the periodic table. d-Block ele- ments are the elements which lie between mtost electropositive s- and most electronega- tive p-biocks in the long form of the periodic table. They ure so called because last clectronin them entersin the d-orbitals of the (-1) of penaltimate (last but One) shell which gets expanded from eight to cighteen by the addition of d-clectrons. Their last two shells are incomplete. They are also called trausition elements because their properties lie in between those of s-block and p-block elements and represent a transition (change) from them. . Definition of transition cicmenis. A trai cH element miay be Getic das an vl whose atom in the ground state or ion in one. of the common oxidation states has incom: plete d subshell i.e. has electrons between 1 to9. General electronic configuration of the tran- sition elements is (4 — 1) d!~!ns!~2 where nis the outermost shell, ‘The definition excludes Zn, Cd and Hg from transition elements because they do not have incomplete d-subshell in the atomic’state or 3. poo | their common oxidation state (viz, Zn , C+, Hg?+) which are 3,4 a0 and 5d" respectively. They do not show pro- porties of transition elements to any appreci- able extent except for their ability to form complexes. In order to maintain a rational classification of elements, they arc generally studied with the d-block elements and arc called non-typical traxsition elements. REMEMBER i Alltransition elements are d-block- elements | but all d-block clements are not transition | elements. To justify this statemeat we take | the examples of'Zn, Cd and Hg which are j the last members of each d-block series. ! These elements are not called transition cle- | ments because they have (n — 1) d! ns?! type of coraplete!y silled electronic con-! figuration and do not show the charac: ! : teristi i of transition elements | Soine exceptions electronic configurations of trensition elements are as follows : L G=3d4s!, Cu=3dqst, TLNb=4d*5s!, Mo=4u5Sst, Ru=4d’5s!, Rh=4a85st, Pd=4dl55°, Ags 4adl055l, ULPt=Sa@6s1, Au=Sad6st Scanned with CamScannerThe irregularities in the observed configura- tions of Cr, Cu, Mo, Pd, Ag and Au are explained on the basis of the concept that half filled and completely filled orbitals ure rela- tively more stable than other d-orbital con- figurations. But it is not easy to explain irregularities found in the observed con- figurations of the atoms of other elements. This can, however, be explained by other factors such as @ nuclear-electronic attraction (i) shielding of one electron by several other electrons i) inter electronic repulsion (js) exchange energy forces. Classification. Each horizontal row of the d-block containing 10 elements is called a transition series. There are {or transition series: {i First transition series or 3 d series (Z = 21—307ie. Sc to Zn) in which 3d subshells is being progressively filled. It is.a part of 4th period. (ii) Second transition series or 4¢ series (Z = 39—48 ie. Y to Gd) in which 4d subshell is being progressively filled. Itis a part of 5th. period. : ‘Third transition series or 5d'series (Z = 57, La and 72~80.¢. Hf to Hg) in which 45d subshell is being progressively filled. It is a part of 6th period. (iv) Fourth transition series = 89, Ac and 104—112;.c.,Rfto Uud-is now a complete series containing ten elements in which 6 d subshell ‘is being progressively filled. It is a part.of 7th period. The outer electronic cunfigtration of Rf, Z = 104 is 62752 and there is a regular increase of one electron in 6 d orbital as Z increases. Thus, there are total 40 transition elements at present in the periodic table. or 6a series (Z 3d series elements Sc Ti Vv Atradius(pm) 144 132 122 4d series elements Y Zr Nb Atcradius(pm) 162 145 134 Sd series elements La HE Ta At.radius(pm) 169 144 134 Cr 82855 849 GENERAL General characteristics (physico-chemical properties) S Transition elements resemble in their physi- cal and chemical, properties as they have similar ns? orbital electronic configuration in the outermost energy shell, n. Thus they are hard metals, have-high tensile strength, duc- tility, malleability and ate good conductors of heat and electricity. They have high melting and boiling points and form alleys with other metals, Their reactivity decreases with the increase in their atomic number. Some of the general characteristics of transi- tion elements are discussed below : |; Atomic and ionic radii. The atomic radii of transition elefnents show the following trends : « (@ They lie in between those of s-andp-bloci. elements i.e., they are smalict than s-block elements and larger than p-block elements in the periodic table. (ii) Ina series, the atomic radii first decre with increase in atomic number upto the mid- dle of the series, then become constant and ct the end of the series show a slight increase. This is due to the fact that in the begining, the atomic radius decresscs s the nuclear charge increases. But with the increase in the d-electrons, scrcening effect incréases which counter balances the increased nuclear charge due to increase in atomic number. As a result, the atomic radii remain practically same after midway of the series. However, near the end of the series, the electron~ electron repulsions betweei the added electrons in, the same d-orbitals are greater than the attractive forces due te increased nuclear charge. This results ix: iis expansion of the electron cloud and thus the atomic radius increases. Ma Fe Co Ni Go Zn 17 AN7 116 15 u7 128 Te ‘Ru Rh Pd Ag Cd 126 «124«= «12528134 HAE Re Os Ir pL Au He 1s 126126129134 14S Scanned with CamScanner(ii) The atomic radii increase down the group from first transition series to the second transition series but the atomic radhi of the second and third transition series are almost the sume. The increase in the atomic radii down the group of the second transition sctics is duc to the increase in the number of shells in the atoms but the similarity in the atomic radii of the elements of second and third transition metals is duc to lanthanoid (/anthanide) coxtraction. Tonic radii of transition metals are different in different oxidaticn states. In gencral, the ionic radii decrease with increase in oxidation state and vice versa. The ionic radii of M2* cations decrease with the increase in atomic number as shown below : M?* cations see ret vet cet Mnt+ Fe?t Cott Nt Cutt Tonicradius(pm) - 9% 8&8 8 8 % 4 72 © M?