aha 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,SO, 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. INCERT Exemplar] [HoTS) Ams. A=KMnO,, B=K,Mn0, C=Mn0,, D=MnCh, 2KMn0, —*+ K,MnO, + MnO, +0, w e © 2MnO, + 4KOH +0, —2K,MnO,+2H,0 ®) MnO, + 4NaCl + 4H,S0, — MnCl, + 4NaHSO,+2H,0+ Cl, o Q.13. 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 solution of compound (B). Compound (B) disproportionates in neutral or acidic solution to give purple compound (C). An alkaline solution of compound (C) oxides Potassium iodide solution to a compound (D) and compound (A) is also formed. Identify A to D and also explain the reactions involved. ‘compounds. INCERT Exemplar| (HOTS| Ans. A=MnO,, B=K,MnO,, C= KMn0,, D= KIO, 2Mn0, + 4KOH +0, —+ 2K,MnO, +2H,0 «“ ®) 3MnO} + 4H" —-2Mno, + MnO, +2H,0 © 2MnO, + H,0+KI—+ 2MnO, + 20H” +KIO, w ©variability in oxidation number of transition elements different from that of non-transition nts? Illustrate with examples. jive reasons: (a) d-block elements exhibit more oxidation states than f-block elements. () Orange solution of potassium dichromate turns yellow on adding sodium hydroxide to it. (©) Zirconium (Z = 40) and Hafnium (Z = 72) have almost similar atomic radii. [CBSE Sample Paper 2017) (i) In transition elements, the oxidation states differ from each other by unity, ¢.8., Fe™ and Fe™ etc. while in non-transition elements (p-block elements), the oxidation states differ by two, e.g., Pb and Pb**, etc. In transition elements the higher oxidation states are more stable for the heavier elements in a group. €.g., Mo(VI) is more stable than Cr(VI) whereas in non-transition elements (p-block elements), the lever oxidation states are more stable for heavier elements due to inert pair effect, e.g., PXtl) is more stable than Pb(IV).(ii) (@) d-block elements exhibit more oxidation states because of less energy gap between d ang 5 subshell whereas f-block elements have large energy gap between f and d subshell. (®) On adding NaOH, pH of solution increases and the orange colour of the solution changes 1, yellow due to conversion of dichromate ion to chromate ion. Cr,07 +20H” == 2107 +H, 0 Dichromate fon Chromate fon (range) (Yellow) (©) This is due to filling of 4f-orbitals which have poor shi ing effect (Lanthanoid contraction).Q.10. (@ Describe the preparation of potassium permanganate from pyrolusite ore. Write balanced themical equation for one reaction to show the oxidizing nature of potassium permanganate. Draw the structures of chromate and dichromate ions. [CBSE Sample Paper 2017| ‘Ans. () Conversion of pyrolusite (MnO,) into potassium manganate (K,Mn0,). 2MnO,+4KOH+0, ——~ 2K,MnO,+2H,0 Electrolytic oxidation: K,Mn0, 2K* +Mn02 Atanode: © MnO} ——+ MnO, +e Atcathode: H’+e° ——+ H, 2H ——~ H, It oxidises oxalate (C,0}>) to carbon dioxide (CO,) in acidic medium. MnO, +8H* +Se7 ——+ Mn™*+4H,0]x2 C,07 —+ 2C0,+2e]x5 2MnO, + 5C,07 +161 — _2Mn™ +1000, +8H,0 Me f ft of oto oT Noo oO oO oO (Chromate ion Dichromate ion(Geers or oving: “The enthalpies of atomisation of transition elements are high. (ii) The transition metals and many of their compounds act as good catalysts. (iii) From element to element, the actinoid contraction is greater than the lanthanoid contraction. (év) The E? value for the Mn**/Mn™ couple is much more positive than that of Cr**/Cr**, (») Scandium (Z = 21) does not exhibit variable oxidation states and yet it is regarded as a transition element. (CBSE 2019 (56/2/3)) ‘Ans. (i) This is because transition metals have strong metallic bonds as they have a large number of unpaired electrons, (li) The catalytic activity of transition metals is attributed to the following reasons: (a) Because of their variable oxidation states, transition metals form unstable i and provide a new path with lower activation energy for the reaction. (®) In some cases, the transition metal provides a suitable large surface area with free valencies on which reactants are adsorbed. (ii) This is due to poorer intermediate compounds ielding by 5f-clectrons in actinoids than that by 4f:electrons in the lanthanoids.(iv) This is due to much larger third ionisation energy of Mn as Mn’ is very stable on account of stable & configuration. (v) This is because scandium has partially filled d-orbitals in the ground state (3d' 45%),cetmcney soreness Q.2. ~d) Complete the balance the following chemical equations: (a) Cr,07-+1-+H* — (6) MnO; + SO} + H* —— (i) Explain the following observations: (a) Transition elements and their compounds are known to act as catalysts. (&) The higher oxidation states are usually exhibited by the members in the middle of a series of transition elements. (©) The metal-metal bonding is more frequently found with the second and third series of transition elements, (CBSE (F) 2012] ‘Ans. (i) (a) Cr,0}" + 14H" + 6e° — 2Cr* +7H,0 2 + 26) x3 Cr,07 +61 + 14H" —— 2Cr* +31, + 7H,0(b) MnO; + 8H* + Se ——> Mn** + 4H,O] x2 SO} + HO —— SO} +2H*+ & 1x5 2Mn0, + + 5807 + 3H,0 (ii) (a) The catalytic activity of transition metals and their compounds is attributed to the following reasons: @ Due to their tendency to show variable oxidation states transition metals form instable intermediate compounds and provide a new path for the reaction with lower activation energy. @ In some cases, the transition metals provide a suitable large surface area with free valencies on which reactants are adsorbed. (b) It is due to greater number of unpaired electrons in (n—1)d and ns orbitals at the middle of the series. (c) In the same group of d-block elements, the 4d and Sd transition elements are larger in size than those of corresponding 3d elements. Hence, the valence electrons are less tightly held and form ® metal-metal bond more frequently.mplete the following reactions: (i) MnO, + KOH + 0, —— (i) 1 + MnO;z + H* ——~ (iii) Cr,07 + Sn?