D and F Block Elements
D and F Block Elements
D and F Block Elements
)
On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is 1
1
not?
ANS: It is because Sc (21) has incompletely filled d-orbital, that is why it is transition element,
whereas Zn(30) does not have incompletely filled d-orbitals, therefore, it is not regarded as
transition element.
2 Why do transition metals show variable oxidation states? 1
ANS: It is because electrons from both ‘s’ and d-orbitals can take part in bond formation.
3 Lanthanoids form primarily +3 ions, while the actinoids usually have higher oxidation states in
1
their compounds, +4 or even +6 being typical. Give reason.
ANS: In Actinoids, 5f, 6d and 7s orbitals have comparable energies and electrons from these
orbitals can take part to show higher oxidation states.
4 Among lanthanoids, Ln(III) compounds are predominant. However, occasionally in solutions or in
1
solid compounds, +2 and +4 ions are also obtained. Give reason.
ANS: Lanthanoids show +3 oxidation state mostly as 2 electrons from outer 6s orbital and one
electron from 5d orbital take part in bond formation. Some show +2 and +4 oxidation states due to
stability of half filled and completely filled 4f orbitals.
5 Out of Cu2Cl2 and CuCl2, which is more stable and why? 1
6 Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate
1
them. Why?
ANS: It is due to almost same size (Zr = 160 pm, Hf = 159 pm) which is due to lanthanoid
contraction.
7 E° of Cu is +0.34 V while that of Zn is –0.76 V. Explain. 1
ANS: It is because Cu(s) is more stable than Cu 2+ due to high ionisation enthalpy which is not
overcome by its hydration energy.
In the case of Zn, after removal of 2 electrons from 4s orbtital, stable 3d 10 configuration is
acquired.
8 Why do the transition metals have higher enthalpy of atomisation? In 3d series (Sc to Zn), which
2
element has lowest enthalpy of atomisation and why?
ANS: It is due to the involvement of greater number of unpaired electrons from (n – 1)d as well
as ns orbitals in the strong inter-atomic metallic bonding. Zinc has lowest enthalpy of atomisation
due to larger size and in the absence of unpaired electrons, it forms weak metallic bond.
9 For the first row transition metals, the E° values are given below:
2
Explain the
irregularity in the above values.
ANS: It is due to irregular variation of sublimation enthalpies and ionisation enthalpies of
elements of 3d transition series.
10 How would you account for the following?
(i) Cr2+ is reducing in nature while with the same d-orbital configuration (d4), Mn3+ is an oxidising
agent.
2
(ii) In a transition series of metals, the metal which exhibits the greatest number of oxidation
states occurs in the middle of the series. or N ame the element showing maximum number of
oxidation states among the first series of transition metal Sc (21) to Zn (30).
ANS: (i) It is because Cr2+ loses electron to become Cr3+ which is more stable due to half filled
t2g orbitals, whereas Mn3+ will gain electron to become Mn2+ which is more stable due to half filled
1
d-orbitals.
(ii) Manganese. It is due to large number of unpaired electrons in d-orbitals in middle of the series.
Mn (25) 4s23d5.
11 Explain the following observations giving an appropriate reason for each.
(i) There occurs much more frequent metal-metal bonding in compounds of heavy transition
2
metals (i.e. 3rd series).
(ii) Mn2+ is much more resistant than Fe 2+ towards oxidation.
ANS: (i) Due to lanthanoid contraction, effective nuclear charge remains almost same
therefore, metallic radii are nearly same, therefore, metal-metal bonding is more.
(ii) Mn2+ (3d5) has stable electronic configuration, therefore, it does not get oxidised. Fe 2+ (3d6)
gets oxidised to form Fe3+(3d5) which is more stable.
12 State reasons for the following:
(i) Actinoids exhibit greater range of oxidation states than lanthanoids.
2
(ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+ ions of the 3d series of elements, the 4d
and the 5d series metals generally do not form stable cationic species.
