4.

THE d- AND f-BLOCK ELEMENTS

QUICK REVISION POINTS:
1. d-block elements
(a) DEFINITION: A transition element is defined as the one which has incompletely filled
d orbitals in its ground state or in any one of its oxidation states. Zinc, cadmium and
mercury of group 12 have full d10 configuration in their ground state as well as in
their common oxidation states and hence, are not regarded as transition metals. Their
Outer electronic configuration is (n -1) d1-10 ns 1-2
(b) MELTING AND BOILING POINTS: High MP & BP which is due to their strong metallic
bond (strong interatomic bonding ) due to unpaired electrons in (n-1) d orbitals.In any
row the melting points of these metals rise to a maximum at d5 except for anomalous
values of Mn and Tc.
(c) ENTHALPIES OF ATOMIZATION: High enthalpies of atomization Because of large
number of unpaired electrons in their atoms they have stronger interatomic
interaction (metal-metal bonding). The metals of the second and third series have
greater enthalpies of atomisation than the corresponding elements of the first series
due to occurrence of much more frequent metal – metal bonding.
(d) VARIATION IN ATOMIC AND IONIC SIZES : In general, ions of the same charge in a
given series show progressive decrease in radius with increasing atomic number The
atomic radii decreases from group 3 to 6 because of increase in effective nuclear
charge gradually, The atomic radii of group 7,8,9 &10 elements is almost same
because Screening effect counter balances increased effective nuclear charge, Group
11 &12 elements have bigger size due to increase inter-electronic repulsion as result
electron cloud expands and size increases. Members of second(4d) and the third (5d)
series in each group of transition elements have similar radii and shows similar
properties because lanthanoid contraction essentially compensates for the expected
increase in atomic size with increasing atomic number.
(e) DENSITY: The decrease in metallic radius coupled with increase in atomic mass
results in a general increase in the density of these elements. Thus, from titanium
(22) to copper ( 29) the significant increase in the density may be noted.
(f) VARIATION IN IONISATION ENTHALPIES OF TRANSITION METALS: There is an
increase in ionisation enthalpy along each series of the transition elements from left
to right due to an increase in nuclear charge which accompanies the filling of the
inner d orbitals. Irregular variation of ionisation enthalpies is mainly attributed to
varying degree of stability of different 3d-configurations (e.g., d0, d5, d10 are
exceptionally stable).
(g) OXIDATION STATES: The transition elements show variable oxidation state due to
small energy difference between (n-1) d & ns orbital as a result both (n-1) d & ns
electrons take part in bond formation. The highest oxidation state of an element is
equal to number of unpaired e- present in (n-1) d & ns orbital.
(h) MAGNETIC PROPERTIES : Most of the transition metal ions are paramagnetic. due
to the presence of unpaired electrons in d-orbitals. Magnetic moment is given by

Where, n = number of unpaired electrons and BM = Bohr magneton (unit of magnetic

moment).

