D and f block elements

1. (a) Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their +3 state?

(b) Why is Zinc [Z=30] not considered a transition element, while Silver [47] is?

2.Why do transition elements show variable oxidation states?

It is because electrons from (n – 1 )d and ns take part in bond formation.

3.How is the variability in oxidation states of d-block different from that of the p-block elements?

4. . (a) Change in pH affects chromates and dichromates. Explain with equations.

(b) Why does the melting point for Manganese dip?

(c ) Why is the +3 oxidation state of Lanthanum (Z = 57) Gadolinium (Z = 64) and Lutetium (Z = 71)
stable?

5. . Explain each reason.

a) Define how Potassium Dichromate is prepared from chromite ore?

b) Mn2+ compounds are more stable than Fe2+.

c) Why is Cr2+ reducing and Mn3+ oxidizing when both have the same d4+ configuration?

6. Why do actinoids show wide range of oxidation states?

(ii) Why is actinoid contraction greater than lanthanoid contraction?

7. What are the transition elements? Write two characteristics of the transition elements.

8. Write one similarity and one difference between the chemistry of lanthanoids and that of
actinoids

9.Transition metals form coloured compounds. Why?

MnO is basic whereas Mn207 is acidic in nature. Why?

Ans: In MnO, Mn has +2 oxidation state, whereas in Mn2O7, Mn has + 7 oxidation state. Higher the
oxidation state, more will be acidic nature, e.g. Mn207. Lower the oxidation state, more will be basic
nature, e.g. MnO.

10. Account for the following:

(i) Cu+ is unstable in an aqueous solution.

(ii) Transition metals form complex compounds

11.How would you account for the following:

(i) Highest fluoride of Mn is MnF4 whereas the highest oxide is Mn2O7

Ans: Oxygen can form double bond, therefore, it can form Mn207, whereas ‘F’ cannot form double
bonds, so, it can form MnF4.

(ii) Transition metals and their compounds show catalytic properties.

12. Account for the following:

(a) (i) EU2+ is strong reducing agent

(ii) Transition metals form coloured compounds

(iii) Zn has lowest enthalpy of atomisation.

13.Account for the following:

(a) (i) Transition elements form interstitial compounds.

(ii) Mns+(3d4) is strongly oxidising, whereas Cr2+(3d4) is strongly reducing.

(iii) Transition metals have high melting points.

(b) What is misch metal? Write its one use.

Answer: a) (i) Small size atoms B, C, H can occupy voids present in transition metals.

(ii) Mn3+ gains one electron to form Mn2+ since 3dD is more stable, whereas Cr2+ loses one
electron for Cr3+(i3p which is more stable, so, it acts as reducing agent.

(iii) It is due to involvement of unpaired ((-electrons to form strong metallic bond.

(b) It contains 95% lanthanoid metal, 5% iron and traces of S, C, Ca and AI.

Use: Its magnesium based alloy is used to produce bullets, shells, flints.

14. Describe the general trends in the following properties of first series 3d of transition elements:

(i) number of oxidation states exhibited (ii) formation of oxometal ions.

Answer:

(i) The tendency to show number of oxidation states increases from Sc to Mn and then decreases
because number of unpaired electrons increases till Mn, then decreases.

(ii) Tendency to form oxometal ions increases from Sc to Cr and then decreases due to increase in
unpaired electrons and ability to form multiple bonds with oxygen.

15.Which of the 3d-block elements may not be regarded as the transition elements and why.

Assign suitable reasons for the following:

(a) The Mn2+ compounds are more stable than Fe2+ towards oxidation to their +3 state.

(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 Ti3+ is coloured.

Answer:

(a) Mn2+ has 3d5 (stable electronic configuration), therefore, it does not get oxidised to Mn3+,
whereas Fe2+ has 3d6 which readily changes to Fe3+ (3d5), which has stable electronic
configuration.