ANS: (i) It is due to poor shielding effects of 4f and 5f electrons, more number of electrons take
part in bond formation in actinoids.
(ii) It is because energy required to remove electron is more due to greater effective nuclear
charge which is due to lanthanoid contraction.
13 Assign reasons for each of the following:
(i) T ransition metals generally form coloured compounds.
2
(ii) Manganese exhibits the highest oxidation state of + 7 among the 3d series of transition
elements.
ANS: (i) It is because transtion metals have unpaired electron in d-orbitals and undergo d-d-
transitions by absorbing light from visible region and rediate complementary colour.
(ii) Mn has electronic configuration (Ar)4s2 3d5 and all the electrons in ‘s’ as well as ‘d’ orbitals can
take part in bond formation, therefore, it shows +7 (highest) oxidation state.
14 Explain the following observations:
(i) Generally there is an increase in density of elements from titanium (Z = 22) to copper (Z = 29)
in the first series of transition elements. 2
(ii) T ransition elements and their compounds are generally found to be good catalysts in chemical
reactions.
ANS: (i) It is because atomic mass increases more than atomic volume, therefore, density
increases from titanium (Z = 22) to copper (Z = 29).
(ii) It is because they show variable oxidation states and have vacant d-orbitals forming unstable
intermediates which readily change into products.
15 Explain the following observations:
(i) Transition elements generally form coloured compounds. 2
(ii) Zinc is not regarded as a transition element.
ANS: (i) It is due to presence of unpaired electrons in d-orbitals, therefore, they undergo d-d
transitions by absorbing light from visible region and radiate complementary colour.
(ii) It is because neither Zn nor Zn2+ ion has incompletely filled d-orbital.
16
2
Complete the following equations:
ANS:
17
2
Complete the following equations:
2
ANS:
18
2
Complete the following chemical equations:
ANS:
19 Name the oxometal anions of the first series of the transition metals in which the metal exhibits
2
the oxidation state equal to its group number.
ANS: In MnO4–, oxidation state of Mn is +7 which is equal to its group number.
In CrO42–, oxidation state of Cr is +6 which is equal to its group number.
20 Write complete chemical equations for:
(i) Oxidation of Fe2+ by Cr2O72– in acid medium. 2
(ii) Oxidation of S2O32– by MnO4– in neutral aqueous medium.
ANS:
21 Write one similarity and one difference between the chemistry of lanthanoids and that of actinoids. 2
ANS: Similarity
Lanthanoids show lanthanoid contraction like actinoids contraction.
Dissimilarity
Lanthanoids show mostly +3 oxidation state. Few show +2 and +4, whereas Actinoids show +3,
+4, +5, +6 and +7 oxidation states.
22 Give reasons for the following observations:
(i) Mn(II) ion shows maximum paramagnetic character amongst the bivalent ions of first transition
2
series.
(ii) Scandium (At. no. 21) salts are white.
ANS: (i) It is due to presence of five unpaired electrons.
(ii) Sc3+ does not have unpaired electrons, therefore, cannot undergo d-d transition by absorbing
light from visible region. Therefore, its salts are white.
23 State reasons for the following observations:
(i) The enthalpies of atomisation of transition elements are quite high.
2
(ii) There is a greater horizontal similarity in the properties of the transition elements than of the
main group elements.
ANS: (i) It is due to smaller size of transition metals and strong metallic bonds due to the
presence of large number of unpaired electrons.
(ii) It is due to similarity in atomic and ionic size, there is more horizontal similarity. Secondly, in
transition elements incoming electron goes to inner shell (d-orbitals), whereas in main group
elements, the incoming electron goes to outermost shell.
24 Assign suitable reasons for the following:
(a) The Mn2+ compounds are more stable than Fe 2+ towards oxidation to their +3 state.
3
(b) In the 3d series from Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of Zn is the lowest.
(c) Sc3+ is colourless in aqueous solution, whereas Ti 3+ is coloured.