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 (i) FORMATION OF COLOURED IONS: Due to the presence of unpaired electrons in d-
orbitals of the transition metal ions & because of d– d transitions occurring in a
transition metal ions by the absorption of visible light.
(j) FORMATION OF COMPLEX COMPOUNDS :- Due to smaller sizes of the metal ions,
their high ionic charges and the availability of d orbitals for bond formation.
(k) CATALYTIC PROPERTIES: Due to Variable oxidation states & Large surface area.
(l) FORMATION OF INTERSTITIAL COMPOUNDS: Transition elements form interstitial
compounds because size of C, N, O, and B is similar to size of interstitial voids of
transition metals.
(m) ALLOY FORMATION: As the atomic sizes are very similar, one metal can replace
the other metal from its lattice and form a solid solution which is the alloy.
(n) STANDARD ELECTRODE POTENTIALS: Transition elements have lower negative
value of Standard Electrode Potentials due to high ionization potential, high heat of
sublimation & low enthalpy of hydration. The E0 (M2+/M) values are not regular which
can be explained from the irregular variation of ionization enthalpies and also the
sublimation enthalpies which are relatively much less for manganese and vanadium.
(o) Oxide of transition metals in lower oxidation states are generally basic while those
in the higher oxidation states are acidic. Acidic character increases with increase in
oxidation state is due to decrease in size of metal ion and increase in effective nuclear
charge.e.g. MnO (basic), Mn3O4 (amphoteric), Mn2O7 (acidic).
2. LANTHANOIDS
(a) The 14 elements after Lanthanum having atomic number 58 to 71 are collectively
known as Lanthanoids. The general electronic configuration of these elements is [Xe]
4f1-14, 5d0-1,6s2.
(b) LANTHANOID CONTRACTION (ATOMIC AND IONIC SIZES): The overall decrease in
atomic and ionic radii from lanthanum to lutetium is due to poor shielding of 4f
electrons is known as lanthanoid contraction. Due to lanthanoid contraction:-
(a)basic character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3,
(b) Sizes of 4d and 5d metal pairs like Zr and Hf; Nb and Ta are almost similar.
(c) OXIDATION STATES: Most common oxidation state of these elements is +3,
However, occasionally +2 (Eu+2 and Yb+2)and +4 ions (Ce+4 and Tb+4) in solution or in
solid compounds are also obtained.
(d) COLOUR FORMATION :Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be attributed to the
presence of unpaired electrons in f subshell.
(e) MAGNETIC BEHAVIOUR: The lanthanoid ions other than the f 0 type (La3+ and Ce4+)
and the f 14 type (Yb2+ and Lu3+) are all paramagnetic.
(f) USES : A well-known alloy is mischmetall which consists of a lanthanoid metal(~ 95%)
and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in
Mg-based alloy to produce bullets, shell and lighter flint.
3. ACTINOIDS
(a) The 14 elements after Actinium having atomic number 90 to 113 are collectively
known as Actinoids
(b) The actinoids are radioactive elements These facts render their study more
difficult.
(c) Electronic Configurations: The general electronic configuration of these elements
is [Rn] 5f1-14, 6d0-1,7s2

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 (d) Ionic Sizes(Actinoid contraction): The overall decrease in atomic and ionic radii
across the series due to poor shielding of 5f electrons is known as Actinoid
contraction
(e) The actinoid contraction is, however, greater from element to element in this series
resulting from poor shielding by 5f electrons.
(f) Oxidation States: The actinoids show in general +3 oxidation state. The actinoids
exhibit a larger number of oxidation states, which is in part attributed to the fact
that the 5f, 6d and 7s levels are of comparable energies. The elements, in the first
half of the series frequently exhibit higher oxidation states. For example, the
maximum oxidation state increases from +4 in Th to +5, +6 and +7respectively in
Pa, U and Np but decreases in succeeding elements.
(g) The actinoids are highly reactive metals, especially when finely divided.
(h) The magnetic properties of the actinoids are more complex than those of the
lanthanoids. Although the variation in the magnetic susceptibility of the actinoids
with the number of unpaired 5 f electrons is roughly parallel to the corresponding
results for the lanthanoids
4. POTASSIUM DICHROMATE (K2Cr2O7)
(a) Preparation: - It takes place in three steps-
1. 4FeCr2O4+ 8Na2CO3 +7O2 ⎯ ⎯→ 8Na2CrO4(yellow solution)+ 2Fe2O3 +8CO2
2. 2Na2CrO4 + 2H ⎯ +
⎯→ Na2Cr2O7(orange sodium) + 2 Na+ + H2O
3. Na2Cr2O7 + 2 KCl ⎯ ⎯→ K2Cr2O7(Orange crystals)+ 2 NaCl
(b) The chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solution. 2 CrO42– + 2H+→Cr2O72– + H2O
Cr2O72– + 2 OH-→2CrO42– + H2O
(c) Potassium dichromate in acidic solution act as oxidizing agent.
• Cr2O72–+ 6I–+ 14H+→ 2Cr+3+ 3I2 + 7H2O
• Cr2O72–+ 3H2S+ 8H+→2Cr+3+ 3S+ 7H2O
• Cr2O72–+ 3Sn2++ 14H+→2Cr+3+ 3Sn4++ 7H2O
• Cr2O72–+ 6Fe2++ 14H+→2Cr+3+ 6Fe3+ + 7H2O
(d) Structure of chromates and dichromates

