are also used for the synthesis
are higher. lower. of transuranic elements.

Shielding They have They have

TOPIC - 3
effect poor shield- even poor Objective Type Questions (1 mark)
ing effect. shielding ef-
fect than lan- 1. Which of the following has abnormally
thanoids low value of third ionization enthalpy.

Magnetic They are par- They are also (a) Lanthanum

properties amagnetic paramagnetic, (b) Gadolinium
and their but their mag-
(c) Lutetium
magnetic netic proper-
properties ties cannot be (d) All of the above
can be easily easily ex-
2. Which of the following oxidation state is
explained. plained.
common for all lanthanoids ?
(a) +2 (b) +3
(c) +4 (d) +5

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Never give up, never stop learning • .

3. There are 14 elements in actinoid series. Reason (R) Colour of these ions due to
Which of the following elements does not the presence of f-electrons.
belong to this series ?
Short Answer Questions (2 marks)
(a) U (b) Np
7. Write one similarity and one difference
(c) Tm (d) Fm between the chemistry of lanthanoids and
4. Outermost electronic configuration of that of actinoids.
lanthanide is 8. What are the inner-transition elements ?
(a) 4f1-14 5d0 6s2 Decide which of the following atomic
numbers are of the inner-transition ele-
(b) 4f1-14 5d0-1 6s2 ments 29,59,74,95,102, 104?
(c) 4f0-14 5d0-2 6s2 9. Actinoids contraction is greater from ele-
(d) 4f0-14 5d1 6s2 ment to element than lanthanoids contrac-
tion. Why?
5. Choose the appropriate option about the
misch metal. 10. Although, Zr belongs to 4d and Hf be-
longs to 5d transition series but it is quite
(a) It is an alloy which consist of a lan- difficult to separate them, why?
thanoid metal (~95%) and iron
(~5%) and traces of S, C, Ca and Al 11. Name the members of the lanthanoids se-
ries which exhibit +4 oxidation states and
(b) Used in Mg based alloy to produce those which exhibit +2 oxidation states.
bullets, shell and lighter flint Try to correlate this type of behaviour
(c) It finds application in making aero- with the electronic configuration of these
plane body elements.

(d) Both (a) and (b) 12. Chemistry of actinoids is complicated as

compared to lanthanoids. Give two rea-
Assertion & Reasoning (1 mark) sons.
DIRECTION: In the following questions. An 13. Give reasons:
Assertion (A) is followed by a corresponding
Reason (R) Use the following keys to choose Actinoids show irregularities in their elec-
the answer. tronic configurations.

(a) Both (A) and (R) are correct, (R) is 14. How would you account for the follow-
the correct explanation of (A). ing:

(b) Both (A) and (R) are correct, (R) is Actinoid contraction is greater than lan-
not the correct explanation of (A). thanoid contraction?

(c) (A) is correct ; (R) is incorrect. Short Answer Questions (3 marks)

(d) (A) is incorrect ; (R) is correct. 15. Compare the chemistry of actinoids with
that of the lanthanoids with reference to
6. Assertion (A) Many trivalent lanthanoid
ions are coloured both in solid state and in (i) Electronic configuration
aqueous solution. (ii) Oxidation state

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Make your parents proud and be happy yourself • .

(iii) Chemical reactivity ANSWER

16. What are alloys? Name an important alloy
TOPIC - 1
which contains some of the lanthanoids
metals. Mention its uses. 1. (b) 26
17. Which is the last element in the series of 2. (a) Cu (II) is more stable
the actinoids ? Write the electronic con- 3. (d) Cu
figuration of this element. Comment on
the possible oxidation state of this ele- 4. (b) 3d5
ment. 5. (b) CuF2
18. What is lanthanoid contraction? Name an 6. (d) The are chemically very reactive
important alloy which contains some of
the lanthanoid metals. 7. Elements which in their ground state or in
any of their oxidation state have partially
19. Give three points between lanthanoids filled d-orbital are called transition ele-
and actinoids. ments. The name transition given to the
Long Answer Questions (5 marks) elements of d-block is only because of
their position between s-block and p-
20.(i) Yb2+ acts as a reductant while Tb4+ act block elements.
as an oxidant. Why ?
The two characteristics of transition ele-
(ii) Account for the following. ments are:
(a) Paramangnetism is shown by lan- (i) They show variable oxidation states.
thanoid ions. Comment.
(ii)They generally form coloured com-
(b) Lanthanoids do not form their pounds.
carbonyl compounds.
8.(i) Because it has incompletely filled d-
21.(i)(a) Which transition element in 3d series orbitals in one of its oxidation states i.e.
Cu2+ ([Ar]3d9).