ANS: (a) Mn2+ has 3d5 (stable electronic configuration), therefore, it does not get oxidised to
Mn3+, whereas Fe2+ has 3d6 which readily changes to Fe 3+ (3d5) which has stable electronic
configuration.
(b) Zinc does not have unpaired electrons and larger in size, therefore, has weak metallic bonds.
That is why it has least enthalpy of atomisation.
(c) Sc3+ is colourless as it does not have unpaired electron and cannot undergo d-d transition,
3
whereas Ti3+ is coloured due to presence of unpaired electrons, and undergoes d-d transition by
absorbing light from visible region and radiate complementary colour.
25 How would you account for the following?
(i) The atomic radii of the metals of the third (5d) series of transition elements are virtually the
same as those of the corresponding members of the second (4d) series.
3
(ii) The E° value for the Mn3+/Mn2+ couple is much more positive than that for Cr3+/Cr2+ couple or
Fe3+/Fe2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride.
ANS: (i) It is due to lanthanoid contraction which is due to poor shielding effect of f-electrons.
(ii) It is because Mn2+ is more stable than Mn3+ due to stable half filled 3d5 configuration, whereas
Cr3+(t2g3) and Fe3+(3d5) are more stable than Cr2+ and Fe2+ respectively.
(iii) It is because oxygen and fluorine are strong oxidising agents, highly electronegative, small
size and can provide energy for formation of transition metal ion in higher oxidation state.
26 Give reasons for each of the following:
(i) Size of trivalent lanthanoid cations decreases with increase in the atomic number.
(ii) T ransition metal fluorides are ionic in nature, whereas bromides and chlorides are usually 3
covalent in nature.
(iii) Chemistry of all the lanthanoids is quite similar.
ANS: (i) It is due to poor shielding effect of f-electrons, effective nuclear charge increases, so,
ionic size decreases.
(ii) F is more electronegative than Cl and Br, therefore, fluorides are ionic; whereas chlorides and
bromides are covalent.
(iii) It is due to similar ionic size which is due to lanthanoid contraction, they resemble in their
properties.
27 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. 3
What different stages of the reduction do these represent and how are they carried out?
ANS: Oxidising behaviour of KMnO4 depends upon pH of solution. Different compounds with
different colours are formed at different pH.
4
ANS:
29 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 crystallised from the solution. When compound 3
(C) is treated with KCl, orange crystals of compound (D) crystallise out. Identify A to D and also
explain the reactions.
ANS:
30 When an oxide of manganese (A) is fused with KOH in the presence of an oxidising 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 3
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.
5
ANS:
31 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 conc. H 2SO4 and NaCl, 3
chlorine gas is liberated and a compound (D) of manganese along with other products is formed.
Identify compound A to D and also explain the reactions involved.
ANS:
(b)
33 (a) How would you account for the following:
(i) Highest fluoride of Mn is MnF4 whereas the highest oxide is Mn 2O7.
Or Mn shows highest oxidation state of +7 with oxygen but with fluorine it shows the
3
highest oxidation state +4.
(ii) T ransition metals and their compounds show catalytic properties.
(b) Complete the following equation:
3MnO42– + 4H+ →
6
ANS: (a) (i) Oxygen can form double bond, therefore, it can form Mn 2O7 , whereas ‘F’ cannot
form double bonds, so, it can form MnF4.
(ii) Transition metals show variable oxidation states, therefore, they and their compounds act as
catalyst.
(b) 3MnO42– + 4H+ → MnO2 + 2MnO4– + 2H2O
34 (a) How would you account for the following:
(i) The chemistry of actinoids is more complicated as compared to lanthanoids.
(ii) Transition metals form complex compounds. 3
38 (a) What are the different oxidation states exhibited by the lanthanoids?
(b) Write two characteristics of the transition elements. 3
(c) Which of the 3d-block elements may not be regarded as the transition elements and why?