(b) Zinc does not have unpaired electrons and larger in size, therefore, it 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,
whereas Ti3+ is coloured due to presence of unpaired electrons and undergoes d-d transition

16.Name the element of 3d transition series which shows maximum number of oxidation states.
Why does it show so?

(ii) Which transition metal of 3d series has positive E°(M2+/M) value and why?

(iii) Out of Cr3+ and Mn3+, which is a stronger oxidizing agent and why?

(iv) Name a member of the lanthanoid series which is well known to exhibit + 2 oxidation state.

(v) Complete the following equation:

MnO4– + 8H+ + 5e- ———->

Answer:

(i) Mn because it has five unpaired electrons and 2 electrons in s-orbital which can take part in bond
formation, therefore, it shows maximum number of oxidation states.

(ii) E°CU9+/CU has +ve value due to high ionisation enthalpies and sublimation energies and lower
hydration energy.

(iii) Mn3+ is stronger oxidising agent because it can gain electrons to become Mn2+ which is more
stable due to 3d5 (half filled d-orbitals), whereas Cr3+ is stable due to f3 (half filled orbitals).

(iv) Europium shows +2 oxidation state. Ytterbium (Yb) also shows +2 oxidation state.

(v) Mn04 + 8H+ + 5e- ———> Mn2+ + 4H20.

17. (i) Zr (Z = 40) and Hf (Z = 72) have almost identical radii.

Ans: It is due to lanthanoid contraction which is due to poor shielding effect off-electrons, due to
which

effective nuclear charge increases, therefore, Zr and Hf have almost identical radii.

(ii) Transition metals and their compounds act as catalyst.

Ans: (ii) It is because they show variable oxidation states and form unstable intermediates which
readily change

18. How is potassium dichromate prepared?

(i) Zr (Z = 40) and Hf (Z = 72) have almost identical radii.

19.

Coordination compounds
1. (a) What is meant by chelate effect? Why are low spin tetrahedral complexes not formed?

(b) How is the dissociation constant of a complex defined?

2.
(iii) One mole of Cr Cl3 (H2O)6 , will give one mole of AgCl precipitate on treating with AgNO3.
Write the formula of the complex 3.

4. Give the formulae of the following compounds :

(a) Potassium tetrahydroxidozincate (II)

(b) Hexaammineplatinum (IV) chloride

(c ) Potassium trioxalatoaluminate (III)

(d) Tetraammineaquachloridocobalt (III) chloride

(e) Pentaamminecarbonatocobalt (III) chloride

(f) Potassium tetracyanidonickelate (II)

5. What type of isomerism is shown by the complex [Co(NH3)5 NO2] Cl2 ?

6. (a) Give the IUPAC name and electronic configuration of central metal atom in terms of t2g and eg
of K4[Mn(CN)6].

(b) What is meant by ‘Chelate effect’ ? Give an example.

7.Write the hybridisation and magnetic characters of the following complexes :

(i) [Fe(CN)6]4– (ii) [CoF6]3– (iii) [Ni(CO)4]

[Atomic number : Fe = 26, Co = 27, Ni = 28]

8. (a) Write the IUPAC name and hybridisation of the complex [CoF6]3–

(Given : Atomic number of Co = 27)

(b) What type of isomerism is shown by the complex [Co(en)2Cl2]2+ ?

9.Name the structure of an isomer of this complex which is optically active.

10. (a) How can you show that complexes [Co(NH3)5 Cl] SO4 and [Co(NH3)5 SO4] Cl are

ionization isomers ?

(b) Write the formula of the following complex using IUPAC norms :

Potassium trioxalatochromate (III)

11. Write IUPAC name and hybridization of the following complexes :

(i) [Ni(CO)4] ( (Atomic number Ni = 28,)

12. Write the IUPAC name and hybridisation of the following complexes :

(i) [Co(NH3)6]3+ (ii) [NiCl4]2–

(Given : Atomic number : Ni = 28, Co = 27)

13. (a) Write the IUPAC name and hybridisation of the complex [Fe(CN)6]3–

.(Given : Atomic number of Fe = 26)

(b) What is the difference between an ambidentate ligand and a chelating ligand ?