(b) Name a member of lanthanoid series (ii) Cr2+ ([Ar] 3d4) changes to Cr3+ ([Ar]
which is well known to exhibit +4 3d3) while Fe2+ ([Ar]3d6) changes to Fe3+
oxidation state and why ? ([Ar] 3d5).

(ii)(a) The highest oxidation state is exhib- In aqueous medium, the configuration
ited in oxonions of transition metals. [Ar] 3d3 is more stable than the configu-
ration [Ar] 3d5 . Hence, Cr2+ is a strong-
(b) HCl is not used to acidify KMnO4 er reducing agent.
solution.
9. In aqueous solution, copper (I) Undergoes
(c) Transition metals have high enthalpy disproportionation reaction.
of atomization.
2Cu2+ (aq) → Cu2+ + Cu (s)
The highest stability of Cu2+ ion in aque-
ous solution is due to negative enthalpy of
hydration.
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Reading lights up your world • .

Hence, Cu+ is not known (or unstable) in 14. Transition metal and their compounds
aqueous solution. show catalytic properties because of the
following reason:
10. The valence electronic configuration of
cobalt (Co) is 3d7, 4s2. (i) Due to their variable oxidation state,
they form an intermediate complex,
M2+ (aq) ion means, it loses two electrons.
there by providing a new path for re-
Hence, valance electronic configuration action.
becomes d7.
(ii) Availability of empty d-orbital which
Now, Number of unpaired electrons = 3 provides good surface area for reac-
tion.
Spin only magnetic moment
15. Melting point of transition metal is high
because of the involvement of greater
number of electrons from (n-1) d in addi-
Where n = number of unpaired electrons
tion to the ns electrons in the interatomic
Putting n = 3 metallic bonding.
Generally, greater the number of unpaired
electrons, higher is the melting point.
Final answer: 16. Configuration of Cu+2 -[Ar]3d9
μ = 3.87 BM Zn-2 -[Ar]3d10
11. Transition metal ions with incompletely Copper has an unpaired electron which
filled d orbitals are colored and those with acts as a F- centre and allows electron
completely filled d orbitals (or vacant d transition in visible region importing col-
orbitals) are colorless. our while Zn+2 is having no unpaired elec-
Ti3+ , V3+ , Mn2+ and Co2+ are colored due trons hence colourless.
to d-d transition in incompletely filled d 17. Copper (I) compounds are white whereas
orbitals. Copper (II) compound are colored be-
Cu+ , Sc3+ are colorless due to completely cause, in Cu+1 (3d10) there is absence of
filled and empty d orbitals respectively. unpaired electrons while in Cu+2 (3d9)
compounds are colored due to unpaired e-
12. Transition metals are defined as the ele- shows d-d transition.
ments having incompletely filled d orbit-
18.(i) Sc = [Ar] 3d1 4s2 ; Sc3+ = [Ar] ; it has no
als. Since Zn, Cd and Hg have completely
unpaired electron so diamagnetic
filled d orbital, they are not regarded as
transition elements. Cr = [Ar] 3d5 4s1 ; Cr3+ = [Ar]3d3 ; it
has three unpaired electrons paramag-
13. All D-block elements have different val-
netic
ncies or different oxidation numbers.
Scandium (Sc=21) does not exhibit varia- (ii) Chromium (Cr) has a higher melting
ble oxidation states. The oxidation state point because of the half filled stability.
exhibited by scandium is +3. For scandi- Its electronic configuration is
um, the number of electrons in the 3d and 1s2 2s22p6 3s2 4s1 3d5.Due to the half
4s orbitals is 1 and 2 respectively filed d-orbital, the unpaired electrons
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Learn maths is to do maths • .

