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COMPOUNDS OF TRA N SITION ELEMENTS
Heat O 2H 0
1. 2MnO
2
+ 4KOH + 0 2 2K2Mn 4 + 2

Heat K MnO 4 + MnO2 + 02

2. 2KMnO 4 2
2KOH + 2MnO 2 + 2H20 + 3S
3. 2KMnO 4+ 3H 2S
4. 2KMnO + Kl + H O
2
---+ 2MnO 2 + 2KOH + KI03
4
2KMnO + BH SO + l0KI ---+ 6K 2SO 4 + 2MnS04 + 8H20 + 512
5. 4 2 4
6. 2KMnO + 3H so + SH c o ---+ K 2so 4 + 2MnS0 4 + 8H20 + 10C02
4 2 4 2 2 4
7. 2KMnO + BH SO + 10FeSO ---+ K 2SO 4 + 2MnSO4 + SFe2(S04h + BH 20
4 2 4 4
8. 2KMnO . + 3H so + SH 2S ---+ K 2so 4 + 2MnS0 4 + 8Hz0 + SS
4 2 4
9. K Cr O
2 2 7
+ 2KOH ---+ 2K2CrO 4 + H 20
10. K Cr O + 7H
2 2 7 2 4
so
+ 6KI ---+ 4K2so 4 + Cr2 (S04 h + 7H20 + 31 2

11.
K2Cr O + 6FeSO + 7H SO
2 4
---+ 3Fe 2 (SO 4) 3 + K 2S04 + Cr2 (S0 4) 3 + 7H 20
2 7 4
12. KzCrzO
7
+ 4H SO + 3HzS
2 4
---+ K 2so 4 + Cr2 (S04h + 3S + 7H 20
KzCr O + H SO + 3SO 2 ---+ K 2SO 4 +' Cr2 (S04 h + 3H 20

-
13. 2 7 2 4

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I
I [NCERT_ Pg. 230} 5. To provide acidic medium during the (1) Mn> Cr> Ti> V
Brass is an alloy of
oxidising reactions of KMn04, H2S04 is used (2) Cr> Mn > V > Tl
(1) Zn and Sn (2) Cu and Zn
1 instead of HCI. T~is is mainly because of
(3) Cu and Sn (4) Zn and Ni (3) Cr> Mn > Ti > V
[NCERT Pg. 234}
1 2. The most basic oxide among the following is (4) V >Ti> Mn> Cr
[NCERT Pg. 231} (1) HCI is a monobasic acid (NCERT Pg. 237)
9. Mischmetal contains
(2) FeO (2) HCI is stronger acid than H2S04
(1) Ti0 ( 1) Actinoids ( = 90%) and Iron ( = 10%)
(3) CrO (4) VO (3) HCI is oxidized by KMn04 to C'2
(2) Lanthanoids (= 95%) and Iron(= 5%)
3. In alkaline medium MnO oxidises r into
4
(4) Rate of reaction is slower in presence of
HCI (3) Lanthanoids
[NCERT Pg. 234}
6. Which among the following ions has a (= 90%)and calcium(= 10%)
(1) 10; magnetic moment of 5.92 BM? (4) Actinoids (=95%) and calcium (=5%)
(2) 10; [NCERT Pg. 228} 10. Among •3d series, the enthalpy of
(3) '2 (1) Zn 2 + (2) V3+ atomization is lowest for [NCERT Pg. 220)
(4) 10; (3) Fe2 + (~) Mn 2+ (1) Mn (2) Sc
4. The correct order of ionic radii of I .7. Most common oxidation state of fanthanoids (3) Zn (4) Cu
Eu34-, La 3+ and y 3 +is is fNCERT Pg. 235}
fNCERT Pg. 236] 11. The nature of Cr2 • and Mn 3 • respectively are
(1) +3 (2) [NCERT Pg. 224)
(1) Eu3+ > La3+ > y3+
(3) +2 (4) +5 (1) Oxidising and reducing
(2) y 3+ > Eu3+ > La 3+
B. Which of the following options represents (2) Oxidising and oxidising
(3) Lal+ > Eu3+ > y3+ the correct order of decreasing second
(3) Reducing and reducing
(4) Lal+ > y 3+ > E u3+ ionization enthalpy for the given elements?
[NCERT Pg. 2201 (4) Reducing and oxidizing
12. The incorrect statement regarding interstitial 17. Which of the following group elements are 23. Ferrates (VI) decomposes to give ---
compounds Is [NCERT Pg. 230) called coinage metals? [NCERT Pg. 239) (NCERT Pg; 226]
(1) These_are usually non stoichiometric (1) Group-10 (2) Group-12 (1) Fe203 and 02 (2) FeO and Oa
· (2) These have high melting points, higher (3) Group-11 (4) Group-9 (3) Fe30, and 03 (4) Fe and az· 1\
than those of pure metals. 18. Which of the following species is not 24. Which ~f ~e fol~~~ng pairs of elements 1
(3) These are neither typically ionic nor obtained when KMnQ4 is decomposed at exhibit similar radn? [NCERT Pg. 220] •
covalent 513 K? [NCERT Pg. 233) (1) Zr, Hf
(4) These are chemically more reactive than (1) K2MnQ4 (2) 02 (2) Ti, Zr
pure metal . (3) MnO (4) MnO2 (3) Cu, Ag
13. Cu(II) halides are known except 19. Among 3d series elements first ionization (4) Mn, Tc
[NCERT Pg. 226) energy is maximum for [NCERT Pg. 220] 25. V2Os reacts with alkalies to give
(1) Iodides (2) Bromides (1) Cu (2) Mn [NCERT Pg. 226]
(3) Chlorides (4) Fluorides (3) Zn (4) Ni · (1 > vo 2+ (2) V2O4
14. Which of the following elements is not 20. Select the incorrect statement among the (3) VQ43- (4) V203
regarded as transition element? following . [NCERT Pg. 236,237,238]
26. The colour of KzMn04, Na2Cr2Cn.2HzQ
[NCERT Pg. 215) (1) Mixed oxides of lanthanoids are used as · KzCr0 4 respectively are [NCERT Pg. 231]
catalysts in petroleum cracking.
-_(1) Cd (2) Mn (1) Yellow, Orange, Dark green
(2) All actinoids are radioactive elements
(3) Os (4) Nb (2) Orange, Yellow, Purple
(3) The melting point of samarium is 1623 K
15. The correct increasing order of oxidizing (3) Dark Green, Orange, Orange
power of MnO4, er2 ~ - and vo; is
(4) The actinoid contraction is lower from
(4) Dark Green, Orange, Yellow
element to element than the lanthanoid
[NCERT Pg. 226] , 27. The element which has the highest enthalpy
contraction.
(1) vo; < MnO4 < cr2 ~ of atomisation is [NCERT Pg. 22~
21 . Which of the following elements of 5d series
has the highest melting point? (1) Ti (2) V
(2) vo; < cr2~ - < MnO4
[NCERT Pg. 218) (3) Cr (4) Mn
(3) Cr2~ - <MnO4 <VO; 28. The correct order of ionic radii is
(1) Ta (2) W
(4) MnO4 <Cr2~ - <Vo; (3) Re (4) Os . [NCERT Pg. 23~
0
22. The element which has positive E MA3+JMA2+ is (1) Pm3• > Nd 3• > Sm3• > pr3+
16. Which of the following aquated transition
metal ion is colourless? [NCERT Pg. 229] [NCERT Pg. 220) (2) . Sm3• > Pm 3• > Nd3+ > pr3+
(1) Cu 2• (2) Ti4• (1) Ti (2) V (3) pr3+ > Nd 3• > Pm 3• > Sm3•
(3) Mn 3• (4) Co2• (3) Cr . (4) Fe (4) Nd 3• > pr3+ > Pm 3+ > Sm3+
 ~ reffT .
~ i c h of the following elements, the 6d
(3) Tl < V < Cr < Mn: Density
.......--~ ·---·--· --···-··
37. Complete the followlng flff In Che bllnkl I, b,
29. :;,,,,tal is vacant? [NCERT Pg. 237]
(4) Tl < Mn < Fe < Zn: First ionization c and d by using_followlng given opUonl
(1) Lr (2=103) (2) Cm (2=96) energy (NCERT Pg. 228)
(3) Np (2=93) (4) Fm (2=100) .
34. Select the correct option related to oxidation (a) The ability of fluorine to atablllled the
highest oxidation state Is due to either
0 The metals which are present in Ziegler
3. state of transition metals (NCERT Pg. 222)
natta Catalyst are [NCERT Pg. 240] higher ......or higher....
(a) Copper and zinc generally do not show
(1) V _and Ti (2) Ti and Al _ (b) All copper 01) halides are known
stable oxidation state more than +2
(3) Ti and Mg (4) Zr and Zn except... ...
(b) Titanium (Ill) Is more stable than of
(c) V20s on reaction with alkalies and acids
31. Number of unpaired electrons in 4f- subshell Titanium (II) while less stable than of
respectively fonns ... and ...
In trivalent state of Nd, Tb and Tm metals Titanium (IV) .
(d) CrO Is .... but Cr03 Is ....
respectively are (Atomic number of Nd = 60, (c) MoO3 is better oxidizing agent than Cr03
(1) Lattice energy, bond enthalpy, bromide,
Tb = 65 and Tm = 69) [NCERT Pg. 236] but weaker oxidizing than WO3
orthovanadate Ion (V04)>",
(1) 3, 5, 1 (2) 3,6,2 (d) Low · oxidation states are found in dioxovanadium Ion basic, basic
(3)3,7,2 (4)2,5,1 complex compounds having n-acid (2) Lattice energy, bond enthalpy, fluoride,
32. Select the correct statement(s) in the ligands
orthovanadate Ion (V04)>",
following [NCERT Pg. 226] (1)_Only a (2)Only a and d dioxovanadium basic, basic
(a) In mercurous ion metal-metal bond is (3) Only a, band d . (4)Only a, band c (3) Bond enthalpy, hydration energy,
present · 35. Incorrect statement about the chloride, orthovanadate Ion (V04)>",
(b) FeCl2 and SnCl2 compounds can exist characteristics of interstitials compound is dioxovanadium basic, acidic
together '[NCERT Pg. 230] (4) Lattice energy, Bond enthalpy, Iodide,
(c) All the metals of 3d series except (1} They are having higher melting points orthovanadate Ion (V04 )3-,
scandium can form oxide of +2 oxidation than parent metals dioxovanadium basic, acidic
-state (2) They are very hard, some borides 38. How many statement(s) is /are correct?
(d) Co3O4 is an example of mixed oxide and . approach diamond in hardness [NCERT Pg. 235]
having similar lattice structure as of (3) They retain metallic conductivity (a) Formation of Ce (IV) ion Is favoured by
Fe3O4 its noble gas configuration.
(4) They are chemically more reactive than
(1) only a and c (2) only a and b (b) Pr, Nd, Tb and Dy in its oxides can
parent metals
exhibit +4 oxidation state
(3) only a, b and c (4) a, b, c and d . 36. Number of mole (s) of permanganate ion
(c) Yb (II) is a reductant while Tb (IV) is an
33. Select the incorrect order of property required to oxidize one m9ie thiosulphate
oxidant
mentioned [NCERT Pg. 218] ion completely in faintly alkaline medium, is
(d) Lanthanoids can liberate hydrogen from
(1) Hf< Ta <W < Re: Melting point [NCERT Pg. 234] dilute acids
(2) Zn < Mn < Fe < V: Enthalpy of (1) 2 (2) 1.5 (1) 1 (2) 2
atomisation (3) 0.33 (4) 2.67 · (3) 3 (4) 4
 - - - - - - - - - - - - - - - - - - - - - - - - - - - : - - - : - ( c ~ ) Due to comparable energies of --c:.
s,, ed
39. The aqueous solution of which of the 40. Select the correct statement(s) about and 7s orbitals, they have smallerral'IQI
following ions will be_ colourless? (Atomic Actinoids among the following of oxidation states
Number, Co= 27, Ti= 22, Er= 68, Ce= 58 ) [NCERT Pg. 2381 (d) + 3 and + 4 ions of these elementa do
(a) Neptunium shows highest number of not hydrolyse .
[NCERT Pg. 229) - possible oxidation states. ( ) Only a (2) Only a Bild d
(1) Ce (Ill) 1
(2) Er (111) (b) Sf-orbitals present in these elements are ( ) Only a and c (4) a, b, c and d
(3) Co(III) much more buried than 4f orbitals of 3
(4) Ti (IV)" .
lanthanoids