* cations sot TRY Vet Cot Mn+ Fe} Cott NBT Cult Ionicradius(pm) 75 76 74699 0H———si (56M . Metallic character. All the transition clements are metals having hep, cep or bcc lattices. Metallic bonding is caused due to the presence of one or two electrons in the outermost energy level (ns) and also unpaired d-clectrons. Greater the number of unpaired d-elcctrons, stronger is the metallic bonding and metals will be hard ¢.g., Cr, Mo and W. Thus, transition elements are more metallic than the representative clements. On the other hand, absence of unpaired electrons resullsinaweak inetallic bonding and the metals will be soft e.g., Zn, Cd and Hg. 3. Melting and boiling points. These metals have very high melting and boiling points due to stronger metallic bonding. ‘The melting points of the transition elements first rise to u maximum and then fall as the etomic number increases. Marganese and technetiuns have abnormatly low mc! ng points. Ina particular series, the metallic bond strength increases upto the middl ar of unpaired electrons. Tans Cr, Mo acd W have maximum number of unpaired d- electrons and have highest melting points in their respective series. Tungsten has the highest metting point (3683 K} among the d- bluck elements. As there are no unpaired electrons in Zr. Cd and Hg they have low melting points. Hg ix quia ut ordinary temperature with lowest melting point (234 K) among the transition * Transition elements (except Zn, Cd and Hg) are much harder and less volatile. “They exhibit bigh enthalpies of atomization: The maximum value lies at about middle of each series isdicating that interatomic interaction increases with the number of unpaired d-electrons. The metals of 4d and 5 4 transition series have greater enthalpies of atomization than the corresponding elements of the first (3 d) series. This is duc to much more frequent metal-metal bonding in their compounds. Element Sc Ti V Go Ma Foo Me Enthalpyof 326 473 575 397-281 416. 25430339128 atomization : (J mo!) Density. Because of large number of valence electrons involving ns and (1-1) d-orbitals in transition metals, they have strong metallic bonding due to which these metals possess high densities. iridium has the highest density (22-61 g cms") whereas scandium has the lowest (31g cm™5) andis the lightest transition element. Osmium has slightly lesser density (22:59 g cm73) than iridium, Ionization enthalpies. The first ionization enthalpies of d- block elements are higher than those of s-block elements and are fesser than those of p-block elements. The ionization enthalpies of 3 d and 4d- series are irregular but increase across the series while those of 5 d-series are mutch higher than 3dand4d-clements. This is because of the weak shielding of nuclous by 4f electronsin 5d- transition series which results in greater effective nuclear charge acting on the outer valence electrons. Element Sc Ti ve Cr Mn Fe Co Ni Cu Zn IE, (kJ mol!) 631 656 = «650 652. nT 162 758, TH 74S 90S x = ” Scanned with CamScanner6. Thermodynamic stability of transition metal compounds. Thermodynamic stability of the com. pounds depends upon the values of ionization enthalpics of the metals. Smaller the ionization enthalpy of the metal, stabler is its ermpound. For example, 1 Ey + 1E, for Ni and Pt are 2-48 x 10° and 2:66 ¥ 10? kS mol! respectively Hence Ni (II) compounds are more stable than Pt (ff) compounds. Ox the other hand, 1B, + 1E, + 1 E3 + 1E, for Ni and Pt are 11-29 x 193 and 9-36 x 103kJ mol! respectively. Hence Pt (IV) compounds are more stable than Ni (Iv) compounds. Thus K, [PtCl,] having Pt (IV) is a well known compound whereas K, [NiCI,] is unknown. . Standard electrode potentials (E*) and reducing charact:r. Quantitatively the sta metal ions in different oxidation states in solution ca: he determined on the basis of electrade potential data, The lower the electrode, potential (i.¢., more negutive the standard reduction potential) Of the electrode, more stable is the oxidation state of the transition metal ion in aqueous solution Electrode potential values depend upon energy of sublimation of the metal, the ionization enthalpy a the hydration enthalpy. E® values (M?+/M) for tirst row (3 d-series) transition metals arc given petow : Element Ti v cr Mn Fe Co Ni Cu Zn 2 1° (M2*/M) = 1-63 -1-18 0-90 -L-18 0-44 41-28 -0-25 +: 0-34 -0-75, in volts (V) | EB (M3+/M2+) © 0-37 0-26 0-41 4157 +077 41-97 - - 7 in volts (V) This cata shows that (i) all the elements of 3d-series are good reducing agents except cop- per. However they aze weaker reducing agents than s-block elements. The ions Ti*,V2+,Cr2+ are stroxg reducing agcntsaad willliberate H, from acids, -t 202+ +2H* —> 2Ch+4+H, iZowever, Mn?+ and Co?* behave as strongest oxidising agents in aqueous solution. The irregular E°-values are explained by ir- regniar variation of ionization and sublima- tion enthalpies. (ii) More negative E° values thaa expected for Mz, Ni and Zn show greater stability for Mn?2* (a5), Ni2* and Zn?* (1°). The excep- tional E® value of Ni** is duc to its high negative enthalpy of hydration. (iif) The comparatively high value of E* (Mn3+/Mn?*) shows that Mn?* is very stable which is on account of stable d§ con- figuration of Mn+. - (iv) The comparatively low value of Et (Fe3+ /Fe?*) is on account of extra stability of Fe3+ (D), t dil. (~) The comparatively low value of E (¥3+/V2+) is on account of the stability of V2* jon due toits half-filled 4, configuration (discussed in Unit 25). ,_Avi) Copper is unique in showing positive value of 2°. This explains why it does not liberate fl, gas from acids. The reason for positive value of E® for Cu is that the sum of enthalpies of sublimation and ionization is nc! vatanced by hydration enthalpy. 8. Oxidation states. All transition elements ex the first and the iasi member ia each ics show variable oxidation states. This is because difference of energy in the (1) 4 and ns orbitals is very little, Hence clectzuas from both the energy levels can be used for bond furmation, @ The highest oxidation states of transition metals are found in fiuavides and oxides since fiuorine and oxygen aro. the mest electronegative clements. The highest ox tion state shown by any trazsition element + 8, Both Os and Ru show + 8 oxidation states but the most stable oxidation state is of OsQ,. Manganese shows + 7 highest Scanned with CamScannerThe must common oxidation state of 3d- fon metals is + 2 (exeepl Sc) which shows + 3 oxidation state). Gii) Mostly ionic bonds are formed in + 2 and + 3 oxidation states. But higher oxidation states give covalent hondy. For example, in MnO; and CrQ} where manganese and chromium show + 7 and + 6 oxidation states, all the bonds between metal atoms and oxygens are covalent, {iv) Higher oxidation states are stabitzed by atoms of high electronegativity like O or F whereas lower oxidation states (zero or + 1) are stabilized by digaady which can accept electrons from the metal through a-bending (such as CO) (¥) In going down a group, the stability of higher oxidation states increases while Ghat of lower axidation states decreases. i) Transition metals also show low oxida- tion states of zero and + i in their com- pounds. . ii) The relative stability of different oxida- tion states of eansition metal atoms with respect to oxidation can be determined with the help of standard electrode potential data. For example, E° values for the couples cBt/cPt = - 0-41 volts and Mitt/Mn2* = + 1-51 volts suggest that C+ is unstable and is oxidised to Cr¥* (which is more stable) and acts as a reducing agent whereas Mn? is unstable and is reduced to Mn21 (which is more stable) and acts as an oxidising agent. [t may be noted that both Cr2* and Mn3* are a species, Similarly Fe?