forms strong intermetallic bonds hence (iii) It is because oxygen can form multiple
resulting in high melting and boiling bonds, whereas fluorine can only form
point. Whereas the electronic configura- single bonds with metals.
tion of copper (Cu) is 1s2 2s22p63p6 4s2
22.(i) E0 value of Cr3+/Cr2+ is negative (-0.41
3d9 . It does not have filled stability.
V) while that of Mn3+/Mn2+ is positive
19. Cu+ is unstable in aqueous solutions. This (+1.57 V). This means that Cr2+ ions
is because in aqueous solution Cu+ under- can lose electrons to form Cr3+ ions
goes disproportionation to form a more and acts as a reducing agent while
stable Cu2+ ion. Mn3+ ions can accept electrons and can
act as an oxidizing agent.
(ii) Cobalt (III) ion has greater tendency to
The higher stability of Cu2+ ion in aqueous form complexes than cobalt (II) ion.
solution may be attributed to its greater Therefore, Co (II) ion being stable in
negative ΔHyd H0 then that of Cu+ . It com- aqueous solution, changes to Co (III)
pensates the second ionisation enthalpy of ion in the presence of complexing rea-
Cu involved in the formation of Cu2+ ions. gents and gets oxidized.
20. Transition elements show variable oxida- (iii) Ions of transition metals with d1 con-
tion state due to their ability of utilizing figuration tend to lose one electron to
single or multiple 4s and 3d electrons. acquire d0 configuration that is quite
(i) Mn (manganese) shows the maxi- stable. Therefore, such ions (with d1)
mum number of oxidation states. undergo either oxidation or dispropor-
tionation, hence unstable.
(ii) Scandium shows only +3 oxidation
state. 23.(a) Mn2+ compounds are more stable due to
half-filled d-orbitals. Fe2+ compounds
21.(i) Mn3+ /Mn2+ has large positive E0 value. are comparatively less stable as they
Hence, Mn3+ can be easily reduced to have six electrons in their orbitals. So,
Mn2+ because Mn2+ has half-filled elec- they tend to lose one electron from Fe2+
tronic configuration, so it is stable and and get stable 3d5 - configuration in
Mn3+ is least stable. Therefore, it is a Fe3+. Therefore, comparatively high
good oxidizing agent. positive value of E0 for Mn3+/Mn2+ in-
(ii) There is decreasing negative electrode dicates the stability of Mn2+(d5) where-
potentials of M2+/M in the first transi- as comparatively low value for Fe3+/
tion series due to increase in the sum of Fe2+ indicates the extra stability of Fe3+
IE1 and IE2 . It shows that in general, (d5).
the stability of +2 oxidation state de- (b) Energy required to convert metallic
creases from left to right. Exceptions crystal into individual atom is enthalpy
are Mn and Zn in which the greater of atomization. In transition row ele-
stability of +2 state for Mn is due to ments upto middle element and then
half-filled d-subshell (d5) in Mn2+ and decreases. This is because of strong
that of Zn is due to completely filled d- inter atomic interaction due to unpaired
subshell (d10) in Zn2+ . electron.

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Intelligence plus character is the goal • .