9Jhinking i_n Context

1. The trend of steady increase in second 16. TiCl 4 with ___ forms the basis of the
9. The formula of chromite ore is _ __
ionization enthalpy breaks for _
the formation Ziegler catalysts, used to manutacture
[NCERT Pg. 231)
of ___ along 3d series. polythene. [NCERT Pg. 240)
10. Manganese (II) ion salts are oxidised by
[NCERT Pg. 221) 17. Sodium dichromate is soluble than
peroxodisulphate to _ __
potassium dichromate.
2. Manganese exhibits all the oxidation states [NCERT Pg. 233]
from +2 to___ [NCERT Pg. 223) [NCERT Pg. 232]
11. The almost identical radii of Zr and ___is 18. For 3d series the value of E (M 2•1M) for Mn,
0

3. In 3d series, _the E 0
(M 2•/M)value for _ __ a · consequence of the lanthanoid
is positive. [NCERT Pg. 220) contraction. [NCERT Pg. 235] --- and Zn are more negative than
expected from the trend.
4. The highest Mn fluoride is 12. Pr, Nd, Tb and Dy also exhibit +4 oxidation [NCERT Pg. 227]
[NCERT Pg. 226) state but ohly in _ _ . [NCERT Pg. 235)
19. For the compounds of the first series of
5. In aqueous solution, the colour of Fe3• ion is 13. In General, in chemical behavior, .the earlier ·transition metals, the contribution of the
[NCERT Pg. 229) members of the lanthanoid series are quite angular momentum is effective~
6. Iron (Ill) catalyses the reaction between reactive similar to _ __ quenched and hence is of no significance,
iodide and ___ ions. [NCERT Pg. 230] [NCERT Pg. 236) [NCERT Pg. 228]
7. Bronze is an alloy of copper and 14. In general, actinoids show oxidation 20. The dichromate ion consists of two
[NCERT Pg. 230] state. [NCERT Pg. 238) tetrahedral sharing one comer with
Cr - 0 - Cr bond angle of _ _.
8. Among 3d series all the metals except 15. _ _ _ is manufactured specially for the
- -- form MO oxides. [NCERT Pg. 231] pigment industry. [NCERT Pg. 239)
[NCERT Pg. 232]
8.1. Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transi on element?
Ans: The outer electronic configura on of Ag (Z=47) is 4d105s1. It shows+1 and + 2 O.S. (in AgO and AgF2).
And in + 2 O.S., the electronic configura on is d9 i.e, d-subshell is incompletely filled. Hence, it is a
transi on element.

8.2. In the series Sc(Z = 21) to (Z = 30), the enthalpy of atomisa on of zinc is the lowest i.e., 126 kJ mol-
1
. Why?
Ans: The enthalpy of atomisa on is directly linked with the stability of the crystal la ce and also the
strength of the metallic bond. In case of zinc (3d104s2 configura on), no electrons from the 3d-orbitals
are involved in the forma on of metallic bonds since all the orbitals are filled. However, in all other
elements belonging to 3d series one or more d-electrons are involved in the metallic bonds. This means
that the metallic bonds are quite weak in zinc and it has therefore, lowest enthalpy of atomisa on in the
3d series.

8.3. Which of the 3d series of the transi on metals exhibits the largest number of oxida on states and
why?
Ans: Manganese (Z = 25) shows maximum number of O.S. This is because its outer EC is 3d 54s2. As 3d
and 4s are close in energy, it has maximum number of e-1 s to loose or share. Hence, it shows O.S. from
+2 to +7 which is the maximum number.

8.4.

Ans.

8.5. How would you account for the irregular varia on of ionisa on enthalpies (first and second) in the
first series of the transi on elements?
Ans: There is a irregularity in the IE’s of 3d-series due to alterna on of energies of 4s and 3d orbitals
when an e-1 is removed. Thus, there is a reorganisa on energy accompanying ioniza on. This results into
release of exchange energy which increases as the number of e -1 s increases in the dn configura on. Cr
has low 1st IE because loss of 1 e- gives stable EC (3d6). Zn has very high IE because e~ has to be
removed from 4s orbital of the stable configura on (3d10 4s2) A er the loss of one e–, removal of 2nd e–,
becomes difficult. Hence, 2nd IE’s are higher and in general, increase from le to right. However, Cr and
Cu show much higher values because 2nd e– has to be removed from stable configura on of Cr+ (3d5) and
Cu+ (3d10)

8.6. Why is the highest oxida on state of a metal exhibited by its fluoride and oxide only? (C.B.S.E.
Delhi 2010)
Ans: Both fluorine and oxygen have very high electronega vity values. They can oxidise the metals to the
highest oxida on state. As a result, the highest oxida on states are shown by the fluorides and oxides of
the metals; transi on metals in par cular.