(e) Uses: Potassium dichromate is a very important chemical used in leather industry
and as an oxidant for preparation of many azo compounds. Potassium dichromate
is used as a primary standard in volumetric analysis.
5. POTASSIUM PERMANGNATE [KMnO4]
a) Preparation: -- It takes place in two steps:-
• 2MnO2 + 4 KOH + O2 ⎯ ⎯→ 2 K2MnO4 (Dark green)+ 2H2O
• 3 MnO4 +4H ⎯
2- +
⎯→ 2MnO4-(Purple)+MnO2 +2H2O [Disproportionation]
b) Properties of KMnO4
• Potassium permanganate are isostructural with those of KClO4.
• When heated KMnO4 decomposes at 513 K.
• 2KMnO4 ⎯⎯ ⎯→ K2MnO4 + MnO2 + O2
Heat , 

• KMnO4 act as Oxidising agent in acidic, alkaline & neutral medium.

• MnO4– + 8H+ + 5e– ⎯ ⎯→ Mn2+ + 4H2O (Acidic)
• 2MnO4– + 16H+ + 5C2O42 ⎯ ⎯→ 2Mn2+ + 8H2O +10CO2
• MnO4– + 8H+ + 5Fe2+ ⎯ ⎯→ Mn2+ + 4H2O + 5Fe3+
• 2MnO4– + 16H+ + 10I– ⎯ ⎯→ 2Mn 2+ + 8H2O +5I2

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 • 5NO2- +2MnO4–+ 6H+ ⎯ ⎯→ 2Mn 2+ + 3H2O +5NO3-
• 5SO32-+2MnO4– + 6H+ ⎯ ⎯→ 2Mn 2+ + 3H2O +5SO42-
• oxidising reactions of KMnO4 In neutral or faintly alkaline solutions.
• 2MnO4–+ H2O + I– ⎯ ⎯→ 2MnO2 + 2OH- + IO3–
• 8 MnO4– +3 S2O32- + H2O ⎯ ⎯→ 8MnO2 + 2OH- +6 SO42-
• 2 MnO4–+3Mn+2+ 2H2O ⎯ ⎯→ 5MnO2+ 4H+
6. Permanganate titrations in presence of hydrochloric acid are unsatisfactory since
hydrochloric acid is oxidised to chlorine.
7. Uses: Besides its use in analytical chemistry, potassium permanganate is used as
a favourite oxidant in preparative organic chemistry. Its uses for the bleaching of
wool, cotton, silk and other textile fibres and for the decolourisation of oils are also
dependent on its strong oxidising power.
8. Structure of Permanganate & Manganate:

MULTIPLE CHOICE QUESTIONS (1 MARKS)

