6:53 PM OAKBIS d-Biock Elements 4. TRANSITION ELEMENTS AND COMPLEXES * Inthe tong form of periodictabio oloments are dlassiied based on electronic configuration. The eloments Which are cisified betwoen’s’ and p’ block are block elemants or Transition elements. In these elements the differentiating electron enters in the ‘orbitals of penultimate shell * General configuration for‘ block elements is ns" (n-1}6""9. ie, ind’ block elements the valence shell has ‘constant numbar of elactrene Whereas the number of elecirane n penutimate snail goon mereasing. * Elements which have atleast one unpaired electron in their’ exbital in atomic or any oxidation state are called 2s Trorston elements, Thus altranstion otomonts aro! block olamantsbutal'f Bick clomonts may notbo ‘rarsion elements or te elements having incomplete led 'd orbtas arecated as ransiion elements + Transiton elomenis are clssiid between's’ and ‘blocks from fourth period onwards. Series of tansiton ciomonts ro four + 4#'Series~They reclassified in fourth period ae are called as "3d saves of elements, Thei atomic numbers ar021(S¢) 030 (2r). 24 Series- They are cassifed in fith period and are calle as 4c! series of elements, Their atomic numbers are 997) 10 48/C), 3* sories-They are classifed in sith period and are called as 0" series of elements, Their atomic numbers are 57(La).72(H 10 80(H%9) 4 Serlas- They are cassifiee In tho soverth parca and aro called as "serie of elements. Ths Is an incomplete series. Thr atemic numbers are B9(Ac), 104(Ku)to 112 (ub) + Electronic configuration oft series of transition elements. ‘Atomic number | Element ‘Symbol _| Electronic configuration 2. ‘Scandium Se TAn4sad 2 Taare T tan 4s?50? ZB Vanadium v (aryastad? 2 Chromium a tanas'ad® 2. Manganese a tan as%o08 26 tron Fo (Andee? 2. Cobelt © tAnas?ad 2 Nicket Ni [anyastsa? 2, cooper cu [any4sisdi? 30 Zee 2 tans?" * _Chromianvand copper are slemenis having excaptonalelscrenic contguratone Off] 4s!345 end Ar] 4e'3a"° instead ofr] 452 and far} ds 250° + 2n(G0)is ry 4s%aa"® (Co (48) is [Kr] 52a? Hg (60} is [Xe] 652.4814 54” These three elements do not have any unpaired electrons in ther orbitals in 2tornic as well as In ionic slates, Therefore they ate only classified as ‘block elemenis and nol as transition elements. Copper, Siver ‘and Gold, the elemants of IB group i.e. coinage metals, have ns! (n-1}d"° configuration. They are transiton ‘elements 2¢ in their higher oxication state thay have an Unpaired electron in thai’ orbital, ia's Best Exam Preparation f Ss h - Download Now6:53 PM 6.OKB/s 0.6 151004) 24 Melting and iling points MP. and b, p.of d-block > s-block (the reason is stonger metalic bond and presence of covalent bond formed by unpaired d-electrons.) * tn 2n,Ca, and Hg thereis no unpaired electron present in d-obital, hance due toabsenceof covalent bond, their m.p.and b.p. are very ow. (Volaile metals Zn, Cd, Hg) In Sdseries Sc -+Crm.p. bp increases Mn ->Zn imp. bpdecreases Mn and Te possess comparatively ow m.p.,itdue to stable configuration (Half filed) * Lowest mp Ha~26°C Highast mp. W = 340°C * Characteristic properties of transition elements are (a) Variable oxidation state (b)Colouredions (c) Paramagnetis propertes (d) Cetalytc properties (e} Formation af atoye (0 Formation of intersiial compounds and (g} Formation of comploxes. (8) Variable valency or variable oxidation states: ‘They exhibit variable valeney dus to involvement of (ns) and (n-td electrons in bonding, This is dus fo less energy difference between these electrons. ‘The oxidation states ofl irarsition elements of 3d serias are as follows, So [40% 3 Ta dstad? (2344 Vv [anpastsa? 