[Link] is a stronger reducing agent Cr2+ or Fe2+ and why?

Ans: Cr2+ is a stronger reducing agent than Fe2+. This is because E°(Cr3+/Cr2+) is nega ve (- 0.41V) whereas
E°(Fe3+/Fe2+) is posi ve (+ 0.77 V). Thus, Cr2+ is easily oxidised to Fe3+ but Fe2+ cannot be easily oxidised to
Fe3+.

[Link] the ‘spin only’ magne c moment of M2+(aq) ion (Z = 27).

Ans:

[Link] why Cu+ ion is not stable in aqueous solu ons?

Ans: Cu+ (aq) is not stable, while Cu2+ (aq) is stable. This is becuase ΔhydH of Cu2+(aq) is much higher than
that of Cu+(aq) and hence it compensates for the 2nd IE of Cu. Thus, many Cu(I) compounds are unstable
in aqueous solu on and undergo dispropor ona on as follows :
2 Cu+ —–> Cu2+ + Cu

8.10. Ac noid contrac on is greater from element to element than lanthanoid contrac on. Why?
(C.B.S.E. Sample Paper 2011, Jharkhand Board 2010)
Ans: The decrease or contrac on in atomic radii, as well as ionic radii in ac noid elements (ac noid
contrac on), is more as compared to lanthanoid contrac on because 5/ electrons have more poor
shielding effect as compared to 4f electrons. Therefore, the effect of increased nuclear charge leading to
contrac on in size is more in case of ac noid elements.

NCERT EXERCISES

8.1. Write down the electronic configura on of (i) Cr3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+(v) Co2+ (vi) Lu2+(vii)
Mn2+ (viii) Th4+.
Sol: (i) Cr3+ = [Ar]183d3
(ii)Pm3+ = [Xe]54 4f4
(iii)Cu+ = [Ar]18 3d10
(iv)Ce4+ = [Xe]54
(v)Co2+ = [Ar]18 3d7
(vi)Lu2+ = [Xe]54 4f14 5d1
(vii) Mn2+ = [Ar]18 3d5 (viii)Th4+= [Rn]86

8.2. Why are Mn2+ compounds more stable than Fe2+ towards oxida on to their+3 state?
Sol: Electronic configura on of Mn2+ is 3d5. This is a half-filled configura on and hence stable. Therefore,
third ioniza on enthalpy is’very high, i. e., third electron cannot be lost easily. Electronic configura on of
Fe2+ is 3d6. It can lose one electron easily to achieve a stable configura on 3d5.

8.3. Explain briefly how+2 state becomes more and more stable in the first half of the first row
transi on elements with increasing atomic number?
Sol: Here a er losing 2 electrons from j-orbitals, the 3d-orbital gets gradually occupied with increase in
atomic number. Since the number of unpaired electrons in 3d orbital increases, the stability of the
ca ons (M2+) increases from Sc2+ to Mn2+.

8.4. To what extent do the electronic configura ons decide the stability of oxida on states in the first
series of the transi on elements? Illustrate your answer with examples.
Sol: In the first series of transi on elements, the oxida on states which lead to exactly half-filled or
completely filled d-orbitals are more stable. For example, Mn (Z = 25) has electronic configura on [Ar]
3d5 4 s2. It shows oxida on states + 2 to + 7 but Mn (II) is most stable because of half-filled configura on
[Ar] 3d5. Similarly Sc3+ is more stable then Sc+ and Fe3+ is more stable than Fe2+ due to half filled it f-
orbitals.

8.5. What may be the stable oxida on state of the transi on element with the following delectron
configura ons in the ground state of their atoms: 3d3,3d5, 3d8 and 3d4?
Sol: (a) 3d3 4s1 = + 5.
(b) 3d5 4s2 = + 2, + 7,3d5 4s1 =+6.
(c)3d84s2 = + 2.
(d)3d44s2 = 3d5 4s1 = + 6(and + 3).

8.6. Name the oxometal anions of the first series of the transi on metals in which the metal exhibits
the oxida on state equal to its group number.
Sol: Cr2072- and Cr042- (Group number = Oxida on state of Cr = 6).
Mn04– (Group number = Oxida on state of Mn = 7).

8.7. What is lanthanoid contrac on? What are the consequences of lanthanoid contrac on?
Sol: Lanthanoid Contrac on : In the lanthanoids , the electrons are ge ng filled in the 4f-subshell. On
moving from le to right, the nuclear charge increases and this increase is expected to be compensated
by the increase in the magnitude of shielding effect by the 4 f- electrons However,
the f-electrons have very poor shielding effect. Consequently, the atomic and ionic radii decrease from
le to right and this is knwon as lanthanoid contrac on.
Consequences of lanthanoid Contrac on
(a)Separa on Lanthanoids: All the lanthanoids have quite similar proper es and due to this reason they
are difficult to separate.
(b)Varia on in basic strength of hydroxides: Due to lanthanoid contrac on, size of M3+ ions decreases
and thus there is a corresponding increase in the covalent character in M—OH bond. Thus basic
character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3.
(c)Similarity in the atomic sizes of the elements of second and third transi on series present in the same
group. The difference in the value of atomic radii of Y and La is quite, large as compared to the difference
in the value of Zr and Hf. This is because of the lanthanoid contrac on.
(d)Varia on in standard reduciton poten al: Due to lanthanoid contrac on there is a small but steady
increase in the standard reduc on poten al (E°) for the reduc on process.
M3+ (aq) + 3e– —–> 4 M(aq)
(e)Varia on in physical proper es like mel ng point, boiling point, hardness etc.

8.8. What are the characteris cs of the transi on . elements and why are they called transi on
elements? Which of the d-block elements may not be regarded as the transi on elements?
Sol: General characteris cs of transi on elements.
(i)Electronic configura on – (n -1) d1-10 ns1-2
(ii)Metallic character – With the excep ons of Zn, Cd and Hg, they have typical metallic structures.
(iii)Atomic and ionic size-ions of same charge in a given series show progressive decrease in radius with
increasing atomic number.
(iv)Oxida on state-Variable; ranging from+2 to +7.
(v)Paramagne sm – The ions with unpaired electrons are paramagne c.
(vi)Ionisa on enthalpy – Increases with increase in charge.
Forma on of coloured ions – Due to presence of unpaired electrons.
(viii) Forma on of complex compounds – Due to small size and high charge density of metal ions.
(ix)They possess catalj^c proper es – Due to
their ability to adopt mul ple oxida on states. .
(x)Forma on of inters al compounds.
(xi)Alloy forma on.
They are called transi on elements due to their incompletely filled d-orbitals in ground state or in any
stable oxida on state and they are placed between s and p- block elements. Zn, Cd and Hg have fully
filled d- orbitals in their ground state hence may not be regarded as the transi on elements.

8.9. In what way are the electronic configura on of the transi on elements different from non-
transi on elements?
Sol: Electronic configura on of transi on elements : (n – 1)d1-10 ns1-2. Electronic configura on of non-
transi on elements : ns1-2 or ns2np1-6. From comparison, it is quite evident that the transi on elements
have incomplete d-orbitals (s- orbitals in some cases) while the non-transi on elements have no d-
orbitals present in the valence shells of their atoms. This is responsible for the difference in the
characteris cs of the elements belonging to these classess of elements.

8.10. What are the different oxida on states exhibited by the lanthanoids?
Sol: Lanthanides exhibits + 2, + 3 and + 4 oxida on states. The most common oxida on state of
lanthanoids is +3.