1. In which of the following pairs, both the ions are coloured in aqueous solutions?
[Atomic no of Sc = 21, Ti = 22, Ni = 28, Co = 27, Cu = 29]
(a) Sc3+, Ti+3 (b) Sc3+, Co2+ (c) Ni2+, Cu+ (d) Ni2+, Ti3+
2. Which of the following is most stable in aqueous solution?
(a) Mn3+ (b) Cr3+ (c) V3+ (d) Ti3+
3. KMnO4 is not acidified by HCl instead of H2SO4 because
(a) H2SO4 is stronger acid than HCl
(b) HCl is oxidised to Cl2 by KMnO4
(c) H2SO4 is dibasic acid
(d) rate of reaction is faster in presence of H2SO4
4. Manav poured some potassium chromate solution in test tube for qualitative
analysis. The yellow colour of potassium chromate soon turned orange in colour.
Manav realised that this happened because the test tube was not clean and
contained a few drops of some liquid. Which of the following were the liquid drops
most likely to be.
(a) Drops of water (b) methyl orange solution (c ) NaOH solution (d) HCl solution
5. Generally, transition elements form coloured salts due to the presence of unpaired
electrons. Which of the following compounds will be coloured in solid state?
(a) Ag2SO4 (b) CuF2 (c) ZnF2 (d) Cu2Cl2
6. When KMnO4. solution is added to oxalic acid solution, the decolourisation is slow
in the beginning but becomes instantaneous after some time because
(a) CO2 is formed as the product. (b) Reaction is exothermic.
(c) MnO4– catalyses the reaction. (d) Mn2+ acts as auto catalyst.
7. Which of the following are d-block elements but not regarded as transition
elements?
(a) Cu, Ag, Au (b) Zn, Cd, Hg (c) Fe, Co, Ni (d) Ru, Rh, Pd
8. Transition elements form alloys easily because they have
(a) Same atomic number (b) Same electronic configuration
(c) Nearly same atomic size (d) None of the above.
9. Which of the following ion has magnetic moment value of 5.9?
(a) Mn2+ (b) Fe2+ (c) Ni2+ (d) Cu2+
10. Which of the following lanthanoids show +2 oxidation state besides the
characteristic oxidation state +3 of lanthanoids?
(a) Ce (b) Eu (c) Tb (d) Dy.

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 ASSERTION REASON TYPE QUESTIONS(1MARKS)
In the Following questions a statement of Assertion(A) is followed by a statement
of Reason(R). Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
11. Assertion(A) : Magnetic moment values of actinides are lesser than the
theoretically predicted values.
Reason(R) : Actinide elements are strongly paramagnetic.
12. Assertion(A) : KMnO4 act as an oxidising agent in acidic, basic or neutral
medium.
Reason(R) : KMnO4 oxidises ferrous sulphate to ferric sulphate.
13. Assertion(A) : Of the 3d4species Cr2+ is strongly reducing and Mn3+ is strongly
oxidising.
Reason(R) : Cr+3 state is stable due to half-filled t2g set, Mn+2 is stable due to
half- filled d orbitals
14. Assertion(A) :In the series Sc to Zn the enthalpy of atomisation of Zinc is the
lowest.
Reason(R): Zinc has greater number of unpaired electrons
15. Assertion(A) :Magnetic moment of Mn2+ is less than that of Cr2+.
Reason(R): Magnetic moment depends on the number of unpaired electrons.
VERY SHORT ANSWER TYPE QUESTIONS( 1 MARK)
16. Which element has highest melting point in 3d series ?
17. Out of Cu2Cl2 and CuCl2 which is more stable in aqueous solution.
18. Which element of the first transition series don’t exhibit variable oxidation states?
19. Name an oxo anion having oxidation number of metal (3d series) equal to its
group number.
20. Name two elements of 3d series which show anomalous electronic configuration.
21. Identify the Transition metal of 3d series that acts as a strong reducing agent in +2
oxidation state in aqueous solution.
22. Name a member of lanthanoid series which is well-known to show +4 oxidation
state.
23. Among the elements of 3d series which element is soft?
24. Arrange the following in increasing order of acidic character: CrO3,CrO, Cr2O3
25. Complete the following equation :
3MnO42- +4H+
VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
26. Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
27. Among Elements of 3d transition series: Write the element
(a) Which is not regarded as transition element.
(b) Which shows maximum number of oxidation states.
(c) Which forms stable divalent(M2+) ion
(d) Which shows only +3 state?
28. What is Lanthanoid contraction? Give its cause. What are its Consequences?
29. When pyrolusite ore MnO2 is fused of with KOH in presence of air,a green
coloured compound (A) is obtained which undergoes disproportionation reaction
in acidic medium to give purple coloured compound (B).
(i) Write the formulae of (A) & (B).
(ii) What happens when compound (B) is heated.
30. When chromite ore FeCr2O4 is fused with NaOH or (Na2CO3) in presence of air, a
yellow coloured compound (A) obtained which on acidification with dilute