14. Discuss the nature of bonding in metal carbonyls

15. Out of Cis–[Pt(en)2Cl2]2+ and Trans–[Pt(en2)Cl2]2+, which one isoptically active

16. Define ambidient nucleophile with an example

17. Write IUPAC name of the complex [Pt(en)2Cl2].

18.Draw structures of geometrical isomers

for this complex.

(i) Hexaamminecobalt(III) sulphate (ii) Potassium trioxalatochromate(III)

19. Write IUPAC name of the complex [Cr(NH3)4Cl2]+. Draw structures of geometrical

isomers for this complex.

20.Using IUPAC norms write the formulae for the following :

(i) Pentaamminenitrito-O-cobalt(III) chloride (ii) Potassium tetracyanidonickelate(II)

21. Out of [CoF6]3– and [Co(en)3] 3+, which one complex is (i) paramagnetic (ii) more stable

(iii) inner orbital complex and (iv) high spin complex (Atomic no. of Co = 27)

22. Out of [CoF6]3– and [Co(C2O4)3]3– , which one complex is (i) diamagnetic (ii) more stable

(iii) outer orbital complex and (iv) low spin complex ? (Atomic no. of Co = 27)
23. Write the hybridization and magnetic character of following complexes :

(i) [Fe(H2O)6]2+ (ii) [Fe(CO)5] (Atomic no. of Fe = 26)

24. Write IUPAC name of the complex [Co(en)2(NO2)Cl]+ . What type of structural isomerism

is shown by this complex ?

25. Using IUPAC norms, write the formulae for the following complexes :

(a) Hexaaquachromium(III) chloride (b) Sodium trioxalatoferrate(III)

26. Define the following terms with a suitable example of each :

(a) Chelate complex (b) Ambidentate ligand

27.Using IUPAC norms, write the formulae for the following complexes :

(a) Tetraamminediaquacobalt(III) chloride

(b) Dibromidobis(ethane-1,2-diamine)platinum(IV) nitrate

28. (a) Using valenc bond theory, write the hybridisation and magnetic character of the

complex [Fe(CN)6]4– . (Atomic no. of Fe = 26)

(b) Write the electronic configuration of d6 on the basis of crystal field theory when

(i) o < P and (ii) o > P

29. Define the following terms with a suitable example of each :

(a) Polydentate ligand (b) Homoleptic complex

30. Using IUPAC norms, write the formulae for the following complexes :

(a) Potassium tri(oxalato)chromate(III) (b) Hexaaquamanganese(II) sulphate

31. (a) Although both [NiCl4]2– and [Ni(CO)4] have sp3 hybridisation yet [NiCl4]2– is

paramagnetic and [Ni(CO)4] is diamagnetic. Give reason. (Atomic no. of Ni = 28)

(b) Write the electronic configuration of d5 on the basis of crystal field theory when

(i) o < P and

(ii) o > P

32. Write IUPAC name of the complex [Co(en)2(H2O)(CN)]2+

33. (a) Give one chemical test as an evidence to show that [Co(NH3)5Cl]SO4 and

[Co(NH3)5(SO4)]Cl are ionisation isomers.

(b) [NiCl4]2–is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral.

Why ? (Atomic no. of Ni = 28)

(c) Write the electronic configuration of Fe(III) on the basis of crystal field theory when it

forms an octahedral complex in the presence of

(i) strong field ligand, and (ii) weak field ligand. (Atomic no. of Fe = 26)

34. Write IUPAC name of the complex K3[Cr(C2O4)3]

Using

36. Write IUPAC name of the complex [Co(en)2Cl2]+.

37. When a coordination compound CrCl3 . 6H2O is mixed with AgNO3, two moles of AgCl

are precipitated per mole of the compound. What is the structural formula of the

coordination compound?