Greater the number of unpaired elec- 26.(i) Due to small size and high ionic charge/
tron, stronger will be bonding and thus availability of d orbitals.
enthalpy of atomization will also be (ii) Higher is the oxidation state higher is
more. Since iron has more unpaired the acidic character/as the oxidation
electron than copper therefore its en- state of a metal increases, ionic charac-
thalpy of atomization is more. ter decreases.
(c) The metal ions with partially or incom- (iii)Because Mn2+ has d5 as stable configu-
plete filled d-orbitals will be coloured ration whereas Cr3+ is more stable due
in aqueous solution. While the metal to stable t32g following transition metals
ions having either empty or completely form large number of complex com-
filled d-orbitals are colourless. pounds.
The colour will be due to d-d transition 27.(i) Electrode potential value is the sum of
of electrons. Thus, the outer electronic three factors, enthalpy of atomization,
configuration of metal ions are Sc3+ : ionization enthalpy and hydration en-
3d0 , Ti3+ : 3d1 thalpy. In case of copper the sum of
Hence, among the given ions, Ti3+ will enthalpy of atomization and ionization
exhibit colour in aqueous solution enthalpy is higher than hydration en-
while Sc3+ will be colourless. thalpy. Therefore E0Cu2+/Cu value is ex-
ceptionally positive.
24. This problem is based on the concept of
Fajans’ rule. As the oxidation state in- (ii) Mn2+ has stable electronic configura-
creases, size of the ion of transition ele- tion (3d5). The ionization enthalpy is
ment decreases. As per Fajans’ rule, when less than that of hydration enthalpy.
the size of metal ion decreases, covalent Therefore E0 value is more negative.
character of the bond formed increases. (iii) Cr2+ is stronger reducing agent than
Therefore the halide of transition elements Fe2+ due to more negative E0 value.
become more covalent with increasing 28.(i) Transition metals have very high intera-
oxidation state of the metal. tomic metallic interaction due to the
involvement of greater number of elec-
25.(i) Cr2+ is a strong redusing agent, because
trons from (n-1)d in addition to the ns
the stable state of chromium is +3 due
electrons. Greater the number of va-
to configuration.
lence electrons, stronger is the resultant
(ii) Cu+(aq) is unstable in aqueous solution bonding due to the greater overlapping
due to more negative of half filled orbitals. Hence, more
Δhyd H0 of Cu2+(aq) than Cu+(aq) amount of energy is required to break
these metallic bond. Thus enthalpy of
(iii) Mn3+ is a strong oxiding agent, because atomisation of transition metal is very
the most stable state of manganese is high.
+2 due to half filled configuration i.e
3d5 (ii) Paramagnetic arises due to the presence
of unpaired electrons, each such elec-
tron has a magnetic moment associated
with it due to its spin angular momen-

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Roots of education are bitter but the fruit is sweet • .

tum. Transition metals have in its tallic bonds. Thus it requires least en-
ground state or ionised state have num- thalpy to get atomized.
ber of unpaired d-electrons which gives
(iii) MO3F is MnO3F.
it a paramagnetic behaviour.
In MO3F
(iii) Colour of transition metal - compounds
is due to the excitation of an electron Let the oxidation state of M is x.
from a lower energy d-orbital to a high- x + 3 × (-2) + (-1) = 0
er energy d orbital. The energy of exci-
tation corresponds to the frequency of Or, x = +7, i.e. M is an oxidation state
light absorbed and the colour observed of +7. Hence, the given compound is
corresponds to the complementary col- MnO3 F.
our of the light absorbed (whose fre-
quency lies on the visible region). The
frequency of the light absorbed de- It shows the stability of Cr3+ in solu-
pends on the nature of ligand. Transi- tion cannot be reduced to Cr2+ ions.
tion metals form coloured compounds Mn3+ has high positive value of E0.
due to presence of vacant d-orbitals for Thus, Cr3+ is the most stable, Mn3+ is
the d-d transition of e’ which causes least stable.
the colour.
(v) The tendency to form complex com-
(iv) The catalytic activity of transition met- pounds is due to :
als is ascribed to their ability to adopt
multiple oxidation states and to form (a) Small size and high charge on metal
complexes. Catalyst at a solid surface ion.
involve the formation of bonds be- (b) The availability of d orbitals for ac-
tween reactant molecules and atoms of commodating electrons donated by
the surface of the catalyst, this has the the ligand.
effect of increasing the concentration
of the reactants at the catalyst surface 30. (H2O)6]n+ . As water is a weak field lig-
and also weakening of the bonds in the and, therefore, in case of octahedral com-
reacting molecules. Transition metals plex, pairing takes place, when each t2g
have d and s orbitals to from these and eg orbital is singly occupied [t2g (dxy ,
bonds. dyz , dzx ) set is of lower energy and eg
(dz2 , dx2 - y2) is higher energy].
29.(i) Electronic configuration of Mn2+ =
[Ar]18 3d5 Num- Number
2+ Con- ber of of un-
Electronic configuration of Fe = Occupancy of
Ions figur 3d paired
[Ar]18 3d6 ation elec- elec-
3d orbitals
trons trons
Mn2+ having half filled d-orbitals, will
be more stable than Fe2+ , as it has
Ti2+ 3d2 2 2
partially filled d-orbitals.
(ii) Zinc has completely filled d-orbitals, V2+ 3d3 3 3
which limits its tendency to form me-