8.11. Explain giving reasons:

(i)Transi on metals and many of their compounds show paramagne c behaviour.
(ii)The enthalpies of atomisa on of the transi on metals are high.
(iii)The transi on metals generally form coloured compounds.
(iv)Transi on metals and their many compounds act as good catalyst
Sol: (i) Magne c proper es: Transi on elements and many of their compounds are paramagne c, i.e.,
they are weakly a racted by a magne c field. This is due to the presence of unpaired electrons in atoms,
ions or molecules. The paramagne c character increases as the number of . unpaired electrons
increases. The paramagne c character is measured in terms of magne c moment and is given by
μ=n(n+2)−−−−−−−√ where n – number of unpaired electrons.
(ii) Because of large number of unpaired electrons in d-orbitals of their atoms they have stronger
interatomic intefac ons and hence stronger metallic bonding between atoms resul ng in higher
enthalpies of atomisa on.
(iii) Forma on of coloured compounds (both in solid state as well as in aqueous solu on) is another very
common characteris cs of transi on metals. This is due to absorp on of some radia on from visible light
to cause d-d transi on of electrons in transi on metal atom. The d-orbitals do not have same energy and
under the influence of ligands, the d-orbitals split into two sets of orbitals having different energies;
transi on of electrons can take place from one set of d-orbitals to another set within the same sub-shell.
Such transi ons are called d-d transi ons. The energy difference for these d-d transi ons fall in the
visible region. When white light is incident on compounds of transi on metals, they absorb a par cular
frequency and remaining colours are emi ed impar ng a characteris c colour to the complex. Zn2+ and
Ti4+ salts are white because they do not absorb any radia on in visible region.
(iv)Cataly c proper es: Many of transi on metals and their compounds act as catalyst in variety of
reac ons, e.g., finely divided iron in manufacture of NH3 by Haber’s process, V2O5 or Pt in manufacture
of H2S04 by Contact process, etc.). The cataly c ac vity is due to following two reasons.
(a)The ability of transi on metal ion to pass ” easily from one oxida on state to another
and thus providing a new path to reac on with lower ac va on energy.
(b)The surface of transi on metal acts as very good adsorbent and thus provides increased
concentra on of reactants on their surface causing the reac on to occur.

8.12. What are inters al compounds? Why are such compounds well known for transi on metals?
Sol: Transi on metals form large number of inters al compounds. They are able to entrap small atoms
of elements like H, G, N, B, etc., in their crystal la ce and even can make weak bonds with them.
Due to forma on of inters al compounds, their malleability and duc lity decreases and tensile .
strength increases. Steel and cast iron are hard in comparison to wrought iron due to the presence of
trapped carbon atoms in inters al spaces.

8.13. How is the variability in oxida on states of transi on metals different from that of the non-
transi on metals? Illustrate with examples.
Sol: The transi on metals show a number of variable oxida on states due to the par cipa on of (n – 1) d
electrons in addi on to ns electrons in the bond forma on. They therefore, exhibit a large number of
variable oxida on states. On the other hand, the non-transi on metals generally belonging to s-block do
not show variable oxida on states because by the loss of valence s-electrons, they acquire the
configura on of the nearest noble gas elements.

In the p-block the lower oxida on states are favoured by the heavier members (due to inert pair effect),
the opposite is true in the groups of d-block. For example, in group 6, Mo(VI) and W(VI) are found to be
more stable than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising
agent, whereas MoO3 and WO3 are not.
8.14. Describe the prepara on of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solu on of potassium dichromate?
Sol: Potassium dichromate is prepared from chromate, which in turn is obtained by the fusion of
chromite ore (FeCr2O3) with sodium or potassium carbonate in free excess of air. The reac on with
sodium carbonate occurs as follows:

The yellow solu on of sodium chromate is filtered and acidified with sulphuric acid to give a solu on
from which orange sodium dichromate, Na2Cr,07.2H20 can be crystallised.

Sodium dichromate is more soluble than potassium dichromate. The la er is therefore, prepared by
trea ng the solu on of sodium dichromate with potassium chloride.

Orange crystals of potassium dichromate crystallise out. The chromates and dichromates depending
upon pH of the solu on. If pH of potassium dichromate is increased it is converted to yellow potassium
chromate.

8.15. Describe the oxidising ac on of potassium dichromate and write the ionic equa ons for its
reac on with:
(i)iodide
(ii)iron (II) solu on and
(iii)H2S
Sol: K2Gr207is a powerful oxidising agent. In dilute sulphuric acid medium the oxida on state of Cr
changes from+6 to + 3. The oxidising ac on can be represented as follows:

8.16. Describe the prepara on of potassium permanganate. How does the acidified permanganate
solu on react with (i) iron (II) ions (ii) S02 and (iii) oxalic acid? Write the ionic, equa ons for the
reac ons.
Sol: Potassium permanganate (KMn04) is prepared by the fusion of a mixture of pyrolusite
(Mn02),potassiufn hydroxide and oxygen, first green coloured potassium manganate is formed. 2MnO 2 +
4KOH + 02 —> 2K2Mn04+2H20 The potassium manganate is extracted by water, which then undergoes
dispropor ona on in neutral or acidic solu on to give potassium permanganate.

8.17. For M2+/M and M3+/M2+ systems the E° values

for some metals are as follows:
Cr2+/Cr –> -0.9 V
Mn2+/Mn –> -1.2V
Fe2+/Fe –> -0.4 V
Cr3+/Cr2+ –> -0.4 V
Mn3+/Mn2+ –>+ 1.5V
Fe3+/Fe2+ –>+ 0.8V
(ii)the ease with which iron can be oxidised as compared to a similar process for either chromium or
manganese metal.
Sol: (i) Cr3+/Cr2+ has nega ve reduc on poten al. Hence, Cr3+ cannot be reduced to Cr2+. Mn3+/Mn2+ has a
large posi ve reduc on poten al. Hence, Mn3+ can be easily reduced to Mn2+. Fe3+/Fe2+ has small
posi ve reduc on poten al. Hence, Fe3+ is more stable than Mn3+ but less stable than Cr3+.
(ii)From the E° values, the order of oxida on of the metal to the divalent ca on is : Mn > Cr > Fe.

8.18. Predict which of the following will be coloured in aqueous solu on?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+, Co2+.
Sol: Only those ions will be coloured which have incomplete d-orbitals. The ions with either empty or
filled d-orbitals are colourless. Keeping this in view, the coloured ions among the given list are :
Ti3+(3d1), V3+(3d2), Mn2+(3d5), Fe3+(3d5), Co2+ (3d7)
Sc3+ (3d°) and Cu+ (3d10) ions are colourless.

8.19. Compare the stability of +2 oxida on state for the elements of the first transi on series.
Sol: In general, the stability of +2 oxida on state in first transi on series decreases from le to right due
to increase in the sum of first and second ionisa on energies. However Mn2+ is more stable due to half
filled d-orbitals (3d5) and Zn2+ is more stable due to completely filled d-orbitals (3d10).

8.20. Compare the chemistry of ac noids with that of the lanthanoids with special reference to
(i)electronic configura on,
(ii)atomic and ionic sizes and
(iii)oxida on state
(iv)chemical reac vity.
Sol: (i) Electronic configura on: The general electronic configura on of lanthanoids is [Xe]54 4f1-14 5d0-
1
6s2 and that of ac noids is [Rn]86 5f0-14 6d0-1 7s2, lanthanoids . belong to 4 f series whereas ac noids
belong to 5f-series.
(ii) Atomic and ionic sizes: Both lanthanoids and ac noids show decrease in size of their atoms or ions in
+ 3 oxida on state as we go from le to right. In lanthanoids, the decrease is called lanthanoid
contrac on whereas in ac noids, it is called ac noid contrac on. The contra bn is greater from element
to element in ac nodes due to poorer shielding by 5f electrons.
(iii)Oxida on state: Lanthanoids show limited oxida on states (+ 2, + 3, + 4) out of which + 3 is most
common whereas ac noids show +3, +4, +5, +6, +7 oxida on [Link] is because of large energy gap
between 4f 5d and 6s orbitals. However, ac noids show a large number of oxida on states because of
small energy ap- between 5f 6d and Is orbitals.
(iv) Chemical reac vity: The earlier members
of the lanthanoids series are quite reac ve similar to calcium but, with increase in atomic number, they
behave more like aluminium. The metals combine with hydrogen when . gently heated in the gas.
Carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated with carbon. They liberate
hydrogen from dilute acid and burn in halogens to form halides. They form oxides M 203 and hydroxides
M(OH)3.
Ac noids are highly reac ve metals, especially when finely divided. The ac on of boiling water on them
gives a mixture of oxide and hydride and combina on with most non-metals take place at moderate
temperatures. HCl a acks all metals but most are slightly affected by nitric acid owing to the forma on
of protec ve oxide layers, alkalis have no ac on. Ac noids are more reac ve than lanthanoids due to
bigger atomic size and lower ionisa on energy.
8.21. How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing.
(ii) Cobalt (II) is stable in aqueous solu on but in the presence of complexing reagents it is easily
oxidised.
(iii) The d1 configura on is very unstable in ions.
Sol: (i) E° value for Cr3+/Cr2+ is nega ve (-0-41 V) whereas E° values for Mn3+/Mn2+is posi ve (+1.57 V).
Hence, Cr2+ ion can easily undergo oxida on to give Cr3+ ion and, therefore, act as strong reducing agent
whereas Mn3+ can easily undergo’ reduc on to give Mn2+ and hence act as an oxidizing agent.
(ii) Co (III) has .greater tendency to form coordina on complexes than Co (II). Hence, in the presence of
ligands, Co (II) changes to Co (III), i.e., is easily oxidized.
(iii) The ions with dx configura on have the tendency to lose the only electron present in d-subshell to
acquire stable d° configura on. Hence, they are unstable and undergo oxida on or dispropor ona on.