ANS: (a) Lanthanoids, mostly show +3 oxidation state but some of them show +2 and +4
oxidation states also due to the stability of electronic configuration (4f 0, 4f 7 and 4f 14).
(b) (i) They show variable oxidation states.
(ii) They form coloured ions.
(c) Zn may not be regarded as transition metal because neither Zn nor Zn 2+ have incompletely
filled d-orbital.
7
39 (a) Transition metals can act as catalysts, why? How does Fe(III) catalyse the reaction between
iodide ion and persulphate ions? 3
(b) Mention any three processes where transition metals act as catalysts.
ANS: (a) Transition metals act as catalyst because they show variable oxidation states as
explained below:
Reaction between iodide and persulphate ions is
(b)
ANS: (i)
(ii) Ce shows +4 oxidation state.
(iii) MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
(iv) Mn3+ (3d4) has 4 unpaired electrons, therefore, it is more paramagnetic than Cr 3+ (3d3) which
has three unpaired electrons.
42 (a) Complete the following chemical equations: 5
8
(b) How would you account for the following?
(i) The oxidising power of oxoanions are in the order
ANS:
43 In which of the following pairs, both the ions are coloured in aqueous solutions?
1
[Atomic no of Sc = 21, Ti = 22, Ni = 28, Co = 27, Cu = 29]
ANS: (b) Cr3+ ∵ t2g3 (half filled p-orbitals) are more stable.
45
The number of moles of KMnO4 that will be needed to react with one mole of in acidic
solution. (a) 1 (b) 3/5 1
(c) 4/5 (d) 2/5
ANS:
46 The correct order of decreasing second ionisation enthalpy of Ti(22), V(23), Cr(24) Mn(25)
(a) V > Mn > Cr > Ti (b) Mn > Cr > Ti > V 1
(c) Ti > V > Cr > Mn (d) Cr > Mn > V > Ti
9
47
1
Which of the following pairs has the same ionic size?
48 Acidified K2Cr2O7 solution turns green when SO2 gas is passed through it due to formation of
(a) Cr2(SO4)3 (b) CrO42– 1
(c) Cr2(SO3)3 (d) CrSO4
ANS: (a) Mn2+ (3d5) is most stable, Fe2+ (3d6), Cr2+(3d4), Co2+(3d7)
ANS:
51 Which of the following lanthanoid ion is diamagnetic?
(At No. of Ce = 58, Sm = 62, Eu = 63 Yb = 70)
1
(a) Eu2+ (b) Yb2+
(c) Ce2+ (d) Sm2+
ANS: (b) Yb2+ (4f14) does not have unpaired election, therefore, diamagnetic.
10
ANS: (b) 2KMnO4 + 16 HCl → 2KCl + 2MnCl2 + 5Cl2 + 2H2O
56 Out of Mn2O7, V2O3, V2O5, CrO, Cr2O3, the basic oxides are
(a) Mn2O7, V2O3 (b) V2O3, V2O5 1
(c) V2O5, CrO (d) V2O3 and CrO
ANS: (d) V2O3 and CrO are basic oxides due to lower, oxidation states.
57 The oxidation state of Cr in final product formed by reaction of KI and acidified dichromate
solution is
1
(a) +4 (b) +6
(c) +2 (d) +3
ANS:
59 The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10. Which of the following is
correct? [NCERT Exemplar Problem]
(a) Cu(II) is more stable
1
(b) Cu(II) is less stable
(c) Cu(I) and Cu(II) are equally stable
(d) Stability of Cu(I) and Cu(II) depends on nature of copper salts
60 Metallic radii of some transition elements are given below. Which of these elements will have
highest density? [NCERT Exemplar Problem]
Element Fe Co Ni Cu
1
Metallic radii/pm 126 125 125 128
(a) Fe (b) Ni
(c) Co (d) Cu
61 Generally transition elements form coloured salts due to the presence of unpaired electrons.
Which of the following compounds will be coloured in solid state?
