Topic 1 the d-Block Elements Very Short Answer Type Questions QA. Write the formula of an oxo-anioy in which it shows the oxi group number. Ans. MnO; /KMnO, Q.2. Transition metals form coloured compounds. [eBSE eth! 2015) Ans. Transition metals contain incompletely filled orbitals and unpaired electron which absorb light from visible region and can undergo dd transition During d-d transitions they radiate complementary colours and form coloured ions. se" (3°), cu" (3d"®),2n2* (34), ca?*(4a"®) have no unpaired electrons and can not undergo ded transition. Hence, they are white. Q.3. Complete the following equation 2Mn0; +6H’ +5NO; —> [CBSE De!hi 2015) ‘Ans. 2Ma0; +6H* +5NO; — + 2Mn™* +3#,0+ 5NO5 Q.4. Complete the following equation. 2MnO; +6H" +580} —> [CBSE All india 2015) ‘Ans, 2Mn0; +6H* + 580} —>2Mn** + 5S0}-+3H,0 Q.5. What are transition elements ? Ans. A transition elements is defined as the one which has incompletely filled d-orbitals in its ground state or in any one of its oxidation states. Q.6. Zincis not regarded as a transition element. Explain, [CBSE Deihi 2010] Ans. Zinc is not regarded as a transition element because Zn has completely filled d-orbitals in its ground state as wellas in its common oxidation state. (Zn”* state). Q.7. Silver atom has completely filled d-orbitals(4a")inits ground state. How can you say that itis a transition clement ? [HOTS] INCERT] Ans. Silver in some compounds show +2 oxidation state. In +2 oxidation state, it has incompletely filled d- orbitals. That's why it can be regarded as a transition element. Q.8. Which element of the first transition series shows the highest number of ox states ? ‘Ans. Manganese (Mn) Q.9. Explain the following observation: Among the divalent cations in the first series of transition elements, manganese exhibits the maximum paramagnetism. {CBSE All India 2010), [1 Mark] #f Manganese (Mn) fon state equal to its [CBSE Dotni 2017) Ans, Mn?* has maximum number of unpaired electrons ive, Selectrons and paramagnetic nature is directly proportional to the number of unpaired electrons. ‘Thus, it exhibits maximum paramagnetism. Q.10, V** and Cr are strong reducing agents. Why ? Ans. + 4is the stable oxidation state for vanadium and +3 is the stable oxidation state for chromium in their aqueous solutions. So, ?* and Cr?* get oxidized to their stable state and act as strong reducing agents. Q.11. Why do Zrand Hf show similar properties ? Ans. It is due to similar ionic size, which is due to Ianthanoid contraction. Q.12. Although Zr belongs to 4d and Hf belongs to 5d transition series, but it is quite difficult to separate them. Why ? (Exemplar NCERT} ‘Ans. Zr and HE are present in different series but have almost similar sizes due to lanthanoid contraction. ‘Thus they have similar properties and are difficult to separate. Q.13. Why are Ca?" salts white? [CBSE All Ingia 2007] Ans. Cd?* salts are white because Cd?* has completely filled d-orbitals (d") ie, no unpaired electrons are there. Why does Ti** ion show diamagnetic nature ? . Ti** ion show diamagnetic nature because it does not have any unpaired electron init. Q.15. Why NagCi0, is not used in volumetric analysis ? THoTS} Ans. Because of its deliquescent nature, Na,Ci0, is not used in volumetric analysis. Q.16. Why is the orange solution of K,Ch,0, turns yellow on adding NaOH? ‘Ans. Itis due to the formation of C103" ions. x,03- +208" —> 20103" + 4,0 sichroate ‘Orerte (Orange) low Q.17. Explain the oxidizing property of K,C1,0,. ‘Ans. K,C1,0, acts as an oxidizing agent. In acidic medium it undergoes reduction to Cr* CyOF" + 1411? +66" — 2Ce* +780 Q.18, Write an ionic equation representing the oxidizing property of acidified KMn0, solution. Ans. Mrl0j +81 Se” —> Mn?" + 41,0 (in acidic medium)Q.19, Ans. Q.20. Ans. 21. Q.22. Ans. Q.23. 25. 2.26. What is meant by disproportionation reaction ? Give an example, INCERT] A reaction in which same species is oxidized as well as reduced is called disproportionation reaction. Many copper (I) compounds are unstable in aqueous solution and undergo disproportionation. 2Cu* — cu? + Cu ‘Other example : MnO} disproportionates ina neutral or acidic solution to give permanganate. 3.MnO{~ + 4H *—+ 2MnO; + MnO, +2H,0 ‘What does the £° value of M'*/M?* show for Mn?* and Co?* ( + 1.57 V and +1.97V respectively) ? The high E® value of M°*/M?* for Mn?* and Co** shows that they are the strong oxidizing agents in aqueous solutions among all the rest of transition metal series. They have strong tendency to be reduced their stable oxidation state viz. +2. Why does not copper liberates hydrogen from acids? [Exemplar NCERT] Copper has positive E* value and is placed below hydrogen in the electrochemical series. Itis unable to displace hydrogen of the acid. Therefore, hydrogen gas is not liberated Avange CrO,CrO, and Cr,0, in increasing order of acidic strength. (Hors) CrO< Cr0,< CrO, (Higher the oxidation state, higher is the acidic character). How would you account for the increasing oxidizing power in the series VO,’ < Cr,0?" * (aq) rather than Cu" (ag) is dueto the much more negative Spy H of Cu2*(eq) than Cu? which is more than that compensates for second ionisation enthalpy of Cu Q.28. Out of CuCl; and CuCl;, which is more stable and why? [Exemplar NCERT] ‘Ans, CuCl, is more Stable than CuCl; because Cu®* (aq) ion has more negative enthalpy of hydration (A yyjH” )as compared to Cu (aq) ion due to its smaller ionic size. Q.29. Transition metals and their compounds generally exhibit a paramagnetic behaviour. Give reasons. ~ {CBSE All Inca 2011} Ans. This is because of the presence of unpaired electrons in d- orbitals of transition metals. Q.30. Why do the transition elements exhibit higher enthalpies of atomisation ? INERT] Ans. The transition elements exhibit higher enthalpies of atomization because of large number of unpaired electrons in their atoms, due to which they have stronger interatomic interaction and hence stronget bonding. Q.31. Cr* is a strong reducing agent whereas Mn™ with the same (d*) configuration is an oxidizing agent. [HOTS] [NCERT; CBSE Delhi 2011 C] CH get easily oxidized to Ce? and acts 25 2 reducing agent. Its configuration changes from ‘1 @ (ie, half-filled th, level). On the other hand, the change from Mn3* to Mn?* results in the more stable half-filled (a°) configuration. Thus, it behaves 3 oxidizing agent. Explain why a transition metal exhibits highest ‘oxidation state in oxides and fluorides ? {HoTS! {CASE AN incia 2011) Ans. A transition metal exhibits highest oxidation state i? oxides and fluorides, due to high electronegativitY Ans. Q.32,- dn aie Properties of oxygen and M ty of oxygen to stabilize these high oxidation states exceeds that of fluorine. For example, Mn forms the highest fluoride as MnF, whereas the highest oxide is Mn0,, This is due tothe tendency of oxygen to form multiple bonds, 0.33. Although fluorine is more electronegative. than oxygen, but the ability of oxygen to ‘stati higher oxidation states exceeds that of fluorine. Why? [Exemplar NCERT] Ans. Ability of oxygen to stabilize these high oxidation states exceeds that of fluorine. For example, Mn forms the highest fluoride as Mnf, whereas the highest oxide is Mn,0;. This is due to the tendency of oxygen to form multiple bonds. Q.34. Why is the E® value for the Mn*/Mn”* couple much more positive than that for Cr°*/Cr2* or Fe™*/Fe?*? Explain. INcerT] ‘Ans. Mn?” has a stable d° electronic configuration due to which its third ionisation energy (where the required change is d° to d*) is much larger. This is mainly responsible for much more positive value of E® for the Mn**/Mn?* couple than that for Cr°*/Cr?* or Fe™*/Fe**. Moreover Cr**(t3,)and Fe**(d°)are stable. Q.35. Why do transition elements show variable oxidation states? ‘Ans. The transition elements show variable oxidation state due to small energy difference between (nt — 1) d and ns orbital. As a result both (n—1)d and ns electrons take part in bond formation. 0.36. Explain why transition elements have many irregularities in their electronic configurations ? ‘Ans. Inthe transition elements, there isa litle difference in the energy of (n— 1) @-orbitals and ns-orbitals, Thus, incoming electron can occupy either of shell. Hence, transition elements exhibit many irregularities in their electronic configurations. Q.37. Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25. [NCERT] ‘Ans. The divalent ion in aqueous solution with atomic number 25 will have d° configuration (five unpaired electrons). The magnetic moment, is w= (nie) BM. = (5642) 592 BM. Q.38. Unlike CrP’*, Mn?*, Fe®* and the subsequent other M?* ions of the 3d- series of elements, the 4d and the 5¢- series metals generally do not form stable cationic species. {HOTS} [CBSE All India 2011, 10), Short Answer Type Questions Aas. This is because energy required to remove electron is more due to greater effective nuclear charge which is ue to the poor shielding effect of f-electrons. Q.39. In the series Se(Z = 21) to Zn (Z = 30), the enthalpy of atomisation ofzincisthe lowest, ie, 126 kI mol”'. Why? INceRT] Ans, Enthalpy of atomization depends upon the strength ‘of metallic bonding. In case of zinc, metallic bonding is weak as it lacks unpaired electrons that can take part in metallic bonding. Thus, enthalpy of atomization is lowest for zinc. Q.40, When Cu?* ion is treated with KI,a white precipitate is formed. Explain the reason with the help of chemical equation. tHoTS] Ans, I ion reduces Cu?* ion to Cu* ion and white precipitate of Cul, is formed . The chemical equation for the reaction is, 2Cu%(aq) +40 (aq) —> Cugh +1; ‘oie pp, Q.41. Complete the following equi MnO; +8H* + 5° —> Ams. MnO; +8H* +5e” —> Mn?” + 41,0 [CBSE Delhi 2014 [2 Marks] Q.1. Complete and balance the following chemical equations : (a Fe + M+ (b) MnO; +H,0+1T — [cBSE All india 2018) ‘Ans. (a) 5Fe* + MnO; +8H' —> Mn’* +4H,0+5Fe™ Fer ‘Gere (b)2MnO; +H,0+ _T —+ 2MnO, +20H + 105 itis) (dst Q.2. Complete the following chemical equations : ( 8MnO; +38,03 +H,0 —> (ii) CRO} +35" +14H" —> — [eBSE Demi 2016) () 8MnO; +38,0} + H,0 —> 8MnO, +650} +20H7 (i) CO} -+14H +35n®* —2Cr*+38n'*+7H,0 Q.3. When chromite ore FeCr,O, is fused with NaOH in presence of air, a yellow coloured compound (A) is obtained which on acidification with dilute sulphuric acid gives a compound (8). Compound (8) on reaction with KCI formsa orange coloured crystalline compound (C). (i) Write the formulae of the compounds (A), (B) and, ©. (ii) Write one use of compound (C). {CBSE Delhi 2016) Ans. (i) 4FeCr,O, +16NaOH+70, > 8Na,CrO, +2Fe,O, +8H,0 Ans.Qa. Ans. Qs. Ans. Qs. Ans. Q7. 2Na,CrO, + H,S0, —> Na,Cr,0, + Na,SO, +H,0 Na,Cr,0, +2KC1—+ K,Cr,0, +2NaCl Compound A is Na,CrO, Compound B is Na,Cr,0, Compound C is K,Cr,0, (ii) Compound C, K,Cr,0,, is a strong oxidising agent. Given reasons: (® Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest oxidation state of +4. (ii) Transition metals show variable oxidation states. [CBSE Delhi 2016] (i This is due to the ability of oxygen to form multiple bond. (ii) This is because of very little difference in energies of ns and (n—1)d orbitals. What are the transition elements? Write two characteristics of the transition elements. [CBSE Delhi 2015] Transition elements are the elements which have incompletely filled d-subshells or readily give rise to ions with incomplete d-subshells. ‘Two characteristics of transition elements are : i They exhibit several oxidation states. 2. They have a tendency to form co-ordination compounds (complexes) with Lewis bases which are able to donate an electron pair. Why do the transition elements have higher enthalpies of atomisation ? In 3d-series (Sc to Zn) which element has the lowest enthalpy of atomisation and why? [CBSE All India 2015} Transition metals contain large number of unpaired electrons thereby having strong interatomic force of attractions. Therefore, the heat required to break the metal lattice into free atoms will be high i.e, transition metals have high enthalpies of atomisation. The element which has no unpaired electron will have weak interatomic (metal-metal) bonding, In 3d series, Zn has no unpaired electron. Thus, Zn has lowest enthalpy of atomisation in 3d series (Sc to Zn) due to weakest interatomic bonds. What are transition elements ? Which d- block elements are not regarded as transition elements and why ? ‘An element which has partially filled (n 1) d-orbital either in its ground state or in any of its common oxidation states is known as transition elements. Group 12 elements ie, Zn,Cd, Hg have completely Qs. Ans. a9. Q.10. Ans. Quit. Ans, 12. Ans, filed (n- 1) d-orbital in their ground state and y,, Is are ‘common oxidation states and thus these elemen not considered as transition elements. ‘On what ground can you say that scandium(Z. ‘a transition element but zinc (Z =30)is not ? TCBSE AI ina 20 Scinits ground state hasincompletely filled d-orbita, Ga! 4), So it is regarded as transition element orbitals in the zinc are completely filled in the groung state as well as in its common oxidation state (+) ‘Therefore, Zn is not regarded as transition elemen, How is variability in oxidation states of the transition elements different from that of the non-transition elements? Illustrate with examples. INCERT; CBSE Deth 2006 ‘The variability in oxidation states of transition elements isdue to the incomplete filling of d-orbitalsin such a way that their oxidation states differ from each other by unity, e,, Mn shows + 2,+3,+4,+5,+6,+7, while in non-transition elements, the variability in oxidation states is due to inert pair effect and is normally differ by a unit of two.eg.,Pbshows +2 and +4 oxidation states. On moving down the group, in non-transition elements lower oxidation state becomes stable dueto increase in inert pair effect but in case of transition elements, for heavier members, higher oxidation states are stable. For example, in group 6, Mo (VI) and W (VI) are found to be more stable than Cr (VI). What are interstitial compounds? Why are such compounds well known for transition metal? [NCERT] Compounds of transition metal with relatively smaller non-metals are known as interstitial compounds. These compounds are well known for transition metals because size of C, N, O and Bis similar to size of interstitial voids of transition metals Why E® values for Mn,Ni and Zn are more negative than expected ? [HOTS; Exemplar NCERT] This is related to the extra stabilities of the divalent cations which are formed by these metals by the los of two electrons. The extra-stabilities of Ma*’ and Zn? ionsis due to the presence of half filled (")and fully filled orbitals (3d'°) configurations respectively However, the extra stability of Ni?” ions is because! its high negative enthalpy of hydration. The paramagnetic character in 3d-transition sen elements increases upto Mn and then decrets* Explain why ? In the 3d-transition series as we move from S¢(2))® Mn (25) the number of unpaired electrons incre and hence, paramagnetic character increases, AM Mn, the pairing of electrons in the d-orbital startsthe number of unpaired electrons decreases and hence, paramagnetic character decreases. (0413. For the first row of transition metals the E® values more stable. ¢, the electronic configuration of Fe is [Ar]3d*4s2.ttshows +2.as well as+3oxidation states but Fe (Il) is more stable than Fe(II) as Fe™ has stable are: @ configuration, peValues Vo Ce Mn Fe Co Niu Q.18. Assign reasons for each of the following : M/M -L18 -091 -1.18 -044 0.28 -025 4034 (i) Transition metals generally form coloured ‘compounds. (ii) Manganese exhibits the highest oxidation state of +7 among the3d-series of transition elements. [case Deini 2011), Ans, (i) Transition metals generally form coloured compounds because transition metals have Explain the irregularity in the above values. {NCERT] ‘Ans. The E® (M?*/M)values are not regular which can be explained from the irregular variation of ionization energies (8H, +4\H,) and also the sublimation enthalpies which are relatively much less for manganese and vanadium. More negative value for Mn is also attributed to the stable electronic configuration of Mn?*, unpaired electron in d-orbitals which ean undergo dd transition by absorbing light from visible region and radiate complementary colour. ii) Electronic configuration of Mn is[Ar] 45? 34° since all the electrons in’s‘as well as'd’can take part in 0.14. Why are Mn”* compounds more stable than Fe’ towards oxidation to their +3 state ? ‘Ans. The electronic configuration of Mn?* is [At] 3d, ic, " all five orbitals are singly occupied. Thus, this is bond formation ie, seven electrons, therefore, it stable electronic configuration and further loss of shows +7 (highest) oxidation state, electron requires high energy. On other hand, the @.19, Account forthe followin electronic configuration of Fe" is{Ar]3a°. Loss of one (In the series Seto Zn, the enthalpy of atomization electron requires low energy as the loss of one aaa ieee electron will lead to half filled d-subshell ic, 3 oa p, (ii) E® value for the Mn" /Mn”* couple is much more Egle Cen 0.15. Explain briefly how + 2 oxidation state becomes more pasdtive than that foe Cia Coa and more stable in the first half of the first row [GREE Dalhl 2610.) transition elements with increasing atomic number. ‘Ans. (j) Enthalpy of atomization depends upon the Ans. In M* ions,3d-orbitals get occupied gradually as the strength of metallic bonding. In case of zinc, atomic number increases. Since, the number of empty orbitals decreases, the stability of cations increases from Sc* to Mn*-Mn?* is most stable as all orbitals are singly occupied. Q.16. There is 2 greater horizontal similarity in the properties of the transition elements than of the main group elements. [CBSE Foreign 2003} Ans. This is because in transition elements, the differentiating electron goes to the inner shell orbitals and the valance shell electronic configuration remains same whereas in main group elements the differentiating electron goes to the valence shell. Moreover, there is not much variation in size in the transition series but there is the significant decrease in atomic size in the period of main group elements. That's why there is greater horizontal similarity in the properties of the transition elements. Q.17. To what extent does the electronic configuration decide the stability of oxidation state in the first series of the transition elements? Ilustrate your answer with an example. [HOTS] ‘Ans, Ina transition series, the oxidation state which lead to exactly half filled or completely filled orbitals are metallic bonding is weak as it lacks unpaired electrons that can take part in metallic bonding, Thus, enthalpy of atomization is lowest for zinc. (i) The comparatively high value for Mn**/Mn2* couple is due to the fact that Mn?*(d°) is very stable and Mn°* can easily be reduced to Mn?" whereas comparatively low value for Cr°* /Cr** is because of the extra stability of Cr°*(H,). Therefore, Cr** cannot be reduced to Cr". Q.20. Explain the following observations : (i) The enthalpies of atomization of transition metals are quite high. (ii) There is a close similarity in physical and chemical properties of the 4d and 5¢-series of the transition elements, much more than expected on the basis of usual family relationship. [CBSE Foreign 2010) Ans, (i) Transition metals have high enthalpies of atomization because of strong metallic bonding which is due to their smaller size and incompletely filled d-orbitals while covalent bonding is also there due to did overlapping of unpaired d-electrons,(il) Due to the lanthanoid contraction, the metals of the Sd-series of transition metals have similar metallic radii as those of the corresponding group members of the 4d-series. This results in close similarity in their physical and chemical Properties. Q.21. Explain giving a suitable reason for each of the following ( Transition metals and their compounds are generally found to be good catalysts. (i) Metal-metal bonding is more frequent for the 4d and 5d-series transition metals than that for the 3d-series, {CBSE All India 2011] Ans. (i) Transition metals and their compounds are ‘generally found to be good catalysts because they can form unstable intermediate compounds and provide a new path with lower activation energy for the reaction. In some cases transition metals provide a suitable surface for the reaction to take place. Gi) This is because less energy is required for the more number of electrons to take part in metal-metal bonding. Q.22. Describe the preparation of : (@ Potassium dichromate from sodium chromate and (ii) KMn0, from K;Mn0, ICBSE Foreign 2010; CBSE Dethi 2007] Ans. (i) Sodium chromate solution is acidified with H,SO, to form orange sodium dichromate. 2Na,CrO, +2H* —+ NagCn0, +2Na* + H,0 Sodium dichromate solution is then treated with potassium chloride to get orange potassium dichromate crystal. NazCr,0; +2KCI—+ K,C10, + 2NaCI (i) In neutral or acidic solution, K MnO, disproportionate to yield permanganate. 3Mn0j~ + 4H* —>2MnO, + MnO, +2H,0 Commercially, KMnO, is obtained by the electrolytic oxidation of manganate (VI) in alkaline medium. sno? as Mn0; jon iallaline solution ” p, foo Q.2 3. How would you account for the following ? () Many of the transition elements are known to form interstitial compounds. (ii) The metallic radii of the third (5d) series of transition metals are virtually the same as those of the corresponding group member of the secong (4d) series. [CBSE Dethi 2013, Ans. (i) In the crystal lattice, transition elements have interstitial vacant sites into which small sizeq non-metal atoms such as H, B, Cor N are trapped, ‘These compounds are known as. interstitial compounds. These are _non-stoichiometric, neither typically ionic nor covalent, ¢” Till, 7, ZH 9, VElose, FesC. TIC, Fea yO ete Metallic radii of third (Sd) series of transition metals are virtually same a3 those of second (44) series because of the lanthanoid contraction. This is associated to the intervention of the 4 f-orbitals which are filled before the 5d series of elements starts. The filling of 4 f orbitals before Sd-orbitals results in a regular decrease in atomic radii, called lanthanoid contraction which compensates the expected increase in atomic size with increasing atomic numbers. The electrons in the f-subshell offer poor shielding effect. Q.24, Account for the following statements: (j) Cobalt (11) is stable in aqueous solution but in the presence of strong ligands, it can be oxidized to Co (Mh). [OTs] (ii) The d' configuration is very unstable in ions. Ans. (i) Strong ligands force cobalt (M1) to lose one more electron from 3d-subshell and thereby induced °sp° hybridisation which leads to the more stable electronic configuration ¢§, in Co (IN). (ii) The ion with d' configuration try to lose the only electron in order to acquire noble gas configuration which leads to the extra stability. Q.25. Complete the following reactions in the aqueous medium [CBSE Foreign 2011] () Mn0j + C02 + HY —s (ii) Cr,05> + HS + H* —> Ans. (i)2MnO, + 5C,0}~ +16H*—> 2Mn?* + 10C0, +8H,0 (ii) Crg05” +3H,S+ 8H? — 2Cr** +38 +7 H,0 Q.26. Write balance chemical equations of two reactions in which KMnO, acts as an oxidizing agent in the acid ‘medium, [CBSE Delhi 2011 Cl Ans, Oxidizing reactions of KMnO, in acid solutions (i) Iodide ions are oxidized to liberate iodine 101 +2 MnO; +16H* —> 2Mn +81,0+5h (ii) Fe?* ion (green) is oxidized to Fe? * (yellow). 5 Fe? + MnO; +8 I’ —> Mn?* + 4H,0+5 Fe"27. Explain the following observations : (i) Co?* is easily oxidized to Co? * in the presence of a strong ligand. (i) COisa stronger complexing reagent than NH). [eBSE Doth 2012] ‘Ans. (j) The electronic configuration of Co™ is[Ar}3d°4s°. So, pairing occurs in the presence of a strong ligand. In the presence of a strong ligand, Co** has stable ¢, configuration, Thus, there are no unpaired electrons and it is highly stable. However, in Co®* (electronic configuration of which is3d’), there is one unpaired electron even, after pairing occurs in the presence of a strong, ligand. Hence, Co** is oxidized to more stable co. (ii) In comparison to NHg, CO produces strong field, which results in larger splitting of d-orbitals. That's why COis a stronger complexing reagent than NH. 0.28. How is K,Ch,0, prepared ? ‘Ans. K;Cr,0; is prepared from chromite ore (FeC0,)-The following steps are involved : (a) Fusion of chromite with Na,CO, in free access of air. 4FeCx,0, +8 Na,C03 +70; — 8 Na,CrO, +2 Fe,03 +8 CO, (0) Acidification of NaCrO, 2. NaCrO, +2 H* —> NazCh0; +2 Na* + H,0 (©) Treating the solution of sodium dichromate with potassium chloride. NazCr0, +2KC1 —> K,Ch,0, +2NaCl Orange crystals of potassium dichromate crystallize out. 0.29. How is KMn0, obtained from pyrolusite ? ‘Ans. Pyrolusite is fused with KOH and air. This produces a ‘green coloured mass, i., potassium manganate. 2Mn0, + AKOH + 0, —> 2KyMnO, +2H,0 Manganate ion disproportionate in neutral or acidic medium to give pink coloured permanganate. 3Mn0}” + 4H* —+ 2Mn0, + MnO, +2H,0 Q.30. Whatiis the effect of pH on dichromate ion solution? Ans. Dichromate ion is orange in acidic solution (pH <7) and turns yellow in basic (pH > 7) olution. Itis due to interconversion of dichromate ion and chromate ion. Following reactions take place: 2Cr0}" +21" —s C0} + H,0 tom) (one) Cr,03” + 20H” —+ 2Cr0F" + H,O ome ‘elon Q.31. Complete the following chemical reaction equations : [CBSE Delhi 2012 ; CBSE All India 2012) @ CROP +P +H (i) Mno; + NO; + HY —> Ans. ()) CO} +61 +14 1 —3 20°" +7H,0+3 Gi) 2 MnO; +5 NO; +61" — 2-Mn®* + 5NO3 +311,0 Q.32, Complete the following chemical equations : [CBSE All India 2011, 10] (i) MnO¥ (aq) + $,03> (aq) + H,0(1) —> (i) COR (ag) + Fe2* (aq) + H* (aq) —> Ans. (i) 8Mn0j (aq) + 38,07" (aq) + H,0(1) —> 8 MnO, +6 SO,” +2 OH” (ii) Cr," (aq) + 6Fe?* (aq) + 14H (ag) —> 2Cr* +6 Fe +7 H,0. Q.33. How would you account for the following ? (i) The E® M**/M for copper is positive (0.34V). Copper is the only metal in the first series of transition elements showing this behaviour. (ii) The metallic radii of the third (5d) series of transition metals are nearly the same as those of the corresponding members of the second series. (4a) [CBSE All India 2012) ‘Ans. (i) The enthalpy of atomization and second ionization enthalpy is very high for Cu. The high energy required to transform Cu (s)to Cu>* (aq)is not balanced by its hydration enthalpy. Thus, E° value is positive. (ii) Metallic radii of third (5d) series of transition metals are virtually same as those of second (4d) series because of the lanthanoid contraction. Q.34. Explain the following observations : (i) Many of the transition elements are known to form interstitial compounds. ) There is a general increase in density from titanium (Z = 22) to copper (Z = 28). [CBSE All India 2012] ‘Ans. (i) In the crystal lattice, transition elements have interstitial vacant spaces into which small sized non-metal atoms such as H,B,C, or N are trapped. These compounds are known as interstitial compounds. (i) As we move from left to right along a transition series (from Ti to Cu), the atomic radii decrease due to increase in the nuclear charge. Therefore, atomic volume decreases with increase in atomic mass. That's why density of transition metals from Ti to Cu increases.0.35. For M"*/M and M*/M™ systems, the E® values for some metals are as follows : crticr = -o9v |crtjcet = -04Vv Mn?*/Mn = —1.2V, Mn3*/Mn?*= +1.5V Fe*/Fe = -o4v |re't/Fe* = +08V Use this data to comment upon : (@ The stability of Fe** in acid solution as compared toCr?‘or Mn?* and Gi) The ease with which iron can be oxidized as compared to a similar process for cither chromium or manganese metal. [HOTS] INCERT] Ans. (i) E° for Cr°*/Cr** is -04V ie. negative, 1 means Cr°* ions in the solution cannot be reduced to Cr?* easily ie. Cr°* is stable. As Mn** /Mn?* is +15 Vie, positive means Mn?* ‘can easily reduced to Mn? “ions in comparison to Fe?” ions. Thus, relatively stability of these ions is:Mn?* Cr> Fe. Q.36. (i) Complete the following equation : MnO; +8H" +5" —> (i) Out of Mn?* and Cr°*, which paramagnetic and why ? (Atomic mass : Mn =25,Cr=24) [CBSE All India 2014] Ans. (i) The complete equation is as follows: MnO, +8 H’ +5e” —> Mn?*4+41,0 (i) Mn°* has four unpaired electrons (d!) in its valence shell whereas Cr? *(d°)has three unpaired electrons. Thus, Mn** is more paramagnetic than ot Q.37. How do you prepare: (@ KyMn0, form Mn0,? i) NazC1,0, from Na,Cr0,? [CBSE Dethi 2014) (i) KMnO, can be prepared from pyrolusite (Mn0,). ‘The oreis fused with KOHin the presence of either atmospheric oxygen or an oxidizing agent, such as KNO, or KCIO,,to give K;Mn0,, 2 MnO, + 4 KOH + 0; —*+ 2 K,Mn0, +2 H;0 green (ii) Na,Cr,0, can be prepared from Na,CrO, in the following way : For the preparation of sodium dichromate, the yellow solution of sodium chromate is acidified with sulphuric acid to give a solution from which ‘orange sodium dichromate, Na,Cr,0,-2H,0 can be crystallized. more An Balanced equation for above reactions ig follows: 2 NagCrO, +2 HY PNayC40; +2 Nat +44 Yalow Grange i 2.38, Account for the following: (i) Mn?* is more stable than Fe** towards Oxidation to+3state. (i) The enthalpy of atomisation is lowest for Zn ingg series ofthe transition elements. [CBSE Del arg Ans. (i) Electronic configuration of Mn?* is[Ar]'* 345, Electronic configuration of Fe** is [Ar}'* 34°, Itis known that half-filled and fully-filled orbit, are more stable. Therefore, Mn in +2 state has, stable d° configuration. Therefore, Mn®* shows resistance to oxidation to Mn?*. Also, Fe?* hay 3d® configuration and by losing one electron, iy configuration changes to a more stable 3/5 configuration. Therefore, Fe** gets oxidized to Fe™* easily. (i) The extent of metallic bonding an clement undergoes, decides the enthalpy of atomisation, ‘The more extensive the metallic bonding of an element, the more will be its enthalpy of atomisation. In all transition metals (except Za, electronic configuration: 3d"° 4s”), there are some unpaired electrons that account for their stronger ‘metallic bonding. Due to the absence of these unpaired electrons, the inter atomic electronic bonding is the weakest in Zn and as a result, ithas, the least enthalpy of atomisation. Short Answer Type Questions Q.1. Give reasons : (@) E*value for Mn®* /Mn?* couple is much more Positive than that for Fe*/ Fe". (b) Iron has higher enthalpy of atomization than that of copper. (©) Sc** is colourless in aqueous solution wheres Ti" is coloured. [CBSE All India 2018) Ans. (a) The comparatively high value for Mn™*/Mn"” couple is due to the fact that Mn?*(d°) is very stable and Mn** can be easily reduced to Mn’ whereas comparatively low value for Fe™/ Fe” is because of extra stability of Fe". (b) Iron has high enthalpy to atomisation that Copper it is due to high effective nuclear charg and a large number of valence electrons. Hence, it can form strong metallic bonds. As a result, it has high enthalpy of atomisation. [3 Marks](© Sc is colourless because no unpaired electron is, present in Sc!* which can undergo d-d transition whereas in Ti** unpaired electrons are present which can absorb light of suitable frequency and can undergo d-d transition to produce colour, @.2. Account for the following : (i) Transition metals show variable oxidation states. (i) Zn, Cd and Hg are soft metals. (iii) E® value for the Mn**/Mn?* couple is highly positive (+ 1.57 V) as compared to Cr™*/Cr?* [CBSE Alt India 2017) Ans. (i) Variable oxidation statesiis due to the incomplete filling of d-orbitals in such a way that their ‘oxidation states differ from each other by unity. (i) Completely filled d-orbitals/absence of unpaired d-electrons cause weak metallic bonding (where the required change is d° to d*). (iii) Because Mn** has d® as a stable configuration due to which its third ionization energy is much larger. This is mainly responsible for its high +ve value. Moreover Cr**#3, are stable. Q.3. (i) How is the variability in oxidation states of transition metals different from that of the p-block elements? (ii) Out of Cu* and Cu”, which ion is unstable in aqueous solution and why? (iii) Orange colour of Cr,0}” ion changes to yellow, when treated with an alkali. Why? [CBSE Delhi 2017) ‘Ans. (i) In pblock element is the difference in oxidation state is2 and in transition metals the difference is 1 (i) Cu’, it undergoes disproportionation reaction to give Cu and Cu. (iii) Due to formation of chromate ion (CuO}) which is yellow in colour. Q.4. Account for the following + () Transition metals form large number of complex compounds. (ii) The lowest oxide of transition metal is basic whereas the highest oxide is amphoteric or acidic. (iii) E® value for the Mn?*/Mn?* couple is highly positive (+ 1.57 V) as compare to crt/cr* [CBSE Delhi 2017} Ans. (i) Variable oxidation states is due to incomplete filling of d-orbitals in such a way that their oxidation states differ from each other by unity. Higher is the oxidation state higher is the acidic character/as the oxidation state of a metal increases, ionic character decreases. Because Mn? has d° as a stable configuration due to which its third ionization energy (where required change isd° tod") is much larger. This is mainly responsible for its high positive value. Moreover Cr** (12, )are stable. Q.5. Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition metal. (NCERT] Ans. The following points justify that the given statement istrue: Ionization enthalpies of heavier transition ‘elements are higher than the elements of 3d series. Consequently, heavier transition elements are less reactive in comparison to3d elements. (ii) Melting points of heavier transition elements are higher than 3d elements. (iii) Higher oxidation states of heavier transi elements are stable whereas lower oxidation states are stable in3d elements. Q.6. How would you account for the following? [CBSE Dethi 2013) () Transition metals exhibit variable oxidation states. (ii) Zr (Z= 40) and Hf (Z =72) have almost identical radii. (iii) Transition metals and their compounds act as catalyst. Ans. ()) ns and (1-1) delectrons of transition metal participate in bonding because of their comparable energies, which results in various oxidation states. When only ‘ns’ electrons take part in bonding, they exhibit lower oxidation states whereas when ‘(n-1)d'-electrons along with ‘ns’ electrons participate in bonding, they exhibit higher oxidation states. (ii) Because of lanthanoide contraction, the atomic radii of 4d and 5d transition series elements are similar. ‘That's why 2r(Z almost identical radi (li) Owing to their ability to adopt variable oxidation states the transition elements show catalytic activity. Transition metals also provide a suitable surface for the reactions to occur. 0) and HE (Z=72) haveAns. (i) Metal-metal bon Q.7. How would you account for the following ? {(@) Metal-metal bonding. is more extensive in the 4d and 5¢-series of transition elements than the 34 series. (ii) Mn (IID undergoes disproportionation reaction easily. (ii) Co (Il) is easily oxidized in the presence of strong ligands. [CBSE Foreign 2011] 1g is more extensive in the 4d and 5é-series of transition elements than the 34 series because less energy is required for more number of electrons to take part in metal-metal bonding. (i) In +3 oxidation state, Mn is unstable. It is intermediate oxidation state, soit gets reduced to more stable Mn?*and simultaneously oxidizea to more stable higher oxidation states like Mn” *. (iii) In the presence of strong complexing ligand, cobalt gets oxidized from+2 to+ 3state because it provides energy to remove an electron from Co”*. Moreover, Co (Il) is more stable than Co (I) due to more stable ff, configuration in octahedral complexes. Q.8. Explain giving reasons: ( The enthalpies of atomisation of the transition metals are high. (i) The transition metals generally form coloured compounds. (ii) Transition metals and their many compounds act as good catalyst. Ans. (i) Transition elements have high effective nuclear charge and a large number of valence electrons. Therefore, they form very strong metallic bonds. ‘As a result, the enthalpy of atomization of transition metals is high. (ii) Most of the complexes of transition metals are coloured.This is because of the absorption of radiation from visible light region to promote an electron from one of the d-orbitals to another (d~ d transition). (iii) The catalytic activity of the transition elements can be explained by two basic facts. (a) Owing to their ability to adopt variable oxidation states. (b) Transition metals also provide a suitable surface for the reactions to occur. Q.9. Decide giving reason which one of the following pairs exhibits the property indicated: ( Sc**or Cr** (exhibits paramagnetism) Gil) V or Mn (exhibits more number of oxidation states) (iii) V* or V%* (exhibits colour) ‘Ans. (i) Se=[Ar}3d'4s? ; Se?* = [Ar] i a8 10 unpsicy electron so diamagnetic. cr=[Ar]3d°4st :Cr?* =[Ar]3d°; it has three unpaired electrons so paramagnetic. (ii) V=[Ar]30°48?; Mn = [Ar]3d°4s*, Thus, V_ exhibits oxidation states +2,+3,44,+5 whereas Mn exhibit oxidatig, states of +2 to-+7. (iii) V4* = [Ar] 3d" — coloured ; Vt =[Ar—, colourless Q.10. (i) Name the elements of 3d transition series thy show maximum number of oxidation states. Why does this happen ? (i) Which transition metal of 3d series has positive E°(M?*/M)value and why ? (iii) Out of Cr+ and Mn3*, which is a stronger oxidizing agent and why? [CBSE Dethizotq ‘Ans. (i) In 3d-series of transition metals, manganese has an atomic number of 25 that gives the electronic configuration as[Ar] 3d°4s?, where we see that the maximum number of unpaired electrons is found in manganese atom; so, it can show a maximum oxidation state upto +7. (i) Copper is the transition metal of 3d series that exhibits positive E°(M?*/M). The value of E® (M?*/M)for copper is (+ 0.34 V). This happers because the high energy to transform Cu(s) Cu*(aq) is not balanced by its hydration enthalpy. (ii) Out_of Crt and Mn**, Mn°is a_ stronger oxidizing agent because it has 4 electrons in is valence shell and when it gains one electron form Mn?*, it results in the half-filled (#) configuration that has extra stability. Q.11. Write the preparation of potassium dichromate from iron chromite. What happens when potassiut dichromate reacts with (a) hydrogen sulphiée (b) Fes, ? Ans. Preparation of potassium dichromate from if chromite takes place in three steps : ( Conversion of chromite ore to sodium chroma" AFeCr0, + 8Na,CO, +70, —> BNa,Cr0, +2Fe,03 +8 Gi) Conversion of sodium chromate to soi dichromate : 2 Nazi, +2H* —y Na,Cy0, +200" +H? (iil) Conversion of sodium dichromate to potass™™ dichromate : NazCr,0, +2KCl—s K,Cr,0, +2 NaC!Reactions that take place are : (a) CO” +8H* +31, —> 281 438+711,0 (b) C034 141146 Fe?! 5 2.Cr* 46Fe™ +71,0 Q.12. Complete following re () Moy +H + Fe?* —>. Gi) MnOy + C077 +H? — .... MnO, + OH™ +17 Ans. (i) MnOg +8H" pete" tints agree 4H,0 (i) 2MnOy + 5C,0; +16H* — 2Mn?* +10CO; +810 (iil) 2Mn0, + H,0+ F—> 2Mn0, +2011 ~ + 105 Long Answer Type Questions [5 Marks] Q.1. (a) Following are the transition metal ions of3d series: Ti"*,VMn*,Cr™ (Atomic numbers : Ti=22,V =23,Mn Answer the following : (@ Which ion is most stable in an aqueous solution and why (i) Which ion is a strong oxidising agent and why? Gi) Which ion is colourless and why? (©) Complete the following equations : (i) 2MnO, +16H" +58 —> (ii) KMn0, Ans. (a) (i) Cr®, half filled #3, (ii) Mn**, due to stable d° configuration in Mn?* (iii) Ti, no unpaired electrons (b) (i)2MnO; +16H* + 5S?” —> 58+2Mn”* +8H,O (i)2KMnO, — K,MnO, + MnO, +O, Q.2. (a) Account for the following : (i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest oxidation state of + 4. (ii) Zirconium and Hafnium exhibit similar properties. (ii) Transition metals act as catalysts. (©) Complete the following equations : (i) 2MnO, + 4KOH+ 0, 49 (ii) CO} +14H* +61" — {CBSE All India 2016] Ans. (a) (i) This is due to the tendency of oxygen to form multiple bonds. ‘This is due to the lanthanoid contraction. Zr and Hf have similar sizes, due to which they exhibit similar properties. (Gii) Transition metals act as catalysts due to their ability to. show variable valencies. They can 25,Cr =24) [CBSE All India 2017] i form unstable intermediates and carry out the reaction with alternate pathway with lower activation energy. (©) () 2MnO, + 4KOH+0, —> 2KMnO, +2H,0 (i) COP +14? 467 — 2Ce?* +7H,0+3h2 Q.3. The elements of 31 transition series are given as: Se Ti V Cr Mn Fe Co Ni Cu Zn Answer the following : (i) Write the element which is not regarded as a transition element. Give reason. (ji) Which clement has the highest melting point? (ii) Write the element which can show an oxidation state of +1 (iv) Which element is a strong oxidizing agent in +3 oxidation state and why? {CBSE All India 2016] Ans. (i) Znis not regarded as transition element as it has fully filled d-orbitals in its ground state as well as in its common oxidation state i, +2. (ii) Cr has the highest mp. due to the strongest metallic bonding. (iil) Cu can show +1 oxidation state as in +1 oxidation state, ithas read noble gas configuration. "ut : [Ar] 3d! (iv) Mn is a strong Paced agent in +3 oxidation poate the3d° configuration of Mn"* in [Ar] 34° (highly stable). QA. Describe a preparation of potassium permanganate. How does the acidified permanganate solution react with (a) iron (If) ons (b) SO, and (¢) oxalic acid ? Write the ionic equations for the reactions. Ans. Pyrolusite (MnO,) is fused with KOH and air. This, produce: a green coloured potassium manganate. 2MnO, + 4KOH + 0; —> 2KyMn0, +2H,0 Manganate ion disproportionate in neutral or acidic medium to give pink coloured permanganate. 3Mu0}"+4H* —+ 2Mn0; + MnO, +21,0 Permangaite (@) Acidified KMnO, solution oxidizes Fe (Il) ions to Fe (Ill) ions ie, ferrous ions to ferric ions. MnOj +8H” +56 —> Mn? + 41,0 Ure? +e1x5 5Fo™ + MnO; +81" —> Mn™ +411,0+5Fe* ort (b) Acidified potassium permanganate oxidizes SO, to sulphuric acid, [Mn0; +81" +5 &° —> Mn?" + 44,0] x2 [80, +2H,0 — SO}" + 4H" +267] x5 2MnO, +580, +2H,0— 2Mn?* +580," +4"(© Acidified potassium permanganate oxidizes oxalic acid to carbon dioxide. MnO, + 8H? +5 e° —+ Mn?* + 41,0] x2 [Q07° — 200, +2 & x5 2Mn0, + 5C.0}~ +16" —> 2Mn?? + 81,0+10 CO, a: Give reasons for the following : (@ Transition metals have high enthalpy of hydration, Gi) Z2n.Cd and Hg arenot regarded as transition metal Gii) d-block elements exhibit a large number of oxidation state than f-block elements. (iv) The second and third members in each group of transition element have similar atomic radii. (¥) Kz{P1Clg] is well known compound whereas the corresponding Ni compound is not known, Ans. (i) Transition metal ions are smaller and have higher charge density, therefore have high enthalpy of hydration. (ii) Group 12 elements ie.,Zn,Cd,Hg have completely filled (n~1) d-orbital in atomic and any of the ‘oxidation state and thus these elements are not considered as transition elements. i) The difference in the energy of (n—1)d-orbital and nsorbital is very small and thus both sub shells are used for bond formation whereas in f-block elements (n ~ 2) f-orbitals lie undemeath and hence, are not readily available for the bond formation. (iv) The second and third members in each group of transition element have similar atomic radii due to lanthanoid contraction. It arises due to the poor shielding of d and f electrons. (¥) The oxidation state of Pt in K,[PtCl,]is + 4 which is stable for Pt. The + 4 oxidation state for Ni is very difficult to achieve because the sum of first four ionization enthalpiesis very high. Hence, the corresponding Ni (IV) compounds are unknown, Q.6. Give reasons for the following : (i) Fe*.as higher melting point than Cu. (ii) [Ti(H,0),]°* is coloured while [Sc(H,0),]°* is colourless. (iii) The 4d and 5d series of transition metals have more frequent metal-metal bonding in their ‘compound than do the3d metals. (iv) Transition metals sometime exhibit very low oxidation state such as + 1 and 0, (¥) Hg is not considered a transition metal. Ans. (i) This is because in Fe(3d° 4s") four unpaired electrons in 3d-subshell are there to take part in metallic bonding while Cu (3d"° 4s! )has only one ‘unpaired electron in 4sshell which can take part in metallic bonding. Hence, metallic bonding ig stronger in Fe than those in Cu. (ii) The oxidation state of Tiin[Ti (H,0),) * is + 3and its configuration in [Ar]3d' i.e, one unpaired electron which can take part in d-d transition is present and hence, itis coloured. Whereas the ‘oxidation state of Sc in[Sc(H,0),]°* is +3 and its configuration is [Ar] 3d° ie,, no unpaired electron is present and hence it is colourless In the same group of d-block elements, the 4d and 5d transition elements are larger size than that of 3d elements. Hence, the valence electrons are less tightly held and form metal-metal bond more frequently. (iv) +1 oxidation state is shown by elements like Cu because after loss of one electron, it acquire stable configuration. Zero oxidation state is shown in metal carbonyl, because n-electrons donated by CO are accepted into the empty orbitals. (v) The characteristic properties of transition metal are due to partially filled d-orbitals. Hg has completely filled d-orbital in its ground state as well as in any of its oxidation state. As a result it doesn’t show properties of transition metals and hence is not considered as transition metal. Q.7. Explain giving reasons: ( Transition metals and many of their compounds show paramagnetic behavior. (ii) The enthalpies of atomisation of the transition metals are high. (iii) The transition metals generally form coloured compounds. (iv) Transition metals and their many compounds act, as good catalyst. (v) Transition metals have strong tendency to form complexes. Ans. (i) Transition metals and many of their compounds show paramagnetic behavior due to the presence of unpaired electrons is (n~ 1) d-orbitals. i) The enthalpies of atomisation of the transition metals are high because of large number of unpaired electrons in their atoms, they have stronger interatomic interaction and hence, strong metallic bonding is present between atoms. (ii) The transition metals generally form coloured compounds due to presence of unpaired electrons in(n~ 1)d-orbitals and thus they can undergo d-¢ transition, iv) Transition metals and their many compounds act as good catalyst due to their variable valencies. ‘Transition metals sometimes form unstable intermediate compounds and provide anew pathReactions that take place are: (a) C03” +8H* +3H,8 —5 2 2Cr*+38+7H,0 (0) CgO} +1401 *46Fe?* 2Cr* +6Fe™ +7H1,0 .12. Complete following reactions : (@) MnOg + H* + Fe?* —y (i) MnO; + C077 + Ht — (ii) MnOy + OH #17 at " ‘Ans. (i) MnOy +8H* + 5Fe** —4 Mn?* +5Fe?* +4H,0 (i) 2Mn0; +5C,0; +16H* — 2.Mn?* +10 CO, +8 H,0 (ii) 2Mn0, + H,0+ T—s 2Mn0, + 20H" + 105 tong Answer Type Questions [5 Marks] Q.1. (a)Following are the transition metal ions of series: TV? Mince" (Atomic numbers : Ti =22, V =23,Mn=25,Cr =24) Answer the following : () Which ion is most stable in an aqueous solution and why? (ii) Which ion is a strong oxidising agent and why? (ii) Which ion is colourless and why? (b) Complete the following equations : () 2MnO; +16H" +5S**— (i) KMno, 5 Ans. (a) (i) Cr®*, half filled (ii) Mn, due to stable d* configuration in Mn** (ii) TH, no unpaired electrons () ()2MnO; +16H" +5S** —s 58+2Mn®* +8H,0 (i) 2KMnO, — K,MnO, + MnO, +O, Q.2. (a) Account for the following : () Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest oxidation state of + 4. (i) Zirconium and Hafnium exhibit similar properties. (Gi) Transition metals act as catalysts. (&) Complete the following equations : (i) 2MnO, + 4KOH+0,—49 (ii) CROP +14H* +61" — [CBSE All India 2016} Ans. (a) (i) This is due to the tendency of oxygen to form multiple bonds. (i) This is due to the lanthanoid contraction. Zr and Hf have similar sizes, due to which they exhibit similar properties [CBSE All India 2017] (ii) Transition metals act as catalysts due to their ability to show variable valencies. They can form unstable intermediates and carry out the reaction with alternate pathway with lower activation energy. (©) (i) 2MnO, + 4KOH+ 0, — 2KyMn0, +2420 (i) CeO} +148" +67 —s 2Cr** +7H,0+31 Q.3. The elements of 3 transition series are given a Sc Ti V Cr Mn Fe Co Ni Cu Zn Answer the following : (i) Write the clement which is not regarded as a transition element. Give reason. (ii) Which element has the highest melting point? (ii) Write the element which can show an oxidation state of +1. Gv) Which clement is a strong oxidizing agent in +3 oxidation state and why? [CBSE All india 2016] Ans. (i) Zn is not regarded as transition element as it has fully filled d-orbitals in its ground state as well as in its common oxidation state ie, +2. Cr has the highest mp. due to the strongest ‘metallic bonding. (ji) Cu can show +1 oxidation state as in +1 oxidation state, it has pseudo noble gas configuration. Cut :[Ar]3d” (iv) Mn is a strong oxidising agent in 43 oxidation state due to the3d° configuration of Mn’*. Mn** :[Ar]3d° (highly stable). QA. Describe the preparation of _potassium permanganate. How does the acidified permanganate solution react with (a) iron (II) ions (b) SO, and (c) oxalic acid ? Write the ionic equations for the reactions. Ans, Pyrolusite (Mn0,) is fused with KOH and air. This produce» a green coloured potassium manganate. 2MnO; + 4KOH +0, — 2K;MnO, +2H,0 Manganate ion disproportionate in neutral or acidic ‘medium to give pink coloured permanganate. 3Mn0}"+4H* —» 2MnO; +MnO, +2H,0 Permanganate (@) Acidified KMn0, solution oxidizes Fe (II) ions to Fe (Ill) ons i, ferrous ions to ferric ions. MnO, +8H™ +5 e° —> Mn?* + 4H,0 [Fe?* —> Fe? 40°] x5 (i (b) Acidified potassium permanganate oxidizes SO, to sulphuric acid. [MnOj +8H* +5 &°"—> Mn?* + 4H,0] x2, [SO, +2H,O— SO}” + 4H" +26] x5 Mn" +5S0,001L0 Lo nh ee 2MnO, + 580, +2H,0 —> 2Mn?*+5S0" +4H* arom Min 580" +4"(©) Acidified potassium permanganate oxidizes oxalic acid to carbon dioxide. IMnO, +811" +5 e° — Mn?* + 41,0)x2 [G0}> —+ 200, +2 6° 1x5 2MnO, + 5C,0;~ + 16H* —> 2Mn?* +811,0+10 CO, Q.8. Give reasons for the following : () Transition metals have high enthalpy of hydration. (i) Zn.Cd and Hig are not regarded as transition metal Gi) d-block elements exhibit a large number of oxidation state than f-block elements. (iv) The second and third members in each group of, transition element have similar atomic radii. (&) Ka[PtC\,] is well known compound whereas the corresponding Ni compound is not known. Ans. (i) Transition metal ions are smaller and have higher charge density, therefore have high enthalpy of hydration. Gi) Group 12 elements ie., Zn,Cd,Hg have completely filled (n=1) d-orbital in atomic and any of the ‘oxidation state and thus these elements are not considered as transition elements. (ii) The difference in the energy of (n-1) d-orbital and ns-orbital is very small and thus both sub shells are used for bond formation whereas in f-block elements (n - 2) f-orbitals lie underneath. and hence, are not readily available for the bond formation. (iv) The second and third members in each group of transition element have similar atomic radii due to lanthanoid contraction. It arises due to the poor shielding of d and f electrons. (v) The oxidation state of Pt in K,[PIClg]is + 4 which is stable for Pt. The + 4 oxidation state for Ni is very difficult to achieve because the sum of first four ionization enthalpies is very high. Hence, the corresponding Ni (IV) compounds are unknown, Q.6. Give reasons for the following : Gi Te".as higher melting point than Cu, (ii) [Ti(H,0),}°* is coloured while [Sc(H1,0),]°* is colourless. (ii) The 4d and 5d series of transition metals have more frequent metal-metal bonding in their compound than do the 3d metals. (iv) Transition metals sometime exhibit very low oxidation state such as +1 and0. (v) Hg is not considered a transition metal. Ans. ({) This is because in Fe(3d° 4s?) four unpaired electrons in 3d-subshell are there to take part in metallic bonding while Cu (3d"° 4s" )has only one unpaired electron in 4s-shell which can take part in metallic bonding. Hence, metallic bondi stronger in Fe than those in Cu. (i) The oxidation state of iin Ti (H,O),)*is+3anq its configuration in (Ar]3d' ie, one unpaire, electron which can take part in de transition ¢ present and hence, it is coloured. Whereas the oxidation state of Se in{Se (H,0),}°* is +3 and ig configuration is[Ar]3d? i.e., no unpaired electton is present and hence it is colourless i) In the same group of d-block elements, the 4dang 5d transition elements are larger size than that» 3d elements. Hence, the valence electrons are less tightly held and form metal-metal bond mor frequently. (iv) +1 oxidation state is shown by elements like Cu because after loss of one electron, it acquire stable configuration. Zero oxidation state is shown in metal carbonyl, because n-electrons donated by COare accepted into the empty orbitals. (v) The characteristic properties of transition metal are due to partially filled d-orbitals. Hg has completely filled d-orbital in its ground state as well as in any of its oxidation state. As a result it doesn’t show properties of transition metals and hence is not considered as transition metal. ing is Q.7. Explain giving reasons: () Transition metals and many of their compounds show paramagnetic behavior. i) The enthalpies of atomisation of the transition metals are high. (ii) The transition metals generally form coloured ‘compounds. Gv) Transition metals and their many compounds act as good catalyst. (¥) Transition metals have strong tendency to form complexes. Ans. (i) Transition metals and many of their compounds show paramagnetic behavior due to the presence of unpaired electrons is (n ~ 1) d-orbitals. (ii) The enthalpies of atomisation of the transition metals are high because of large number of unpaired electrons in their atoms, they have stronger interatomic interaction and hence strong metallic bonding is present betwee atoms, (ii) The transition metals generally form coloured compounds due to presence of unpaired electrons in(n~ 1)d-orbitals and thus they can undergo d+! transition, (iv) Transition metals and their many compounds ac as good catalyst due to their variable valencies Transition metals sometimes form unstable intermediate compounds and provide a new pathwith lower activation en ‘ergy for the reaction. surface for the reaction to take place. (¥) Transition metals have a strong tendency to form complexes. Most of transition elements form complex compounds due to the small size, high charge and presence of vacant d-orbital which cen accept lone pairs of electrons donated by other groups (ligands). Q.5. (a) Complete the following equations : (@ C,03" +20H” —> (il) MnO +4H* +3.6° > (b) Account for the following : (i) Za isnot considered as a transition clement. (i Transition metals form a large number of complexes. (iii) The E® value for the Mn°*/Mn?* couple is much more positive than that for Cr°*/Cr?* couple. [CBSE All India 2014) ‘Ans. (a) The balanced chemical equations are the following: Topic 2_ the f+ ee Len. cats ery Short Answer Type Questions [1 Mark] Q.1. Give resson: Actinoids show irregularities in their electronic configurations. [CBSE Delhi 2016] ‘Ans. This is because 5 f,6d and 7s levels have comparable energies. Also, the stability of f°, f” and f" affects the electronic configurations. Q.2. How would you account for the following : ‘The chemistry of actinoids is more complicated as ‘compared to lanthanoids. [CBSE All India 2015) Ans. Inlanthanoids 4forbitals are progressively filled with general E.C.(n—-2) fi (n-1)d°* ns? Due to large energy gap between 4 f and 5d subshells lanthanoids show limited number of oxidation states (OS) +2, +3 and +4 (+3 is most common OS). Inactinoids Sf orbitals are progressively filled but due to small energy gap between 5 f,6d and 7s orbitals actinoids show a greater range of oxidation states +3, ++4,+5,46,47 (in Np and Pu). It makes the chemistry of actinoids more complicated as compared to lanthanoids. Q.3. How would you account for the following? ‘Actinoid contraction is greater than lanthanoid contraction. {CBSE Delhi 2015) Ans. In actinoids 5f-orbital is progressively filled while in lanthanoids 4f-orbital is progressively filled. (i) C03” +201 —s 2C10;" + H,0 (ii) MnO, + 411" +3 e~ —+ Mn0 +21,0 (b) (i) Zinc has the stable filled valence shell d"° electronic configuration in its ground state as well as in its most common oxidation state of +2 - Hence, itisnot considered asa transition element. (ii) Ions formed by transition metals have small sizes and high ionic charges. Also they possess vacant orbitals to accommodate lone pairs of electrons for bond formation. As a result transition metals form a large number of complexes. (iii) The E® value for the Mn?* /Mn?* couple is much more positive than that for Cr?* /Cr?* couple. is because Mn? * ionis particularly stable due to the extra stability of its half filled valence electronic configuration (d°) Thus Mn?* ion has a very high tendency to gain an electron and form the much more stable Mn®* ion. Cr” has stable £2, electronic configuration, which is difficult to reduce, Poor shielding effect of 5felectrons as compared to that of ffelectrons causes increase in effective nuclear charge which results in decrease is atomic and ionic size along actinoid series. That is why actinoid contraction is greater than lanthanoid contraction. Q.A. What are inner transition elements ? Ans. The f-block elements in which the last electron is accommodated in (n—2) f-subshell are called inner transition elements. These include atomic numbers 58 to 71 and from 90 to 103. Q.5. Write the electronic configuration of an element with atomic number of 102. [CBSE All India 2006) Ans, [Rn] 5 "47s? Q.6. Namea member of the lanthanoid series which is well known to exhibit + 4 oxidation state. [CBSE Allindia 2014) ‘Ans, Cerium (Z = 58) is the lanthanoid element which is, well known to exhibit + 4 oxidation state. Q.7, Name a member of the lanthanoid series that is well known to exhibit + 2 oxidation state. (CBSE Dethi 2014) Ans, Europium (Eu)is well known to exhibit +2 oxidation state due to its half filled f-orbital in +2 oxidation state, Q.8, Of the Lanthanoids only Cerium (Z = 58)is known to exhibit quite stable +4 oxidation state in solution. Why? {CBSE All India 2006 C)Ans, This is due to the fact that Ce in + 4 oxidation state acquires noble gas configuration which is quite stable. Q.9. What are different oxidation states exhibited by lanthanoids ? Ans. The common stable oxidation state of lanthanoids is, +3. However, some members also show oxidation states of +2 and +4 Q.10. Account for following: Actinoid elements show wide range of oxidation states. TCBSE Delhi 2014) Actinoids exhibit larger oxidation states because of very small energy gap between 5f, 6d and 7s sub shells. Q.11, Why is +4 oxidation state observed for Ce in many of its compounds? Ans. The configuration of Ce is [Xe] 4 f", 5d', 6s. There is no much difference between the energy of 4 f,5d and 6sorbitals and thus, Cecan utilize electrons present in these orbitals and hence, oxidation state of + observed. Q.12. Why does Cerium (IV) actas strong oxidizing agent? Ans. Ce shows + 4 oxidation states due to the stable noble ‘gas configuration, but it is a Strong oxidizing agent and gets reduced to Ce?* which is its common ‘oxidation state. Its E° values for Ce** /Ce™ is + 1.74V Q.13. What is misch-metal ? Ans. It is an important alloy, which contains 95% lanthanoid metal and 5% Fe along with traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter flint. Q.14. Name an important alloy, which contains some of the lanthanoid metals. Mention its uses. ‘Ans. An important alloy containing lanthanoid metals is misch-metal, which contains 95% lanthanoid metal and 5% Fe along with traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter flint. Short Answer Type Questions [2 Marks] Q.1. Write one similarity and one difference between the chemistry of lanthanoid and actinoid elements, [CBSE All India 2017; Delhi 2017] Ans. Similarity Both are stable in + 3 oxidation state. Difference Actinoids are radioactiveand lanthanoids 7 are not. Q.2. Chemistry of actinoids is complicated as compared to anthanoids. Give two reasons, (CBSE Delhi 2017) Ans. Actinoids are radioactive, actinoids show wide range of oxidation states. Qs. Ans. Ans. Qs. Ans. a6. Ans. Qu. With reference to structural variability and chemicay reactivity, write the differences between lanthanoids and actinoids [CBSE AI! India 2014 The differences between lanthanoids and actinoids with reference to structural variability and chemi 1, are as follows : (a) Actinoids have far greater irregularities in metallic radii than lanthanoids, as a result actinoids display a variety of structures, (b) The ionization enthalpies of the early actinoids is lower than those of the early lanthanoids. (©) Actinoids are more reactive and have more complex magnetic properties than lanthanoids, (a) Actinoids form oxocation while lanthanoids do not form oxocations. . The chemistry of actinoid elements is not so much smooth as that of lanthanoids. Ju: statements by giving some examples from the oxidation state of these elements. Lanthanoids show limited number of oxidation states ie, +2, +3, + 4 (out of which +3 is most common). This is because of a large energy gap between 4 f,5d and 65 subshell. The dominant oxidation state of actinoids is also +3 but they show a number of other oxidation statealsoeg.,+ 4, + 5,and + 7.Thisis dueto small energy difference between 5f,6d and 7eorbitals. Tonisation enthalpies of Ce, Pr and Nd are higher than those of Th, Paand U.Why? [Exemplar NCERT] Ce, Pr and Nd belong to lanthanoids (4 f-orbitals are filled) while Th, Pa and U are actinoids (5 f-orbitals are filled). As 5 f-orbitals have less penetration in the inner core as compared to 4 f-orbitals, so, ionization enthalpies of lanthanoids are expected to be more than those of actinoids. () What is actinoid contraction ? (ii) Why is La (OH), stronger base than Lu (OH);? (@ The size of actinoid and its trivalent ion decreases from Ac to Lr. It is known as actinoids contraction, It is due to poor shielding of 5f electrons. Due to lanthanoid contraction size of Lu?’ is, smaller than La?*. Asa result Lu—O bond will have more covalent character than La—0 bond: Hence, La (OH) is a stronger base than Lu (Ol: Long Answer Type Questions [5 Marks} Whaat is lanthanoid contraction 2 What is its cause? Write three consequencesof lanthanoid contraction? INCERT; CBSE Delhi 2004; CBSE All india 1994)‘ans. Lanthanoid Contraction: The regular decrease (Contraction) in the atomic and ionic radii of lanthanoids with increasing atomic number is known as lanthanoid contraction. Cause: As we move along the lanthanoid series, the imperfect shielding of 4 f-electrons is unable to counter balance the effect of the increased nuclear charge. Hence, the net result is contraction in the size though the decrease is very small. Consequences: Lanthanoid contraction has the following causes : () Difficulty in separation of lanthanoids : Since the change in ionic radii in lanthanoids is very small and their chemical properties are similar. ‘This makes the separation of lanthanoids in pure state difficult. Q) Similarity in size of elements belonging to same group of 2™ and 3" transition series: The similarity in size of the atoms of the elements belonging to the same group of second and third transition series after lanthanium is evidently due to the effect of lanthanoid contraction. (3) Effect on the basic strength of hydroxide: As the size of the lanthanoids ions deceases from La? * to Lu?*, the covalent character of the hydroxides increases and hence, the basic strength decreases. Thus, La (OH); is most basic whereas Lu (OH), is least basic.