425 Cr IATA tad? ON) 42 419 04) 5) 46 Oxidation Mo (A data 429344 (45) (68) 7 States in brackets Fo [Ar] as?3c® 4243 (64) (45) (48) tsfere unstable Co aasted 1201344 Ni ar astc® 23) cu aniaetaa'® 1 * Highest exiation state of transition elements can be calculated by =n + 2 (9 = no, of unpaired &) (itis mot apelieg for Grand Cu) * The transition meta ens having stable configuration are stable Netalions of 8¢' srios having 8 configuration Se", Ti"# and V*S etc ae sable. ‘Transiton metal ons having 3° configuration are stable Ike Mn", Fe“? In aqueous madium Cr'9is stab Co"? and N"? are stable. ‘Transition metal ion with 36 confguration which s tables Cu". In aqueous medium Cu"? is more stable than Cu" * Most common eaidation state among the wanstion elements is +2 + Highoot oxidation state shown by tronston elements of 6! and'5d series ie +8. The elements showing tis ‘xiation state ara Ruthonum (4) and Osmium (76) The common oxidation stat shown by elaments of IIB i.e, So, ¥, LaandAcis +3 as their divelent compounds aro hight unetabio, | DOWNLOAD NOW6:53 PM 1.OKBIS #4 + Inlower axidationstate trans elements form oniccompounds and in higher oxiaton sate theircompounds arecovalent. 2.1m chromate ion CrO,2, the bonds bewaen Cr and O are covalent. * General higher oxdation states are exhibited in thacompounds which reformed wt highy electronegative stements ike O end F. + Trey also shows 2ero oxidation statin thir carbony compounds ike NCO), * Usual renston metal ion in ther wor oxidation state act as reducing agents and in higher oxiation stato they aro oxicising agents. 29.-Ti, V, Fe"?, CoM ete are reducing agents Ccr¥8, Mn‘7, Mn'4 Mn'8, Mn*® ete are oxidising agents, 25 Colour Property: * Most the trensition metal ions exhibit colour property This s due tothe presence of unpaired electonsin the ‘d orbitals. They require less amount af energy to undergo excitation of electrons. Hence they absorb visible region of light exhibiting colour. TtArlad?, Vitara ote. ‘These are having unpaited electrons lo thet orilals therefore they are coloured * Transition metal ins which do not have any unpaired elctrons in their‘ orbitals ike 34° and 34° configura: tione, do nct exhibit any colour property. 2g. So [Are®, CuvTAqa", TIMIAT2C® ete are colouriess ions, + Aransition metal on absorbs a part of visible region o ight and emits est ofthe six colours, the combination ‘of which isthe colour of emitted Fght. The colour of metal ions the colour of the emitted light * In transition metal onthe orbitals splitinto lower energy set ig orbitais and higher energy set ag orbitals. The elections from tag sel get excited to higher eneray sete, eg Sel. This excitation of electons is called as U- transition. As d-d transition requires less amount of energy they absorb visible region of ight. Due to this "dd transition the transition metal ions exhibit colour property, Lower energy set = 139 Higher energy set = eu. ea) pews) {TOT TTI Jot 7 Tee % * Kin, (dark pink), K-20, (orange) having & configuration are coloured dus to charge transfer spectrum. ‘Some of the coloured metal lons are as follows 18. Purple ort Green Mn*?- Light pink et? Palegreen Fot® yellow Cote. Blue Nr? greon cur. Bus 26 — Magnetic properties Mater, in ganeral is associated witn magnetic properties. Majority of substances are ether paramagnetic or diamagnelc. & paramagnetic substance is one whichis attracted into @ magnetic fled, Paremagnelism is mainly due t the presence of unpaired elactions in atoms or ions or molecules, Diamagnetie substances one which is sfghtlyrepeiee by a magnet field + Teas, 8 asa. vA, Cpe? [Ass evcent most of the tanston metal ons have unpared electons in tele orblls. Hence most of he ‘rarston metal ions are paramagnetcin nature. Transtion meta ‘ons having 3c and 3 configuraten exhibit damagneticnature 48 {Block DOWNLOAD NOW Video Lectures study Matra | ets | va |6:53 PM 1.OKBIS ea [An unpaired electron spins