1
(a) Ag2SO4 (b) CuF2
(c) ZnF2 (d) Cu2Cl2
ANS: (b) CuF2 is coloured due top resence of unpaired electron in d-orbital
62 On addition of small amount of KMnO4 to concentrated H2SO4, a green oily compound is obtained
which is highly explosive in nature. Identify the compound from the following. [NCERT Exemplar
Problem] 1
(a) Mn2O7 (b) MnO2
(c) MnSO4 (c) Mn2O3
65 In the form of dichromate, Cr (VI) is a strong oxidising agent in acidic medium but Mo (VI) in MoO 3
and W (VI) in WO3 are not because _________________. [NCERT Exemplar Problem]
(a) Cr (VI) is more stable than Mo(VI) and W(VI).
1
(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.
ANS: (b) and (c) higher oxidation states are more stable.
66 Which of the following actinoids show oxidation states upto +7? [NCERT Exemplar Problem]
(a) Am (b) Pu 1
(c) U (d) Np
ANS: (a) and (d) Pu and Np show oxidation state upto +7.
68 Which of the following lanthanoids show +2 oxidation state besides the characteristic oxidation
state +3 of lanthanoids? [NCERT Exemplar Problem]
1
(a) Ce (b) Eu
(c) Yb (d) Ho
ANS: (b) and (c) Eu2+ (4f7) and Yb2+ (4f14) are more stable.
69 Match the catalysts given in Column I with the processes given in Column II.
Column I (Catalyst) Column II (Process)
(a) Ni in the presence of hydrogen (i) Zieglar Natta catalyst
(b) Cu2Cl2 (ii) Contact process
(c) V2O5 (iii) Vegetable oil to ghee 1
(d) Finely divided iron (iv) Sandmeyer reaction
(d) TiCl4 + Al (CH3)3 (v) Haber’s Process
(vi) Decomposition of KClO3
12
ANS: (a) (iii) (b) (iv) (c) (ii) (d) (v) (e) (i)
70 Match the compounds/elements given in Column I with uses given in Column II.
Column I Column II
(Compound/element) (Use)
(i) Production of iron
(a) Lanthanoid oxide
alloy
(b) Lanthanoid (ii) Television screen
(c) Misch metal (iii) Petroleum cracking 1
(d) Magnesium based
(iv) Lanthanoid metal + iron
alloy is constituent of
(e) Mixed oxides of
(v) Bullets
lanthanoids are employed
(vi) In X-ray screen
ANS: (a) (ii) (b) (i) (c) (iv) (d) (v) (e) (iii)
71 Match the properties given in Column I with the metals given in Column II.
Column I (Property) Column II (Metal)
(a) An element which can
(i) Mn
show +8 oxidation state
(b) 3d block element that
(ii) Cr 1
can show upto +7 oxidation state
(c) 3d block element with
(iii) Os
highest melting point
(iv) Fe
13
74
1
ANS: 10 CO2
75 1
ANS: 3I2
76 1
ANS: 6 Fe3+
77 Cu2+ is reduced by CN– to Cu+ which forms the complex [Cu(CN)4]3–. [True/False] 1
ANS: True.
78 The number of moles of Mohr’s salt required per mole of dichromate ion are 6. [True/False] 1
ANS: True
79 The colour of light absorbed by an aqueous solution of CuSO 4 is orange red. [True/False] 1
ANS: True
82 Name the gas that can readily decolourised by acidified KMnO 4 solution.
(a) SO2 (b) NO2 1
(c) P2O5 (d) CO2
14
(c) La3+ < Eu3+ < Lu3+ < Y3+
(d) Y3+ < Lu3+ < Eu3+ < La3+
ANS: (d) Y3+ < Lu3+ < Eu3+ < La3+ due to lanthanoid contraction.
86 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? [NCERT
Exemplar Problem]
(a) They have high melting points in comparison to pure metals. 1
(b) They are very hard.