38 What is the difference between a complex and a double salt ?

39. Write the hybridization and magnetic character of the following complexes :

(i) [Fe(H2O)6]2+ (ii) [Ni(CN)4] 2- [Atomic number : Fe = 26, Ni = 28]

40. What type of isomerism is shown by complex [Co(NH3)5Cl]SO4 ?

Arrange the following in increasing order of crystal field splitting energy :

[Cr(CN)6]3–, [Cr(NH3)6]3+, [CrCl6]3–

41. Using valence bond theory, predict the hybridization and magnetic character of the

following :

(a) [Co(NH3)6]3+ (b) [Ni(CO)4][At. no. : Co = 27, Ni = 28]

42. Using valence bond theory, predict the hybridization and magnetic character of the

following :(a) [CoF6]3– (b) [Ni(CN)4] 2– [At. no. : Co = 27, Ni = 28]

33. Using valence bond theory, predict the hybridization and magnetic character of the

following :

(a) [NiCl4]2– (b) [Co(C2O4)3]3– [At. no. : Co = 27, Ni = 28]

34. Write the coordination number and oxidation state of Platinum in the complex

[Pt(en)2Cl2].

35. (a) Write the formula of the following coordination compound :

Iron(III) hexacyanoferrate(II)

(b) What type of isomerism is exhibited by the complex [Co(NH3)5Cl]SO4 ?

(c) Write the hybridisation and number of unpaired electrons in the complex [CoF6]3–

.(Atomic No. of Co = 27)

36. Using IUPAC norms write the formulae for the following :

(a) Sodium dicyanidoaurate(I)

(b) Tetraamminechloridonitrito-N-platinum(IV) sulphate

37. (a) What type of isomerism is shown by the complex [Co(NH3)5 (SCN)]2+ ?

(b) Why is [NiCl4]2- paramagnetic while [Ni(CN)4]2- is diamagnetic?

(Atomic number of Ni = 28)

(c) Why are low spin tetrahedral complexes rarely observed?

38. Using IUPAC norms write the formulae for the following :

(a) Tris(ethane-1,2-diamine)chromium(III) chloride

(b) Potassium tetrahydroxozincate(II)

39. Using IUPAC norms write the formulae for the following :

(a) Potassium trioxalatoaluminate(III) (b) Dichloridobis(ethane-1,2-diamine)cobalt(III)

40. (i) What type of isomerism is shown by the complex [Co(NH3)6] [Cr(CN)6] ?

(ii) Why a solution of [Ni(H2O)6]

2+ is green while a solution of [Ni(CN)4]2–is colourless ? (At. no. of Ni = 28)

(iii) Write the IUPAC name of the following complex: [Co(NH3)5(CO3)]Cl.

41. (i) What type of isomerism is shown by the complex [Co(en)3]Cl3 ?

(ii) Write the hybridisation and magnetic character of [Co(C2O4)3]3– . (At. no. of Co = 27)

(iii) Write IUPAC name of the following Complex [Cr(NH3)3Cl3]

42. (a) Write the IUPAC name of the isomer of the following complex : [Pt(NH3)2Cl2]

(b) Write the formula for the following : Tetraammineaquachloridocobalt(III) nitrate

43. (a) Define crystal field splitting energy. On the basis of crystal field theory, write the

electronic configuration for d4ion if Δo< P.(b) [Ni(CN)4]2–is colourless whereas [Ni(H2O)6]

2+ is green. Why? (At. no. of Ni = 28)

44. (a) Write the IUPAC name of the following complex : [Co(NH3)4Cl(NO2)]Cl

(b) Write the formula for the following : Dichloridobis(ethane-1,2-diamine)cobalt(III)

chloride

45. (a) Write the IUPAC name of the isomer of the following complex : [Co(NH3)5Cl]SO4

(b) Write the formula for the following : Diamminechloridonitrito-N-platinum(II)

47. When a coordination compound 𝐂𝐨𝐂𝐥𝟑. 𝟔𝐍𝐇𝟑 is mixed with 𝐀𝐠𝐍𝐎𝟑, 3 moles of AgCl are

precipitated per mole of the compound. Write

(i) Structural formula of the complex (ii) IUPAC name of the complex.