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 sulphuric acid gives a compound (B). Compound (B) on reaction with KCl forms
an orange coloured crystalline compound (C).
(a) Write the formulae of (A), (B) & (C).
(b) Write one use of compound (C).
SHORT ANSWER TYPE QUESTIONS (3 MARKS)
31. Explain giving a suitable reason for each of the following
(a) Metal –metal bonding is more frequent for the 4d & 5d series of
transition metals than that for the 3d series.
(b) Cu+ salts are colourless while Cu2+ salts are Coloured
(c) Mn2+ exhibits maximum Para magnetism
32. Account for the following
(a) Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite
difficult to separate them.
(b) There is in general increase in density of element from titanium to copper.
(c ) Most of the transition metals and their compounds act as good catalysts.
33. Explain the following observations.
(a) Mn Shows the highest oxidation state of +7 among 3d series elements
(b) Mn Shows the highest oxidation state of +7 with oxygen but with fluorine it
shows the highest oxidation state of +4.
(c )MnO is basic while Mn2O7 is acidic in nature.
34. Account for the following
(a) Cu+ ion is not stable in aqueous solutions.
(b) The d1 configuration is very unstable in ions.
(c )Eo value for the Mn2+/Mn much more than expected.
35. Assign reasons for the following.
(a) Scandium is a transition element but Zinc is not.
(b) Silver atom has completely filled d orbital (4d10) in its ground state, yet it is
transition element.
(c )In the series Sc(Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the
lowest.
LONG ANSWER TYPE QUESTIONS (5 MARKS)
36. Give Reasons for the following
(i) Ce4+ in aqueous solution is a good oxidising agent.
(ii) Actinoids contraction is greater from element to element than lanthanoid
contraction.
(iii) The actinoids exhibit a larger number of oxidation states than the
corresponding lanthanoids.
(iv) La3+ and Lu3+do not show any colour in solutions.
(v) Chemistry of all the lanthanoids are quite similar.
37. Complete & balance the following reactions: -
a) Cr2O72–+ Fe2++ H+→
b) MnO4– + H+ + C2O42- ⎯ ⎯→
c) KMnO4 ⎯⎯⎯→ Heat , 

d) MnO4– + H2O+ I- ⎯ ⎯→
e) Cr2O7 + OH →
2– -

CASE BASED QUESTIONS

The Following questions are case based questions carries 4 (1+1+2) marks.
Read the given passage carefully and answer the questions that follow:
38. The transition metals react with a number of non-metals like oxygen, nitrogen,
Sulphur and halogens to form binary compounds. The first series transition metal
oxides are generally formed from the reaction of metals with oxygen at high
temperatures. These oxides dissolve in acids and bases to form oxo metallic salts.
Potassium dichromate and potassium permanganate are common examples.