8.22. What is meant by dispropor ona on? Give two examples of dispropor ona on reac on in
aqueous solu on
Sol: Dispropor ona on reac ons are those in which the same substance undergoes oxida on as well as
reduc on, i.e., oxida on number of an element increases as well as decreases to form two different
products.

8.23. Which metal in the first transi on metal series exhibits +1 oxida on state most frequently and
why?
Sol: Cu with configura on [Ar] 4s13d10 exhibits +1 oxida on state and forms Cu+ ion because by losing
one electron, the ca on or posi ve ion acquires a stable configura on of d-orbitals (3d10).

8.24. Calculate the number of unpaired electrons in the following gaseous ions : Mn 3+, Cr3+, V3+ and
Ti3+. Which one of these is the most stable in aqueous solu on.
Sol: Mn3+ = 3d1 = 4 unpaired electrons, Cr3+ = 3d3 = 3 electrons,V3+ = 3d2 = 2 electrons, Ti3+=3d1 = l
[Link] of these, Cr3+ is most stable in aqueous solu on because of half-filled t2g level.

8.25. Give examples and suggest reasons for the following features of the transi on metal chemistry:
(i) The lowest oxide of transi on metal is basic the highest is amphoteric/ acidic.
(ii) A transi on metal exhibits highest oxida on state ih oxides and fluorides.
(iii) The highest oxida on state is exhibited in oxoanions of a metal.
Sol: (i) The lower oxide of transi on metal is basic because the metal atom has low oxida on state
whereas higher once are acidic due to high oxida on state. For example, MnO is basic whereas Mn2O7is
acidic. Oxides in lower oxida on state are ionic hence basic. Oxides in higher oxida on state are covalent
hence acidic
(ii) A transi on metal exhibits higher oxida on states in oxides and fluorides because oxygen and fluorine
are highly electronega ve elements, small in size and strongest oxidising agents. For example, osmium
shows an oxida on states of + 6 in O5F6and vanadium shows an oxida on states of + 5 in V2O5.
(iii) Oxo metal anions have highest oxida on state, e.g., Cr in Cr2072- has an. oxida on state of + 6
whereas Mn in Mn04– has an oxida on state of + 7. This is again due to the combina on of the metal
with oxygen, which is highly electronega ve and oxidizing agent.

8.26. Indicate the steps in the prepara on of:

(i)K2Cr207from chromite ore
(ii)KMn04 from pyrolusite ore.
Sol:

8.27. What are alloys? Name an alloy which contains some lanthanoid metals. Men on its uses.
Sol: An alloy is a homogeneous mixture of different metals or metals and non-metals.
Misch metal is an alloy of cerium (Ce). lanthanum (La), neodymium (Nd), iron (Fe) and traces of carbon,
sulphur, aluminium etc. It is used in making parts of jet engines.

8.28. What are inner transi on elements? Decide which of the following atomic numbers are the
atomic numbers of the inner transi on elements: 29,59,74,95,102,104.
Sol: The f-block elements in which the. last electron enters into f-sub shell-are called inner-transi on
elements. These include lanthanoids (Z=58 to 71) and ac noids (Z=90 to 103). Thus, the elements with
atomic numbers 59,95 and 102 are the? inner transi on elements.

8.29. The chemistry of the ac noid elements is not so smooth as that of the lanthanoids. Jus fy this
statement by giving some examples from the oxida on state of these elements.
Sol: Lanthanoids show limited number of oxida on state, viz, + 2, + 3 and + 4 (out of which + 3 is most
common). This is because of large energy gap between 4f 5d and 6s subshells. The dominant oxida on
state of ac noids is also + 3 but they show a number of other oxida on states also. For example,
uranium (Z=92) and plutonium (Z – 94), show + 3, + 4, + 5 and + 6, neptunium (Z = 94) shows + 3, +4, + 5
and + 7, etc. This is because of the small energy difference between. 5f, 6d and 7s orbitals of the
ac noids.

8.30. Which is the last element in the series of the ac noids? Write the electronic configura on of this
element. Comment on the possible oxida on state of this element
Sol: Last ac noid=Lawrencium (Z = 103)
Electronic configura on = [Rn]86 5f14 6d1 7s2 Possible oxida on state = + 3.

8.31 Use Hund’s rule to derive the electronic configura on of Ce3+ ion, and calculate its magne c
moment on the basis of ‘spin-only’ formula.
Sol.

8.32. Name the members of the lanthanoid series which exhibit +4 oxida on state and those which
exhibit +2 oxida on state. Try to co-relate this type of behaviour with the electronic configura on of
these elements.
Sol: +4 oxida on state : 58Ce, 59Pr, 65Tb
+ 2 oxida on state : 60Nd, 62Sm, 63Eu, 69Tm, 70Yb.
In general +2 oxida on state is exhibited by the elements with configura on 5d06s2 so that two electrons
may be easily lost. Similarly +4 oxida on state is shown by the elements which a er losing four electrons
acquire configura on either close to 4f0 or 4f7.

8.33. Compare the chemistry of ac noids with that of lanthanoids with reference to:
(i)Electronic configura on
(ii)Oxida on states
(iii)Chemical reac vity
Sol: (i)Electronic configura on : In lanthanoids 4f- orbitals are progressively filled whereas in ac noids
5f-orbitals are progressively filled.
(ii)Oxida on states : Lanthanoids shows +3 oxida on state. Some elements shows +2 and +4 oxida on
state also. Ac noids shows +3, +4, +5 +6, +7 oxida on states. Although +3 and +4 are most common.
(iii)Chemical reac vity : Ac noids are more reac ve than lanthanoids due to bigger atomic size and
lower ionisa on energy.

8.34. Write the electronic configura ons of the elements with the atomic numbers 61,91,101 and 109.
Sol: Z=61 (Promethium, Pm) [Xe]544f55d0 6s2
Z = 91 (Protac nium, Pa) => [Rn]86 5f2 6d1 7s2
Z = 101 (Mendelevium, Md)=> [Rn]86 5f13 6d0 7s2
Z = 109 (Meitnerium, Mt) [Rn]86 5f14 6d7 7s2

8.35. Com pare the general characteris cs of the first series of the transi on metals with those of the
second and third series metals in the respec ve ver cal columns. Give special emphasis on the
following points:
(i)electronic configura ons
(ii)oxida on states
(iii)ionisa on enthalpies and
(iv)atomic sizes
Sol: (i) Electronic configura on: The elements in the same ver cal column generally have similar
electronic configura on. First transi on series shows only two excep ons, i.e., Cr = 3d5 4s1 and Cu =
3d10 4s1. But second transi on series shows more excep ons, i.e., Y = 4d1 5s2, Nb = 4d1 , 5s1 ,
Mo=4d5 5s1 , Ru=4d1 5s1 , Rh=4d8 5s1 , Pd , =4d10 5s°, Ag=4d10 5s1 . In third transi on, there are two
excep ons, i.e„ Pt = 5d9 6s1 and Au = 5d10 6s1 .
Thus in the same ver cal column, in a number of cases, the electronic configura on of the elements of
three series are not similar.
(ii) Oxida on states: The elements in the same ver cal column generally show similar oxida on states.
The number of oxida on states shown by the elements in the middle of each series is maximum and
minimum at the extreme ends.
(iii)Ioniza on enthalpies: The first ioniza on enthalpies in each series generally increases gradually as
we more from le to right though some excep ons are observed in each series. The first ioniza on
enthalpies of some elements in the second (4d) series are higher while some of them have lower value
than the elements of 3d series in the same ver cal column. However, the first ioniza on enthalpies of
third (5d) series are higher than those of 3d and Ad series. This is because of weak shielding of nucleus
by 4f-electrons in the 5d series.
(iv)Atomic sizes: In general, ions of the same charge or atoms in a given series show progressively
decrease in radius with increasing atomic number though the decrease is quite small. But the size of the
atoms of the Ad series is larger then the corresponding elements of the 3d series whereas size of
elements of the 5d-series nearly the same as those of Ad series because of lanthanoid contrac on.