* is unstable in acrated water and is oxidised to Fe3* and Cut is unstable in water as it may undergo oxidation to © cut+ Fhe greater stability of Cu2* (aq) than Cut (aq) is duc to much more negative.en:__ -thalpy_of hydration of .Cu2+ (aq) than Ci ‘u* (aq) which more thasi compensates for i¢ high second icnization enthalpy of Cu. The stable oxidation states shown by 3d-tran- sition series are : Sc (111), Ti (IV), V (¥), Cr (V1), Mn (VIN), Fe UE, 141), Co (i, Hi), Ni (), Cu (1) and Zn (I). The maxioum oxidation states correspond in vale to the sum of 5 and d- electrozis upto Mu. 1 hid : First member of each transition series ie., Se, Y, Laand Acda not show variable valen. cy. They show only +3 oxidation state. Catalytic properties. Many transition metals (like Co, Ni, Pt, Fe, Mo etc) and their com- pounds are used as catalysts because of the following reasons : (i) Because of variable oxidation states, they casily absorb and re-emit wide range of ener- gies to provide the necessary activation energy. (ii) Because of variable oxidation states, they casily combine with one of the reactants to form an intermediate which reacts with the second reactant to form the final products. For example, iron (II) catalysed reaction between iodide and persutphate ions 217 + 8,03> — 1, +280}7- can be explained as follows : 2Fe3+ +217 -—> 2Fe* +1, 2+ + $02" ——= 2Fe5™ +251 (iif) Because of presence of free valencie~ on the surface, they can adsorb the reacring molecules, thereby incceasing the concentra- tion of the reactants on te surface and Bence th ‘ of reaction. Por example, 1403 is used in the manufacture of H)SOq by contact process, Co-Th alloy is used in the Fischer-Tropsch process in the synthesis of gasoline (petrol), finely divided Ni 1s used in the hydrogenation of oils into fats platinum is used in the H,SQ, by contact process and in the oxida- tion of ammonia of nitric acid by Ostwald's process, [ron is used in the synthesis of am- monia by Haber’s process and malvbdenum is used as a promoter. Coloured tons, Most of the transition metal compounds are coloured both in 2: soliel state and in aqueous solution Thisis because of the presence of incompletely filled d-orbi- tals. When a transition metal compourd is formed the degenerate d-orbitals of the metal split into ove sets, one (having (hree orbitals dy, dyz and dz culled £3, orbitals) with lower cnergy and the other (having two orbitals de?—y? and a2? called +, orbitals) Scanned with CamScannerwith slightly higher energy in an octahedral field. This is called crystal field splitting. When white light falls on these compounds, some wavelength is absorbed for promotion of electrons from one set of lower energy orbitals to another sc! of slightly higher ener- gy within the same d-subshell. This is called d-d transition. The remainder light is reflected which has a particular colour. Fur example, in case of hydrated Cu?* salts (where H,0 is the ligand), red wavelength is, absorbed and the complementary colour greenish blue, is reflected. Since energy re- quired for d-d transition is very small, radia- tions of light corresponding to such smail amount of energy are available within the visible region of light. [Cu (NH3),]?* ion is violet. as it absorbs _ yellowish green wavelength. [Ti(H,0),)°* ion is purple (mixed effect of blue and red colours) as it xbsorbs yellow wavelength. The complemen- tary colour of blic is yellow and of green is red. Sec3+ .Te* and V_(V) have’ completely canpty d-orbitals and hence are colourless. Similarly, Cu*,Ag*, Au* ,Zn?* , Ca?* and Hg"*+ have completely filed d-orbitals and there zre no vacant d-orbitals for promo- tios of electrons and hence are colovriess. The colours of some of 3 @ metal ions (equated) are : T#+ (3d!) is purple, V4* (3d!) is blue, v3+ Gd?) is green, Cr+ (3d) is violet green, Mn3+ (3 d*) is violet, Cr?* (3 d4) is bine, Mn?* (3 d) is pink, Fe3+ (3 d°) is yel- low, Fe?* (3 2°) is green, Co (3 d’)is pink, Ni2+ ( d$) is green and Cu2* (3d?) is blue. Colours of — Cr,037 , CrO}- , MnO;, MnO3- , Cu,O and Ni-DMG complex are due to charge transfer transitions, Compounds of s and p-block elements are generally white as high energy is required for promotion ofs and p-electrons of incomplete subshells. REUMEMBE i { @ Transition metals are coloured due to! j dd transition and charge transfer tran tion. Colour dus to d-d_ transition shown by transition metal compounds! containing : d',d?, 2, d', dB, d, d7, d8, d? systems. The compounds containing d? and d" con- figurations are coioured due to charge transfer transitions as there is no possibility of dl transitions. | @i) Charge transfer transition always | produces intense colours since the restric- tions of selection rules do not apply to tran- sitions between atoms. MnOg ion has an intense purple colour in solution duc to | charge transfer transition. In MnOg, an electron is momentarily transferred from O. to the metal, thus momentarily changing ! O2- toO7 and reducing the oxidation state | of the metal from Mn (VII) to Mn (VI). » Charge transfer transition requires that the. : energy levels on the two different atoms | involved are fairly close. (iii) The s- and p-block elements donot have | a partially filled d shell so there cannot be any d-d transitions, The energy to promote . ans orp electron toa higher energy level is much greater and corresponds to U.V. fs! | being absorbed. Thus the compound will not ; be coloured. 11. Magnetic properties. Duc to the presence o! unpaired ciectronsin the (1-1) d-orbitals, the most of the transition metal ions and their compounds ave paramagnetic £e., they arc attracted by the magnetic field. As the num- ber of unpaired electrons increases from 1 to, 5, the magnetic moment and hence paramag- netic character also increases. Those transi- tion clements which have paired electrons are diamagnetic i.e., they are repelled by magnetic field. Metals like Fe, Co and Ni possess very high (special type) of paramag. netism where they obtain permanent magetic | momentand are referred to as ferromaguetic Alnico which is an alloy of Al, 12%, Ni, 20%. | Co, 50% and rest Fe is used to make per- manent magnets, The magnetic moment is expressed in Boht magnetoms (B.M.) 1B.M. where h is the Planck’s constant, ¢ is the electronic charge, cis the velocity of tight and vis the mass of electron. Scanned with CamScanneree oe - svt way species depends upon the sw of orbital and spin contributions for cach unpaired electron present. In transition metal ions, the orbital magnetic moment is largely suppressed or quenched by the electrostatic field of other atoms, ions or molecules surrounding the metal ion, Thus the effective magnetic mo- ment arises mainly from the spin of electrons. A paramagetic substance is characterised by its effective magnetic moment (tigq) which is given by the expression Hep = Vii iF 3) BM. where n is the number of ‘unpaired electrons and B.M. stands for Bohr magneton. The above relation is also called “spin only” for- mula to determine eg. Using spin only for- mula, the /1¢y values for various number of unpaired electrons is given below : Ton Sor Tet) Tet | met | vet | crt [att Tree Tce [ni [ut [zn Elect. config. oe | ee ee ee eee ele glere [@ | ae No. of unpaired oO a 2 3 4 5 4 3 Olea oj electrons | \He¢p (B.M.) 0 1-73 | 2-83 | 3-87 | 4.90 | 5-92 | 4-90 | 3-87 | 2.83 i 1-73] 0 (Calculated) j { 1 (Observed) a 1-75 | 2-76 | 3-86 | 4-80 | 5-96 | 5.3- 1 i 1-8- 0 | I 5:5 3-9 | 2-2 Thus, the magnetic moment or paramagnetic property of a substance increases with in- crease in the number of unpaired electrons. Mercurous ion is diamagnetic in nature which explains that it exists as dimer, Hg3* and not as monomer, Hg* | REMEMBE i | The magnetic moment #¢¢ of a transition | | metal can give important information about } ' the number of unpaired clectrons present in | ' the atom and the orbitals that are occupied | ' and sometimes indicates the structure of the | | molecule or complex. If the magnetic mo- ! ment is due entirely to the spin of unpaired | | electrons, then t | Meg = VISCFT) BM. i | where $ is the total spin quantum number, | This equation is related to the number of | i unpaired electrons n by the equation { | Mg = Var 3 BM. ! ei nn | 12, Complex formation. Transition metal ions form a large number of complexes in which the central metal ion is linked to a number of ligands. This is because of the following char- acteristic propertics of transition metal: @ They have high nuclear charge and small size i.e. charge/size ratio (charge density) is large. 13. (i) They have. empty d-orbitals to accept the lone pairs of electrons donated by the ligands. ‘Thus in complexes metal ions behave as Lewis acids and ligands behave as Lewis bases. Complexes can be linear (sp-hybridization), Square planar (dsp?-hybridization) tetra- hedral (sp>- hybridization), octahedral (Psp?- hybridization) oz trigonal bipyracsidal (sp3d- hybridization), The stability of complexes increases with in- crease in atomic number of the element in a series aad with decreasing size of its atoms. Moreover, higher valent cations form more stable complexes, Interstitial compounds. Transition metals form a number of interstitial compounds in which small non-metal atoms such as H, C, B, N and He occupy the empty spaces (jntersti- tial sites) in their lattices and also form bonds with them. These new compounds known us hydrides, carbides, borides, nitrides and helides respectively have higher melting points than those of pure metals, retain metallic conductivity, are chemically inert, hard and rigid eg., stecl and cast iron which compounds of Fe and C are hard where maileabitity and ductility of the metal decreases but tenacity increases. Scanned with CamScanner14, . Applicati Alloy formation. Due to simitarity j i sizes, atoms of onc transition mel ea easily take up positions in the crystal lattice of the other in the molten state and arc miscible with each other forming homogeneous solid solutions and smosth alloys on cooling, Al- loys are generally harder, have higher melt Points and more resistantto corrosion than the WandMnareuscalstiere ence ee nesk aad tales seed steels. Alloys containing mercury as one of the constituent elements are called amalgams. Fe and Pt do not form amalgams, Non-stoichiometric compounds. Non- stoichiometric compounds are those in which the chemical composition does not cor- respond to their ideal chemical formulae. The compounds of transition metals with O, S, Se and Teare generally non- stoichiometric and have indefinite composition. The non- stoichiometry is due to 4) variable valency of transition metals and (ii) presence of defects in their solid state (structure). For example, wustite contains Fe and O atoms and the composition varies between. Fep.g4O and Feo.9,0. Therefore, ferrous oxide should be written with a bar over the formula FeO to indicate that the ratio of Fe and O atoms is not exactly 1 :.1. VHp.s6y TiH,.7 are other examples of non- stoichiometric compounds. ans of d-block elements and their compounds. (1) Iron and steel. The most abundant transition metal, iron and steel (ab- tained by adding suitable amounts of C and, metals like Cr, Mn and Ni to iron) are most important construction materials. (2) Coinage metals. Group 11 elements Cu, Agand Au called coinage metals are used in making coins. For example, UK copper coins are copper coated steel. UK silver coins are made of Cu-Nialloy. Gold and silver are used in making jewellery. (3) Zinc, nickel and cadmium are used in the battery industry. (4) Compounds for special purposes. TiO, is used in pigment industry while MnQ, is used in dry battery cells. (5) As catalysts in chemical industry. For example, (i) V0 and Pt used for oxidation of SO, te SOy in the contact process for the manufac. ture of H2SO,. (ii) TiCl, + Al(CHg)3, called Ziegler-Natti. catalyst is used in the manufacture of polythene (polymerisation of alkenes). (ii) Fe + Mo are used as catalyst and promoter in the manufacture of NH, ty Haber’s process. (iv) Ni (finely divided) ‘is used in the een of oils to convert them inte fats. (v) PdCl, is used as catalyst in the Wacker process for the oxidation of cthyne {a ethanal. (vi) Rh-complex (Ph,P);RbCI called ‘Wilkinson's catalystis used inthe hydrogena tion ef alkenes. (© In photographic industry. AgBr which i very sensitive to light is used in making c: photographic films. i (7) TiCl, and TiO, are used in smoke screens ; tantalum is used in surgical venal:- and analytical weights; chromium is used in stainless steel and chrome plating ; molyb- enum is used in X-ray tubes ; platinum is used in resistance thermometers ;zincis uscd, in galvanising iron sheets while cadmium: used for making joints in jewellary. TiO, is also used as white pigment in paints. Cerius:) is used as a scavenger of oxygen and sulphur in many metals. i (8) There are many compounds of transit metals which are used as catalysts. For example,’ Adam's catalyst—PUPtO Brown's catalyst —Nickel boride (9) There are many compounds of transition, clements which are used as reagents in laboratory/industry. For example, Bacyer’s reagent — Dilute alkaline solutioa KMn0, Tollen’s reagent—AgNO; solution 4 NaOH solution + NH,OR Nessler's reagent— Alkaline solution of Ka[Helat Scanned with CamScannerBenedict’s solution— CuSO, solution + sodium citrate + Na,CO, Febling solution A — CuSO, solution Fenton's reagent—FeSO, + H,0, Etard’s reagent—Cr0,Cl, Bordeaux mixture CuSO, solution + lime Luca's reagent—conc. HCI + anhydrous ZnCl, Barfoed’s reagent—Cu(CH,COO), + CH,;COOH Milon’s reagent—Solution of mercuric and mercurous nitrate (10) Scheele’s green is a bright green com- pound of cupric arsenite Cus (AsO;)).2H,0 used as pigment and in- secticide. Paris green also known as Schwein furt green is cupric aceto arsenite Cu (CHjCOO),3Cu (AsO,), used as pig- ment, insecticide and wood preservative. (11) Schweitzer’s reagent is blue coloured [Cu (NH,),] SO, complex salt which is used for dissolving cellulose in the manufacture of tificial silk. | © Lightest transition metal is Sc, heaviest | | and densest transition clement is Ir, transi- | | Hon metal having highest melting point is W | | and having lowest melting point isHg. | | Gi) Thesyathetic transition metal is Te while | | the synthetic lanthanoid is Pm. ! | (ii) Fe, Co and Ni are called ferrous metals # ; Ru, Rh, Pd, Os, Irand Pt are called platinum’; | metals whereas Cu, Ag and Au are called | | coinage metals, i (iv) Both Au and Pt are inert and noble me-' ; tals but they dissolve in aqua regia (3 Parts , cone. HCl +1 part conc. HNOs) due to the | ; formation of HpPtCl, and HAuCl, respec- | | tively, i i (+) Finely reduced form of Pt in the form af| | velvety black powder is called platinum } ck, | | | (#) A mixture of TiO, and BaSO, is called | dtanox ».nite a mixture of ZnS and BaSO, is | galled tithopone, FeSO,.7H,O and ZnSO4.7H,0 are : | isomorphous. ' (viii) Basic copper acetate ' (Cu(CH,COO),.Cu (OH),) is called Ver- digris which is used as a green pigment in paints, (&) Copper acetate, Cu, (CH,COO),.2 H,0 is dimeric in vapour state. (&) Silver is not attacked by aqua regia but it Feacts with conc. HaSO, and HNO3. (i) Mercury does not react with steam or water and hence cannot form any hydroxide. (xii) Rinman’s green is green pigment con-| taining Zn0.CoO. (xii) Zinc sulphide containing trace of radium salt (1 part in 10 million parts) is used. | as luminuous paint for watch dials. (xiv) Due to high ionic potential (charge/radius ratio), transition metal ca- tions generally undergo hydrolysis in‘ aqueous solution. x») Most stable oxidation state for Cu is + 2, Agis + Land for Auis + 3. (xvi) The monovalent Cu*, Ag+ and Aut salts are insoluble in water and colourless except Cu,0 which is red. The red colour is duc to charge transfer transitions. (xvii) Most abundant transition metal is iron. (wii) Copper is second most useful metal: (the first being iron). (xix) Mercury is the only transition metal which is liquid at room temperature. This is due to the very high ionization. enthalpy makingit difficult for electrons to participate in metallic bonding, 17. General properties of first row transition 1/7 metal compounds. (a) Oxides and oxometal ions, (i) Oxides of metals in low axidation ‘states + 2and + 3 (MO, MO, and M,O,) are generally basic except Cr,0, which is amphoteric in character. (ii) Oxides of metals in higher axidation states 2 +5 (MOs,MO3,M,07) are generally idic in character, }) Oxides of metals in their intermediate axidation states + 4 (MO,) are generaliy amphoteric in nature, Scanned with CamScannerBesides the oxide: an s, the oxocatioy i stabilise V (V) species is Vos, V (IV) species is VO2+ i Tio2*. and Ti (IV) species is (@W) As the oxidation . the oxide increases, soe te metal in decreases and acidic cha Thus, a 4200 -48/3 43 a MnO Mn,0, Mn,0; MnO, Mn,0, —— Ionic character decreases —— Acidic character increases (b) Halides. (i) The order of reactivity of halogens with 3 d-transition metals is F > Cl >Br>L Gi) Metals form fluorides in their highest oxidation states since fluorine is most reactive and oxidises the metals. (iii) Haalides in higher oxidation states of the metals get easily hydrolysed giving white fumes in air due to the formation of hydrogen balideseg., 7 TiCl, + 2H,O —> TiO, + 4HCI (iv) Fluorides of metals are ionic and ionic character decreases from fluorides toiodides ice., ionic character is in the order M-F > M-Cl > M-Br > M-1 Cu, is ionic while CuCl, and CuBr, are covalent. (©) Sulphides. (#) Sulphides are formed with metals in their lower oxidation states as sul- phur is not a geod oxidising agent. (@ Sulphides are usually coloured and ar insoluble in water. eg, MaS is flesh coloure: black while ZaS is di character ‘acter increases. ore or ferrochrome or chrome iron (FeCr30, or FeO.Cr,03) through the following steps : (@ Fusion of the ore with molten alkali in presence of air to obtain sodium chromate 4 FeCr,0,4 + 16 NaOH + 70, — 8 Nay CrO, + 2Fe203 + 8H,0 ees or roasting of the ore with NayCO and quick lime in presence of air 4 FeO . Cr,03 + 8Na,CO3 + 70,—> 8 Na,CrO, + 2 Fe,03.+ 8 CO, ‘The fused or roasted mass is extracted with water and filtered. (i) Conversion of sodium chromate into sodium dichromate by treating the filtrate with dil H,SO, 2Nay CrO, + H,SO, — Na,Cr,07 + Na,SO, + H,0 Na,SO, being less soluble is separated as Na,SO,.10 H,0 by fractional crystallisation. (iii) Conversion of sodium dichromate into potassium dichromate by heating with KCI Na,Cr,07 + 2 KC] —> K,Cr,07 + 2 Nacl Potassium dichromate being less soluble is obtained by fractional crystz'lisation. 2. Properties. (i) These are orange red coloured crystals soluble in water. ; (i) In the solution, dichromate’ ioss (Cr,03-) exist in equilibrium with chromate ions (CrO3~) as follows : = cr,07- + HO = Orange Ht In alkaline solution, equilibrium shifts in the forward direction and the solution is yellow. In the acidic medium, equilibrium shifts in the backward’ direction and the solution is orange. This conversion takes place with change in pH of the solution. Gil) Itis a strong oxidising agent in the acidic. medium K,Cr,07 + 4H,SO, — K,S0, + Cr, (SO4)3 + 4H,0 + 3(0) Inother words Cr.037 ion takes up electrons and hence acts as an oxidising agent CrOF + 14Ht + 6 7 — 203+ +7H,0 (B= +1 (ase reaction Cr (+ 6) is reduced to 2CrOj- + 2H* ‘Yellow Therefore, equivalent weight of KyCr30. one sixth the molecular mass of KsCrj0; 294/6 = 49, _ Scanned with CamScannerOxidation of some substances is given below : (vi) Action of alkalies, When an alkali 1s 2KI + HySO, + (0) — added to an orange red solution of dichromat Me i S04 + H,0 +1 yellow solution results duc t as} e: Riana the formation of chromate q 2 2 2K,Cr.07 + 2KOH — 2K, C104 + H,0 2 FeSO, + H,SO, + (0) —> On acidifying, the colour again changes to Fe, (SOy)3 + H,0 * orange red due toreformation of dichromate Na,SO, + (0) —> Na,SO, 2KCrO, + H2S0, — Na,S,03 + (0) —* Na,SQ, + $ K,€r,07 + K,SO, + 0 NaNO, + (0)—> NaN (vif) Action of concentrated sulphuric acid. laNO, + (0) laNO3 (a) Incold, red crystals of chromic anhydride 2HCI + (0) —+H,0 + Ch (CrO,) are formed. CrO is highly acidic and SO, + (0) + H,O —> H,80, is called “chromic acid”. SnSO, + HySO, + (0) -—* $n (S04) + HO K,Cr,07 + 2HSO, — CH,CH,OH + (0) —> CH,CHO oo 2.CrO, + 2KHSO, + H,0 Ethanol HO acetaldehyde (6) On heating, oxygen is evolved © oe 2 CH;COOH “2K,Cr,07 + 8 HSO, -— aint a Aeteott 2K,$0, + 2 Cr, (SO,); + 8H,0 +30," 2 eee ean SRO, an aa (viii) Reaction with H,03. Acidified solution : . sy, of dichromate ion forms a deep blue.colour HSO ies Ee chloride with H,0, due to the formation of. peroxo (Cr0,C1,) i compound [Cr0 (0,)3] or CrOs, The blue K,Cr,0, + 4KCl + 6 HSO, — colour fades away due to the decomposition 2.Cr0, Cl, + 6 KHSO, + 3,0. of CrOs to Cr3* and oxygen. ‘These are passed through dilute NaOH solu- es couse tion to give yellow solution, of NayCrO,. Ye!- CrOF + 4,02 + 2HT— Iow solutionis acidified with CH,COOH and 2Cr0; + 5H,0 — lead acetate solution is added to give yellow o oO precipitate of PbCrO, The structure of CrOsis_ | Ce | in Cr0,Cl, + 4NaOH — OO ° NagCrOq+ZNaCl +210 which Cris in 4 6 oxidation state, Na,CrO, + Pb (CH;COO), —> 3. Uses. In volumetric analysis, in chrome tan- PbCrO, + 2CHyCOONa ning in leather industry, in the preparation of yellow ppt +. chrome alum, in calico printing and in or- This reaction is used in the detection of ganic chemistry as an oxidizing agent. chloride ions in qualitative analysis. () Action of heat. When heated to a white heat, it decomposes with the evolution of oxygen * 7 A _ REMEMBE} K,Cr,07 is preferred to in volumetric analysis (titrations) because } _ the Na-compound is hygroscopic whilst the , 4K Ct)07 OS 4 Ky CrO, + 20703 +30, | sala is not, Thus K,Cr,0; can be used as a primary standard, Scanned with CamScanner4, Structures of chromate and dichromate ions. i : J™ ‘0 ° \ ° Chromatic ion ©: e oe Oo 126° ‘Two tetrahedra sharing one ‘oxygen atom at one corner Structure of chromate ion CrO}” is tetrahedral (Cr is sp>-hybridized) in which all Cr-O bonds are equivalent. The dichromate ion (Cr,0;)?