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Be a warrior not a worrier • .

9. (a) KMnO4 oxidises oxalic acid to CO2

Cr3+ 3d3 3 3 and itself changes to Mn2+ ion, which is
colourless, because KMnO4 acts as an ox-
Mn2+ 3d5 5 5 idizing agent. Both (A) and (R) are correct
and (R) is the correct explanation of (A).
Fe2+ 3d6 6 4
10. (b) Both (A) and (R) are correct but R is
not the correct explanation of (A). The
Fe3+ 3d5 5 5 highest oxidation state of Osmium is +8
due to its ability to expand their octet by
Co2+ 3d7 7 3 using its all 8 electrons (2 from 6s and 6
from 5d).
Ni2+ 3d8 8 2
11. (b) Due to larger surface area and varia-
ble valencies, transition metals form inter-
Cu2+ 3d9 9 1 mediate absorbed complex easily, hence
they are used as good catalysts. Thus,
TOPIC - 2 both (A) and (R) are correct but (R) is not
the correct explanation of (A).
1. (a) (i)
12. Potassium dichromate is a powerful oxidiz-
2. (c) Sn4+
ing agent in acidic medium. In the presence
3. (d) Mn2+ acts as autocatalyst. of dilute sulphuric acid, it liberates nascent
oxygen
4. (a) Mn2 O7
K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 +
5. (c) IO3-
4H2O + 3(O)
6. (a) 2/5
Nascent oxygen
7. (a) First ionization enthalpy of Cr is low-
In acidic medium, dichromate ion takes up
er than that of Zn due to the stability of d5
electrons and acts as an oxidizing agent.
by losing one electron from outer s-orbital
and the value for Zn is high due to stable
d10 s2 configuration.
The net ionic equations for its reaction
Both (A) and (R) are correct and (R) is the with (i) iodide (ii) iron(II) solution and
correct explanation of (A). (iii) H2S are as shown below.
8. (c) Cr2+ is reducing, while Mn3+ is oxidiz-
ing when both have d4 configuration. Cr2+
is reducing as its configuration changes
from d4 to d3 , the latter having a half
filled t 2g level. On the contrary, the
change from Mn3+ to Mn+ results in the
half-filled (d5) configuration which has 13. When oxalic acid is added to acidic solu-
extra stability. Thus, (A) is correct but (R) tion of KMnO4 , its colour disappear due
is incorrect. to the reduction of MnO4– ion to Mn2+.
Chemical reaction occurring during this

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Impossible is a word in the dictionary of fools • .

neutralization reaction is as follows : lating oxidation state

X + 4 × (oxidation state of oxygen ion) =
total charge on ion(-1)
(Coloured) (Colourless)
X + 4 × (-2) = -1
X = 7 = oxidation state of Mn which is
equal to its group number.
19.