8.36. Write down the number of 3d electrons in each of the following ions:Ti 2+, V2+, Cr3+, Mn2+, Fe2+,
Fe2+, Co2+, Ni2+ and Cu2+. Indicate how would you expect the five 3d orbitals to be occupied for these
hydrated ions (octahedral).
Sol:

8.37. Comment on the statement that elements of first transi on series possess many proper es
different from those of the heavier transi on elements.
Sol: The heavier transi on elements belong to fourth (Ad) and fi h (5d) and sixth (6d) transi on series.
Their proper es are expected to be different from the elements belonging to the first (3d) series due to
the following reasons :
(i) The atomic radii of the elements belonging to Ad and 5d series are more due to greater number of
electron shells. However, the difference in Ad and 5d transi on elements are compara vely less because
of lanthanoid contrac on.
(ii) Because of stronger inter atomic bonding, the m.p. and b.p. of the elements of Ad and 5d series are
higher.
(iii) Ionisa on enthalpies are expected to decrease as we move from one series to the other. However,
the values for the elements of 5d series are higher as compared to the elements belonging to the other
two series due to lanthanoid contrac on.
Actually atomic size decreases on account of it and effec ve nuclear charge increases. As a result, there
is an increase in ionisa on energy in case of 3d elements.

8.38. What can be inferred from the magne c moment values of the following complex species?

Sol:
Question 1. Electronic configuration of a transition element X in +3 oxidation state is
[Ar] 3d5. What is its atomic number?
(a) 25 (b) 26 (c) 27 (d) 24
Solution:

Question 2. The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10.
Which of the following is correct?
(a) Cu(II) is more stable .
(b) Cu(II) is less stable
(c) Cu(I) and Cu(II) are equally stable
(d) Stability of Cu(I) and Cu(I) depends on nature of copper salts.
Solution: (a) Cu(II) is more stable due to greater effective nuclear charge of Cu(II).

Question 3. Metallic radii of some transition elements are given below. Which of these
elements will have highest density?

Solution: (d) On moving left to right along period, metallic radius decreases while mass
increases. Decreases in metallic radius coupled with increase in atomic mass results in
increase in density of metal.
Hence, among the given four choices Cu belongs to right side of Periodic Table in
transition metal, and it has the highest density (89 g/cm3).

Question 4. Generally, transition elements form coloured salts due to the presence of
unpaired electrons. Which of the following compound will be coloured in solid state?
(a) Ag2SO4 (b) CUF2 (c) ZnF2 (d) Cu2Cl2
Solution: (b) Cu2+ has 1 unpaired electron in CuF2, hence, it is coloured in solid state.

Question 5. On addition of small amount of KMnO 4 to concentrated H2SO4, a green oily

compound is obtained which is highly explosive in nature. Identify the compound from
the following:
(a) Mn2O7 (b) MnO2 (c) MnSO4 (d) Mn2O3
Solution: (a) 2KMnO4 + 2H2SO4(Conc ) –> Mn2O7 + 2KHSO4 + H2O

Question 6. The magnetic nature of elements depend on the presence of unpaired

electrons. Identify the configuration of transition element, which shows the highest
magnetic moment.
(a) 3d7 (b) 3d5 (c) 3d8 (d) 3d2
Solution: (b) The greater the number of unpaired electron, the higher will be its value of
magnetic moment. Since, 3d5 has 5 unpaired electrons hence highest magnetic
moment.

Question 7. Which of the following oxidation state is common for all lanthanoids?
(a) +2 (b) +3 (c) +4 (d) +5
Solution: (b) +3 oxidation state is most common for all lanthanoids.

Question 8. Which of the following reactions are disproportionation reactions?

Solution:

Question 9. 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) Mn04 catalyses the reaction (d) Mn2+ acts as autocatalyst
Solution: (d) When KMnO4 solution is added to oxalic acid solution, the decolourisation
is slow in the beginning but becomes instantaneous after some time because Mn2+
acts as an autocatalyst.
Question 10. There are 14 elements in actinoid series. Which of the following element
does-not belong to this series?
(a) U (b) Np (c) Tm (d) Fm
Solution: (c) Tm (Thulium) is a lanthanoid.

Question 11. KMnO4 acts as an oxidizing agent in acidic medium. The number of moles
of KMn04 that will be needed to react with one mole of sulphide ions in acidic solution
is

Solution:

Question 12. Which of the following is amphoteric oxide?

Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
(a) V2O5, Cr2O3 (b)Mn2O7, CrO3 (c) CrO, V2O5 (d) V2O5, V2O4
Solution: (a) V2O5 and Cr2O3 are amphoteric oxides because both react with alkalies as
well as acids.
Remember: In lower oxides, the basic character is predominant while in higher oxides,
the acidic character is predominant.

Question 13. Gadolinium belongs to 4f series. Its atomic number is 64. Which of the
following is the correct electronic configuration of gadolinium?

Solution: (a) 64Gd: [Xe] 4f7 5d1 6s2

Question 14. Interstitial compounds are formed when small atoms are trapped inside
the crystal lattice of metals. Which of the following is not the characteristic property of
interstitial compounds?
(a) They have high melting points in comparison to pure metals
(b) They are very hard
(c) They retain metallic conductivity
(d) They are chemically very reactive.
Solution: (d) Interstitial compounds are chemically inert.

Question 15. The magnetic moment is associated with its spin angular momentum and
orbital angular momentum. Spin only magnetic moment value of Cr 3+ ion is
(a) 2.87 B.M. (b) 3.87 B.M. (c) 3.47 B.M. (d) 3.57 B.M.
Solution: (b) The magnetic moment is associated with its spin angular momentum and
orbital angular momentum.

Question 16. KMn04 acts as an oxidizing agent in alkaline medium. When alkaline
KMnO4
is treated with KI, iodide ion is oxidized to
(a) I2 (b)Io– (c) I03 (d) I04
Solution: (c) 2KMnO4 + KI + H2O –> 2K0H + 2MnO2 + KI03

Question 17. Which of the following statement is not correct?

(a) Copper liberates hydrogen from acids
(b) In its higher oxidation states, manganese forms stable compounds with oxygen and
fluorine
(c) Mn3+ and Co3+ are oxidizing agents in aqueous solution
(d) Ti2+ and Cr2+ are reducing agents in aqueous solution
Solution: (a) Copper does not liberate hydrogen from acids.
Cu + 2H2S04 –> CuSO4 + S02 + 2H2O
3Cu + 8HNO3 –> 3CU(N03)2 + 2NO + 4H2O

Question 18. When acidified K2Cr2O7 solution is added to Sn2+ salts, Sn2+ changes to
(a) Sn (b) Sn3+ (c) Sn4+ (d) Sn+
Solution: (c) When acidified K2Cr2O7 solution is added to Sn2+ salt, Sn2+ changes to Sn4+.
The reaction is given below

Question 19. Highest oxidation state of manganese in fluoride is +4 (MnF 4) but highest
oxidation state in oxides is +7 (Mn2O7) because
(a) fluorine is more electronegative than oxygen
(b) fluorine does not possess d-orbitals
(c) fluorine stabilizes lower oxidation state
(d) in covalent compounds fluorine can form single bond only while oxygen forms
double bond
Solution: (d) The highest oxidation state of manganese in fluoride is +4 (MnF 4) but in
oxides it is +7 (Mn2O7) because in covalent compounds fluorine can form single bond
only while oxygen forms double bond.

Question 20. Although zirconium belongs to 4d transition series and hafnium to 5d

transition series even then they show similar physical and chemical properties
because
(a) both belong to d-block
(b) both have same number of electrons
(c) both have similar atomic radius
(d) both belong to the same group of the periodic table
Solution: (c) Zirconium and hafnium have similar atomic radius hence they show similar
physical and chemical properties.

Question 21. Why is HCl not used to make the medium acidic in oxidation reactions of
KMnO4 in acidic medium?
(a) Both HCl and KMn04 act as oxidizing agents.
(b) KMnO4 oxidises HCl into Cl2 which is also an oxidizing agent.
(c) KMnO4 is a weaker oxidizing agent than HCl.
(d) KMnO4 acts as a reducing agent in the presence of HCl.
Solution: (b) HCl is not used to make the medium acidic in oxidation reactions of
KMnO4 in acidic medium. The reason is that if HCl is used, the oxygen produced from
KMnO4 + HCl is partly utilized in oxidizing HCl to Cl, which itself acts as an oxidizing
agent and partly oxidises the reducing agent.
More than One Correct Answer Type

Question 22. Generally, transition-elements and their salts are coloured due to the
presence of unpaired electrons in metal ions. Which of the following compounds are
coloured?
(a) kMnO4 (b) Ce(SO4)2 (c) TiCl4 (d) Cu2Cl2
Solution: (a, b) KMnO4 and Ce(S04)2 are coloured due to charge transfer.