- consists of two tetrahedra sharing an oxygen atom at the common comer. Here all Cr-O bonds are not equivalent. The two Cr-O bonds which share an oxygen atom at the common vertex of the two tetrahedral units are /onger (bond length 179 pm) than the other equivalent six Cr-O bonds (bond length 163 pm). The Cr-O-Cr bond angle at the common vertex is 126°. Here Cr (VI) in CrO}~ and Cr,037 has d° configuration, so the yellow and orange colours respectively arise from charge trans- + ferand not from d-d transition. 1:-Preparation. It is prepared from pyrolusite ore (MnO,) through the following steps : (@ Conversion of pyrolusite into potassium manganate. The finely powdered pyrolusite ore is fused with KOH or K,CO; in the presence of air or oxidising agent such as KNO, or KCIO; (potassium chlorate) to give green coloured potassium — mangana:+ (K,MnO,) 2MnO, + 4KOH +O, — . 2K,MnO, + 2H,0 2MnO, + 2K,CO; + 0, — 2K,MnO, + 2CO, MnO, + 2 KOH + KNO; — K,MnO, + KNO, + HO 3MnO, + 6KOH + KCIO, — 3K,MnO, + KCI + 2H;C Gi Oxidation of potassium manganate %¢ potassium permanganate. (a) Chemical oxidation, The fused mass is extracted with water and the solution after filtration is con- verted into KMnO, by bubbling CO;, Cl, or ozonised oxygen through the green solution. 3K,MnO, + 2CO, — 2KMnO, + MnO, | +2K,CO3 2K,MnO, + CL —> 2KMnO, + 2 KCL 2K,MnO, + H,O0 +O; — 2KMnO, + 2KOH + 0, K,MiO, undergoes disproportionation in « neutral or acid medium to give KMnO,. 3MnO}~ + 4H+ —> 2KMn0, + MnO, + 2H;0 (6) Electrolytic oxidation. This is the most preferred method, The manganate solution is electrolysed between iron electrodes. separated by diaphragm. The electrode reac- tions are as follows : Scanned with CamScannerMnOQ}" —> MnOZ + e~ Green Purple At cathode: 2H* + 20e7—+ Hy The oxygen evolved at the anode converts manganate to permanganate 2K,MnO, + H,0 +O —> 2KMnO, +2KOH The solutions filtered and evaporated to get deep purple black crystals of KMnQ,, 2. Properties. (i) It is a deep purple crystalline solid, moderately soluble in water at room temperature. (ii) When heated to 746 K, it readily decom- poses giving oxygen 2KMn0, aE M00, + MnO, + 0; T46K Pot. manganate Atred heat, K)MnQ, further decomposes to potassium manganite (K,MnO3) and oxygen At anode : Red heat 2K,MnO, ————> 2K,Mn0, +0, Gi) With well cooled conc. H,SO4, KMnOs gives Mn,O, (an explosive oil) which on warming decomposes to MnO, 2KMn0, + 2,80, — Mn,0; + 2 KHSO, + H,0 2Mn,0, —> 4MnO, +30, With warm conc. H,SO,, 0, gas is evolved 4 KMnO, + 6H,SO, — 2K,SO, + 4MnSO, + 6H,0 + 50, (iv) When heated in a current of Hp, solid KMn0, gives KOH, MuO and water vapours 2KMn0, + 5H, —> 2KOH +2Mn0 +4H,0 (v) Oxidising property. KMnO, is apowerfirl oxidising agent. (a) In neutral solution. Jt acts as a moderate oxidising agent because of the reaction 2KMnO, + H,O — 2KOH + 2Mn0, +30 or MnOZ + 2H,0 + 3e7 —— MnO, + 4007 In fact, during the course of reaction, the alkali generated renders the medium alkaline even when we start with neutral medium. Obviously, the equivalent weight of KMnO, in alkaline and neutral media is the sante ie, one third of its molecular mass ie., 158/3 = 52-6. A fow examples of substances oxidi 2KMnO, + 3 MnSO, + 2H,0 — K,S0, + 2H,SO, + 5 MnO, BKMn0, + 3 Nay$,0, + HO — 3K,SO, + 8 MnO, + 3 Na,SO, + 2KOH 2KMnOQ,+4H,S —> : 2MnS + S + K,SO, + 4H,0 (6) In alkaline solution. It acts as a strong oxidising agent because cf the reaction Strongly alkaline 2KMnO, + 2KOH —————> 2K,MnO, + H,0 +O MnOj + e~ —> MnOQZ" (E* = + 0-56 V) :. Equivalent weight of KMnO, dare: Mol. wt. _ 158 =r 1 = 158 K,Mn0,is further reduced to MnO when a reducing agent is present ‘Weakly alkaline K,MnOg + 40 ————> MnO, + 2KOH +O or MnOZ” + 2H,0 + 2e7 —> MaO, + 40H7 So the complete reaction is Weakly alkaline 2KMaQ, + H;Q —————> 2MnO, + 2KOH + 30 or MaQz +2H,0 + 3e7 —> MnQ, + 4OH™ (E* = + 1:23 V) which is the same as that formeutral medium. A few examples of the substances oxidized are: 2KMnQ, + H,0 + KI 4+ 2MnO, + 2 KOH + KIO; Pot iodate CH, CH,OH | +4j0+0—+ cH, CH.OH Vu tear Vaivtene glyco! Scanned with CamScannerAlkaline KMnO, when used for olefinic compounds, it is called Baeyer’s reagent. C(HsCHy + 30 —* CgHsCOOH + 1,0 Toluene Benzoic acid (© In acidic medium. In presence of dil. H,SO,, it acts as a strong axidising agent be- cause of the reaction 2KMnO, + 3H,SO, — K,SO, + 2 MnSO, + 3H,0 +50 or MnOz +SHt++5e7 —> Mn?+ + 4H,0 (E° = + 1:51 V) Thus, the equivalent weight of KMnO, is one fifth of its molecular mass ie. 158/5 = 31-6 ‘A few examples of substances oxidised are : 6 KMnO, + 10 FeC,0, + 24H,S0, —. * 3K,SO, + 6 MnSO, + 5Fe2(SO,); : + 20CO, + 24,0 2FeSO, + H,SO, + (0) — Fe, (SO,)3 + H,0 H,0,+0 —> H,0 +0, CH,0, + (0) —> 2CO, + H,0 Cxalic acid HS +(0) —> H,O+S SO, + (0) + H,0 —> H,SO, KNO, + (0) —> KNO3 Na,SO3 + (0) —> Na,SO, 2KI + H,SO, + (0) —* K,S0, + H,0 +h 2HX #(0) — H,0 +X) (K=CLBr,1 CH,CH,OH + (0) — CH,CHO + H,0 Ethyl alcohol Acetaldeyde From the reactions discussed above, it is clear that when KMnO, acts as an oxidi ing agent, it itself is reduced to different spectes such as MnO37 or MnO; or Mn?* as shown by the following half reactions MnOj + e7—* Mn037 5B” = +0°56V MnO; + 4Ht +3e°— MnO, + 2H,0 58° = + 1:69V MnO; + 8H* +5e°—* Met +4H,O;B = + VSLV In these reactions, H* ion concentration plays an important role in influencing the reaction kinetics. At [H*] = 1M, MnO; should oxidise water (E°,, for H,0 = — 1-23 V) but the reaction is extremely slow unless either Mi in2* ions are present or | @ InKMnO, titrations, only sulphuric acid is found to be suitable for making the solution ic because it does not react with KMn0O, or the reducing agent used. KMn0, titrations for acidifying the solution ! | Gi Hydrochloric acid cannot be used in | | as it reacts with KMnO, and introduces an | i error into the results, | | 2MnOj + 10CI” + 16H* — i | 2Mn?* + 5Cl, + 8H,0. | Gii) Nitric acid cannot be used in KMnO, | | titrations as it itself is an oxidising agent and ' | reacts with reducing agents. 3. . Uses. In volumetric analysis, as a strong oxidizing agent in the laboratory as well as in industry, as’Baeyer’s reagent for testing un- saturation, as disinfectant and germicide. 4. Structure of permanganate ion. Mn in MnO; undergoes: sp*-hybridization and hence. four oxygen atoms are arranged tetrahedrally around manganese. Here, Mn (VII) has d° configuration, so the deep purple colour arises from charge transfertran- sition and not from d-d transition. ° 7 Rr | JS Tetrahedral st Permanganate ion RED mm i () Equivalent mass of KMnO,. Equivalent! mass.of an oxidising agent is the number of} | parts by mass of it which give 8 parts by mass, | Of oxygen or itis the molecular mass divided! | by the number of electrons gained by one, Scanned with CamScannermolecul tion. If M is the molecular mass of KMnQ, , (M = 39 + 55 + 64 = 158), then we have (a) In acidic medium \ 2KMnO, + 3 H,SO, — 2M | K,SO, + 2MnSO,+3H,0+ 50 SX 16 = 80 parts | or MnO + 8H* + 5e~ —> Mn** + 4H,0: s+ Equivalent mass of KMnO, (&) In neutral and weakly alkaline medium | { 2KMnO, + H,O —> 2KOH + 2Mn0, 2M | + 30 |! 3.x 16 = 48 parts| or MnOz +2H,0 + 3e7—> MnO, + 4OH™ Equivalent mass of (©) In strongly alkaline medium 2KMnO, + 2KOH— 2K,MnO, + HO + (0) or MnOz +e7—> MnO{- Equivalent mass of KMnO, M _ 158 _ = MAB = 158 (ii) Equivalent mass of K,Cr,07 In acidic medium K,Cr,07 + 4H)SO, —> K,SO, + Cra(SO4)3 1M +4H,0+ (30 3x26 = 48 parts) or Cr,0}- + 14H* +607 — 2Cr+ +7H,0 © Equivalent mass of M K,Cr,0, =F = = 49 (M of K,Cr,0, 2x 39+2x52+7x 16) = 78 + 104 + 112 = 294) IL f-BLOCK ELEMENTS (INNER TRANSITION ELEMENTS- LANTHANOIDS AND ACTINOIDS) The f-block consists of two series, lan- thanoids (the fourteen elements following lanthanum) and actinoids (the fourteen ele- ments following actinium). @ LANTHANOIDS AND ACTH 1. Lanthanoids. The elements with atomic numbers 58 to 71 i.e. cerium to lutetium (which come immediately after lanthanum Z, = 57)are called lanthanoids or lanthanides or lanthanones or rare earths. These ele- ments involve the filling of 4 - orbitals and are also called 4f-block elements ot first inner transition series. Their general electronic configuration is [Xe] 4f 1~¥4 5 d°-1 6s? Promethium (Pm), At. No. 61 is the only syn- thetic (man made) radioactive lanthanoid. Because La closely resembles the lanthanoids, it is also included among the lanthanoids for which the general symbol Ln is often used. . Actinoids. The elements with atomic num- bers 90 to 103 ie. thorium to Jawrencium (which come immediately after actinium, Z = 89) are called actinoids or actinides or actinonés. These elements involve the filling of 5 f-orbitals and are also called 5 f-block elements or second inner transition series. Their general electronic configuration is [Ra] 5f1-4 60-1752 They include three naturally occuring elements thorium, protactinium and uranium and elevert transuranium elements or transitranics which are produced artificially by nuclear reactions. ‘They are synthetic or man made elements. All actinoids ‘are radioactive. Discussion of ac- tinoids also includes Ac besides the fourteen elements constituting the series. Both lanthanoids and actinoids are collec- tively called f-block elements because last electron in them enters into f- orbitals of the antepenultimate (j.e., inner to penultimate) shell partly but incompletely filled in their elementary or ionic states, The name inner transition elements is also given to them be- cause they constitute transition series within transition series (d-block elements) and the last electron enters into antepenultimate ny Scanned with CamScannerthe general electronic configuration of f- block elements is (n-2y f=) PF ns? shell (n-2)f. In addition to incomplete d-sub- shell, their f-subshell is also. incomplete. Thus, these elements have three ee hells i.e., (n-2), (n-1) and n shells an , : Cacti ie are listed in the following table 3. Electronic config. of lanthanoids and actlnoids Taninanoas T 2 Actinoids j Name] Symbol | At. | Configuration I Symbol | At | Configuration 1 No. aan [Ee [87 | pe sdtoat Actinium [Ae | 6 [iRnjeai7e | Cerium al ce | 53 [Xe] 4f2 8.652 |Throrinm Th 90 |[Rn] 5/96 a2 757 Y Prascodymium | Pr | $9 | [xXc}435d%6s2_ |Protactinium | Pa | 91 lrnjs fod! 752 Neodymium Nd | 60 | [xep4s4sc? 6s? [Uranium Ui | 9 |[Rals f36 at 7s? [Promethium Pm | 61 | [xe] 4f55d%Gs? |Neptunium Np | 93 |pRnjsf46d! 75? [Samarium Sm | 62 | [xep4f65d%Gs2_ [Plotonium Pu | 94 |[Rn]5 £69752 Europium Eu | 63} [xe]4f75a%652 |Americium Am | 95 iRn|5 £76975? [Gadolinium Gd | bt] [xeyas75a!Gs? [Curiam cm | 96 Rn} f76d! 752 Terbium To |} 851 [xe] 4f95a%G52 [Berkelium Bk | 97 |frays ye? 64°75? Dysprosium Dy | 66 | [xejafi95 ast |Californium | cr | 98 liRnsf!06 40752 {Holmium Ho | 67 | (xe]4f!15a%6s2 |Einstcinium Es 99 ferns fh 6 P72 | |Esbiam Er | 68 | pxe4p2sd06s? |Fermium | Fm} 100 |{R0j S26 0072 L Thulium Tm | 69] (xejas sas? |Mendelevium| Ma | 101 jiRn sf 649752 \ /Ytterbium Yb | 70 | [xXe]4#!45a%6 52 {Nobelium No 102 |[Rn] 54 6d° 752 1 Lutetivm Lu {71 | txejap@ sats? HLawrencium | te | 103 |irnyss oat 7s? Radii of lanthanoids and actinoids includiag lanthanum and actinum Symbol La | Ce | Pr | Nad [Pm [sm [eu | Ga [tT Dy | Ho Tm | Yb | Lu | Radii(pm) MJ 187 | 183 | 182 | 181 | 181 | 160 | 199 | 180 | s78 | 177 | 176 [175 | 174 | 183 | 1723 P+ | 103 | 102 | 99 | 9$ | 97 | 96 | 95°] 94 | 92 | 91 | 90 | 39 | 88 | 87 | 86 Symbol Ac {Ts | Pa | u | Np| Pu | Am | cm] Bk | cr] es |im|Ma|No| Lr} | M | = | 179 | 163 | 156 } 155 | 159} 173 | 174 | 170 | 1861 186] — | — | — | Radii(pm) y+] 112 | 108 104 | 103 | 101 1001 98 | 97 | 98 | 95 f —| —| —] —] — mt+| — | % | 90 | 89 | 87 86 | 85 | 85 |e j—-}|-|-|-|- 4. Properties of lanthanoids @ These are highly dense metals and possess (iii) Most stable oxidation state of lanthanoids is + 3, Oxidation states + 2 and + 4also high melting points. exist but they revert to + 3 eg Gi) They form alloys easily with other metals Sm°" , Eu?* , Yb? lose electron to become especially iron. e.g. misch metal consists of a rare earth element (94-95%), iron (upto 5%) and traces of S, C, Ca and Al, pyraphoric alloys contain’ Ce (40-5%), La + neodymium (44%), Fe (4-5%), Al (0-5%) and the rest is Ca, Si and C. It is used in the preparation of ignition deviceseg., trace bul Jets and shells and flints for lighters, + 3-and hence are good reducing agents, whereas Ce'* , Pr'+ , Th in aqiteous solu. tion gain clectron to become + 3.and kence are good oxidizing agents. There is a large gap in energy of 4f'and 5d subshells and thus the mimbér of oxidation states is limited, (iv) Lanthanoid contraction. The Tegular in the size of lanthanoid atoms and Scanned with CamScannerions from La/La3* to Lu/Lu>* is known as Janthanoid contraction. I is duc to greater effect of the increased nuclear charge than that of the screening effect, which is at- tributed to the imperfect shielding of one Na+ (red) Pm3* (uncertain) Sm3+ (yellow) Eu3+ (pink) Er3+ (pink) Ho? (yellow) Dy* (yellow) Th?* (pink) electron by another in thie same sub-shell. (v) Consequences of lanthanoid contraction (a) Itresults in slight variation in their chemi- cal properties which helps in their separation byion exchange methods. (b) Each element beyond lanthanum has same atomic radius as that of the clement lying above it in the same group (c.g. Zr 145 pm, Hf 144 pm) ; Nb 134 pm, Ta 134 pm; Mo 129 pm, W 130.pm). (© The covalent character of hydroxides of lanthanoids increases as the size decreases from La3* to Lu?*. Hence the basic strength decreases. Thus La(OH)3 is most basic whereas Lu (OH); is least basic. Similarly, the basicity of oxides also decreases in the order from La** to Lu*. (d) Tendency to form stable complexes from La?* to Lu?* increases as the size decreases in that order. (©) There is a slight increase in electro- negativity of the trivalent ions from La to Lu. ( Since the radius of Yb?* ion (86 pm) is comparable to the heavier lanthanoids Tb, Dy, Ho and Er, therefore, they occur together in natural minerals. (g) Lanthanoid contraction reduces the radii (M3+ ions) of the last four elements, ic., Er3* (89 pm), Tm?* (88 pm), Yb** (87 pm) and Lu?* (86 pm)-in.the Janthanoid series below that for Y3* (90 pm) in the preceding transition series, (vi) Colour. Most of the trivalent lanthanoid ions are coloured both in the solid state and in aqueous solution. This is due to the partly filled f-orbitals which permit f-f transition. ‘The elements with xf electrons have a similar colour to those of (14-x) f electrons. Thus, the lanthanoids can be grouped sym- metrically about the gadolinium ion in terms of their colour. La3+ (colourless) Ce3+ (colourless) Pr3+ (yellow green) Lu3+ (colourless) Yb?* (colourless) Tm3* (green) Ga* (colourless) (vii) Magnetic properties. All lanthanoid ions with the exception of Lu?+, Yb?* and Ce‘+ are paramagnetic because they contain unpaired electrons in the 4 f orbitals. These elements differ from the transition elements in that their magnetic moments do not obey the simple “spin only” —_ formula hey RED (n +2) BLM, where n is equal to the number of unpaired electrons. In transi- tion elements, the orbital contribution of the electron towards magnetic moment is usually quenched by interaction with electric fields of the environment but in case of lanthanoids the 4 f-orbitals lie too deep in the atom for such quenching to occur. Therefore, mag- netic moments of lanthanoids are calculated by taking sideration spin as well as orbital contributions and a more complex formula which involves the orbital quantum number, Land spin quantum number S. (viti) Complex formation, Although the lan- thanoid ions haveahigh charge (+ yet the size Of their ions is very large jielding small charge to size ratio ow charge density. As a consequence, they have poor tendency to form complexes. They form complexes main- ly with strong chelating agents such as plexes with -bonding ligands are known, __ (6) Ionization enthalpies. The first ioniza- tion enthalpies of lanthanoids are around 600, kJ mol™? and the second about 1200 ki mol~! which are comparable with those of Icium, The third ionization enthalpy is low leads to stable empty, half filled or com- pletely filled configuration, as indicated by the abnormally low thitd ionization enthal- pies of La, Gd and Lu, (x) Reducing character. The E* values for M3+ (aq) + 3e~ —> M (s) lie in the range of -.2:2 to - 2-4 V (exception being Eu, E° = = 2-0 V) indicating thereby that they are Scanned with CamScannerHalos 7 §, highly electropositive, readily lose electrons and thus are good reducing agents. (xi) Chemical behaviour. The first few mem- bers of the series are quite reactive, almost like Ca. However, with increasing atomi- number, the reactivity decreases and it be comes similar to AJ. The general reactions are represented below : Ln (Lanthanoid) | c Dilute Bumn| — Heated Heated #0] gen] 273K acids inOo| — withNo} . —withS LnXg Lng, Liberate Ln03 Ln LngS3Ln(OH)y+H Lage, He gas : Unc Uses of lanthanoids. (i) Lanthanoids do not find any use in pure state. They are used mostly in the production of alloy steels to improve the strength and workability of stec!. Misch metal is oné such use. (ii) Oxides of ianthanoids (¢.g., La,O;) are used for polishing glass and for making colaured glasses for goggles as they give protection against UV light and as phosphor for television screens, Mixed oxides are used as catalysts in petroleum cracking. (ii) Because of their paramagnetic and fer- romagnetic properties, tbe compounds of lanthanoids are used in making mag and electronic devi oe (@) Cetic stilphide is used as an important oxidising agent in volumetric analysis, Properties of actinoids @ Oxidation state. The dominant oxidation state of sctinoidsis + 3 which shows increas- ing stability for the heavier elements, Np shows -i 7 dxidation state but this is oxidising and is reduced to the most stable state + 5. Pu also shows states aplo + 7 and Am upto +6 but the most stable state drops to Pu (+4) and Ara (+ 3). Bk in + 4 state is strongly oxidising but is more stable than Cm and Am in'+ 4 state due tof 7 configuration. Similar- ly, No is markedly stable in + 2 state due to itsf™ configuration. : ‘When the oxidation number increases to + 6, the actinoid ions are no longer simple, The high charge density causes the formation of oxygenated ionse.g., U03* , NpO3* etc. The echitition of large number of oxidation states ef actinoids is due to the fact that theres avery small energy gap Between Sf, 6 d and 7's subshells and thus all their electrons can part in bond formation. Though 4f and 5forbitals have similar shapes; but 5/is less deeply buried than 4 f, Hence. Sf electrons can participate in bonding to a far greater extent. Gi) Actinoid contraction. There is a regulat decrease in ionic radii with increase in atomic | number from Th to Lr. Thisis called actinoid | contraction analogous to the lanthanoid cor traction. It is caused due to impertect ski ing of one 5f electron Ly avother in the shell. This results in increase iv the eff nuclear charge which causes contraction in size of the electron cloud. This contraction is greater from elernent to elentent in this series due £0 poorer shielding by \ Sfetectrons, This is because Sf orbitals extend | in space beyond 6 and 6p orbitals whereas 4f | orbitals are buried deep inside the atom. | Gil) Colour of tie ions. Ions of actinoides are generally coloured which is due to f-f trans tions. Tt depends upon .the number of electrons in Sf orbitals, ‘The cations contain: ing 5f° and 5/7 {exactly half filled sub- shell) electrons are colourless. The cations containing 5 f2~S electrons are coloured both in the crystalline state-as well as in aqueous solution, For example, Ac (5f*), Cm3* (5/7), Th3* (56°) are colourless while US (S74) is red, Np?* (574) is blue, Pud* (57%) is violet, Am>* (5) is pink and soon, ivy Magnetic properties, Like lanthanoiés, actinoid elements arc sirongd paramagnesic. . Tho magnetic woments are lesser than the theoretically pre... seal values, This is due to Scanned with CamScannerthe fact that 5f electrons of actinoids are iess effectively shielded which results in quench- ing of orbital contribution. (*) Complex formation. Actinoids have a greater tendency to form complexes because of higher nuclear charge and smaller size of their atoms. They form complexes even with 2- bonding ligands such as alkyl phosphines, thioethers etc. besides EDTA, f-diketones, oxine etc. The degree of complex formation decreases in the order M** > MO3* > M+ > MOF where M is elcment of actinoid series. There isa high concentration of charge onthe metal atom in MO3* which imparts to it relatively high tendency towards complex formation. |. Uses of actinoids The actinoids which find uses as such or in the form of their compounds are Th, U and Pu. (a) Uses of Th. It is used in atomic reactors and in the treatment of cancer. Its salts are used in making incandescent gas mantles. (b) Uses of U. Itis used as a nitclear fuel. 1 salts are used in glass industry (for impart green colour), textile industry, ceramic in- dustry and in medicines. (c) Uses of Pu. It is used as a fuel for atomic reactors as well as for making atomic bon:bs. Scanned with CamScanner