48. (a) For the complex, [Fe(H2O)6]3+ write the hybridization, magnetic character and spin of

the complex. (At. Number: Fe = 26)

(b) Draw one of the geometrical isomers of the complex [Pt(en)2Cl2]2+which is optically

inactive.

49. When a co-ordination compound 𝑪𝒓𝑪𝒍𝟑. 𝟔𝑯𝟐𝑶 is mixed with 𝑨𝒈𝑵O𝟑, 2 moles of AgCl

are precipitated per mole of the compound. Write.

(i) Structural formula of the complex.

(ii) IUPAC name of the complex.

50. For the complex [Fe(CN)6]3−, write the hybridization type, magnetic character and spin

nature of the complex. (At. number: Fe = 26).

51. (i) Write down the IUPAC name of the following complex: [𝑪𝒐(𝑵𝑯𝟑)𝟓𝑪𝒍]𝟐+

(ii) Write the formula for the following complex: Potassium tetrachloridonickelate(II).

52. (i) What type of isomerism is shown by the complex[𝑪𝒓(𝑯𝟐𝑶)𝟔]𝑪𝒍𝟑?

(ii) On the basis of crystal field theory, write the electronic configuration for 𝒅𝟒 ion if

𝚫𝒐>𝑷.

(iii) Write the hybridization and shape of [𝑪𝒐𝑭𝟔]−. (Atomic no. of Co = 27)

53. (i) Write down the IUPAC name of the following complex:

[𝐂𝐫(𝐍𝐇𝟑)𝟐𝐂𝐥𝟐(𝐞𝐧)]𝐂𝐥 (𝐞𝐧 = 𝐞𝐭𝐡𝐲𝐥𝐞𝐧𝐞𝐝𝐢𝐚𝐦𝐢𝐧𝐞)]

(ii) Write the formula for the following complex: Pentaamminenitrito-o-cobalt(III).

54. (i) Draw the geometrical isomers of complex [Pt(NH3)2Cl2]

(ii) On the basis of crystal field theory, write the electronic configuration for 𝒅𝟒 ion if

Δ𝐨< 𝐏.

(iii). Write the hybridization and magnetic behavior of the complex [Ni(𝑪𝑶)4]. (At. no. of

Ni = 28).

55. (i) Write the IUPAC name of the complex [Cr(NH3)4Cl2] Cl.

(ii) What type of isomerism is exhibited by the complex [Co(en)3)]3+?

(iii) Why is [𝑵𝒊C𝒍𝟒]2−paramagnetic [𝑵𝒊(𝑪𝑶)𝟒] is a diamagnetic?

(𝑨𝒕. 𝑵𝒐𝒔. ∶ 𝑪𝒓 = 𝟐𝟒, 𝑪𝒐 = 𝟐𝟕, 𝑵𝒊 = 𝟐𝟖)

56. Which of the following is more stable complex and why? [𝑪𝒐(𝑵𝑯𝟑)𝟔]𝟑+ 𝐚𝐧𝐝 [𝑪𝒐(𝒆𝒏)𝟑]𝟑+

57. Write the IUPAC name of the complex [Cr(NH3)4Cl2]+. What type of isomerism does it

exhibit?