Question 23. Transition elements show magnetic moment due to spin and orbital
motion of electrons. Which of the following metallic ions have almost same spin only
magnetic moment?
(a) Co2+ (b) Cr2+ (c) Mn2+ (d) Cr3+
Solution: (a, d) Co2+ (3d7) and Cr3+ (3d3) have 3 unpaired electrons. Hence they have
almost same spin only magnetic moment.

Question 24. In the form of dichromate, Cr (VI) is a strong oxidizing agent in acidic
medium
but Mo (VI) in MoO3 and W (VI) in WO3 are not because
(a) Cr (VI) is more stable than Mo(VI) and W(VI)
(b) Mo(VI) and W(VI) are more stable than Cr(VI)
(c) higher oxidation states of heavier members of group-6 of transition series are
more stable
(d) lower oxidation states of heavier members of group-6 of transition series are more
stable
Solution: (b, c) In d-block elements, for heavier elements, the higher oxidation states are
more stable. Hence, Mo(VI) and W(VI) are more stable than Cr (VI). That’s why, Cr (VI) in
the form of dichromate is a stronger oxidizing agent in acidic medium whereas Mo03
and W03 are not.

Question 25. Which of the following actinoids show oxidation states up to +7?
(a) Am (b) Pu (c) U (d) Np
Solution: (b, d) Np and Pu show +7 oxidation state.

Question 26. General electronic configuration of actinoids is (n – 2)f 1-14 (n – 1 )d0-2 ns2.
Which of the following actinoids have one electron in 6d orbital?
(a) U (Atomic no. 92) (b) Np (Atomic no. 93)
(c) Pu (Atomic no. 94) (d) Am (Atomic no. 95)
Solution:

Question 27. Which of the following lanthanoids show +2 oxidation state besides the
characteristic oxidation state +3 of lanthanoids?
(a) Ce (b) Eu (c) Yb (d) Ho
Solution: (b, c)

Question 28. Which of the following ions show higher spin only magnetic moment
value?
(a) Ti3+ (b) Mn2+ (c) Fe2+ (d) Co3+
Solution: (b, c) Mn2+ (3d5) and Fe2+ (3d6) have 5 and 4 unpaired electrons hence higher
values of spin only magnetic moment as compared to Ti3+ (3d1) and Co2+ (3d7).

Question 29. Transition elements form binary compounds with halogens. Which of the
following elements will form MF3 type compounds?
(a) Cr (b) Co (c) Cu (d) Ni
Solution: (a, b) Cr and Co form MF3 type of compounds. The ability of fluorine to
stabilize the highest oxidation state is due to higher lattice energy in CoF 3 and higher
bond enthalpy for the higher covalent compound like CrF 6.

Question 30. Which of the following will not act as oxidizing agents?
(a) CrO3 (b) MoO3(c) WO3 (d) CrO42-
Solution: (b, c) A species can act as an oxidizing agent only when metal is present in
high oxidation state but lower oxidation state show stability. As higher oxidations states
of W and Mo are more stable, therefore they will not act as oxidizing agents.

Question 31. Although +3 is the characteristic oxidation state for lanthanoids but
cerium
also shows +4 oxidation state because
(a) it has variable ionization enthalpy
(b) it has a tendency to attain noble gas configuration
(c) it has a tendency to attain f° configuration
(d) it resembles Pb4+
Solution: (b, c) Cerium shows +4 oxidation state also because it has a tendency to
attain noble gas configuration and attain f° configuration.
Ce – 4f15d’6s2 (Ce4+– 4f°)
Short Answer Type Questions

Question 32. Why does copper not replace hydrogen from acids?
Solution: The value of standard reduction potential of copper (E° = +0.34 V) is positive.
Therefore, copper does not liberate hydrogen from acids.

Question 33. Why E° value for Mn, Ni and Zn are more negative than expected?
Solution: Negative E° values of Mn2+ and Zn2+ are because of stabilities of half-filled
(3d10: Mn2+) and fully-filled (3d10: Zn2+) configuration respectively.Mn2+ ion has higher E°
value because of highest negative enthalpy of hydrogen.

Question 34. Why first ionization enthalpy of Cr is lower than that of Zn?
Solution: The electronic configuration of chromium and zinc are respectively:
Cr (24) = [Ar] 3d54s2 Zn (30) = [Ar] 3d104s2
It is easy to remove electron from 4s1-orbital (unpaired) rather than from 4s2-orbital
(paired).

Question 35. Transition elements show high melting points. Why?

Solution: The high melting points of transition metals are due to strong metallic bonds
between the atoms of these elements. This is because of involvements of greater
number of electrons in the interatomic metallic bonding from (n – 1) d orbitals in
addition to ns electrons.

Question 36. When Cu2+ ion is treated with KI, a white precipitate is formed. Explain the
reaction with the help of chemical equation.
Solution: Reduction of Cu2+ to Cu+ takes place due to reaction with F ions. This is given
by the equation.

Question 37. Out of Cu2Cl2 and CuCl2, which is more stable and why?
Solution: CuCl2 is more stable than Cu2Cl2 . The stability of CuCl2 is because of high
enthalpy of hydration of Cu2+ (aq) than that of Cu+ (aq).

Question 38. When a brown compound of manganese

(A) is treated with HCl, it gives a gas
(B) The gas taken in excess, reacts with NH3 to give an explosive compound
(C) Identify compounds A, B and C.
Solution: The compounds A, B and C are as follows:

Question 39. Although fluorine is more electronegative than oxygen, but the ability of
oxygen to stabilize higher oxidation states exceeds that of fluorine. Why?
Solution: The electronic configuration of fluorine is 1s 22s22p5 . Thus it can form only one
bond as it has only one unpaired electron. Electronic configuration of oxygen is
1s22s22p63s23p6.
It may be mentioned that oxygen also has vacant d-orbitals along with two 3p orbitals
containing single electron. Thus, oxygen has greater bond formation capacity. In other
words, it has greater ability to stabilize higher oxidation states.

Question 40. Although Cr3+ and CO2+ ions have same number of unpaired electrons but
the magnetic moment of Cr3+ is 3.87 BM and that of CO2+ is 4.87 BM. Why?
Solution: The electronic configuration of Cr3+ and CO2+ ions are:

Due to symmetrical electronic configuration, there is no orbital contribution in Cr 3+ ion.

However, appreciable contribution occurs in CO 2+ ion.

Question 41. Ionisation enthalpies of Ce. Pr and Nd are higher than Th, Pa and U. Why?
Solution: It is because in the beginning when 5f-orbitals begin to be occupied, they
penetrate less into inner core electrons. Thus, 5f-electrons are more effectively shielded
from the nuclear charge than 4f electrons in the lanthanide series. Therefore, outer
electrons are less firmly held and thus these electrons are available for bonding in
actinoids and their removal is much more easier. On account of this, the ionisation
enthalpies of Th, Pa and U are comparatively lower than Ce, Pr and Nd.

Question 42. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is

quite difficult to separate them. Why?
Solution: Zr, a member of Ad series and Hf, a member of 5d series, belong to same
group. They are chemically so similar that their separation is difficult. This is due to the
fact that both have same size due to lanthanide contraction. The radii of these elements
are 160 pm (Zr) and 159 pm (Hf).

Question 43. Although +3 oxidation states is the characteristic oxidation state of

lanthanoids but cerium shows +4 oxidation state also. Why?
Solution: The electronic configuration of Ce is -4f15d16s2. Usually 5d’ and 6s2 electrons
are lost by the lanthanoids in their reactions i.e., they exhibit +3 oxidation states. But Ce
exhibit +4 oxidation state also because it gains extra stability by losing 4f 1 electron
because it will give rise to completely filled orbitals.

Question 44. Explain why does colour of KMnO4 disappear when oxalic acid is added to
its solution in acidic medium?
Solution: The acidified solution of KMnO4 acts as an oxidising agent. It oxidises oxalic
acid into CO2 and itself changes to Mn2+ ion which is colourless.

Question 45. When orange solution containing Cr 2O72- ion is treated with an alkali, a
yellow solution is formed and when H+ ions are added to yellow solution, an orange
solution is obtained. Explain why does this happen?
Solution: On heating with alkalies, the orange colour of dichromate solution changes to
yellow due to the formation of chromate ions.
Question 46. A solution of KMnO4 on reduction yields either a colourless solution or a
brown precipitate or a green solution depending on pH of the solution. What different
stages of the reduction do these represent and how are they carried out?
Solution: KMnO4 acts as an oxidising agent in alkaline, neutral and acidic mediums, i.e.,
oxidising behaviour of KMnO4 depends on pH of the solution.
In alkaline medium (pH > 7),

Question 47. The second and third rows of tfansition elements resemble each other
much more than they resemble the first row. Explain why?
Solution: Due to lanthanide contraction, the atomic radii of the second and third row
transition elements are almost same. Therefore, they resemble each other much more
as compared to first row elements.