15. In KMnO4, the oxidation state of Mn is +7

(highest oxidation state) and is reduced to
Mn2+ whereas in K2Cr2O7, the oxidation
20.
state of Cr is +6 (highest oxidation state)
and is reduced to Cr3+.
Mn2+ is more stable than Cr3+.
Hence, KMnO4 is a stronger oxidizing
agent than K2Cr2O7
21.
16.(a)

(b)

22. A : Na2 CrO4 ; B : Na2Cr2O7

17. Formula of oxo-anion of chromium (Cr)
in which it shows the oxidation state equal 4FeCr2O4 + 8Na2CO3 + 7O2
to its group number (6) is
→ 8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+
2Cr + (-2 × 7) = -2 + H2O

2Cr - 14 = -2 23. Preparation of potassium dichromate

K2Cr2O7 from chromite ore FeO.
2Cr = 12
Cr2O3 (FeCr2O4):
Cr = +6
(i) Chromite ore is fused with NaOH or
Oxidation of Cr in
sodium carbonate in air to form sodi-
um chromate.

18. The formula of oxo-anion of Manganese 4FeCr2O4 + 16 NaOH + 7O2

→ 8Na2 CrO4 + 2Fe2O3 + 8H2O

Let oxidation state of Mn be x, then calcu- (ii) Sodium chromate solution is filtered
and acidified to form sodium dichro-
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Don't be same, be better • .

mate
2NaCrO4 + H2SO4 → Na2Cr2O7 +
Na2SO4 + H2O
The solution is cooled to remove crys-
tallized sodium sulphate. Sodium di-
chromate remains soluble. 26. When orange solution containing Cr2O72–
ion is treated with an alkali, a yellow solu-
(iii) Equimolar proportions a hot solution tion of CrO42– is obtained. In the same
of sodium dichromate and KCl are way, when H+ ions are added to yellow
mixed to form potassium dichromate. solution, an orange solution is obtained
Na2Cr2O7 + 2KCl → K2Cr2O7 + due to interconversion.
2NaCl
Sodium chloride precipitates out in
hot solution and is removed by filtra-
tion. On cooling, potassium dichro-
mate separates out from the mother
liquor. At pH = 4, there is an equilibri- 27.(i) K2MnO4 can be prepared from pyrolu-
um between chromate ions and di- site (MnO2) . The ore is fused with
chromate ions KOH in the presence of either atmos-
pheric oxygen or an oxidizing agent,
Cr2O72- + H2O ⇌ 2CrO42- + 2H+ such as:
Dichromate ion Chromate ion KNO3 or KClO4, to give K2MnO4
(orange red) (yellow)
By adding alkali, pH can be increased
and the equilibrium reaction will shift
in the forward direction to produce
more chromate ions (yellow color). (ii) Na2Cr2O7 can be prepared from
This is in accordance with Le chate- Na2CrO4 in the following way: for the
lier’s principle. By adding an acid, pH preparation of sodium dichromate, the
can be decreased and the equilibrium yellow solution of sodium chromate is
reaction will shift in the backward di- acidified with sulphuric acid to give a
rection to produce more dichromate solution from which orange sodium
ions (orange-red color). dichromate, Na2Cr2O7.2H2O can be
24.(i) (a) Due to d-d* transition. crystallized.

(b) Due to higher oxidation state of Mn Balanced equation for above reaction is
in Mn2O7/ Due to high polarizing as follows:
power of Mn (VII).

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 You are Brave Stronger Smarter • .

28. Preparation of potassium permanganate,

KMnO4 from pyrolusite ore MnO2. Pyro-
lusite ore is fused with KOH (or K2CO3) H2S → 2H+ + S + 2e- ] × 5
in presence of air (or oxidizing agents The overall reaction is as follows:
such as KNO3 or KClO3) to give potassi-
um manganate K2MnO4 (green mass).