and as tis charged particle, magnetic fed is created due o its spinning Each olectron may, in fact, bo considered as a micro magnet having @ cortain valu of magnotic moment. Tho ‘otal magnetic moment of a substances the resultant ofthe magnetic moments of al he incvidual electrons. Thus substances containing unpaired electrons get altracied towards the magneis exhibiting pareragnetic nature. ‘The magnatic moment (})) created due to spinning of unpaired electrons can be calculated by using us frloz2 Where ‘nis the number of unpaired electrons in the metal ion. i= Magretic moment in Bohr Magnetons (B.N.) The magnatic moment of diamagnetic substances willbe 20", + Asthe number of unpaired electrons inerease the magnetic moment created goes on increasing and hence the eramagnetic nature also increases. ‘Transition metalions having d® configuration wil have maximum number of unpaired electrons therefore they vill bemaximum paramagnetic nature. 27 Catalytic Property Transition eloments and their compounds exhibit catalytic propertos, This is duo to thor variable valency as ‘well as due tote trae vaiencias on that surface. + Whon transiton elements and their compounds aren powdored stale. their catalytic preportios exhibited willbe te-agteater extent. This is due to greator surtace area available in tho pondered stato. ‘Transition metals and their compounds exhibiting cataiic propertes in verious processes are (i) Fe is used in Heber’ process for manufacture. of NH, [i V,04 % usd in contact process for H,SO, manufacture i) Plis used in Ostwald’s process of nitric acid (Ww) Niis used in hycregenation of oils [v) F280, is used in oxidation of Benzene with HO, (i) Cuis used in dehysrogenation of alcobols (wi) TC, is use as catalyst in Viny! polymerisation 28 Formation of Alloy * Transition elements have maximum tendancy to form alloys. Tho roaetivity of transition oloments is ory ese and their izes aro almost similar. Duct this tranetion motal atom in the Latice can be easily replaced by other transiton metal atom and hence they have maximum tendency to form alloys In the alloys ratio of componant matas is fkod. + These areextremlyhard and have high MP. 3. SOMEIMPORTANT ALLOY. 1. Bronze = Cu(75 -90%) +8n (10-25%) 2 Brass: = Cu(60-80 %) +Zn (20-40 %) 3. Gunmatal = (Cu+2n+ Sq) (87:3: 10) 4. German iver = Gutzn+Ni(2st: 4) 5. Bell metal = Cu(@O%) Sn (20%) 6. Nichrome ~ Nis Cr+ Fo) 7. Alico = LNI.Co) 5 Typametal = Pe+sn+sp 9. Alloysof steel (a) Vanacium steet + v(02= 1%) ia's Best Exam Preparation for Class DOWNLOAD NOW6:54 PM OSKBS # f -Block Fulements ‘They wore carter callod as rare earth metals as it was beloved that they axist in earth's crust to a very less. extent fore. Pm, dos nol exst in the earth's rust. Bul his terminology is now not applicable as they exist in oarth’s crust to a sufficent oxen. 14, INNER TRANSITION ELEMENTS Tho elementsin whic the adltional electron enters in (n-2)forbitals are called inner transition elements. or ‘block elements. 444 Position inthe perlodie table Ths lanthanides resemble ytrium in most oftheir properties. So it became necessary to accomodate ell he {toon elomontstogothor at ne pice. This has ton dore by placing tho frst clement, lanthanum bolow yum and placing te remaining fourtsen elements separaelyin te lower part othe period table Lamthanige sarios—(Z=58-71) (Co-Ww) Actiide cones (2=90- 103) (thw) 142 Lanthanides (Lanthanenos) LLanthanides are reactive elements 20 do not found in fre state in nature. Most important minerals for lighter Lantnanices aro -Merzte,contes anc orhite anc for heaver lanthanides - Gacolnite anc Xenebme 143 Electronic configuration Tho goneral configuration of lanthanides maybe given ae 4F5e25p85ef"6s2, Lanthamide have outor three shosincompete ‘Atomic Element | Symbol Outer