The d- and f-Block Elements | 291 @ ee Substances containing unpaired electrons are said to be paramagnet Ser Tit) or dC ee is one in which all the electrons are paired. Except the ions of d° (Se) ) (Cu”, Zn” *) configurations, all other simple ions of transition elements SS electrons in their (n~1)d subshell and are, therfore, paramagnetic. The magn ents (HW) of the elements of first transition series can be calculated with the unpaired electrons (n) by the spin only formula. n= Yn(n+2) BM. (Bohr Magneton) (x) Complex formation: The tendency to form lex i (a) the high charge on the ranstion metal ong SS Se © (b) the availability of d-orbitals for accommodating electrons donated by the ligand atoms (xi) Catalytic property: Most of the transition metals and their compounds possess catalytic Lt ala the catalytic activity of transition metal ions is attributed to the following two reasons: (a) Variable oxidation states due to which they can form a variety of unstable intermediate products. (b) Large surface area so that the reactants are adsorbed on the surface and come closer to each other facilitating the reaction process. (xii) Colour: Most of the transition metal ions in solution as well as in solid states are coloured. This is due to the partial absorption of visible light. The absorbed light promotes the electron from one orbital to another orbital of the same d subshell. Since the electronic transition occurs within the d-orbitals of the transition metal ions, they are called d—d transitions. It is because of these d~d transitions occurring in a transition metal ion by absorption of visible light that they appear coloured. (xiii) Non-stoichiometric compounds: They form non-stoichiometric compounds having indefinite compositions and unique structures, ¢.g.. FeOog4 to FeOoog etc. (xiv) Alloy formation: Most of the transition metals form alloys because of their similar radii and other characteristics, transition metals can mutually substitute their positions in their crystal lattices. (xv) Interstitial compounds: Interstitial compounds are those in which small atoms occupy the interstitial ‘sites in the crystal lattice. Interstitial compounds are well known for transition metals because small-sized atoms of H, B,C, N, etc., can easily occupy positions in the voids present in the crystal lattices of transition metals. (xvi) Reactivity: Though the transition clements are sufficiently clectropositive, yet they are not very reactive because of (a) their high heats of sublimation and (b) their high ionization energies (vi) Oxides: Transitign metals form oxides of the general composition MO. M03, MO,,M0; and MO,. Oxides in the lower oxidation states are generally basic in nature and those in the higher oxidation states are amphoteric or acidic in nature. For example, +2 +3 48/3 +4 + MnO Mn 0; Mn;0, MnO, MnO; Basie Amphotede Amphoteric Amphouric Acidic 3. Potassium Dichromate, K,Cr,0,: It is prepared from the chromite ore. 4Fe0.Cr,0, + 8Na,COs +70, P2824 8Na,CrO, + 2Fe20; + 8CO} Chromite are 2Na,CrO, + H,SO, — Na,Cr0, +Na,SO, +H,0 Na Cr,0, +2KCI—> K,Cr,0; + 2NaCl292 | Xam Idea Chemistry-XII K C10, is separated by fractional crystallization. Wher potassium dichromate is heated with any ionic chloride (oa NaCl, BaCl, ete.) and concentrated H,SO,, red vapours ‘of chromyl chloride are of tained. ae K,Cr,O, + 4KCI + 6H,SO4 5 2€r0,,Cl, T_ + 6KHSO, + 3H ‘Cvom eerie Potties tadecnacin to «omens ante pn th nba Wma vanes Bae, K yCr,0, + 4H,S0, —> K 804 + Cry(SO4)s + 4420 +310] Cr,03> +14H* + 67 —2¢r** +7H,0 K,Cr,0, + 41,0—> 2KOH + 2Cr(OH)s +3[0] Thus, potassium dichromate oxidises, (@ Fe?* to Fe** K C10, +7H,80, + 6FeSO, —> K,S0, + Cr3($O,)3 +3Fe2(SO4)3 +720 Cr,037 +14H* + 6Fe?* —— 21+ + 6Fe?* +7H,0 (i) Sn?* to Sn** K,C,0, +14HCI +38nCl; —> 2KC1 + 2CrCl, +38nCl, +720 or, Cr,027 +14H* +3Sn?* —+3Sn** +2Cr°* +7H,0 Gil) HyS 0S K3Cr,0, + 4H,S0, +3H,S —> K,80, + Crp(SO4)3 +7H20 +38 (Cr,02> +14H* +38?” —> 2Cr?* +38 +7H,0 ) SO, to H,SO, K3Cr,0; + H,S0, +380, —> K,S0, + Crp(SO,)3 +H,0 or, C103 +2H* +380, —>2Cr°* +3805" + H,0 Structures of chromate and dichromate ions: 1 On © oO Cr, oe ao ZS oe ™o So 0 4. Potassium permanganate, KMinO: It is prepared from pyrolusite, MnO. Pyrolusite is fused with KOH and an oxidising agent (c.g., KNO3), fused green mass is extracted with water and then Cl, or CO, is passed. ps 2MnO, + 4KOH + 0, “5 2K, MnO, + 2H,0 Pas permngrte 2K MnO, + Cl, —> 2KMnO, +2KCl 3K )MnO, +2CO, ——> 2KMnO, +2K,CO, +MnO, Potassium permanganate behaves as an oxidising agent in neutral, alkaline and acidic medium. Neutral medium: 2KMnO, + H,0—> 2KOH + 2MnO, +3 [0] MnO} + 2H,0+3e” —— MnO, +40H™ Example, 2KMnO, +4H,S——>2Mns | +S + K,SO, +4H,0Alkaline medium: 2KMnO, + 2KROU AK MnO, EHGLO LOL MnO, 40° > MnO} ‘Acidic medium: 2KMnO, + SSO, + K 80, 4 2MnSO, 1,0 1 S10] MnO, 481" 4 Se yMn? hadi. Some important oxidising reactions of KMaO y ate given below: (i) In acid solutions: (a) Iodine is liberated trom potassium fodide: LOL” + 2MnO, +161" > Mn?! 4AM OF ST, (b) Fe?* ion (green) is converted to Fe" (yellow): SFo™ + MnO; 48H! > Mn?! 41,0456"! (6) Oxalate ion ot oxalic acid is oxidised al 333 Ki SC,07° +2MnO, + 16H" >» 2Mn?* 4 BH,O410CO, (@ Hydrogen sulphide is oxidised, sulphur being precipitated: HS —> 2H’ +S? 58? +2Mn0, +161" > 2Mn** +8H,04 58 (eSulphurous acid or sulphite is oxidised (0 a sulphate or wulphurie ae 8802" +2MnO; + 6H? ——» 2Mn?* A1L,045804 (f) Nitrite is oxidised to nitrate: 5NO} +2Mn0; +6H* ——» 2Mn?* 45NO, +3H,0 (i) In neutral or faintly alkaline solutions: (@ A notable reaction is the oxidation of iodide (o iodate: 2Mn0; +H,0+17 ——» 2MnO, +20H™ +10, (b) Thiosulphate is oxidised almost quantitatively (0 sulphate: MnO; +3S,07 +H,0 ——9 8MnO, + 680} + 201° (©) Manganous salt is oxidised to MnO); the presence of zine sulphate or zinc oxide catalyses the oxidation: 2MnO; +3Mn?* +2H,0 ——» SMnO, +411" Mn in KMn0, is sp? hybridized, and the geometty of the permanganate lon, MaOy 2 ie { “i> Ao ‘Tetrahedral manganate Tetrahedeal permanganate (green) ion (purple) ion is tetrahedral as shown.Shreldong effect’ ~ 294 | Xam Idea Chemistry-X!l INNER TRANSITION ELEMENTS ( The inner transition elements consist of lanthanoids and actino' the ‘f° orbitals. 5. Lanthanoides The series involving the ‘filling of 4f orbitals followin lunthenoid series. There are 14 elements in this series: Lutetium Lu (Z = 71). The lanthanoids * are highly dense metals. * have high melting points. * form alloys casily with other metals. < + are soft, malleable and ductile with Jow tensile strengt > tanthanoid elements is +3, (Oxidation state: The most characteristic oxidation OF the state of Some of the elements also exhibit +2 and +4 oxidation states, 's of lanthanoids are coloured. ELEMENTS) a cK ae ‘¢ characterised by filling, of ids. They ar 7) is called the um La c es ‘with Cerium Ce (Z=58) to due to the absorption in (ii) Colour: Some of the trivalent ion i a have partly filled orbitals, visible region ofthe spectrum, resulting in ff transitions Deeau vve 47° or Af elecironic (iii) Magnetic properties: Among lanthanoids, La eed ee ae configurations are diamagnetic and all the other trivalent lanthanoid ions are paramagnetic because of the presence of unpaired electrons. ; - : (iv) Reactivity: ‘All lanthanoids are highly electropositive metals and have an almost similar chemical oi mic number, the atomic and ionic () Lanthanold Contraction: In lanthanoids, with increasing ato Bue radii deereases from one element to the other, but the decrease is very small. {t is because, for aaa i into a 4f subshell, which is every additional proton in the nucleus, the corresponding ‘electron goes into a h too diffused to esd the nucleus as effectively as the more localised inner shell, Hence, the 100 diffused to oreo far the outermost electrons increases steadily with the atomic number. (r) Uses of Lanthanolds: ‘The pure metals have no specific use. So they are used as alloys or compounds. The alloys are called ‘misch metals’ | © Bice! mixed with La, Ce, Pr and Nd is used in the manufacture of flame throwing tanks. * Lanthanoid oxides are used for polishing glass. Neodymium and praseodymium oxides are used for making coloured glasses for goggles. * Cerium salts are used in dyeing cotton and also as catalysts. Lanthanoid compounds are used as a catalyst for hydrogenation, dehydrogenation and petroleum cracking. + Pyrophoric alloys are used for making tracer bullets and shells. 6. Actinoids: The clements following Actinium Ac (Z = 89), upto Lawrencium (Z = 103), are called actinoids. The actinoids @ are highly dense metals with a high melting point and form alloys with other metals, specially iron, @ are silvery white metals, which are highly reactive. @ get tarnished when exposed to alkalis and are less reactive towards acids. (@® Actinoid contraction: The atomic and ionic size decreases with an increase in atomic number. Electrons are added to the 5f shell, as a result the nuclear charge increases causing the shells to shrink inwards. yf. seetres tremsel f go revede por shreleling (i) Blectronic configuration: The actinoids involve the filling of Sf subshells. Actinium has the electronic configuration 6d'7s?. From thorium (Z = 90) onwards, 5f orbitals get progressively(4 ete EO Th hercere Lol The d- and /-Block Elements | 295 filled up. Because of eq regarding the filling of Sf lanthanoids. ae of Sf and 6d subshells, there are some uncertainities and 6d subshells. Most of their properties are comparable to that of ii) CTT a Generally a +4 oxidation state is preferred in actinoids. A few of the actinoid clements exist ina +6 oxidation state, e.g, uranium, neptunium and plutonium. (iv) Colour: The actinoid ions are coloured (v) Magnetic properties: Many of the actinoid ions are paramagnetic, (vi) Reactivity: They are also highly clectroposit Ree mee me nha highly electropsitve and form salts as well as complexes. Many (vil) Uses of actinoids * Thorium is used in the treatment of cancer and in incandescent gas mantles. * Uranium is used in the glass industry, textile industry, in medicines and as nuclear fuel. * Plutonium is used in atomic reactors and in atomic bombs. Differences between Lanthanoids and Actinoids Lanthanoids (i 4forbital is progressively filled. (ii) +3 oxidation state is most common along] with +2 and 44. (iii) Only promethium (Pm) is radioactive. 4 (iv) They are less reactive than actinoids. (x) Magnetic properties are less complex. Actinoids (i) Sforbital is progressively filled. - (id) They show +2, +3. +4, +5, +6, +7 oxidation States. (iii) Al are radioactive. (iv) They are more reactive. (v) Magnetic properties are more complex. q CERT QUESTIONS (INTEXT) QL Ans. Q2 Ans. Q3. Ans. Q4. ‘Ans. ‘A silver atom has completely filled d-orbitals (4d"° )in its ground state. How can you say that it is a transition element 2 Silver (Z=47) can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (44), hence a transition element. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e., 125 kJ mol~'. Why ? In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always involved in the formation of metallic bonds. That is why the enthalpy of atomisation of zinc is the lowest in the series. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why ? Manganese (Z = 25), as its atom has the maximum number of unpaired electrons. Thus, it shows oxidation states from +2 to +7 (+2, +3, +4, +5, +6 and +7) which is the maximum number. The E° (M2* /M) value for copper is positive (+ 0.34 V). What is possibly the reason for this 2 E° (M?* /M) for any metal is related to the sum of the enthalpy change taking place in the following steps: M(s) +4,H —> M(a). M(g)+4,H —> M™ (a), M* (g) aq. ——? M** (aq) + Anya H Copper has high enthalpy of atomisation and low enthalpy of hydration. (A, H= Enthalpy of atomisation) (A, Hl= Tonisation enthalpy? (Aggy, H= Hydration enthalpy) ES (Cu** (Cu is positive.——————— 296 | Xam Idea Chemistry-XIl * (aq) i anced by its hydration enthalpy ‘The high energy to transform Cu(s) to Cu (aq) is not balance i Q.5. How would you account for the irregular (Ca ation of ionization enthalpies (first and second) in first serics of the transition clements ? : : jl ‘Ans. Irregular variation of ionisation enthalpies is mainly attributed to varying degree | stability of differont 3d configuration (e.g. 4°, ‘di, d'? are exceptionally stable). 0.6 Why is the highest oxidation state of a metal exhibited in its oxide or fluoride onl oo sue to smal size and high electronegativity, oxygen oF fluorine can oxidise a metal to its highest ‘oxidation state, * Q.7. Which is a stronger reducing agent— Cr or Fe** and why ? : ‘Ans. Cr2* is a stronger reducing agent than Fe?* because after the loss of one electron Cr** becomes Ce which has more stable 13, (half filled) configuration in 8 ‘medium like water Reason: d ->d? occurs in ense of Cr°* toCr**. Butd® > d° occurs incase of Fe™* toFe™*.Ina medium (like water) d* is more stable as compared to d?. . Q.8 Calculate the spin only magnetic moment of ‘MP* (aq) ion (Z = 27). ‘Ans. Electronic configuration of M atom with Z=27 is (Ar)3d7 4s? Electronic configuration of M2* = (A1) 3d”, ie, ty antl tit 2 Hence, it has three unpaired electrons. bee + Spin only magnetic moment (1) = yin(u+ 2) BM. = V BG+2 BM.=I5 BM. =3.87 BM. Q.9. Cu* ion is not stable in aqueous solution. Why ? ‘Ans. Cu2* (aq) is much more stable than Cu + (aq). This is because although second ionization enthalpy of copper is large but-Ajyy H for Cu (aq) is much more negative than that for Cu* (aq) and therefore it more than compensates for the second ionisation enthalpy of copper. Thus, many copper (1) compounds are unstable in aqueous solution and undergo disproportionation as follows: ‘3Cu* (ag) —> Cu** (ag) + Cu(s) Q.10. Actinoid contraction is greater from clement to element than lanthanoid contraction. Why ? ‘Ans. This is because the 5f electrons themselves provide poor shielding from element to element in the series. ICERT EXERCISES Q.1. Write down the electronic configuration of @cr* (i) Cut (ii) Co™* (iv) Mn* () Pm* (vi) Ce* (vit) Lu (iti) Th’* : Ans. (0 C7 = {Ar}! 3d? (i Cut =[an}* 3a (i Co®* =[Ar}"® 3d” (in) Mn = [Ar 34° () Pm* =[xey 4f95d5 (ut) Ce! = [Xe (vif) Lu?* = [Xey 4f'45a! witty Th** = [Ry os Q2 we) are Mn ‘compounds more stable than Fe** compounds towards oxidation to their +3