Sulphur is obtained due to the oxidation

of H2S by KMnO4 .
Extraction of green mass with water fol- 30. Compounds A,B and C are
lowed by oxidation with chlorine (or
ozone or CO2) gives potassium permanga- A : Na2CrO4 ; B : Na2Cr2O7 ; C : K2Cr2O7
nate. The reactions involved are as follows
2K2MnO4 + Cl2 → 2KCl + 2KMnO4 4FeCr2O4 + 8Na2CO3 + 7O2 →
On concentrating the solution, dark purple 8Na2CrO4 + 2Fe2O3 + 8CO2
crystals of potassium permanganate sepa-
rates out. 2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+
+ H2O
Note: In neutral or acidic medium, man-
ganate ion will disproportional to perman- Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
ganate ion. 31.
2- + 2-
3MnO4 + 4H → 2MnO4 + MnO2
+ 2H2O
Conversion of manganate to permanga-
nate can also be carried by electrolytic
oxidation.
Reactions of acidified permanganate solu-
tion with (i) iron (II) ions (ii) SO2 and
(iii) oxalic acid: In alkaline solution
2MnO4- + 10Fe2+ + 16H+ → 2Mn2+ + In this reaction iodine is oxidised to io-
10Fe3+ + 8H2O date :
2MnO4- + 5SO2 + 2H2O → 5SO42- +
2Mn2+ + 4H+
2MnO4- + 5C2O42- + 16H+ → 2Mn2+ +
8H2O + 10CO2 In acidified solutions:
29.(i) (a) Vanadium (b) Iron (c) Silver Iodine is liberated from [potassium io-
(ii) On passing H2S gas through acidified dide :
KNnO4 solution, we get S and Mn2+.
The redox reactions are as follows:

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Education is the passport to future • .

TOPIC - 3 10. Separation of Zr and Hf are quite difficult

because of lanthanoid contraction. Due to
1. (d) All of the above lanthanoid contraction, they have the al-
2. (b) +3 most same size (Zr = 160 pm and Hf =
159 pm) and thus, similar chemical prop-
3. (c) Tm
erties. That’s why it is very difficult to
4. (b) 4f0-14 , 5d0-1 , 6s2 separate them by chemical methods.
5. (d) Both (a) and (b) 11. The lanthanides that exhibit +2 and +4
states are shown in the given table. The
6. (a) Many trivalent lanthanoid ions are
atomic numbers of the elements are given
coloured due to the presence of unpaired f
in the parenthesis.
-electrons in solid state as well as in aque-
ous solutions. Both (A) and (R) are cor-
+2 +4
rect and (R) is the correct explanation of
(A).
Nd (60) Ce(58)
7. Comparison of lanthanoids and actinoids
Sm (62) Pr(59)
Similarity:
Both have mainly an oxidation state of Eu (63) Nd (60)
+3.
Tm (69) Tb (65)
Difference:
Lanthanoids have less tendency towards Yb (70) Dy (66)
complex formation whereas actinoids
have greater tendency towards complex Ce after forming Ce4+ attains a stable elec-
formation. tronic configuration of [Xe].
8. Inner transition metals are those elements Tb after forming Tb4+ attains a stable elec-
in which the last electron enters the f- tronic configuration of [Xe] 4f7 .
orbital. The elements in which the 4f and Eu after forming Eu2+ attains a stable elec-
the 5f orbitals are progressively filled are tronic configuration of [Xe]4f7.
called f-block elements. Among the given
atomic numbers, the atomic numbers of Yb after forming Yb2+ attains a stable
the inner transition elements are 59, 95, electronic configuration of [Xe] 4f14.
and 102. 12. Chemistry of actinoids in complicated as
9. The decrease in atomic (or ionic) radii compared to lanthanoids because of the
(actinoid contraction) in actinoids is great- following reasons:
er than lanthanoid contraction because 5 f- (i) Actinoids are radioactive
electrons have poor shielding effect as
(ii) Actinoids show wide range of oxida-
compared to 4 f-electrons. Therefore, the
tion states as energy difference be-
effect of increased nuclear charge leading
tween 5f, 6d and 7s subshells of the
to contraction in size, is more in case of
actinoids is small.
actinoids.

12th Chemistry Winner’s Coaching Centre D & F Block Elements

 Speaking is silver, Listening is gold • .