electronic|configuration Number Atomic Js3 ton 8 ‘Corum ce 4632 oy 59 Praseodymism| Pr 46 652 4e 60 Neodymium | Ni att 632 46 6 Promethium | Pm 41632 as 8 ee a6 552 a6 63 europum — | eu at? 632 a6 4 Gacciium | Ga af 5 6x2 # 65 “ect ” 4 632 ae 66 Dysprosium | Dy 4110632 ae or Hoimium to Mos? ao 68 Etbium & art? 532 ant 69, Thum Tm 4652 are 70 Yuerbiom — | Yo 4M os? are n Lutecum | 41M 5a 662 ara {is tobe noted here that filing of orbitals nthe aloms fs nol regular. ASG eeclron appears in gadolinium (2 = 64) with an outer electronic configuration of4'5d'6s®(and not Es"). This is because the Af and 6 electrons are at about te same potential energy ancthat the aloms nave a tendency o rein stable hat tiled eonigura ton nthe other hand, he fing of foils egularin triposive ions. Ate losing outer lecrons, the forties shrink in size and became mere stable. Pm is the only synthetic redioactvelantharige. Oxidation states 144 DOWNLOAD el ied6:54 PM SSKBIS iy 1 aI0eK] Oxidation states 144 Tanthanides Oxidation States Coss 13.4 Pra 23.04) Nip 3 Pres 2 Sigg (2).28 Ess 1293 Gag 8 Tes 34 P¥e5 re) Hose 3 Ere (2).43 Tm (e2)-43 Yor 1293 Ly, 2 + Oxidation staies in brackets ave unstable Slates * The lanthanides contains two s elecrons in the outermost shel they are therefore expected to exhibite charac teristic oxidation sto of +2. Bu for the lanthanides, the +3 oxidation is commen, + This corresponds to the use of two outermest elactions (852) alongwith one inner electron. The Inner elaction used isa Sd electron (in La, Gd and Lu), or one of the 4f electron if no 6d electrons prosant. * All the lanthanides attains +3 oxidation state and only cerium, Praseodymium, and terbium exhibit higher oxidation state (+4) (Oxidation stetes + 2 and +4 occur particularly when they lead to ()Anoble gas configuration og. Ca¥ () (A talf fled t orbital eg. Eu, To", (?) GAcompletey fled orbital e.g. Yo" ‘Thorofore, in higher oxidation state, they act as oxidising whi in lower state as reducing agents 145 Magnetic properties In tpositive lanthanide fons the numberof unpairac electrons reguiar increases from lanthanum to Gadolinium (© 0 7) and then continuously decreases upto lutecium (7 to 0). Se lanthanum end lutecium ions which are diamagnetic, al ther triposive lanthanide ions are Paramagnetic Colour - The lanthanide ions have unpaired elecrons in the'r 4f orbitals. Thus these ions absorbs visible reaion flight and undergo 1 transition and nance exhibit colaur. The colour extvbted depencs on the number of unpaired electronsin the 4f orbitals, The ons often with 4" configuration have similar colourto those ions having 40 configuration. Lanthanide ions having 4, 7 41! are colourless. Lanthanide lons 4t! and 4a are also colouriess. 145 Other Properties (@) Highly dense metals wth high m.pts. (do not show any regular trend}. {(b)lonieation Energies - Lantnanidas have fairy ow onication anercios comparable to akaline earth motals. (€) Electro positve Character - High due to low 1. (6) Complex formation -Do not have much tendency to form complexes dus to low charge density because of their latge size. Lu’S is smallest in size can only form complex (@) Reducing Agent - Thay readty iose elacttones so are good radicing agent + In+Bexidation states, ritrates, perchlorates and sulphates of lanthanides and actinides are water soluble, while their hydroxides, fluorides and carbonates aro water insoluble, * Alloys of lanthanides with Fe are called misch metals + LalOH), is most basic in nature while Lu(OH), least bas * Lanthanides form MC; type carbide with carbon, which on hydrolysis gives CH, 45. LANTHANIDE CONTRACTION * Inthe lanthanide series with increasing atornic number, thers iss progressive decrease in ti ‘num to lutecium or from La" to Lu*S. Thie contraction in size is known as