Question 48. E of Cu is +0.34 V while that of Zn is -0.76 V. Explain.

Solution: High ionisation enthalpy to change Cu(s) to Cu2+ is not balanced by hydration
enthalpy. Therefore, it exhibits a positive E° value. However, Zn exhibits a lower value of
ionization enthalpy because a stable 3d10 configuration is attained after losing two
electrons. The hydration energy for Zn2+ is comparable to that ofCu2+. Therefore, E° for
Zn is negative.
Question 49. The halides of transition elements become more covalent with increasing
oxidation state of the metal. Why?
Solution: As the oxidation state of the element increases, its charge increases.
According to Fajans rules, as the charge of the metal ion increases covalent character
increases because the positively charged cation attracts the electron cloud on the anion
towards itself.

Question 50. While filling up of electrons in the atomic orbitals, the 4s orbital is filled
before the 3d-orbital but reverse happens during the ionization of the atom. Explain
why?
Solution: According to n +l rule: For 3d=n + l = 5
4s = n + l = 4
Therefore, the electron will enter in 4s orbital first and then in 3d orbitals. Ionisation
enthalpy is responsible for the ionisation of atom. 4s electrons are loosely held by the
nucleus. So electrons are removed from 4s orbital prior to 3d.

Question 51. Reactivity of transition elements decreases almost regularly from Sc to

Cu. Explain.
Solution: Reactivity of an element is dependent on the value of ionization enthalpy. In
moving from Sc, the first element to Cu, the ionization enthalpy increases regularly.
Therefore, the reactivity degreases as we move from Sc to Cu.

Matching Column Type Questions

Question 52. Match the catalysts given in Column I with the processes given in
Column II.
Solution: (i—> c), (ii —> d), (iii —>b), (iv—> e), (v —> a)

Question 53. Match the compounds/elements given in Column I with uses given in
Column II.
Solution: (i —> b), (ii —> a), (iii —> d), (iv e), (v—> c)

Question 54. Match the properties given in Column I with the metals given in Column
II.

Solution: (i —> c), (ii —> a), (iii —>b)

(i) Osmium is an element which show +8 oxidation state.
(ii) 3d block element that can show up to +7 oxidation state is manganese.
(iii) 3d block element with highest melting point is chromium.

Question 55. Match the statements given in Column I with the oxidation states given in
Column II.
Solution: (i —> c), (ii —> a), (iii —> e), (iv —> b)

Question [Link] the statements given in Column I with the Colours given in Column
II.

Solution: (i —> d), (ii —>a), (iii —> b), (iv—> e), (v —>f)
Question 57. Match the property given in Column I with the element given in Column II.

Solution:

Question 58. Match the properties given in Column I with the metals given in Column
II.
Solution: (i —> c), (ii —> d), (iii —>b), (iv—> e)

Assertion and Reason Type Questions

In the following questions, a statement of Assertion (A) followed by a statement of

Reason (R) is given. Choose the correct answer out of the following choices:
(a) Both Assertion and Reason are true and the Reason is the correct explanation of
Assertion.
(b) Both Assertion and Reason are true and the Reason is not the correct explanation
of Assertion.
(c) Assertion is not true but the Reason is true.
(d) Both Assertion and Reason are false.

Question 59. Assertion (A): Cu2+ iodide is not known.

Reason (R): Cu2+ oxidises I to iodine.
Solution: (a) Cu2+ oxidises iodide to iodine hence cupric iodide is converted to cuprous
iodide.
Question 60. Assertion (A): Separation of Zr and Hf is difficult.
Reason (R): Because Zr and Hf lie in the same group of the periodic table.
Solution: (b) Separation of Zr and Hf is difficult as both have same size.

Question 61. Assertion (A): Actinoids form relatively less stable complexes as
compared to lanthanoids.
Reason (R): Actinoids can utilize their 5d orbitals along with 6d orbitals in bonding but
lanthanoids do not use their 4f orbital for bonding.
Solution: (c) Actinoids are more reactive and show greater range of oxidation states.

Question 62. Assertion (A): Cu can not libirate hydrogen from acids .
Reason (R): because it has positive electrode potential.
Solution: (a) Cu can not libirate hydrogen from acides due to positive electrode
potential.

Question 63. Assertion (A): The highest oxidation state of osmium is +8.
Reason (R): Osmium is a 5d-block element.
Solution: (b) The highest oxidation state of osmium is +8 due to its ability to expand
their octet by using its all 8 electrons.

Long Answer Type Questions

Question 64. Identify A to E and expain reaction involves

Solution:

Question 65. When a chromite ore (A) is fused with sodium carbonate in free excess of
air and the product is dissolved in water, a yellow solution of compound (B) is
obtained. After treatment of this yellow solution with sulphuric acid, compound (C) can
be crystallized from the solution. When compound (C) is treated with KCl, orange
crystals of compound (D) crystallise out. Identify A to D and also explain the reactions.
Solution: The compounds A, B, C and D are given as under:

Question 66. When an oxide of manganese (A) is fused with KOH in the presence of an
oxidizing agent and dissolved in water, it gives a dark green solution of compound (B).
Compound (B) disproportionates in neutral or acidic solution to give purple compound
(C). An alkaline solution of compound (C) oxidises potassium iodide solution to a
compound (D) and compound (A) is also formed. Identify compounds A to D and also
explain the reactions involved.
Solution: The compounds (A), (B), (C) and (D) are given as under:

Question 67. On the basis of lanthanoid contraction, explain the following:

(a) Nature of bonding in La2O3 and Lu2O3.
(b) Trends in the stability of oxo-salts of lanthanoids from La to Lu.
(c) Stability of the complexes of lanthanoids.
(d) Radii of Ad- and 5d-block elements.
(e) Trends in acidic character of lanthanoid oxides.
Solution: (a) Due to lanthanide contraction the size of the atom decreases with the
decrease in size, the covalent character increases. Therefore, La 2O3 is more ionic while
Lu2O3is [Link] covalent in nature.
(b) As the size decreases from La to Lu, the stability of the oxo-salts also decreases.
(c) Stability of complexes from La to Lu, increases as the size of the central atom
decreases.
(d) Radii of the elements of Ad- and 5d-blocks in the same vertical columns are nearly
the same.
(e) The acidic nature of lanthanoid oxides increases from La to Lu.

Question 68. (a) Answer the following questions:

(i) Which element of the first transition series has highest second ionization enthalpy?
(ii) Which element of the first transition series has highest third ionization enthalpy?
(iii) Which element of the first transition series has lowest enthalpy of atomization?
(b) Identify the metal and justify your answer:
(i) Carbonyl M(CO)5 (ii) MO3F
Solution: (a) (i) Cu, because the electronic configuration of Cu is 3d 104s1. So second
electron needs to be removed from completely filled tf-orbital.
(ii) Zn. The electronic configuration of Zn is 3d104s2 . The third electron needs to be
removed from completely filled d-orbital.
(iii) Zn. There is no unpaired electron in Zn for metallic bonding.
(b) (i) Fe(CO)5 as per EAN rule.
(ii) Mn03F. Mn shows +7 oxidation state; d-electrons are not involved in bonding.
Question [Link] the type of compounds formed when small atoms like H, C and N
get trapped inside the crystal lattice of transition metals. Also give physical and
chemical characteristics of these compounds.
Solution: Compounds formed when small atoms like H, C and N get trapped inside the
crystal lattice of transition metals are called interstitial compounds. Properties of such
compounds are:
(i) High melting points higher than those of pure metals.
(ii) These compounds are very hard.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.

Question 70. (a) Transition metals can act as catalysts because these can change their
oxidation state.
How does Fe(III) catalyse the reaction between iodide and persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.
Solution: (a) Reaction between iodide and persulphate ions is:

Question 71. A violet compound of manganese (A) decomposes on heating to liberate

oxygen and compounds (B) and (C) of manganese are formed. Compound (C) reacts
with KOH in the presence of potassium nitrate to give compound (B). On heating
compound (C) with cone. H2SO4 and NaCl, chlorine gas is liberated and a compound (D)
of manganese along with other products is formed. Identify compounds A to D and
also explain the reactions involved.
Solution: The compounds A, B, C and D are given as under: