ee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET The dand f-Block Elements Fastracl« Revision > The dBlock Elements > The elements are lying In the middle of periodic table belonging to groups 3 to 12 are known as block elements. > Their general electronic configuration is (n—1) d™® 1as'2, where, (n= 1} stands For penultimate shell > Transition Elements > Atransition element is defined as the one which has incompletely filled d-orbltals in its ground state or in any one of its oxidation states. > Zinc, cadmium and mercury are not regarded as transition metals due to completely filled d orbital > Four Transition Series > 3dtransition Series: It consists of elements with atomic number 21(Sc) to 30(2n) and having incomplete 3dorbitals. It is called the First ‘Transition Series > Adtransition Series: It consists of elements with atomic number 39(¥) to 48(Cd) and having incomplete 4dorbitals. tis called Second Transition Series, > Sdttransition Series: It consists of elements with atomic number S7(La), 72(HF) to 80(Hg) having Incomplete Sc-orbitals. It Is called Third Transition Series > 6dtransition Sories: it consists of elements with atomic number 89(Ad), 108(RA) to 112(Cn) having incomplete 6ctorbitals. itis called Fourth Transition Series > General Characteristics of Transitian Elements > Metallic Character: All transition elements are metallic in nature, Le. they have strong metallic bonds. This is because of presence of unpaired electrons. This gives rise to properties like high density, high enthalpies oF atomisation and high melting and boiling points. > Atomic Radi: The atomic radii decreases from Scto Cr because the effective nuclear charge increases. ‘The atomic size of Fe, Co and Ni are almost same because the attraction due to Increase in nuclear charge is cancelled by the repulsion because of increase in shielding effect. Cu and Zn have bigger size because the shielding effect increases and electron-electron repulsion increases. > lenlsatlon Enthalpy: the ionisation enthalpy ‘of Sdttransition series Is much higher than 30 ‘and 4dtransition series because of Lanthanoid contraction, > Oxidation State: Transition metals show variable oxidation states due to tendency of (n-1)d as well as nselectrons to take parti bond formation > Magnetic Properties: Most of transition metals are paramagnetic in nature as a result of which they give coloured compounds and it sal due to presence of unpaired electrons. It increases From Se to Cr and then decreases because number of unpalred electrons incteases from Sc to Crand then decreases, They are rarely diamagnetic. > Catalytic Properties: Most of transtion metals are used as catalyst because of (i) presence of incomplete or empty d-orbitals, (i) large surface area, (ili) variable oxidation state, (iv) ability to Form complexes, eg, Fe, Ni V0, Pt, Mo, Co are used a: catalyst > Formation of Coloured Compounds: They form coloured ions. Due to the presence of incompletely Filed corbitls and unpaired electrons, they can undergo dd transition by absorbing colour from \isblereglon and radiating complementary colour. > Interstitlal Compounds: Transition metals have voids of interstlials in which C, HN, B, etc, ‘can Fit into resulting in formation of interstitial compounds. They are non-stoichiometric, /.e, thelr composition is not Fixed, eg,, steel. They are harder and ess malleable and duct, » Alloy Formation: They form alloys due to similar ione siz, Metals can replace each other In crystal late, eg, brass, bronze, steel, ee > Potassium Dichromate, C0, > Potassium dichromate is an acidic compound in which Cris presentin 6 oxdation state > Preparation tis prepared from sodium chromate, hich Is obtained by Fusion of chramite ora, 4FeCr,0, + 8N9,CO, 70, —-» 8Na,CrO, + 2Fe0, + 8C0;t 2N0,Ch0, +2H'—+ Na,Ch0, +2Na* + HO NajCF,0, + 2KCI—> KCF,0, + 2NaCl > Properties of Potassium Dichromate > tscolour depends upon the pl ofthe solution > Itis used as primary standard solution in volumetsle analysis in aclle madlum, > Itacts as a strong oxidising agent. > Potassium Permanganate, KMnO, > —KMnO, Is an acidic compound In which Mn has (+7) oxidation state> Preparation: It is prepared by fusion of pyrolusite ‘ore (MnO,) with alkali metal hydroxide In the presence of O, 2MNO, + 4KOH + 0, —> 2K,MnO, + 2H,0 + 4H" —> 2Mn0; +Mn0, +2H,0 » Properties of Potassium Permanganate > kMinO isa dark purple coloured crystalline solid. > kMind, decomposes to lve K,MnO, and MnO, on heating and evolve O,. 2kMno, 2524, K,Mn0, + MnO, +037 Mano} +e"——+Mn0 > kino, acts as an oxidising agent in all the three medivins le, acide, basic and neutral > The Block Elements » The elements constituting the block are those in which af and 5/-orbitals are progressively Filed in the latter two long periods. @ Multiple choice Questions y Q1. In transition elements, the element belongs to 44 series ee ee) 2. Which etectron(s) is/are released to achieve the maximum oxidation state of a transition metal? a. nselectron b. (n+ I}d electron © (n=Hdelectron d,s + (n= Ndelectron 3. Which one among the following metals of 3d series has the lowest melting point? (cbse 2023) afe obMn cin acu (4. Which of the transition element does not exhibit variable oxidation state? atl by c Fe Sc 5. Which of the following transition metals shows +1 and +2 oxidation states? (cose 2023) aMn —— bZn cS acu Q6. Match the properties with the elements of 3d es: (cose 2023-24) (i) Lowest enthalpy of atomisation (p) Sc (ii) Shows maximum number of (@)Mn oxidation states (ii) Transition metal that does not (azn form coloured compounds (s)Ti 2. (HE). W@). WP) &. (+). (W5).() 49) & (xP). (C9). iC). Wels) dC). (it)-(p) Q7. Which of the following ions has the maximum number of unpaired d-electrons?- (CBSE 2023) a. Fe? b. ve eT d. Sc {Atomic number: Fe = 26,V = 23,Tl = 22,Sc= 21) EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ee > These elements are called inner transition elements and thelr general electronic configuration is (0=2) F4 (n= 1) ns? > Lanthanoids: The 14 elements immediately Following Lanthanum, Ze, Cerium (58) to Lutetium (71) are called Lanthanoids. They belong to first inner transition series. > Their electronic configuration is Ke] 4f'""4 Sd16 s2 > They mainly give +3 oxidation state while some elements glve +2 and +4 oxidation states. > The radii of members of Sdseries are similar to those of corresponding members of the 4d-series due to lanthanold contraction. > Actinolds: The 14 elements immediately fallo aetiium Le, Therm (0) to Lawrendum (13) are called actinolds in which 5 orbitals are progressively Filed > Their general electronic configuration is, Sf'4600792 > In general, actinoids show +3 oxidation state. These resemble the Lanthanoids in having more compounds in +3 state than in the +4 state. However, +3 and +4 lons tend to hydrolyse. x Practice Exercise Qa. The most common and stable oxidation state of a Lanthanold is: (c8se2023) a +2 b+3 c +4 +6 9. Formation of coloured ions is possible, when the compound contains: a. paired electron b. unpaired electron . non-bonding electron 4. None of these Metallic radii of some transition elements are given below: Which of these elements will have highest density? Element Fe [co [Ni [cu Metallic radii/pm [426 [425 [125 [128 (CERT EXEMPLAR) gio. aFe bn cco d.cu The ions of metals of Group 12 (Zn, Cd and Hg) have completely filled d orbitals and so they: (cose2023) qu. fa. behave lke semiconductors 'b. are very high melting solids . do nat behave like transition metals i. behave Uke superconductors Which of the following characteristics of transition metals is associated with their catalytic activity? (case 2023) qu. ©. Paramagnetic nature Colour of hydrated ions High enthalpy of atomisation Variable oxidation statesee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET gis. qu. Qs. Que. qu. Qs. qs. ‘The trend of which property is represented by the following graph? (cBSe Sop 2023-24) 10 18 v 16 18 1“ 13 Radiusinm so VG Mn Fe Co NI Gu an lonization enthalpy Atomic radi Enthalpy of atomization Melting point Match the Column I with Column il and mark the appropriate cholce. nee Column | Column th (Property) (Metal) ‘A Element with highest second (I) Cr lonisation enthalpy & Element with highest third (i) Cu lonisation enthalpy Min AMCO), is (li) Zn D. Element with highest heat of (iv) V atomisation aaa) aww) © by) a) c(i) i) iv) 2m @ i) Ww KMn0, acts as an oxidising agent in alkaline medium. When alkaline KMnO, is treated with Kl, lodide lon is oxidised to: (cenr exexpLan) b. 10- 4.104 (case sop 2022-23) 103 KMnO, is coloured due to: a. dd transitions b. charge transfer from ligand to metal © unpaired electrons In d-orbital of Ma d. charge transfer from metal to ligand Bil Lanthanold element among the following elements Is: Rh b. Ce CAC zr Gadolinium belongs to 4f series. Its atomic number is 64. Which of the following is the correct electronic configuration of gadolinium? (NCERT EXEMPLAR) a. (Ke) 4F*5a'6s? bi. (Ke) 4F5¢2652 c. (Xe) 4860? 4d. (Xe) 495s! There are 14 elaments in actinoid series. Which of the following elements does not belong to this serles? (NCERT EXEMPLAR) au bNp 0 ctm dm 20. gan za. za, Which of the following is/are amphoteric oxide? Mn,0,,C10,,Cr,05, Cr0,V,0.,V,0, a V,05,€r,0, b. Min, C10, cc GONV,0, d. V,05 V0, The magnetic moment is associated with its spin angular momentum and orbital angular ‘momentum. Spin only magnetic moment value of ce a. 2876M b 3.87 6M 3.47 BM. d. 3578M. Interstitial compounds are formed when small atoms are trapped inside the crystal. lattice of metals. Which of the following is not the characteristic property of interstitial compounds? 2. They have high melting points in comparison to pure metals. b. They are very hard. © They retain metallic conductivity. 4. They are chemically very reactive Out of the following transition elements, the lum number of oxidation states are shown by: (case 2020) a. $c (Z=21) b. Cr (Z=24) ©. Mn (2=25) J. Fe(2=26) -Y Assertion & Reason tyoe Questions Directions (Q. Nos. 24-35): Each of the fallawing questions consists of two statements, one is Assertion (A) and the other is Reason (R). 24, ges. 926, Q27. 26. Give onswer: a. Bath Assertion (A) and Reason (R} are true and Reason (R) isthe correct explanation of Assertion (A). b. Both Assertion (A) and Reason (R) are true but Reason (R) is not the correct explanation of Assertion (A) Assertion (A) is true but Reason (A) Is false, d. Assertion (A) is false but Reason (R) is true Assertion (A): Cu2* lodide Is not known, Reason (R): Cu?" oxidises I" to iodine. (ucenrexemPLan) ‘Assertion (A): Copper is 8 non-transition element. Reason (R): Copper has completely filled d-orbitals in its ground state. (case 2023) Assertion (A): Transition metals show their highest oxidation state with oxygen. Reason (R): The ability of oxygen to form multiple bonds to metals. (case 2023) Assertion (A): Transition metals have high enthalpy of atomisation. Reason (R): Greater number of unpaired electrons in transition metals results In weak metallic bonding (case 2023) Assertion (A): 2r and Hf have almost identical radi Reason (R): oth Zr and Hf exhibit similar properties (cose 2023)30. gal 6 2 3 4. 15. ee . Assertion (A): Separation of Zr and Hf is difficult. Reason (R): Because Zr and Hf lie in the same group of the periodic table, (CERT EXEMPLAR) Assertion (A): Actinolds form relatively less stable complexes as compared to lanthanoids. Reason (R): Actinoids can utilise their Sf orbitals along with 6d orbitals in bonding, but lanthanolds do not use their 4f orbital for bonding (Ncenr ExeniPLan) Assertion (A): Magnetic moment values of actinides are lesser than the theoretically predicted values. Reason (R): Actinide elements are strongly paramagnetic. (cose sop 2022-23) Q 32. 33, 34. 35. Assertion (A): Zinc is not regarded as a transition element Reason (R): In zinc, 3o-orbitals are completely filled in its ground state as well asin its oxicised state. (case 2025) Assertion (A): Fe? acts as a reducing agent. Reason (R): Fe state is stable due to 305 configuration (c0se2023) Assertion (A): Cu cannot liberate hydrogen from acids. Reason (R): Because it has positive electrode potential (wcenrexempLan) Assertion (A): The highest oxidation state of osmium is +8. Reason (R): Osmium Is a Sd-block element. (NCERT EXEMPLAR) bade (b) 4d-series consists of ten elements from atomic number 39 to atomic number 48. (0) (a—Nd electron ‘The +1and +2 oxidation states involve the participation of ns-electrons, but higher oxidation states such as +3, +4, +5, +6 etc. involve the use of (n ~I)d electrons, In addition to ns-electrans for bond formation. 1 (6) 2 Due to the absence of d-electrans, zlnchas the lowest melting point in 3d series. (d) Sc (a) cu (2) (+r), Ga). (il)4p) Zine has no unpaired electrons in 3d or 4s orbitals, 50 enthalpy of atomization is low Mn = 305452 shows, 42, 43, 44, 45, 46 and 47 oxidation state, maximum, number in 3d series. (0) Fe Fe has the maximum number of unpaired electrons. le, 1. (b) +3 1. (b) unpaired electron (b) Ni {q do not behave like transition metals ‘Transition metals have partially fled d-orbital either in their elemental state orin most common oxidation state but ions of metals of Group 12 (Zn, Cd and Ha) have completely filled c-orbitals and so they do not behave like transition metals (d) variable oxidation states The transition elements on account of thelr variable valency are able to form unstable intermediate compounds very readily and hence show catalytic behaviour (b) atomic radii (b) A-(iv). B-(il), C-(i). D-(ll) (9105 2Mn0; +H,0 +1 —» 2MnO, + 20H” + 10; 16 u. 9 2 22, 23, 25, 26. 2. (0) charge transfer from Ugand to metal The Mn atom in KMnO, has +7 oxidation state with electron configuration (Ar}3d° 45°. Since no Unpaired electrons are present in it. d-d transitions, are not possible. The molecule should, therefore be colourless, Its intense purple colour is due to LM (igand to metal) charge transfer ie. 2p(L) of Oto 30M) oF Min. (ice WB. (2) (Xe) 4F75d"6s? (Tm 20. (2) V-05.C1,0, (0) 387M ‘Number of unpaired electrons in Ce3* fons Spin only magnetic moment of Cr » 5(3-2) eVi5 ©3987 8M (4) They are chemically very reactive Interstitial compounds are chemically inert (c) Mn (Z= 25) Transition Element | __Oxidate States Sc 3 cr 42,4344, 65,56 Mn 42,43, +0, 45,4647 Fe $2.43, 44.46 (2) Both Assertion (A) and Reason (R) are true and Reason (R) s the correct explanation of Assertion (A) (d) Copper is a transition element but it has completely filled d-orbitals In its ground state Hence. assertion Is false but reason is true (@) The ability of oxygen to form multiple bonds with ‘metals results in the formation of stable compounds in which metals can exist In thelr highest oxidation states (©) Transition metals have high enthalpy of atomisation because they have high effective nuclear charge, greater number of valence electrons and some unpaired electrons which result in strong, metallic bonding Hence. assertion Is true but reason Is falseEERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET 28. (b) Zr and Hf have almost identical radii due to lanthanoid contraction, Also, both Zr and Hf exhibit similar properties. Hence. assertion and reason bath are true but reason is not the correct explanation of assertion. 29, (b) Goth Assertion (A) and Reason (R) are true but Reason (R) is not the correct explanation of Assertion (A). 30, (d) Assertion (A) is false but Reason (R) Is true Assertion Is false because actinolds form more stable complexes as compared to lanthanaids. 31. (b) The magnetic moment is less as the Sf electrons of actinides are less effectively shielded which results in quenching of orbital contributions. Also. they are strongly paramagnetic due to the presence of unpaired electrons. 32, (2) Zinc is not regarded as a transition element because it forms only Zn? ions with all the 3d electrons present. 2n has 3d- orbital completely filled by 10 electrons that are paired. Hence. they can't release these electrons and can only lose electrons. (0) Fe2" acts as a reducing agent due to the Increasing stability of the lower species to which they are reduced, Hence, assertion is true Also, Fe state is stable due to 30% configuration Le. half filled electranic configuration. So, reason Is also {rue and tis also the correct explanation of assertion. 34, (2) Both Assertion (A) and Reason (R) are true and Reason (Ris the correct explanation of Assertion (A. 35, (b) Goth Assertion (A) and Reason (R) are true but Reason (R) is not the correct explanation of Assertion (A) Case Study Based Questions y 3: Case Study 1 When an orange coloured crystalline compound [A] was heated with common salt and concentrated sulphuric acid, an orange red coloured gas (B] was evolved. The gas (B) on passing through NaOH solution gave a yellow solution [C]. The solution on reacting with an aqueous solution of lead acetate gave a yellow precipitate Read the given passage carefully and give the answer of the following questions: QL. The crystalline compound [Al is: a. cobalt nitrate b. manganese sulphate ©. potassium dichromate 4, ammonium dichromate 2. The gas [8] is: a. chlorine . chromyl chloride . bromine 4, nitrogen peroxide Q3. What happens when potassium iodide reacts with acidic solution of potassium dichromate? 2, It liberates iodine b. Potassium sulphate Is formed c. Chromium sulphate is formed d. All the above products are formed 4. One mole of acidified K,Cr,0,, on reaction with excess KI will liberate. mole (5) of |. ad bd e7 a2 ——— Answers } + (©) potassium dichromate (0) chramyi chloride (@) All the above products are farmed 4. (a)3 Case Study 2 In basic solution with pH 6, CrO, forms the tetrahedral yellow chromate ion, CrO?. Between pH 2 and 6, HCrO;and the orange red dichromate ion, Cr,O%, are in equilibrium. At pH values below, 1, the main species is H,CrO,. The equilibria are: HCry, == CrO% + He, K = 1089 HCr, = HCr0; +H, K=4.1 C1,0% + H,0 = 2HCIO;, K « 1072 In addition, these are base-hydrolysis equilibria CO% + OH = HCr0; + CrO* HCr,0; + OH C10; +H,0 ‘The pH dependent equilibria are quite labile and on addition of cations that form insoluble chromates, (c.g, Bu?*, Pb® and Ag"), the chromates and not the dichromates are precipitated Read the given passage carefully and give the answer of the following questions: 11. Which of the following statement Is correct? a. Acid solutions of dichromate are strong 1 2 3 oxidants bin alkaline solution, the chromate lon is strong oxidant ©. Acid solutions of dichromate are poor oxidants 4, Both a, and b Q2. In the redox reaction involving Cr,03~ and Fo? ions, the number of electrons absorbed per chromium atoms Is: at ba co 46 8. What happens when a solution of potassium chromate Is treated with an excess of dilute nitric acid? a, * andCr403> are formed b. C103- andH0 are formed €. FOZ" fs reduced to +3 state of cr d, CrOJ” Is oxidised to +7 state of Cree EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET Q4. When acidified K,Cr,0, solution Is added to Sn?" salts, then Sn?” changes to: a $n . Sn? c Sn 4. Snt Answers 1. (@) Acid solutions of dichromate are strong oxidants 2 (0)3 3. (b) Cr,0 andl,0 are formed 4 (c) Sn Case Study 3 The d-block occupies the large middle section flanked between s- and p-blocks in the periodic table. The name ‘transition’ given to the elements of d-block is only because of their position between s and p-block elements The d-orbitals of the penultimate energy level in their atoms receive electrons giving rise to the three rows of the transition metals, ie., 3d, 4d, and Sd. The fourth row of 6d is still incomplete. First transition series or 3¢-series: Scandium (Sc) to Zine (Zn). Second transition series or d-series: Yttrium (Y) to Cadmium (Cd). Third transition series or Sd-series: Lanthanum (La) to Mercury (Hg) excluding Ce to Lu Pourth transition series or 6d-series: Actinium (Ac) to Copernicium (Cn) excluding Th to Lr. Read the given passage carefully and give the answer of the following questions: QL Silver atom has completely filled d-orbitals, (40°) in its ground state. How can you say that itisa transition element? In the series Sc (Z = 21) to Zn (2 = 30), the enthalpy of atomisation of zinc is lowest, (¢., 126 KI mol", Why? Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? oR value of copper is positive ge. Qa THe Faery (+0.34V). What is the possible reason for this? Answers Silver In its +1 oxidation state, exhibits 4f%5<° Configuration. But in some compounds, It also shows, +2 oxldation state, so the configuration becomes 4c? 5s0,Here, dorbital is nat completely filled. Therefore. silver fsa transition element. Zine has stable ground state due to its completely filled corbitals. It therefore, has least tendency to form metallic bonds, in the series and thus requires least enthalpy of atamisation to get atomised v 3. Oxygen and fluorine both have small size and high value of electronegativity So, they can oxidise the metal to their highest oxidation states. oR E>; Value of copper is positive as value of hydration enthalpy is less than the sum of values of lonisation enthalpy and enthalpy of ionisation, Very Short Answer Type Questions y QL Ans. Transition elements exhibit variable valency. Why? ‘Transition elements exhibit varlable valency because of the presence of electronsin (n—1}dand.ns-subshells and very closeness of shel of dand s-subshells. Thus, transition elements readily lose electrons from the inner shell and hence, the oxidation state increases. In 3d series of transition elements, which element exhibit maximum number of oxidation states and why? Manganese (2 = 25, electronic configuration = (Ar) 305432) coniaing Five unpaired electrons In 3d orbital and 2 electrons in 4s orbital. So, it exhibits oxidation states from + 2 to +7, which isthe largest number of oxidation state exhibited in 3d series. Why are :3 and 4 oxidation states of cerium (atomic number = $8) more stable? aCe = 15? 25? 2p8, 35? 3p 30%, 452 46 ad!” 4f?, Bs? 5p, 65% In cerlum, the energy order of subshells Is af < 4d Thus. 4F subshell contains 2 electrons which are ramoved one by one with the two electrans of 6s to exhibit +3 and 44 oxidation states, which are stable. Most of the transition metals exhibit paramagnetic behaviour. Why? In transition metals, ¢subshellof (n-1) shellcontains unpaired electrons (with the exception of Zn. Cd and Hg). Because of the presence of unpaired electrons. transition metals usually exhibit paramagnetic behaviour Write the chemical equation for obtaining chlorine from potassium permanganate. 2KMinO, + 3H,SO, + TOHC—> K,50, + 2MnS0, 4 8H,0+ SC? Why is the highest oxidation state of a metal ‘exhibited by Its uoride and oxide only? (cent inrexT) Both fluorine and oxygen have very high electronegativty values. They can oxidise the metals to the highest oxidation state. As a result, the highest oxidation states are shown by the fluorides and oxides of the metals: transition metals in particular What is the effect of increasing pH on the colour of K,Cr,0, solution? When pH is less than 7 (acidic medium), K,Cr,0, (C,0,2") has orange colour, In the basic medium with pH mare than 7. the colaur ofthe solution changes to low due tothe formation of K,CeO (CrO,?* lon Qa. Ans. 93. Ans. 4. Ans. Qs. Ans. 6. Ans. a7, Ana, eea6 a9. Ans, Quo. Qu, Ane. Qs, 16, Ans. EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ee Why Is third ionisation enthalpy of manganese exceptionally high? 3. Mn?* has the configuration (4r]3d% with highly symmetrical configuration. the removal of third electron Is very difficult. Therefore. third lonisation enthalpy of the metal Is exceptionally high (aH = 3200 KJ mot"), Why are all salts of scandium white? In these salts, scandium exists as Sc® ion which is isoelectronic _with (Ar)™ with completely filled ‘orbitals, the salts of SC are white ‘What happens when H,0, is shaken with acidified K,Cr,0, solution? The colour of the solution changes from orange to bive, (OF + 4,0, + 2" 2610, + 5H,0 ane Blue When H,S is passed through dilute solution of K,Cr,0,, mitkiness appears. Why? This Is due to oxidation of H,S to sulphur which ls of colloidal nature. Therefore, the solution appears to be ‘milky white or pale yellow. Transition metals tend to be unreactive with increasing atomic numbers in a series. Why? . This Is because of gradual increase in the values of ionisation enthaipies which make the participation of electrons rather difficult. ‘There is a greater range of variable oxidation states among the actinolds than among the lanthanoids. Why? . In actinolds, there is less energy difference in the S5f, 6d and 7s orbitals as Compared to 4f. 5d and 6s rbitals in case of lanthanoids. This means that mare electrons are available for bonding In actinolds as compared to the members of lanthanoid farnlly. Why is there a general increase in density of elements from titanium (Z= 22) to copper (2 = 29)? In general. the atomic radi_and the atomic volumes of the elements gradually decrease along 3d series. However, their atomic masses increase. This means that the densities (Mass/Volume) of the elements are Ukely to increase from left tothe right in the series. ‘There occurs much more frequently metal-metal bonding in the compounds of heavy transition elements (3d series). Assign reason. . In transition elements, a number of ns and (n—1)d electrons are avallable for bonding since these are unpaired, As a result, metal-metal bonding Is quite Frequent in these. These are supported by the fact that ‘metals are lustrous, hard and have high melting and bolting potats, ‘Why is Cu" fon not stable in aqueous solution? OR ‘Why is Cu" not known in aqueous solution? Cu() compounds involving Cu" jons are unstable in aqueous solution and undergo disproportionation 2eur—9 Cu + Cu au. Ans. qua. Ans. aus, Ans. qa. Ans, ga. Ans. Qee. Ans. 23. Ans. gaa, Ans, The stability of Cu? ions as compared to Cu" ionis due to more negative AnH” of Cu? (ag) than Cu* (ag) which compensates the second ionisation enthalpy of Cu involved in the formation of Cu? ion, ‘Among the divalent cations in the first tra series, manganese exhibits maximum paramagnetic character. Explain. IMn2* ion has 30 configuration and has maximum of fiveunpaired electrons. Therefore. texhibitsmaximum paramagnetic character amiong the divalent cations of First transition series. La® (2 = $7) and Lu (Z = 71) do not show any colour in solution. Assign reason, 2 jon has the configuration of Xe while Lu? ion Xe) 4F has completely filled orbitals and there is no transition. Therefore, both these ions da not show an colour Write the formula of an oxo-anion of manganese (Mn) in which it shows the oxidation state to its group number. (case 2017) |MnG; Is an ox0-anlon of manganese (Mn) in which it shows the oxidation state equal to its group number. Here. oxidation state of Min is +7 which Is same as Its ‘group number (7). ‘Write the formula of an oxo-anton of chromium (Cr) in which it shows the oxidation state equal to its group number. (cast 2017) The formula is Cr2OF (dichromate ion) in which coxldation state af Cris 26 wich Is equal to its group number (6). Complete the following reactions: () 1,07" + Sn? + He —> Gi) Mog + Fe? + Hs —- () C07" + 14H! + 35n2 —> 2C13* + 35n* + 7H,0 (i) 2Mn0 5 + 16H" + 10Fe2* — » 2M? + BHO + 10Fe* Explain why Zn? salts are colourless while Ni? salts are coloured. 2n2* with configuration (Ar)#3d"® has all_filed orbitals, Therefore. its salts are colourless, N= with configuration (Ar]!® 3d° has some half-iled orbitals, Therefore. its salts are coloured ‘Why is +2 oxidation state of manganese quite stable while the same not true for iron? The electronic configurations of bath the fans are: Mn2*: (Ar]3d3: Fe? (Ar)d6 The in?" lon has more symmetrical configuration than Fe® ion and is therefore, more stable. Thus +2 Oxidation state of manganese s quite stable white that of iron is not Write the electronic configuration of an element with atomic number 102. ‘Theconfiguration of the element (2. 102) is (Rn}SF'752, itis Nabetium (NoAns Ans. 28. Ans. Qa. Ans. 30. Ans. Qa 26. 27. Why is La(OH), more basic than Lu (OH),? La(QH), {s more basic than Lu(GH), because the latter has greater covalent character as compared to the former on account of lanthanold contraction. The release of OH fon from Lu(OH), is more dificult and 1s ess basic than La(OH), Why are Zn, Cd and Hg quite soft and have low ‘melting points? These metal atoms have completely filled d-orbitals {0 configuration). This means that d-electrons are ‘not readily available for metallic bond formation. Quite obviously the metallic bonds are weak and as a result these metals are quite soft and also have low ‘melting points. Discuss the relative stability in aqueous solutions of +2 oxidation states among the elements: Cr, Mn, Fe and Co. The relative stabilty of the +2 oxidation states (decreasing order) can be compared in terms of E° values. (M?/M) Ma? (-18 V) » Ce" (4090 (028 V) Why is potassium permanganate thermally unstable at 513K? At 513K. potassium permanganate _undergoes disproportionation reaction, The products are more Stable than the reactants, x F “4 2K Wind, 22" K, MnO, + K, Mind, +O, Name the transition metal which shows maximum number of oxidation states in the first transition series. Tho element manganese (Min) shows maximum ‘number of oxidation states (+2, +3.+4, +5.+6 and +7), Which metal of the first transition series exhibits + 1 oxidation state most frequently and why? The element copper (Cu) shows +1 oxidation state most frequently. Its configuration is (Ar) 3d%4s!. By losing one electron, it acquires a stable electronic configuration Explain the following: (i) Cu’ is colourless and Cu?" is coloured. (i) Zn shows only 2 oxidation state in its compounds, ()Cus_has_ 3d configuration (no dd transition of ‘actrons) wile Cu?" lon has 34? configuration (cd transition is possible). As a result, Cur Is colourless and Cu?" Is coloured. (i) The configuration of Zn is (Ar) 3d ds2 By losing two electrons, Zn?* ion has (Ar) 30% configuration _wihich_is_symmetrical Zn?" ion has no tendency to lose any more electrons. Therefore, Zn shows only +2 oxidation state in its compounds. > Fe2! (0.44 V) » Co? Qsz. Ans. 933, Ans. Qs. Ans. Q35. Ans, 936. Ans, Qa. Ans. 938. Ans. Q39 Ans, ee Explain why is zine not regarded as a transition ‘element? Zinc (Zn) fs the last element of first transition series (84 configuration). t does not fulfill the criteria of 2 transition element which must have incompletely Filled d-orbtals in ts ground state. Therefore. Els nat 2 transition element. Explain why is Co fon a strong oxidising agent. coher co (-ovaaton sae) (3 oncauon tate) Ce jon is a strong oxidising agent because +3 oxidation state is more stable than + 4 oxidation State in the transition series of metals, the metal which exhibits the greatest number of oxidation states ‘occurs in the middle of the series. Expl In the middle of the series (0° configuration there is a participation of two ns electrons and five (n — 1)d electrons in the bond formation. Therefore, the elements in the middle of the transition series exhibit maximum oxidation state. (eg. Mn present in 3d series) Metal-metal bonding is more extensive in the 4d and Sd series of transition elements than the 34 series, Explain. own the group In the transition metals. the atomic size increases. Therefore. electrons in element belonging to 4d and Sd series are less loosely held by the nucleus as compared to the elements present in the 3d series, butin the same group. The metal-metal bonding is more extensive or stronger. In other words, the metallic character increases down the group. Why does Mn(lll) undergo disproportionation reaction easily? Mo (il) is highly unstable as itis clear from its very Bipaeppar Value (+ 157 VI. As such. ft undergoes Eproportionation reaction as follows: 2mn> (ag) —+ Min?* (aq) + Mn** (ag). Why is enthalpy of atomisation the lowest for Zn in 3d series of transition elements? Zinc (2 = 30) has symmetrical electronic configuration far) 45? 3d AS a result od interactions are ‘negligible and the metallic bonds are quite weak The element has. therefore. lowest enthalpy of atomisation (126 kd mot} in the 3d transition series of elements, ‘Out of Cr5> and Mn}*, which is a stronger oxidising agent and why? Mn? is a strongest oxidising agent because after accepting an electron from the reducing agent. It acquires Nn?> configuration which is quite stable nS (aq) + => Min (oq) (9 (20!) Name a member of the Lanthanold series which is well known to exhibit +2 oxidation state, a stable The element Europium (2 = 63) has o)_ 477 Sa Est By losing two configuration: electrons. it” achieves @ noble gas electronic configuration. The element. therefore, exhibits +2 oxidation state in its compounds eeee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET 40. Silver atom has completely filled d-orbitals (4d) Its ground state, but it Is still regarded as a transition metal. Explain. Ans, ‘The configuration of slver Is (Kr] 40 Sst acquires 4d'® configuration by losing 55" electron. Mareover, the last electron is filled in the 4d subshell Therefore. the element is regarded as a transition metal. Short Answer type-i Questions & QS. Actinold contraction is greater from element to ‘element than lanthanoid contraction. Why? (vcerr inrexr) ‘Ans. The decrease or contraction in atomic radi as well as ionic radil in actinold elements (actinoid contraction) Is, ‘more as compared to lanthanoid contraction because 5f electrons have more poor shietding effect as compared to 4f electrons. Therefore, the effect of increased nuclear charge leading to contraction in size QL What do you mean by variable oxidation states? Explain it in context of transition elements. ‘ans. Variable Oxidation States: When an element exhibits two or more than two oxidation states then the oxidation states are called Variable Oxidation States, With the exception of Zn and Cd of zine group. all ‘other transition elements exhibit variable oxidation states. This is because the energy difference between the energy of s-subshell of the autermost shell and c-subshell of penultimate shel Is very less in case of these elements. so electrons of both the subshells can bbe used for bond formation For example. iron (Fe) exhibits + 2 and + 3 oxidation states and copper (Cu) exhibits + T and +2 oxidation states G2 Which elements are called actinolds? Write their main uses. ‘Ans. In the periodic table, actinium (eoAc) and the 14 elements placed after It (from goTh to g3Lw) are called actinoids. This seriesis formed by the successive filing of electrons in Fsubshel Uses: important uses ofthese elements are as follows () These elements are highly reactive metals. Thus, they can be used as strong reductant (i) These are used for the formation of complex compounds, 3. What are interstitial compounds? Why are such compounds well known for transition metals? Ans. The compounds in which interstitial spaces in the crystal lattice are trapped by small atoms (Uke H.C oF N), are called interstitial campaunds. These are well known for transition metals because the small atoms Uke H,N or C get easly trapped inthe votds prevent in crystal lattice of transition metals Q4. Explain why Cu" fon isnot stable aqueous solutions. (cen next) ‘Ans, Cu" (aq) is more stable than Cu (oq). This is because second lonisation enthalpy of copper is more. but for Cu2™ (aq). Ang H Is more negative as compared to Cur (aq). So It compensates more for the secand lonisation enthalpy of copper. Thus. mostly copper {) compounds are unstable in aqueous solution and disproportionate in the following manner: 2Cu (ag) —» Cu (aq) + Cu(s) is more In case of actinoid elements. Q6. Predict which of the following will be coloured in aqueous solution? (wcenr exencise) TH, V5, Cu, Sc3", Mn? Fe, Co?” ‘Ans. Only thoselonswille coloured whichhaveincomplete orbitals, The Ions with elther empty or filed orbitals are colourless. Keeping this in view. the coloured ions among the given list are TP+(3d). V2+(3d?). Mn?4(309), Fe™(30%). Co” (307) 50" 8d") and Cur (3d) ions are colouriess Q7. For M2"/M and M/M?* systems, the E° values of some metals are given: (weenr exeRcise) CP ycr=0.9V; CB /CPo-04V Mn2/Mn= 1.2; Mn?:/Mn2*=+1.5V Fe2'/Fe-0.4V; Use this data to comment upon: (i) The stability of Fe’ in acid solution as ‘compared to that of Cr5* or Mn". The ease with which iron can be oxidised as compared to the similar process for either chromium or manganese metal. (NCERT EXERCISE) Ans. (i) As E225 negative (.0.4 V), this means that Cr" ions in solution cannot be reduced to Cr" ions ‘oF Cr3" lons are very stable. As further comparison of E values shows that Mn?* ions can be reduced to Mn2* ion more readily than Fe? ions. Thus, in the light of this, the order of relative stablites of different ions is: Feb Fo? = + 0.8V. MnP < Fe? < C3 (l) From the €* values. the order of oxidation of the metal to the divalent cation is Ain > Cr Fee Q8. What must be the stable oxidation state of the transition elements with the following electronic configuration in the ground states of their atoms: 3d, 303, 308, 30%? (wcenr Exercise) Ans. The maximum oxidation states of reasonable stability In the transition metals of 3d series correspond to the sum of 5 and delectrans up to Mn. However, after Mn there Is an abrupt decrease in oxidation states. In the light of this. mast stable oxidation states of the elements are: 3d? 3494s? (« 6): 309+ 34451 (+ 6) and 3435? (+ 7 302 309452 (+ 2): 3d°: 3d %4s? or 31845 "(+ 6EEE EEE EEE EEE EEE EEE EEE EEE EE EEE EEE EIDE EEE EEE EE EE DEED EE EEE IEE EEE EEE EE EDIE EIEI EIEIO IEE Q9. Ans. quo. Ans. Qu. Ans. que. Ans. To what extent do the electronic configurations decide the stability of oxidation states in the first series of the transition elements? Illustrate your answer with an example. (CERT EXERCISE) The presence of half filled or completely filled orbitals imparts stablty to @ particular elements/ jon. Greater the number of such orbitals, mare will be the relative stabilty. For example, let us write the different oxidation states of Mn (Z= 25) along with the electronic configurations: Mn (2 = 25) along with the electronic configurations. Mn = (Ar) 305452 Mn2": (Ar) 30, Mn; (Ad, Mant Ar] 3o 42 onldation state of the element to Ukely to be the most stable because the corresponding electronic Configuration of Mn2” is highly symmetrical (all the Five 3¢-orbitals are half Filed) Silver has completely filled d-orbitals (4c) in its {ground state. How can you say that it Is a transition metal? (wcenrinrexn Silver (Z » 47) belongs to group TI of block (Cu. Ag Au) and its outer electronic configuration is 4d!5s! it shows + 1 oxidation state (4d! configuration) in silver halides (eg. AgCl). However. it can also exhibit +2 oxidation state (4¢° configuration) in compounds Uke Ag, and AgO. Que to the presence of half-filled chorbital. silver isa transition metal How Is KMnO, prepared from pyrolusite? Give steps involved with equations. (case 2019) ()) When pyrolusite is fused with KOH in presence of air or oxidising agent. potassium manganate is produced, 2Mn0, + 4KOH +0,—» 2,Nn0, + 2H,0 (i) Potassium manganate upon further oxidation or disproportionation in a neutral or acidic medium alves potassium permanganate 3K,MnO, + 2H,S0,—> 24,50, + 2KMNO, + 2H,0 {sproportionation wi ,50,) * MnO, wero oxtaon {Aukatiew srvdtum) tend, (at anode) Complete and balance the following equations: (case 2019) () Mnog +I-+He (ii) Na,Cr,0, + KeL—> () 2MnO% + 101+ 16H+ > 2M? 5, + BHO (i) NagCr,0, +2KCl—> K,Cr,0, + 2NaCt Complete the following equations: (i) 2Mn0; + SNO; + 6H’ —> (il) Cr,0}" + 14H" + 60: () 2Mn0; + 5NO5 + 6H"—> 2Mn?* + SNOF + 3H,0 (il) Cr,07" 9 1aHY + Be" > 203 + 7H,O (case 2023) Qs Ans. Qs. 16. Qu. Ans. Explain paramagnetic and_—_ diamagnetic characteristics in transition elements with one example. If dsubshell of the transition metal atonvon contain unpaired electrons then they are paramagnetic eg. Cu lon is paramagnetic Cus 152 252 2p, ast 3p ag? aa reper This fon contains one unpaired electron, so it Is paramagnetic. ‘On the other hand. the transition metal atomyion having no unpaired electron in d-subshell. exhibit diamagnetic behaviour. eg, Cu" ion Cut: Is! 25? apt, 3s? 3p 300 VU A Icantains no unpaired electrans. soit is dlamagnetic. Calculate the ‘spin only’ magnetic moment of M2: (ag) ion (2 = 27). (wcenr intext) Electronic configuration of atom M(Z = 27) = (Ar) 3d” 42 Electronic configuration of M@ = (Ar) 3d? te, Wait ‘Thus it contains three unpaired electrons, Spin only magnetic moment (j:)=fn(n+ 2) BM. ‘where, n= number of unpaired electrons, » BG?2) = Jieou 387 BM Equivalent weight of KMnO, is different in acidic and basic medium. Why? In acidic medium, KMInO, show following reaction 2kalnd, + 3H,50,—> K,S0, + 2MnS0, «34,0 +5 (0) Thus, equivalent weight of KMnO, Molecular wt of KMnd, ‘BOOBOO00000 39455464 _ 158 725 6 In alatne medium, KMind, shows following reaction a 8 2KNInO, + 2KOH—> Kad, = H,0+ (0) ‘Thus, equlvatent weight of KMnO, 9+ 55464 _ 15 a ae What are alloys? Name an important alloy which contains some of the Lanthanold metals. Mention its use. (ncear exercise) Alloys are the homogeneous mixtures of different metals whlch are obtained by mixing different metals, These are Infact, homogeneous solid solutlons in which atoms of one metal are irregulariy dispersed eeee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET in between the ators of another metal This type of alloys are formed by the atoms, metalic radi of which have a diference of 15%6, One such famous alloy Is misch_metal_which contains 505% cerium. 2596 lanthanum and traces of neodymium, praseodymium and other elements. Most of the misch metal is used in alloys Based on magnesium which are used for making bullet for guns. armour or guard and light flint Q18. Complete the following: () 0% (09) = H,S (a) +H" (aq) —> (i) Cu?> (on) = (aq) —> (ill) Mn0z+$,0,2~H,0—> (iv) KMno, et, ‘Ans. () C103" (aq) + 3H,5 (g) + BH” (ag) —+ 2Cr** (09) +7H,0 (09) +35(6) (i) 2Cu?* (aq) + AI-{aq)—> Cush, (5) +1,(5) (li) 2mn0% + 35,02 + HO —> 20H" + 2Mn0, +3502 +35 (Wu) 2kMn0, 5 K,Mnd, + MnO, +0, 7 Q19. K,Cr,0, is a good oxidising agent in acidic medium. Explain. ‘ans. in acidle medium, Cr_undergoes a decrease _In oxidation state from +6 in Cr,02" jon to +3 in C= ion. Since +3 oxidation state Is hore stable than +6 oxidation state therefore. K,Cr,0, is @ good oxidising agent in the acidic medium. a [9] st +e" ap 2Cr| + 7H,0 20. (i) Write an oxidising reaction of K,Cr,0, in the acidic medium. (li) Write one oxidising reaction of KMnO, in the basic medium. ‘Ans. ()K,Cr,0, oxldise H,S to 2 sulphur (yellow ppt) in the acidic medium. KCr,0) + 44,50, + 3H,S—5 K,50, + Cr(50,)y +7H,0 +35 {i) KMn0, oxidise KI to KID, in the basic medium. 2KNINO, + KI + HO—> 2MNO, + 2KOH + KIO, -@ Short Answer tupe-ti Questions w Q1. Define transition metals. Why Zn, Cd and Hg are not called transition metals? How is the variability in oxidation states of transition metals different from that of p-block elements? (cose 2022 Term-2) ‘Ans. Transition metals are defined as metals which have incomplete d-subshell either in neutral atom or in their lons, Zn. Cd and Hg have full d!? configuration in their ground state as well as in their common oxidation states and hence. are not regarded as transition metals, In pblock the lower oxidation states are favoured by the heavier members due to the inert pair effect whereas higher oxidation states are most stable far heavier elements in transition elements 2. Give reasons for the following statements: () Transition elements and their compounds act as good catalysts. (ii) E°(Mn2*/Mn) value is highly negative as compared to other elements. (ill) Cr?* is a strong reducing agent. (C8S€2022 term-2) Ans. (i) Transition elements have the ability to adopt ‘multiple oxidation states and to form complexes which makes them a good catalyst (i) Bpezenany Value is highly negative as compared to other elements due to stability of half-filed d subshell (€?). (ii) Cr* has o® configuration while Cr3* has more stable d? (¢3) configuration. Thus. Cr_has a tendency to acquire Cr3+ due to greater stability of +3 oxidation state. Therefore. Cr?° acts as a stvong reducing agent. Qs. ce lm] [ole [ow]a zost | =e [=o [-028 [-025[-0 | 076 Ee From the given & values of the first row transition elements, answer the following questions: () Why is E'y2n Value highly negative as compared to other elements? (ii) What is the reason for the irregularity in the above E”, values? (ii) Why is Ege, value exceptionally positive? (cBs€2022 Term2) Ans. (i) €° value of (Mn2*/Mn) is highly negative as compared to other elements due to the greater stability of halfiled d-subshel of an?(305 i) The Eye values are not regular which can be explained from the irregular variation of Jonisation enthalpies (a,h, + 4,H,) and also the sublimation enthalpies which are relatively ‘much less for manganese and vanadium, (i) Copper has high enthalpy of atomisation (a. and low enthalpy of hydration (anuK®). Since the high energy to transform Cu(s) to Cu2* (aq) ts not balanced by hydration enthalpy. therefore. E'g2¢,valUe Is exceptionally postive. Q4. Comptote the following chemical equation for reactions in aqueous solution. () Cr OF +H Po? —> (ii) Mn ii) MnO; + C, 07° «He +HPEE EEE EEE EEE EEE EEE IEEE EIDE IE III EI III IDI II II II II II II IIE EE ET Ans. (|) Cr 03° + 1GH™ + 6Fe?—+ 2Cr> + GFe% + 7H,0 (i) 2Mn Oy + 1GH* + 10> 2Mn2* +5, + BHO (ii) 2mn0q + 5¢,02° + 16H” —+ 2Mn?* + 10C0, + BHO Q5. Give reasons for the followin Mn**is a good oxidising agent. (ii) E%y2.py Values are not regular for first row transition metals (3d series). (li) Although ‘Fis more electronegative than ‘0, the highest fluoride of Mn is MnF, while the hhighest oxide is Mn,0,. (c8se 2015) Ans. (i) Mn?" is a good oxidising agent because Ey,3equr is very high (+157 V). As a result. Min? Ton can be sy Aa Non ERAN Therefore, good sg age (i) It Is due to the reason that. the variation in the ile oF ey of sorecli ad CATaLN of hydration for M2- ions are not quite regular. (oh ii probaly acto he reason thet the lent oxen an for. tulpl bans. WT transilon metas but Terie cannat do 50-As 2 result he element Hn exits x4 oddoUon state intin, ond $7 odaton state in yO; i i 7 Nom Se ooo , d S Q6. Give reasons for the following statements: {) Copper does nat cisplace hydrogen fom acs (ji) Transition metals and most of thelr compounds show paramagnetic behaviour. (Zi, ce ay wre soR Meta omeauaza a) Ans. {) Copper does not dsplace hydrogen fram acids because Cu has postive €° Value Le. 1s Less rscta at RAN wade E Value (il) Transition metals and most of their compounds. fina Boretinsnete banaMOUT aoe th presence of ane or more unpaired electrans in dsubshell (Wl) Zn, Cd and Hg have completely filled ctorbltals Jn the ground state as well asin thelr comman oxidation states, Thus, due to absence of any unpaired electrons and weak metal-metal bonding they are softin nature 7. Give reasons for the following: i) The only oxidation state shown by scandium is (ii) [TI(H,0),]* is colourtess. Mn0 is basic while Mn,O, Is acidic. (cose2013) Ans. () Sc (21) has electronic configuration: (Ar]3d'45? Ithas 3 electrons in its outer orbitals. So, to gain d electronic configuration, it has the tendena {0 lose these 3 electrons. At +3 oxidation state. stable d® is obtained. (W) (T(H,0)¢}** is colouriess and it cannot undergo ded transition as it does not have unpaired electrons So. itis colourless. (il) The oxlde in the lower oxidation state of a metal Is basic and in the higher oxidation state of the metal. it is acidic That is why, MnO (oxidation state +2) is basic whereas Mn,0, (oxidation state Tisacidic 8. Answer the following: (i) What is the general electronic configuration of lanthanoids? (ii) What are the common oxidation states of cerium (At. no, 58)? (il) Why do actinolds show a wide range of oxidation states? ‘ans. (i) The general electronic configuration of anthanolds is [Ke] AF 59! 652 (i) The common oxidation states of cerium (At no 58) are +3 and +4 (il) There Is a greater range of oxidation states in actinoids. It fs due to the fact that Sf, 6d and 75 levels are of comparable energies. 9. Give reasons for the following statements: () Scandium (2 =24) is 2 transition element, but 2n (Z= 30) is not. (ii) [Ti(H,0),}** is coloured while [S¢(H,0),}** is colourless. (i) Physical and chemical properties of the 4d and 5d series of the transition elements are quite similar than expected. (case 2022 Yerm-2) Ans. ()) Scandium has incampletely filed d orbitals ai) In Its ground state, soit ls regarded as a transition element. On the other hand, zinc has completely filled d orbitals (3d!) in its ground state as well asin its oxidised state, hence it Is ‘not regarded as 8 transition element. (i) Tin ((H,0) 3s In +3 oxidation state and Sc in (Sc(H,0),}*is in +3 oxidation state TP* has one unpaired electron in 3d orbital to undergo dd transition by absorbing Ught fram ‘stole region and radiating complementary colour, Therefore. (TI(H,O),)>"i6 coloured. Sc} does not _contaln_unpalred electrons to undergo od wansition. Therefore, Sc(H,0),)>" 1s colourless (li) This Is because 4d and Sd series elements have victuslly the same atomic and lonic ra lanthanide contraction. eeQ10. Account for the following: ()) CuCl, is more stable than Cu,Cl,. (ii) Atomic radii of 4d and Sd series elements are nearly same. Hydrochl acid is not used in permanganate titrations. (cose 2017) (In CuCl, Cuts in +2 oxidation state which ks more stable due to high hydration enthalpy as compared to Cu,CL, In which Cus in + oxidation state (i) Atomic radii of 4d and 5d series elements are nearly same due to lanthanoid contraction. (ii) Hydrochloric acid” (HCI) 1S not Used in permanganate titrations because HCl is oxidised to chlorine Note: The lanthanide contraction is greater than expected decrease in ionic racil of the elements in the lanthanide series Account for the following: {)) Eu? isa strong reducing agent. (ii) Orange colour of dichromate ion changes to yellow in alkaline medium, i) Easy Values for transition metals show irregular variation. (case 2017) (i) €u having electronic configuration (Xe}4#7 is a strong reducing agent because in the aqueous solution, it reverts back to the most stable +3 ‘oxidation state. Le Eu (ii) When orange solution containing _Cr,07" {dichromate ion) is treated with an alkall, a yellow solution of Cr,0%- (chromate ion) |s obtained. cy? 9, croz negra Urania eres ton (i) ns and (n= Pd electrons of transition metal have very Utle difference in the enorgles and hence both can participate in bonding, which results in variable oxidation states. When ns electrons take part in Bonding, they exhibit lower oxidation states whereas (n ~ I)d electrons along with ns electrons participate in bonding they exhibit variable oxidation states, Write any two consequences of lanthanold contraction. (ii) Name the element of 3d series which exhibits the largest number of oxidation states, Give (case 2022 Yorm-2) ‘Ans. ()) Consequences of Lanthanold Contraction: {a) Due to lanthanold contraction, the third transition series atom has roughly the same size (atomic and fonic radi) as the second {ransltion series atom. (0) Oue to tanthanoid contraction, the baste strength of oxides and hydroxides of {anthanoids decrease with increase in atom ‘umber Ans. qu. Ans, giz. (i) EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ee (i) Manganese (345 452) has maximum number of electrons to lose or share (all the 3d electrons are unpaired). Hence. it exhibits the largest ‘number of oxidation states (from #2 to +7} Which fon amongst the following is colourtess and why? Tit, CrP", Vr (Atomic number of Ti = 22, Cr = 24, V = 23) (i) Why is Mn?” much more resistant than Fe?” towards oxidation? Highest oxidation state of a metal is shown in its oxide or fluoride only. Justify the statement. (CASE 2022 Term-2) Electronic configuration of given ions Is: Tis (Ar] 34S; C19 = (Ar) 3ePAS® and Ve = (Ar) 3g? 45° Since, TH does not contain unpaired electrons to undergo ded transition. tis colourless. QW). Electronic configuration of Mn? = (Ar]3o8 Electronic configuration of Fe2* = (Ar]3d® Nin2* has stable _o& (halFfilled) configuration while Fe* has 30° configuration and by losing ‘one e*, Its configuration change to more stable 3c configuration. Therefore, Mn?" is much mare resistant than Fe2* towards oxidation. (ii) Oxygen and fluorine act as strong, oxidising agents because of their small size and high electronegativity Hence a transition metal exhibits highest oxidation state in its oxide or fluoride. ‘@ Long Answer type Questions w QL Explain the following observation: () d-block elements exhibit more oxidation states as compared to elements of block, Cu’ salts are colourless, whereas Cu salts are coloured, (Atomic number of Cu = 29). ‘Mn2* ion is more stable than Mn®* ion. Transition elements form several complex compounds. (v) Zn? salts are white whereas Cu? blue (Weblock elements contain a large number of tunpeired electrons which take part in bond formation. Because ofthis, effective nuclear charge Is less, So, they exhibit more number of oxidation states as compared to Folock elements.1n Fblock effective nuclear charge becomes more effective due to weak shielding effect of Forbitals and hence, less electrons take part in bond formation (il) Cu lon does not have unpaired electron. so it can not exhibit d-d transition. Thus, Cu’ salts are colourless. Cu?* salts are coloured because they rave an unpaired electron. so they can show dd transition, They scatter blue colour by absorbing light from visible region, Qu. (i) Ans. (i) salts are Ane.ee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET (ii) Min? 152, 25? 2p, 382 3p 3a (halF-filled) whereas in Mn**, d-subshell of third shell_is incomplete ~~ Nin®* » 152, 22, 2p8, 35? 3p 3a! (incomplete) Half filled subshell (3d5) is more stable that partially filled subshell (3d). So. Min?" jon is more stable than Mn ion (iv) Transition elements form a large number of complex compounds. This Is because of; (@) Their small size and high charge density (b) The availability of vacant subshells. (0) Their different oxidation states 2n2* = 152, 25°Dp8, 35? 3pP Bde In this configuration, ctsubshell_is completely filled due to which the salt is colourless or white whereas, Cur 152, 2572p, 3s? 3p% 3d? In this configuration. d-subshell is partially filed due to which the salt is coloured or blue. 2. (i) Account for the followin: (a) Transition metals form complex compounds. (0) The E%,21/yj, Values for manganese is highly negative whereas E%,3jyq2> iS highly positive. (€) Cu* ion is unstable in aqueous solution. (ji) Write the equations involved in the preparation of KMn0, from pyrolusite ore (MnO), (CBSE 2023) ‘Ans. (i) (a) Due to the comparatively smaller size of the metal ions, high ionic charges and the avallabllty of vacant _d-orbitals for_bond formation, transition metals form a large ‘number of complex compounds (6) E%y,24y, value Is highly negative for manganese due to the greater stability of half-filled dsubshell of Mn®(3d%) whereas. Ey3jay2 18 highly positive due to the fact that Mn?" (9) is quite stable. {c) Cut (ag) is more stable than Cu? (ag). This iS because second ionisation enthalpy of Copper is mare, but for Cu? (oq). Aya H Is ‘more negative as compared to Cu" (oq). So it compensate more for the second ionisation enthalpy of copper. Thus. mostly copper () compounds are unstable in aqueous solution ‘and disproportionate in the following manner: 2Cur (aq) —- Cu?* (aq) + Culs) (i) The equations involved in the preparation of KINO, from pyrotusite ore (Mn0,) are as under. 2NnO, + 4KOH + 0,— 2K, MnO, + 2H,0 3K,MAO, + 2H,S0, —> 24,50, + 2KMNO, + 2H,0 ‘rasan +Mn0, (v) Seer, Kang, (t anode) (asus ee) 03. (Account for the following: (@) Transition metals form alloys. (b) Ce isa strong oxidising agent. (li) Write one similarity and one difference between chemistry of Lanthanolds and Actinoids. (iil) Complete the following ionic equation: (r,03+ 20H” —> Ans. (i) (2) Transition metals have similar atomic sizes due to which one metal can easily replace the other metal from its lattice to form alloy, Also transition metals are miscible with one another in the molten state which on cooling forms an alloy, (be) Cee > ce (+4 oxidation stake) (63 oxidtion sot Ce lon is 2 strong oxidising agent because +3 oxidation state ls more stable than +4 oxidation ‘state, (W) Similarity: Both lanthanold and actinald elements show a common oxidation state + 3 and both are electropositive and very reactive Difference: Lanthanoid have less tendency to form complexes whereas actinoids have greater tendency to form complexes. (ii) Cr,07" + 20H" —> 2Cr0% + HO 4. (j) Identify the following} (2) Transition metal of 34 series that exhi only one oxidation state, (b) Transition metal of 3d series that acts as a strong reducing agent in +2 oxidation state in aqueous solution. (li) Complete and balance the following equations: (2) Cr,03-+ 14H" + 6Fe?* —» ()K04n0, "=, (case 2023) (ili) What is Misch metal? Write its one use. Ans. _() (a) Culsa transition metal of3¢ series that exhibits only one oxidation state (b)Ce is the strongest reducing agent In +2 oxidation state (i (a) Cr,0F + 14H" + GFe? —> 2613+ GFE + 7H,0 (b) 2knIno, ts K,Mind, + MnO, + 0,7 (Ui) Misch metals an alloy that consists of a lanthanold metal (-95%%) and iron (59%) and traces of 5.C Ca and AL Ie used in Mpbased alloy to produce bullets, shell and lighter flint Q5. ()) Account far the following (a) Transition metals show variable oxidation states (b) Zn, Cd and Hg are soft metals, (6) Evalue for the Mn3+/Mn?* couple is highly Positive (+ 1.57 V) as compared to Cr5"/Cr?", (case 2017) its, ee (li) Write one simitarityand one difference between the chemistry of lanthanoid and actinoid elements. Ans. (i) (a) Transition metals have very little difference between ns and (1 ~ 1) Gelectrons and hence Doth can participate in bonding, which results in variable oxidation states. When ns electrons take part inbonding they exhibit lower oxidation states whereas when (n— I)d electrons along with 1s electrons participate in bonding. they exhib variable oxdation states. In Zn, Cd and Hg, all the electrons in d-subshell are paired Hence, weak metallic bonds are BBresent in them. This is the reason, they are soft metals with low melting and boling points {The comparatively high & value for Mn?+/Mn2* is due to the fact that Mn? (5) is quite stable whereas comparatively low Value for Cr°7Cr™ is because of the extra Stability of CO. Therefore. Cr cannot be reduced to Cr (i) Simitarity: Both tanthanoid and actinoid elements show a common oxidation state +3 and both are electropositive and very reactive Difference: Lanthanolds have less tendency to form complexes wereas actinolds have greater tendency to form complexes. 6. (i) Account for the following: (@) Copper (I) compounds are white whereas Copper (ll) compounds are coloured. (b) Chromates change thelr colour when kept in an acidic solution. (Zn, Cd, Hg are considered as d-block elements, but not as transition elements. (li) Calculate the spin-only moment of Co? (Z= 27) by writing the electronic configuration ‘of Co and Co?*, (cast 2020) Ans. (i) (a) Cu’ (3d"2) compounds are white because of absence of unpaired electrons while Cu?* (309) compounds are coloured due to unpaired electrons and they show d-d transition, (b) Chromates change their colour when kept in an acidic solution; because they change to ) Q7. Answer the following: (i) Why are all copper halides known except that copper iodide? (i) Why is the E' yy comparatively low? (iil) Why HCL should not be used for potassium permanganate titrations? (iv) Explain the observation, at the end of each period, there is a slight increase in the atomic radius of d block elements. (¥) What is the effect of pH on dichromate fon solution? ‘ANS. (i) All copper halides are known except that copper iodide because Cu? oxidizes iodide ion to form iodine but copper Tadide Is not farmed whereas ‘other halogens combine to form copper halides. (i) The comparatively tow €° value for Vanadium is due to the stability of V2" (half-filled t2g level) {ii) Potassium permanganate trations in presence of hydrochloric acid are unsatisfactory since hydrochloric acid is oxidised to chlorine. Hence, HCL should not be used for potassium permanganate titrations. ‘The dorbitals complete when it gets filled with ten elzetrons and then it shields the electrons present in the higher s-orbltal to a preater extent resulting in increase in size. So, there is a slight increase In the atomic radius of d block elements atthe end of each period (v) The chromates and dichramates are Interconvertible in aqueous solution depending upon pH of the solution. On increasing the pH (in basic solution) of dichramate ions, a colour change from orange to yellow is observed as dichromate ions change to chromate ions Q8. (Give three points of difference between lanthanoids and actinoids. (ii) Give reason and select one atom/ion which will exhibit asked property: (a) Sc or Cr3: (Exhibit diamagnetic behaviour) (b) Cr of Cu (High melting and boiling point) (case 2020) ans. (\)_ Difference between Lanthanolds and Actinoids value for vanadium dichromates (Cry). (0) Zn, Cd and Hg are considered as d-block elements, but not as transition elements due to completely filled d-orbitals in their ground state as well as in excited state, (i) Electronic configuration of Co (Z= 27) = (Ar) 30” a Co® = (Arad? 8y the electronic configuration of Co2 lon, it Is clear that it has 3 unpaired electrons. Hence, S.No.| _ Lanthanoids ‘Actinolds 1. | Most of the Al actinolds are lanthanoids are | radioactive elements. nonradioactive, | 2. | They donot show| They show a wide a_wide range of | range of oxidation oxidation states. | states. 3, | Most of thelr Ions | Most of thelr ians are arecolourless | coloured, Spin-onty moment of Co, Han (n+ 2) n= 93842) =Vi5 9392 BM WW (@)Sc#: because of absence _of _unpalred electrons. (b) Cr: because of presence of strong intermetallic bonding than Cu.Q9. (Following are the transition metal ions of 3d series: Tite, Mn, Ce (Atomic numbers: Ti = 22,V=25,Mn = 25,Cr=24) ‘Answer the following: (a) Which ion is most stable in an aqueous solution and why? (b) Which ion is a strong oxidising agent and why? (c) Which ion is colourless and why? (ii) Complete the following equations: (a) 2MnO; + 16H" + 5S*. heat (b) KMnO, —> (case 2017) (0) (@) Out of the given four ions, Cr is most stable due to crystal field sptting theory. In Cr, is half-filled. Hence, it Is most stable among the glven other ions. (b) Out of the given four tons. Min Is strangest oxidising agent because in? can easily be ‘changed into Min2* which has @ configuration. itis a stable half-Filled configuration. (@) Out ofthe given four ons, TH Is colourless beacause Xt fag no: uipalad alactrona for excitation tothe higher energy level (i) (0) 2405 5 16H + 55*—> 2M + 84,0 + 5s Ans, a (b) 2kMnO, > KMAd, + MnO, +0,7 Potassium Manganese permanganate manganate oxi. 10. (i) Account for the following: (2) Transition metals from large number of complex compounds. (€) The lowest oxide of transition metal is basic whereas the highest oxide is amphoteric or acidic (¢) E value for the Mn3*/Mn?* couple is highly positive (+ 1.57 V) as compared to Cr*/Cr, (ii) Write one similarity and one difference between the chemistry of lanthanoid and actinoid elements. (case2017) ()(@)Due to the comparatively smaller size of the metal Ions, high ionic charges and the avallabilty_of vacant _d-orbitals for bond formation, ‘ansition metals form a large ‘number of complex compounds (b) In lower oxddation states. transition metals behave Uke metals and metal oxides are Basic_in nature. Thus, In lower oxidation States, transition metal oxides are basic. As the oxidation state increases. its metallic character decreases due to decrease in size. thus. it becomes less metallic or more no metallic, Oxides of a non-metal may be acidic ‘or neutral Thus, in higher oxidation states transition metal oxides are amphoteric or acidic Ans. EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ee (0) The comparatively high €* value for Mn?/ Mn? is due to the fact that Mn?* (dF) is quite stable where, as comparatively [ow value for Go/e be becnuee of the oats stilt of Cee, Therefore, Cr cannot be reduced to a (i) Similarity: Both lanthanold and actinold elements show a common oxidation state + 3 and both are electropositive and very reactive Difference: Lanthanold have less tendency to form complexes whereas actinolds have greater tendency to form complexes Q1L (i) Account for the following: (2) E* value for Mn3*/Mn2* couple is much ‘more positive than that for Cr®*/Cr2 (b) Sc? is colourless whereas Ti is coloured in an aqueous solution. (© Actinolds show wide range of oxidation states. (li) Write the chemical equations for the preparation of KMnO, from MnO,. (0 (a) The comparatively high €° value for Min?*/Min2> is due to the fact that Mn? (05) is quite stable whereas comparatively Tow value for C7 Gre is because of the extra stability of C™. ‘Therefore. Cr cannot be reduced to Cr™. {b) Sc#* does not contain unpaired electrons to undergo ob transition, So. its colourless. TP has one unpaired electron in 3d orbital to undergo dedtransition by absorbing light from Visible region and radiating complementa flout, So. 1s coloured ran aqueous Solution {) There is a greater range of oxidation states in actinolds. It is due to the fact that Sf, 6d and 7s levels are of comparable energies. (ll) The chemical equations for the preparation of tnd, from MnO, are: 2Mni0, + 4KOH + 0,—» 2K, MnO, + 2H,0 3K,Mn0, + 2,50, —-» 2K,S0, + 2KMnO,, + 24,0 haroarion Ans. +Mn0, K:Mn0, HSE» KM, (at anode) (aan medi) (i) (@) How is the variability in oxidation states of transition metals different from that of the prblock elements? {b) Out of Cu" and Cu?*, which ion is unstable In aqueous solution and why? {€) Orange colour of ¢r,03 fon changes to qe. yellow colour when treated with an alkali. Why? (li) Chemistry of actinolds is complicated as compared to lanthanolds. Give two reasons. (cose 2017)ee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ‘ans. (i) (0) The variability in oxidation states of transition metal is due to the incomplete fing of deorbitals in such @ way. that their oxidation states differ from each other by unity. for example. Fe and Fe® etc. in case of pblock elements, the oxidation state differ by units ‘by two. for example. +3 and +5, Moreover, in transition elements, the higher oxidation states are more stable for heavier elements in a group. For example, Mo®* Is more stable than Cr. In prlock elements, the lower oxidation states are more stable for heavier members due {to inert pair effect, for example, PD™ is more stable than PD™. (0) Cur fon Is unstable In aqueous solution than Cu2, This is because. although second ionisation enthalpy of copper_is large, but hydration enthalpy for Cu” is much more ‘negative than that for Cu" and hence. itis more than compensates for the second ionisation enthalpy of copper, Therefore. many Cut Compounds are unstable in aqueous solution ‘and undergo dispraportionation. rcur — a ecu {€) Orange cotour of Cr,0;2-on changes to yellow colour when treated with an alkali because of the formation of chromate ions. c+ 20H —> 2090F + 1,0 oceaiion arate en tongs wu (i) Chemistry of actinolds Is complicated as compared to lanthanoids because (a) Actinoids show a wide range of oxidation states le, 43, +4, 45, and +6 due to small energy difference between Sf 6d and 7s subshells of actinolds. (b) Actinoids are radioactive due to which, their chemistry is complicated 13. (i) Account for the following: (a) 2n?* salts are colourless while Ni2* salts are coloured. (b) Cr?* isa strong reducing agent. (c) Transition metals and their compounds show catalytic activities. (il) Write the tonic equations for the oxidizing action of MnO; in acidic medium with (cost 2023) (a)I-lon, and (b) Fe?* jon, ‘Ans. (I) (a) Zn®* with configuration (Ar)® 3d" has all filled orbitals. Therefore. its salts are colourless. Ni with configuration (Ar! 3¢P has some half: filled orbitals. Therefore, ks salts are coloured (b)Cr2* has @* configuration while Cr?" has more stable d? (ti) configuration, Thus. Cr hhas a tendency to acquire Cr3- due to greater stability of +3 oxidation state Therefore, Cr2° ‘acts as a strong reducing agent. (0)Transition elements have the ability to adopt multiple oxidation states and to form ‘complexes which makes them a good catalyst W (@) 2mn0; +101 + 1G —> 2mn?* +51, + BHO (0) 2Mn0; + IGH* + 10Fe?—> 2Mn® + BHO +10Fe™ QA. Assign reason for each of the following: () Manganese exhibits the highest oxidation state of +7among the 3d series of transition elements. (ii) Transition metals and their compounds are generally found to be good catalysts in chemical reactions. Cr? is reducing in nature while with the same c-orbital configuration (d*) Mn3* is an oxidising agent. (iv) Zn has lowest enthalpy of atomisation. (v) Cu Is unstable in an aqueous solution, ‘ans. (|) Manganese (2 = 25. electronic configuration = (Ar) 305452) contains five unpaired electrons in 3d ‘orbital and 2 electrons in 4s orbital. So. it exhibits ‘oxidation states from + 2 to +7, whichis the largest number of oxidation state exhibited in 3d series (il) This is due to their variable valency and complex forming tendency. Bonds are formed between the reactant molecules and surface atoms of the catalyst at its solid surface. For the bond Formation, metals of first transition series use 3d and 45 electrons, So. the reactant concentration at the catalyst surface increases and the bonds present between reactant molecules become ‘weak leading to decrease in the value of activation energy Thus, transition metals are found to be good catalysts in chemical reactions. (ti) Cr" Is reducing as ts configuration changes from gto & which is a more stable configuration Nin is oxidising as It changes to Nin?* resulting In the half filed o° configuration which has extra ‘Stability. (W)2ine (@ = 30) has symmetrical electronic configuration (Ac}!8 as? 300, As a result dd interactions are negligible and the metallic bonds are quite weak The element has, therefore. lowest enthalpy of atomisation (126 kI mot) in the 3d transition series of elements (v) Cur (oq) is more stable_than Cu? (ag). This is because second lonisation enthalpy of copper Is more, but for Cu? (aq), Sua H Is more negative as compared to Cu* (aq). 50 it compensate more for the second ionisation enthalpy of capper ‘Thus, mostiy copper () compounds are unstable in aqueous solution and disproportionate in the following manner: 2Cu (aq) —> Cu** (09) + Culs)G15. (I) Name two oxometal anions of the 3d series of, the transition metals in which the metal exhibits the oxidation state equal to its group number. (ii) What is the effect of increasing pH on a solution of K,Cr,0,2 (iii) Why is Cu" not stable in aqueous solution? (iv)Name a member of Lanthanoid series which is well-known to exhibit +4 oxidation state. (v)Name two elements of 3d series which show anomalous electronic configuration. ‘Ans. (The two oxometal anions are MnOz and CrO2" Min has +7 oxidation number and group number is 7. Cr has +6 oxidation state and group number is 6. (i) On increasing the pH, KyCr,0 changes into K,CrO, Le orange colour changes to yellow in alkaline medium, (ii) Cu() compounds invatving Cu fons are unstable in aqueous solution and undergo disproportionation. 2Cur—> Cu + Cu ‘The stability of Cu?* lons as compared to Cu* fon Is due to more negative AnH” of Cu2* (ag) than Cu" (ag) which compensates the secondlonisation enthalpy of Cu involved in the formation of Cuion (iv) Cerium ~ CefXe) aF5d°6s2 Formation of Ce™ is favoured by its noble gas configuration Le. Co[ke) 4f° 50° Gs? (v) Cr and Cu are the elements of 3d series which show anomalous electronic configuration, 16. Attempt any five of the following: () Which of the following Ions wilthave a magnetic moment value of 1.73 BM? Sc TH, THY, Cue* Zn? (li) In order to protect iron from corrosion, which one will you prefer as a sacrificial electrode, Ni or Zn? Why? (Given standard electrode potentials of Ni, Fe and Zn are -0.25 V,~0.44V and -0.76 V respectively.) The second ionization enthalpies of chromium ‘and manganese are 1592 and 1509 ki/mol respectively. Explain the lower value of Mn, (iv) Give two similarities in the properties of Sc and 2n, (v) What is actinold contraction? What causes actinoid contraction? (vi) What is the oxidation state of chromium in chromate ion and dichromate ion? (vil) Write the ionic equation for reaction of KI with acidified KMnO,. (cst SOP 2023-24) ‘Ans. () Both TE* and cu?" have I unpaired electron, so the magnetic moment for both will be 1.73 BN (i) Zn.it has a more negative electrode potential so will corrode itself in place of ran (li) Nin* has 364s? configuration and configuration of (v) Sc and Zn both form colourless compounds and they are diamagnetic. (v) The decrease in the atomic and ionic radii_with increase in atomic number of actinoids is actinoid Contraction. It Is caused due to poor shielding effect of Sf electron (4) Inboth chromate and dichromate ion. the oxidation state of Cris (ui) 10F + 2Mn0; + 16H” > 2Mn?> + BH,O+ Sl, (Any five) 17. What can be inferred from the magnetic moment values of the following complex species? Example Magnetic moment (BM) () Ky{MaCn)) 22 ii) [Fe(H,0),)> 53 (ii) KIMnch,) 5.9 (nceRrexencise) Ans. The magnetic moment of a campound Ic given by the relation (h)=Yn(n+2) BM. where n is the number of unpaired electrons, For one unpaired electron (n=) we iftr2) =V3 1738. For two unpaired electrons (a =2}: ne Q2@r2)= Jo =2838M For three unpaired electrons (ns 3}: y= 82) =¥'5 =39780 For four unpaired electrons (0 = 4) ne fa(Gs2) = 24 = 498m For five unpaired electrons (n= 8} n= 5(5+2)= 5 =s9z0m In the light of the above value, let us gather the desired information about the complex species that are mentioned ( KalMn(CN),] Oxidation state of Min: (Mn(CN},) X46 (41) =—4orx2-44+ 6042 ‘The magnetic value of 173 BM. indicates the presence ‘of one unpaired electron in the complex. When six. CN fons (or ligands) approach Mn? ian. electrons in 3d orbitals pair up to make available six vacant orbitals, involving dsp? hybricisation we 4s 4p mazes TT Tsfi] fo une [7 ap? hyaation —————— ot. nena CL 1tTe[e] [Ee] ELE CNON CN CN CN CN ‘The complex s octahedral and is paramagnetic due to ‘one unpaired electron(Fe(H,0),7* Oxidation state of Fe: (Fe(H,O),}2: x + 6 (0) «+2 ‘The magnetic moment value of 53 BM. indicates that there are four unpaired electrons in the complex. This means that the electrons in Fe? ion do not pair up when sic H,0 molecules (or ligands) approach it Since the desired number of vacant orbitals (six) are avallable. the complex formed is sp%¢? hybridsed “The complex is octahedral and is paramagnetic due to four unpaired electrons. It is also called auter orbital complex because 4d (n= 4) orbitals are involved. a KAMaCcl,] Oxidation State of Min (MnCl x44 C1) e—2orxe—2+4o42 The magnetic moment value of 53 8M, indicates that there are five unpaired electrons in the complex This means that all the five 3d orbitals in Mn?* lon are Involved in the bond formation. The complex Is sp? Multiple Choice Questions QL In which of the following compounds manganese hhas oxidation number equal to that of iodine in Ki0,? a. Potassium manganate b. Potassium permanganate © Dimanganese decacarbanyl d. Manganese chloride CuSO, is paramagnetic whil becaus Cu?" ian has 34° configuration white Zn? ion has 3d configuration, Cu?" jan has 34% configuration white Zn? ion has 30° configuration. Cu half filled orbitals while Zn?* has Fully- filled orbitals. 4. CuSO, fs blue In colour while ZnSO, is white Zr and Hf have almost equal atomic and lonic radil because of: 2. diagonal relationship b. lanthanide contraction © actinold contraction 4. belonging to the same group a2. ZnSO, is diamagnetic a3. EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET ee a 4s ® 4d Fe(Z= 26) |] 1] 1,144 t Fe* [Uti [1f4 spe hybridisation aa Sa rettoonl® [1] +] 1] 1] 4 a] Lh E 21h OF; OH,OH:OH © OFOF hhybridised in which one vacant 4s and three vacant 4p orbitals participate Fa 4s © Mo(Z= 26) 171) 4] 444 4 mo [1 i[s]ifi 9 hybridisation C7 imo [4] 4, [+] 1 t] ERT a aac The complex s therefore, tetrahedral in nature. x Chapter Test Q4, The magnetic mament of a divalent ion in aqueous solution with atomic number 25 is: a. 598M b 298M ¢ 698M J 998M Assertion and Reason Type Questions Directions (Q, Nos. 5-6): Each of the following questions consists of two statements, one is Assertion (A) and the ather is Reason (R). Give answer: a. Both Assertion (A) and Reason (R) are true and Reason (R) Is the correct explanation of Assertion (a). . Both Assertion (A) and Reason (R) are true but Reason (R) is not the correct explanation of Assertion (A), © Assertion (A) is true but Reason (R) is false. d, Assertion (A) Is false but Reason (R) is true, Assertion (A):C1?” Is reducing and Mn** is oxidising Reason (R): Cr2* and Mn** have d* configuration Assertion (A): The abllity of oxygen to stabilise high oxidation states exceeds that of fluorine Reason (R): The highest oxidatlon number in the oxides colncides with the group number. Qs. Qo.ee EERE EEE IEEE EE EID EI EI IDI IDI EI IDI ID II II III II II IID IEEE EO ET Case Study Based Question Q7. The transition metals when exposed to oxygen at low and intermediate temperatures form thin, protective oxide films of up (0 some thousands of Angstroms in thickness. Transition metal oxides lie between the extremes of ionic and covalent binary compounds formed by elements from the left or right side of the periodic table. They range from metallic to semiconducting and deviate by both large and small degrees from stoichiometry. Since d-electron bonding levels are involved, the cations exist in various valence states and hence give rise to a large number of oxides. The crystal structures are often classified by considering a cubic hexagonal close-packed lattice of one set of ions with the other ser of ions filling the octahedral or tetrahedral interstices. ‘The actual oxide structures, however, generally show departures from such regular arrays due in part to distortions caused by packing of ions of different size and to ligand field effects. ‘These distortions depend not only on the number of d-electrons, but also on the valence and the position of the transition metal in a period or group, Read the given passage carefully and answer the following questions: (i) Why do cations of transition metals exist in various valence states? (ii) How are oxides and oxoanions of metals formed? (iii) Mention the trend in ionic character when oxidation number of a metal increases, with an example. ‘OR Write two factors on which the distortions in oxides of transition metals depend. Very Short Answer Type Questions Q6. Q9. Explain the following observations. The members of the actinold serles exhibit a Large number of oxidation states than the corresponding members, of the lanthanoid series. How would you account for the following? Many of the transition elements are known to form interstitial compounds. Short Answer Type-I Questions quo. qu. When MnO, is fused with KOH in the presence of KNO, as an oxidising agent, it gives a dark green compound (A). Compound (A) disproportionates in acidic solution to give purple compound (8), An alkaline solution of compound (8) oxidises KI to compound (C) whereas an acidified solution of compound (8) oxidises KI to (0). Identify (A), (8), (Cand (0). Write one similarity and one difference between the chemistry of lanthanolds and that of actinoids. Q16. (i) With reference to structural. vari 12. When chromite ore, FeCr,0, is fused with NaOH in the 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 KCL forms an orange coloured crystalline compound (C). () Write the formutze of the compounds (A), (B) and (C). (li). Write one use of compound (C). Short Answer Type-II Questions Q13. Account for the following: (i) Transition metals and their compounds show catalytic activities. (li) Zn,Cd and Hg are non-transition elements. (lll) Zr and Hf are of almost identical atomic radi Q14. (i) Silver atoms has completely filled ¢-orbitals in its ground state, it is still considered to be a transition element. Justify the statement. (ii) Why are €',, Values of Mn and Zn more negative than expected? (iii) Why do transition metals form alloys? QIS. (i) Why are melting points of transition metals high? (i) Why the transition metals generally form coloured compounds? (iil) Why Evalue for Mn3*/Mn2* couple is highly positive? Long Answer Type Questions lity and chemical reactivity, write differences between lanthanoids and actinoids. (li) Name a member of the lanthanoid series which is well known to exhibit +4 oxidation states. (iil) Out of Mn8* and Cr8*, which is more paramagnetic and why? (Atomic no's: Mn = 25, r= 24). {Iv) Complete the following equation: (1,074 14H" + 6] —> 17. Give reasons: (i) Actinoids show irregularities in their electronic configurations. (i) Transition metals form large number of complex compounds. (iii) Out of Cut and Cu2*, which fon Is unstable in aqueous solution and why? {iv) The lowest oxide of transition metal is basic whereas the highest oxide Is amphoteric or acidic. (¥) Transition metals have high enthalpy of atomisation. el