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 Potassium dichromate is prepared from the chromite ore by fusion with alkali in
presence of air and acidifying the extract. Pyrolusite ore (MnO2) is used for the
preparation of potassium permanganate. Both the dichromate and the
permanganate ions are strong oxidising agents.
(a) What happens when Manganate ions (MnO42− ) undergoes disproportionation
reaction in acidic medium?
(b) Explain why the colour of KMnO4 disappears when oxalic acid is added to
its solution in acidic medium.
(c ) When an orange solution containing Cr2O72– ion is treated with an alkali,
a yellow solution is formed and when H+ ions are added to a yellow solution,
an orange solution is obtained. Explain why does this happen?
OR
A solution of KMnO4 on reduction yields either colourless solution or a brown
precipitate or a green solution depending on the pH of the solution. What
different stages of the reduction do these represent and how are they carried
out?
39. The d-block, which lies between s and p-blocks contains, elements of groups 3-12,
in which d- orbitals are progressively filled in each of four long periods of periodic
table. These elements are also called transition elements or metals.
The elements constituting the f-block are those in which 4 f and 5 f-orbitals are
progressively filled. They are place in a separate panel at the bottom of the periodic
table. The elements of f-block are also called inner-transition
(a) Transition metal are very good catalyst. Why? (1)
(b) Transition metals form a large number of interstitial compounds. Give reason(1)
(c) Why the paramagnetic characteristic in 3d- transition series increases up to Cr
and then decreases? (2)
OR
Out of La(OH)3 and Lu(OH)3, which is more basic and why?
40. In the periodic table, the elements are classified into mainly four blocks, i.e. s, p, d
and f. The d-block elements are called transition elements. The s-block contains
the elements of the group 3-12. They possess properties that are transitional
between the s and p-block elements. Zn, Cd, Hg do not exhibit characteristic
properties of transition elements. All the elements belong to this section are metals.
There are four rows of the transition elements involving filling of 3d, 4d, 5d and 6d
orbitals.
(a) Why does the transition element scandium not exhibit variable oxidation state?
(1)
(b) Why chromium is a typical hard metal while mercury is a liquid? (1)
(c) Fe3+/Fe2+ redox couple has less positive electrode potential than Mn3+/Mn2+
couple.Why? (2)
OR
Copper (I) is diamagnetic, whereas copper (II) is paramagnetic.
41. Within the 3d-series, manganese exhibits oxidation states in aqueous solution from
+2 to +7, ranging from Mn2+ (aq) to MnO-4 (aq). Likewise, iron forms both Fe2+ (aq)
and Fe3+(aq) as well as the FeO42- ion. Cr and Mn form oxo anions CrO42-, MnO4-,
owing to their willingness to form multiple bonds. The highest oxidation states of
the 3d-metals may depend upon complex formation (e.g., the stabilization of Co³+
by ammonia) or upon the pH (thus MnO42-(aq) is prone to disproportionation in
acidic solution). Within the 3d-series, there is considerable variation in relative
stability of oxidation states,
sometimes on moving from one metal to a neighbour; thus, for iron, Fe3+ is more
stable than Fe2+,especially in alkaline conditions, while the reverse is true for
cobalt. The ability of transition metals to exhibit a wide range of oxidation states is