13. The irregularities in the electronic config- 95%), iron (5%) and traces of S, C, Si,
uration of the actinoids is due to stability Ca and Al
of the f0, f7 and f14 occupancies of the 5f-
Uses:
orbitals.
(i) Mischmetal is used in cigarettes and
14. In lanthanoid, 4f orbitals are involved,
gas lighters
whereas in actinoids, 5f orbitals are in-
volved. The shielding effect of 5f orbitals (ii) It is used in flame throwing tanks
is poorer than the shielding effect of 4f
(iii) It is used in flame bullets and shills.
orbitals. Due to this, the valence shell
electrons of actinides experience greater 17. The last element in the actinoid series is
effective nuclear charge than that experi- lawrencium, Lr. Its atomic number is 103
enced by lanthanides. Hence, actinoid and its electronic configuration is [Rn]5f14
contraction is greater than lanthanoid con- 6d1 7s2. The most common oxidation state
traction. displayed by it is +3; because after losing
3 electrons it attains sta-
15.(i) Electronic configuration: Lanthanoids 14
ble f configuration.
have general electronic configura-
tion [Xe] 4f1−14 5d0−1 6s2. Actinoids 18. The steady decrease in the atomic and ion-
have general electronic configura- ic radii (having the same charge) with in-
tion [Rn]5f1−14 6d0−1 7s2. In lanthanoids, crease in atomic number as we move
4f orbital is filled and in actinoids, 5f across the series from lanthanum to luteti-
orbital is filled. um is known as lanthanoid contraction.
Misch metal.
(ii) Oxidation state: Apart from +3 oxida-
tion state, lanthanoids show +2 and +4 19.
oxidation states due to large energy gap
between 4f and 5d subshells. Whereas Lanthanide Actinoids
actinoids show large number of oxida-
tion states due to small energy gap be- Lanthanoids have a low Actinoids show
tween 5f and 6d subshells. tendency to form com- greater tenden-
plexes. cy to form com-
(iii) Chemical reactivity: Highly electropo- plexes.
sitive lanthanoids have almost similar
chemical reactivity. Actinoids (electro In lanthanide the filling In action the
positive and highly reactive) are more of 4f4 orbitals take place. filling of 5f5
reactive (specially in finely divided orbitals take
state) than lanthanoids. place.
16. An alloy is a solid or solution of two or
more elements in a metallic matrix. It can This series includes ele- This series in-
either be a partial solid solution or a com- ments from atomic num- cludes elements
plete solid solution. Alloys are usually ber 57 to 71. from atomic
found to possess different physical proper- number 89 to
ties than those of the component elements. 103.
An important alloy of lanthanoids is
Mischmetal. It contains lanthanoids (4-
12th Chemistry Winner’s Coaching Centre D & F Block Elements
 Enjoy each and every little thing • .

20.(i) The electronic configuration of Ytter-

bium is 4f14 6s2. Yb in +2 oxidation
states acquires half filled (4f7) and ful-
ly filled (4f14) configuration but still
they oxidises to their common +3 state
and thus acts as strong reducing agents
or reductants.
Tb in +4 state has 4f7 half filled stable
configuration but it readily gets re-
duced to common +3 state and hence
acts as oxidant.
(ii)(a) All the lanthanides except La3+ and
Lu3+ contain unpaired electrons. Due
to unpaired electrons they are para-
magnetic.
(b) Lanthanides do not form stable car-
bonyl compounds.
The main reason is that in Ln3+ the
4f orbital is greatly shielded by 5s2
and 5p6 orbitals. So the 4f orbital is
unable to participate in bonding. Al-
so, Ln3+ ions are large and have less
charge density, this also leads to the
poor complex formation of lantha-
nides.
21.(i) (a) Copper; Due to high enthalpy of
atomisation and low hydration
enthalpy.
(b) Cerium ; Due to stable 4f0 configu-
ration/ Tb ; Due to stable 4f7 con-
figuration
(ii)(a) Due to ability of oxygen to form
multiple bond to metal.
(b) HCl is oxidized to chlorine.
(c) Due to strong interatomic metallic
bonding.

12th Chemistry Winner’s Coaching Centre D & F Block Elements