* + Ht —— Ans, (i) MnO, + 4KOH + 0, ——> 2K,MnO, + 2H,O (ii) 101 + 2MnO, + 16H* —— 2Mn* + 8H,O + SI, (iti) Crp07 + 14H* + 3Sn* —— 2¢cr** + 38n** + 7H,0) Why do transition elements show variable oxidation states? (a) Name the element showing maximum number of oxidation states among the first series of transition metals from Sc (Z = 21) to Zn (Z = 30). (6) Name the element which shows only +3 oxidation state. (i) What is lanthanoid contraction? Name an important alloy which contains some of the lanthanoid metals. [CBSE (AD 2013} Ans. (i) Transition elements show variable oxidation states because electrons in ns and (n - 1) d-orbitals are available for bond formation as they have nearly same energy. (a) Manganese (6) Scandium (ii) The steady decrease in the atomic and ionic radii (having the same charge) with increase in atomic number as we move across the series from lanthanum to lutetium is known as lanthanoid contraction. Misch metal.x Os Account for the following: @ Mn,0, is acidic whereas MnO is basic. pues ane ny oHioauuE HyVLyeU 1 op (di) Though copper has completely filled d-orbital (d') yet it is considered as a transition metal, (iii) Actinoids show wide range of oxidation states. [CBSE (F) 2016, () Mn has + 7 oxidation state in Mn,O, and +2 in MnO. In low oxidation state of the metal, some of the valence electrons of the metal atom are not involved in bonding. Hence, it can donate electors and behave as a base. On the other hand, in higher oxidation state of the metal, valence electrons ae involved in bonding and are not available, Instead effective nuclear charge is high and hence it can accept electrons and behave as an acid. Ans. Gi) Copper exhibits +2 oxidation state wherein it will have incompletely filled d-orbitals (34°), hence a transition metal. (iif) This is due to comparable energies of Sf, 6d and 7s orbitals.QA When pyrolusite ore MnO, is fused with KOH in presence of air, a green coloured compound (A) is ‘obtained which undergoes disproportionation reaction in acidic medium to give a purple coloured compound (B). [CBSE South 2016] (HOTS) (® Write the formulae of the compounds (A) and (B). (Gi) What happens when compound (B) is heated? Ans. () A=K,MnO,, B = KMn0, (® 2KMn0, +? K,MnO,+Mn0, +0, —— oa reemangente mmangenateHow would you account for the following: ( Many of the transition elements and their compounds can act as good catalysts, (Gd) The metallic radii of the third (Sd) series of transition elements are virtually the same 25 tg of the corresponding members of the second series. fo There is a greater range of oxidation states among the actinoids than among the lant (CBSE (41) 2009, Ans. (i) The catalytic activity of transition metals is attributed to the following reasons: (a) Because of their variable oxidation states transition metals form unstable intermediate. ‘compounds and provide a new path with lower activation energy for the reaction. (b) In some cases, the transition metal provides a suitable large surface area with free vacancies on which reactants are adsorbed. (ii) This is due to filling of 4f-orbitals which have poor shielding effect or due to lanthanoid contraction. (iii) This is due to more comparable energies of 5f, 6d and 7s orbitals in actinoids. Q.5. (How would you account for the following: (a) Highest fluoride of Mn is MnF, whereas the highest oxide is Mn,O,. () Transition metals and their compounds show catalytic properties. (Gi) Complete the following equation: KS 3MnOz + 4H* —— [CBSE (F) 2015] Ans. (i) (a) As oxygen stabilises manganese more than fluorine by forming multiple bonds. (6) The catalytic activity of transition metals and their compounds is attributed to the following ressous @ Due to their tendency to show variable oxidation states transition metals form unstable intermediate compounds and provide a new path for the reaction with lower activation energy: @ In some cases, the transition metals provide a suitable large surface area with free valencies ‘on which reactants are adsorbed. (i) 3MnO{ +4" —~> 2Mn0, +MnO,+4H,0 Manganateion Permanganat ionQs. Ans. Q.16. Ans. Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction with (i) iodide (i) iron (11) solution (iii) HS. (i) Cr,0F + 14H" + 61> —— 2Cr* +7H,0 + 31, (ii) Cr} + 14H" + 6Fe?* —— 2Cr°* + 7H,0 + 6Fe** (iti) Cr0F +8H*+3H,S —— 2Cr*+7H,0 +38 Describe the preparation of potassium permanganate. How does the acidified permanganate react with (@ iron (II) fons (i) SO, (ii) oxalic acid? Write the ionic equations for the reaction. For preparation, refer to Basic Concepts Point 4(b). (i) MnO; +8H* + 5Fe*™ Mn** + 4H,O + SFe** (ii) 2MnO, +2H,0 +580, ——+ 2Mn* + 4H* + 5SO7 coo (ili) 2MnOj + 16H" +5 | —— 2Mn™ +8H,0 + 10CO, coo" - Rar MEI ana MEAD nrctame £9 «