58. Write the IUPAC names of the following coordination compounds:

(i) [𝐂(𝐍𝐇𝟑)𝟑𝐂𝐥𝟑] (ii) 𝐊𝟑[𝐅𝐞(𝐂𝐍)𝟔] (iii) [𝐂𝐨𝐁𝐫𝟐(𝐞n)𝟐]+, (𝐞𝐧 = 𝐞𝐭𝐡𝐲𝐥𝐞𝐧𝐞𝐝𝐢𝐚𝐦𝐢𝐧𝐞)

59. For the complex [𝑵𝒊𝑪𝒍𝟒]2−, write .(i) the IUPAC name. (ii) the hybridization type.

(iii) the shape of the complex. (Atomic no. of Ni = 28)

60. Name the following coordination entities and draw the structures of their stereoisomers:

(i) [Co (𝐞𝐧)𝐂𝐥𝟐]+(𝐞𝐧 = 𝐞𝐭𝐡𝐚𝐧e−𝟏, 𝟐−𝐝𝐢𝐚𝐦𝐢𝐧𝐞)

(ii)[𝐂𝐫(𝐂𝟐𝐎𝟒)𝟑]𝟑−

(iii) [𝐂(𝐍𝐇𝟑)𝟑𝐂𝐥𝟑](Atomic numbers Cr=24, Co=27)

61. Give the formula of each of the following coordination entities:

(i) 𝑪𝑶𝟑2-ion is bound to one C𝒍−, one 𝑵𝑯𝟑 molecules and two bidentate enthylenediamine

(en) molecules.(ii) 𝑵𝒊𝟐+ ion is bound to two water molecules and two oxalate ions.

Write the name and magnetic behavior of each of the above coordination entities.

(At. Nos. Co=27, Ni =28)

62. Explain the following terms giving a suitable example in each case:

(i) Ambident ligand

(ii) Denticity of a ligand

(iii) Crystal field splitting in an octahedral field.

63. Write the name, stereochemistry and magnetic behavior of the following”

(𝐀𝐭. 𝐧𝐨𝐬. 𝐌𝐧 = 𝟐𝟓, 𝐂𝐎 = 𝟐𝟕, 𝐍𝐢 = 𝟐𝟖)

(i) 𝐊𝟒[𝐌𝐧(𝐂𝐍)𝟔]

(ii) [𝑪(𝑵𝑯𝟑)𝟓𝑪𝒍]𝑪𝒍𝟐

64. (a) What is meant by unidentate, bidentate and ambidentate ligands? Give two examples

for each.

(b) Calculate the overall complex dissociation equilibrium constant for the [Cu(𝑵𝑯𝟑)4]2+ion, given
that 𝜷𝟒 for this complex is 𝟐. 𝟏×𝟏𝟎𝟏𝟑.

65. Give an example of linkage isomerism?

66. Name the following coordination compounds according to IUPAC system of

nomenclature:

(i) [Co(𝐍𝐇𝟑)(𝐇𝟐𝐎)𝐂𝐥]𝐂𝐥𝟐

(ii) [CrCl2(𝐞𝐧)2]𝐂𝐥, (𝐞𝐧 = 𝐞𝐭𝐡𝐚𝐧𝐞 − 𝟏, 𝟐 − 𝐝𝐢𝐚𝐦𝐢𝐧𝐞)

67 Compare the following complexes with respect to structural shapes of units magnetic

behavior and hybrid orbitals involved in units:

[𝑪𝒐(𝑵𝑯𝟑)𝟔]𝟑+, [𝑪𝒓(𝑵𝑯𝟑)𝟔]+, 𝑵𝒊(𝑪𝑶)𝟒 𝑨𝒕. 𝑵𝒐𝒔: 𝑪𝒐 = 𝟐𝟕, 𝑪𝒓 = 𝟐𝟒, 𝑵𝒊 = 𝟐𝟖

69. For the complex [𝑭(𝒆𝒏)𝟐C𝒍𝟐]𝑪𝒍, (en=ethylene diamine), identify

(i) The oxidation number of iron,

(ii) The hybrid orbits and the shape of the complex,

(iii) The magnetic behavior of the complex.

(iv) The number of geometrical isomers,

(v) Whether there is an optical isomer also, and

(vi) name of the complex. (At. No. of Fe = 26)

Alcohols, Phenols , and Ethers