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 marked with metals such as vanadium, where the standard potentials can be rather
small, making a switch between states relatively easy.
(a) Highest fluoride of Mn is MnF4 where as the highest oxide is Mn2O7 (1)
(b) Which is more stable Fe2+ or Fe³+? (1)
(c). The higher oxidation states are usually exhibited by the members in the middle
of a series of transition elements ? (2)
OR
Electrode potential of copper E0 Cu+2 / Cu is positive, where as E0 Mn+2 / Mn is
more negative than expected Why ?
42. Potassium permanganate, (KMnO4) is prepared by fusion of pyrolusite, MnO2 with
KOH in the presence of an oxidising agent like KNO3. This produces the dark green
potassium manganate, K2MnO4 which disproportionates in a neutral or acidic
solution to give purple permanganate ion. Potassium permanganate is an important
oxidising agent in acidic, alkaline as well as neutral medium.
(a) What is the state of hybridisation of Mn in MnO4-? (1)
(b) Write an application of potassium permanganate. (1)
(c) How do the oxides of transition elements in lower oxidation states differ from
those in higher oxidation state in the nature of metal-oxygen bonding and why?
(2)
OR
Draw the structure of permanganate ion. Is it paramagnetic or diamagnetic?
ANSWERS
ANSWERS MULTIPLE CHOICE QUESTIONS:
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
d b b d b d b c a b
11. 12. 13. 14. 15.
b b a c d
16. Cr
17. CuCl2, due to greater hydration enthalpy of Cu2+
18. Sc
19. MnO - or CrO
2-
4 4
20. Cr, Cu
21. Cr
22. Ce
23. Zn
24. CrO < Cr2O3< CrO3
25. 3MnO42- +4H+ 2MnO4- +MnO2+2H2O
26. Mischmetal which consists of 95% of lanthanoid metals, 5% iron and traces of
S,C,Ca and Al. uses. Mischmetal is used in Mg-based alloy to produce bullets, shell
and lighter flint
27. a)Zn(b)Mn (c)Mn (d)Sc
28. Lanthanoid contraction: The regular decrease in the atomic and ionic radii of
lanthanoids with increasing atomic number is known as Lanthanoid contraction.
Cause for lanthanoid contraction: poor shielding of 4f electrons.
Consequences of Lanthanoid contraction:
(i) Difficult to separate the lanthanoids because the change in ionic radii is very
small, their chemical properties are similar. Hence, separation of lanthanoids are
difficult. (ii) Similarity in size of elements belonging to same group of second and
third transition series due to lanthanoid contraction the size of Zr (160 pm) is same
as that of Hf (159 pm).
29. (i) A= K2MnO4 B= KMnO4
(ii) 2KMnO4 ⎯ ⎯→ K2MnO4 + MnO2 + O2

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30. (a) A = Na2CrO4 B= Na2Cr2O7 C= K2Cr2O7
(b) Potassium dichromate is used as a primary standard in volumetric analysis
31. (a) 4d and 5d transition elements (2nd and 3rd series) are Larger in size than the
corresponding 3d elements. Hence the valence electrons are less tightly held and
form M-M bond more frequently
(b) Due to the absence of unpaired electrons in d-orbitals, Cu+ salts are colourless
while due to presence of unpaired electrons in d-orbitals, Cu2+ salts are Coloured
(c) Because Mn2+ contain 5 unpaired electrons in their 3d sub shells
32. (a) because of lanthanoid contraction both Zr &Hf have similar radii and similar
properties
(b) The decrease in metallic radius coupled with increase in atomic mass results in
a general increase in the density.
(c ) The catalytic activity of transition metal ions is due to following two reasons:
Variable oxidation states & Large surface area.
33. (a) Total 7 electrons are present in 3d and 4s in Mn and hence it can
exhibit maximum oxidation state of +7
(b) Because of ability of oxygen to form multiple bonds using 2p orbitals
of oxygen and 3d orbitals of Mn.
(c) Mn in Mn2O7 is in +7 oxidation state and Mn maximum oxidation state is +7.
Hence it is Acidic. If an element in a compound is in lower oxidation state then it
will show basic character. Mn is in+2 oxidation state in MnO hence basic.
34. (a) It disproportionate to give Cu2+ and Cu. Or Due to greater hydration enthalpy of
Cu2+
b) The ions in d1 configuration tend to lose one more electron to get into stable d0
configuration.
c) due to greater stability of half-filled d-subshell (d5) in Mn+2
35. (a) Scandium is a transition element because it has incompletely filled d orbitals
but Zinc has completely filled d orbitals i.e 3d10 configuration
(b) Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely
filled d-orbitals (4d), hence a transition element.
(c) because in the formation of metallic bonds, no electrons from 3d-orbitals are
involved in case of zinc, while in all other metals of the 3d series, electrons from the
d-orbitals are always involved in the formation of metallic bonds
36. (i) because it can readily change to the most stable +3 oxidation state by gaining
one electron (
ii) due to greater poor shielding by 5f-electrons in actinoids than that by 4f-electrons
in the lanthanoids
(iii) because of the very small energy gap between 5f, 6d and 7s subshells.
(iv) due to absence of unpaired electron in f orbital
(v) The change in the size of the lanthanoids due to lanthanoid contraction is very
small
37. (a) Cr2O72–+ 6Fe2++ 14H+→2Cr+3+ 6Fe3+ + 7H2O
(b) 2MnO4– + 16H+ + 5C2O42 ⎯ ⎯→ 2Mn2+ + 8H2O +10CO2
(c) KMnO4 ⎯ ⎯→ K2MnO4 + MnO2 + O2
(d) 2 MnO4 + H2O + I– ⎯
–
⎯→ 2MnO2 + 2OH- + IO3–
(e) Cr2O72– + 2 OH-→2CrO42– + H2O
38. (a) MnO42− ions disproportionate in acidic medium to give Permanganate ions and
Manganese(IV) oxide. 3MnO42− + 4 H+ → 2MnO4− + MnO2 + 2H2O
(b) This is a redox titration. The deep purple colour of KMnO4 disappears due to the
formation of MnSO4
(c ) When Cr2O72– ion is treated with an alkali :
Cr2O72– (orange) + 2 OH-→2CrO42–(yellow) + H2O