lanthanide cont DOWNLOAD NOW Video Lectures6:54 PM * The goneral elactenic contiguration of those elements ie 4F2-N46s%p%a-'ée2, In those olomants the added ‘etcctron enters tha deap seated f-orbtals and therefore experieneas consiseraole pul bytna nuceus. * Such an electron cannot add tothe size ofthe element and also because the intervening 65°p*d electronic shots, tis very ile screening effect on te outermost 6s? sectors, Hence with increasing atomic number, the enhanced nuclear charge leads to contraction inthe sizeof atoms andions, The aiomic volumes of europium and yterblum are unexceptedy large. The large atomic size of Eu and Yb suggest weaker bonding inthe solid clements. Both thase olements have only two electrons extra than the stable contigurations (hal filed, f”, and complately filed, 4), hance they tise two elactrons in matali bond: ings inthe case with barum. 46. EFFECTS OF LANTHANIDE CONTRACTION (Close resembalace of Lanthanides :- The general decrease inthe sizes othe lanthanides with an increase in tneirnuciear charges result in asmallincrease in her ionisation energies. Hence theirbasic and ionic nalire radually decreases from LatoLu, ‘This also explains the variations in properties such as increased tendency for hydrolysis and formation of Complex salts and decreased thermal sibility soibilly oftheir sats (i) Similarity of yttrium with lanthanides :~ The proporios of yttrium are so similar to the lantranis that is considered more a member of he lanthanide series than a congener of scandium. (ii) Anomalous behaviour of postanthanides :-The following anomaiies may be observed inthe behaviour oF post-anthanide elemonts, (@) Atomic size The ionic radi of 214i about 9% more then Ti*4 Similar trendis rot maintained on passing ‘rom the secondo thi transition series, The onicradus of 4, instead of increasing (because of inclusion of ‘ane more electronic shel). decreases (ris vtuelly equal to 2r") as a consequence of he tanthanide contraction. This explains the close similares botwaen the mombors ofthe eecond and thirdtranston series than between the olements of the fist and socord series, (®) lonisation potential and olectronegativty :- The effect of lantranids contraction is also seen in the ‘ncrease in the ioniation potential values and eleetronagatwities ofthe elements ofthe thes transition series, contrary to the general trend, ‘Bacause of the lanthanide contraction, the post-lanthanide elements have stronger posive field and thus the fetzctrons are nald more tently. The greater effective nuclear charge ofthe formermake them mote sectronegative than thealter. {€) High density :- Because of lanthanide contracton the atomic siz0s ofthe post anthanise elements hecome vory small. consequently, the packing of atoms in teir motallic erstais become so much compact that thoir donsites aro very high ‘The densites of te thir transition series elements are almost double to those of the second series elements, 17. APPLICATION OF LANTHANIDES, Cerium is most useful element inthe lanthanises (@)—_Caramic application -Ce0,, La,0y,Nd_O, and Pr,P, [email protected] as dacalourizing agents fr glasses, (@) G28 (m.p,-2000"C)is used in the manufacture of e special type of crucibles and refractories. (2) Lanthanide compounds lice cerium molybdate, cerium tungstate ere used as paints and dyes. (@ —intoxtie and ioatnor industries (Ce sats) 18. ACTINIDES (Sf - BLOCK ELEMENTS) + Thelements in which he extra electron artars Sf-orbitals of (n-2)th main shell are known as actinides, Themen made eleven elements Np9q Lrjg3 are flaced beyond urarium inthe periedictable and are collectively called trans-uranic elements. Th, Pe anc U frst three actinides are natural elements. ia's Best Exam Preparation for Class Video Lectures DOWNLOAD 9 JEE & NEI Gan)