(c) They retain metallic conductivity.
(d) They are chemically very reactive.
87 KMnO4 acts as an oxidising agent in alkaline medium. When alkaline KMnO 4 is treated with KI,
1
iodide ion is oxidised to ____________. (a) I2 (b) IO– (c) IO3– (d) IO4–
89 When acidified K2Cr2O7 solution is added to Sn2+ salts then Sn2+ changes to [NCERT Exemplar
Problem]
1
(a) Sn (b) Sn3+
(c) Sn4+ (d) Sn+
90 Highest oxidation state of manganese in fluoride is +4 (MnF4) but highest oxidation state in oxides
is +7 (Mn2O7) because ____________. [NCERT Exemplar Problem]
(a) fluorine is more electronegative than oxygen.
1
(b) fluorine does not possess d-orbitals.
(c) fluorine stabilises lower oxidation state.
(d) in covalent compounds fluorine can form single bond only while oxygen forms double bond.
ANS: (d) Oxygen can form multiple bonds due to presence of 2 unpaired electrons.
91 Which of the following ions show higher spin only magnetic moment value? [NCERT Exemplar
Problem]
1
(a) Ti3+ (b) Mn2+
(c) Fe2+ (d) Co3+
15
ANS:
92 Transition elements form binary compounds with halogens. Which of the following elements will
form MF3 type compounds? [NCERT Exemplar Problem]
1
(a) Cr (b) Co
(c) Cu (d) Ni
ANS: (a) and (b) CrF3, CoF3 are easily formed ∵ Cr3+ and Co3+ are stable.
93 Which of the following will not act as oxidising agents? [NCERT Exemplar Problem]
(a) CrO3 (b) MoO3 1
(c) WO3 (d) CrO42–
ANS: (b) MoO3 and (c) WO3 because their +6 oxidation states are more stable.
94 Although +3 is the characteristic oxidation state for lanthanoids but cerium also shows +4
oxidation state because _______________. [NCERT Exemplar Problem]
(a) it has variable ionisation enthalpy
1
(b) it has a tendency to attain noble gas configuration
(c) it has a tendency to attain f0 configuration
(d) it resembles Pb4+
95 Match the solutions given in Column I and the colours given in Column II.
Column I
Column II
(Aqueous solution of
(Colour)
salt)
(a) FeSO4.7H2O (i) Green
(b) NiCl2.4H2O (ii) Light pink 1
(c) MnCl2.4H2O (iii) Blue
(d) CoCl2.6H2O (iv) Pale green
(e) Cu2Cl2 (v) Pink
(vi) Colourless
ANS: (a) (iv) (b) (i) (c) (ii) (d) (v) (e) (vi)
96 Match the property given in Column I with the element given in Column II.
Column I (Property) Column II (Element)
(a) Lanthanoid which shows +4 oxidation state (i) Pm
(b) Lanthanoid which can show +2 oxidation state (ii) Ce
(c) Radioactive lanthanoid (iii) Lu
7
(d) Lanthanoid which has 4f electronic configuration in 1
(iv) Eu
+3 oxidation state
(e) Lanthanoid which has 4f14 electronic configuration in
(v) Gd
+3 oxidation state
(vi) Dy
ANS: (a) (ii) (b) (iv) (c) (i) (d) (v) (e) Lu3+(iii)
16
97 Match the properties given in Column I with the metals given in Column II.
Column II
Column I (Property)
(Metal)
(a) Element with highest second ionisation
(i) Co
enthalpy
(b) Element with highest third ionisation 1
(ii) Cr
enthalpy
(c) M in M (CO)6 is (iii) Cu
(d) Element with highest heat of atomisation (iv) Zn
(v) Ni
ANS: more
100 The general molecular formula of compounds formed by heating lanthanoids with sulphur is
1
________ .
ANS: Ln2S3
ANS: True
ANS: True
17