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 When the yellow solution is treated with an acid, we get back the orange solution:
2 CrO42– (yellow)+ 2H+→Cr2O72–(orange) + H2O
OR
In acidic medium, permanganate changes to manganous ion which is colourless.
MnO4– + 8H+ + 5e– ⎯ ⎯→ Mn2+ (colourless) + 4H2O
In alkaline medium, permanganate changes to manganate, which is a green
solution
MnO4-+ e- → MnO42- (green)
In a neutral medium, permanganate changes to manganese dioxide which is a
brown precipitate,
MnO4– + 2H2O + 3e-→ MnO2 (brown) + 4OH-
39. (a) due to variable oxidation state and provides suitable surface area for the reactant
molecule to adsorb on it.
(b) because small sized atom such C.H, N,O etc. occupy the interstitial site.
(c) because up to Cr the number of unpaired electron increases and there after due
to pairing in d orbital the number of unpaired electron decreases. So magnetic
character decreases.
OR
La(OH)3 is more basic, Lu(OH)3 is less basic. Size of Lanthanoids ion decreases from
La3+ to Lu3+, tendency to give hydroxyl ion decreases so basic character decreases.
40. (a) outer electronic configuration of Sc[Ar]3d1 4s2. Hence, it shows +3 as the only
oxidation state, by losing the three electrons it acquires a noble gas configuration.
(b) Cr have 3d5 4s1configuration. Hence, metallic bond is very strong. In Hg, all d
orbitals are fully filled, hence the metallic bond is very weak.
(c)In Mn2+, d5 configuration leads to extra stability of half-filled configuration. So
Mn3+/(d4)tends to get converted to stable d5,onfiguration of Mn2+ by accepting an
electron so Mn3+/Mn2+ redox couple has more positive electrode potential than
Fe3+/Fe2+
OR
Cu = [Ar] 3d have no unpaired electron, so diamagnetic but Cu2+ = [Ar] 3d9
+ 10

configuration so have one unpaired electron, hence paramagnetic.

41. a) As oxygen stabilises highest oxidation state more than Florine by forming
multiple bonds.
(b) Fe3+
(c) It is due to greater number of unpaired electrons in (n-1)d and ns orbitals at
the middle of the series. The lesser number of oxidation states at the extreme
ends stems from either too few electrons to lose or share.
OR
Ans due to less hydration enthalpy of Cu+2 .The high energy to form From Cu (s)
to Cu+2 (aq) is not balanced by its hydration enthalpy. due to low sublimation
enthalpy of Mn and stable half filled d5 configuration of Mn2+
42. (a) Sp3
(b) It is used as an oxidising agent
(c) In the lower oxidation state the transition metal oxides are basic and they are
acidic if the metal is in higher oxidation state. The oxides are amphoteric when the
metal ion is in intermediate oxidation state..
OR

Tetrahedral, diamagnetic.

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