6 General Characteristics of Transition Metals : d-Block Elements Introduction The elements from Sey) to Zny (len elements), Y5y to Cdyg (10 elements) Las;, Hf to Hegy (len elements), Acgs, Ktjoy, Hayos, Unhgs etc. are called transition metals. Since the last electron in the atoms of these elements enters d-sub-shell belonging to penultimate shell. (n — 1Xb sbell}, these elements are also called d-block elements. Thus in these elements the last electron oes 19 tr - 1d sub-shell. Position of d-block elements in the periodic table The position of d-block elements in the periodic table has been shown in Fig. 6.1. From shis figure the following points may be noted: (i) d-block elements lie in between s-and p-block elements, i.e, these elements are located in the middle of the periodic table. (ii) d-block elements are present in 4th (Scjy to Zny = 10 elements), Sth (Yy) 10 Cdyy = 10 elements), 6th (Las;, Hf),10 Hggp = 10 elements) and 7th (incomplete) period which contains 8 elements viz. Acgo, Kijgq 0 Uunyyo (iit) d-block elements are present in WB (3), IVB (4), VB (5), VIB (6), VIEB (7), VIII (8, 9, 10), IB (11) and IIB (12) groups. Electronic configurations and definition Toe electronic configurations of the atoms of d-block elements are given in Table 6.1. In this table (Arh, [Kr]y5, [Xe]sy and [Rn}gg indicaté the electronic configurations of Ar, Kr, Xe and Rn respectively, which are given below: 5 s 2 2 6 [Arh = 2,8, 8 (Three-shells) 1°28 apias.ae, 6 UKi}y = 2,8 18, 8 Four sets) 1Sads295 35° 3p US gel) wp Keka = 28 18, 18, 8 (Five shells) [Roles = 2.8, 18. 32, 18, 8 (Six shells) Th. configurations given in Table 6.1 show that: hehe’ ®> (a) d-block elements can be defined as those elements in which i Cee) ak ements ich the last elecaron (differentiating \ , } orbitals are progressively filled up’ with electrons mimate shell) or in which (n ~ id (b) d-block elements are also defined as those clemen 3 WS Whos => incomplete (ic., parially-filled), ee scayht 240 ‘Scanned with CamScanner‘Scanned with CamScanner syapuraa APO -P 1 1 = Hdne15Wl, Wt a! Liu (M4 tr) [Athy M! 4s? 28 15,2 i = LAIR IO? (F $3) Seal Dish os Rey “rv [Meg] » af [Kish 4 Se 28d {8d 53+) (ra) UKthe 48? $2 wo (a say (are) [Kiy dat? Sst 2.8018, 18.1 fe Se Cg IKehy dat? 502 28 IK 1H? (at Set) mS of d-block elements. Here . 18, 18, 8 and [Raley We given in bracket rations, Mth ox 64 series Ger peso) Lay 9 50 6 t Aen ela Rly Sf? 6d 73 = 2818, = 2,8 18, 32,18, 9,2 (9? 34 sy Gyr 6 78%) Why Koa IXehe af $a gst 2.8. 18, 32, 10, 2 Uf S86) Ty Rela Yt 50 Get : FR] Sf" 6 798 = 2.8, 18, 32, 32, 10,2 ("6 79 Doles Sf! GP 72 28 II ITT Of Ie” Unhina WRiae Sf af 3? 2.5.18, 122 (3) te 2. =yanosnelak Ce, Cie AAD ON { a Classifica’ The el ‘on whether into the foll 1 3as ‘These cleme to 3d-orbital move from § are anomalo. (instead of 9 [Athy 34 45! Complete anc written as fol or Valenc 2. $2505 namely Yyy 10 electron oceup 4d orbitals as anomalous con Rhys. Ply and of nuctear-elec) dlectronic con! Khe = 2,8, Co. e8 Valence, 3. Sd-ser ten clemments » UNs series inw, tliments vir, mvolve the pri “eabitats are Xehe 47" Se9 Ge ty" se est) | Mule im the | tonfiry “iitten as folk Co 18 2 Ne be) ‘Scanned with CamScanner Valence 4. bd-ser Resent in 7th Toot. Hayes and 6d series (four serie - Classifications of d-block elements 9 a 4d, es ne shite 6. show an \ i {-block clemen! ry ie oe ae Sad on 6d vbials, these elements can Be gros, on wi i, {mo the following four seri 1, Sd-series (Ist series r fibese elements Tn the atoms of : ‘These elements are present in Ath period. ese ih electons 5 we dt to 34-orbitals, iz, in this series 3d orbitals are progressively ae es Cp (two elements) "2 move from Sy) 10 Znyp. It may be noted ‘a ery domi 2d Cin has 10 elecuens are anomalous, since Cry, has 5 electrons (instead snd Cap i Cy we 7 Gsicad of 9) in these orbitals. Thus the covrect electron enfin Dey. [Asha 34 45" finstead of [Ary 3445") and ft) 1 3d!° 45° [instead of [Ais : pie ae Compete and valence shel eleeuonic configurations of the atoms of 3d-sere srinen as follows. Here [Arhy = 2, 8, 8 (tbvee shells). <>Sc, 11, WCF ™Mn,Fe, Co, Complete configuration = {Ar} 34" 45? CLL, 2 = 2,8,(8 + 1 10 10), 1 oF 2 (four shells) = 2,8, 9 t0 18), Lor? = 2,8, ipl’, as)? Valence-shell configuration = 34!" 4s! 2 Ad-series (2nd seriec + Sth peried!), Hike Yd-ceres, this series also has ten elements ‘it in Sth period, In this series, the differentiating namely Ysq 10 Ctl These elements are electron occupies 4d onbitals, ic., the elements of this series involve the progressive filling of In this series there are more elements which have 4c oxbitals as we proceed from Yyy 10 C \"- anomalous configurations. The elements having anomolous configurations are Nosy, MOz, Rues, =24?'*? has, Pes and Ags (Sit elements). These aamolous configurations are explained on the basis “A mvclear-election and clection-electron forces esting in these atoms, Complete and valence-shell | lectronic configurations of the atoms of ¢-seties elements can be written as follows. Here | IKrly, = 2, 8, 18, 8 Your shells, I, Complete configuration = {Kr}, 4d‘ '° 55°? = 2,8, 10,8 + 110 10), O 10 2 (five shelis) 2, 8, 18, 9 10 18), 0 10 2 10 5,02 agi 622 i Valence:stell conf 3, Sdeseries (3rd series: 6th period). Like 3d and 4d series, this series also consists of _] seg elements which are Lasy (one element) anid Hf 10 Hyp (nine elements). The elements of this series involve the gradual filling of $4 crbitals, In between Lasy and Hf, there are 14 skments viz. Cesy t0 Lup) which ae called lanthanides or lanthanones. These 14 elements involve the progressive filling of 4f orbitals and hence donot belong to Sd series. Thus 2t Lun 4f orbitals are compktely-filled. Consequently at Las, 4f orbitals are vaco (7? conficuration) | while in the remaining nine elements (If;; 10 Heya) 4f orbitals are compleely-filed (4/'* configuration). The elements namely Pty and Au;, (owo elements) have anamolous configurations. <7 hell electronic configurations of the atoms of Sd-semes elements can be 8, 18, 18, 8 (five shells) dil 69? = 2,8. 18, dstapSal4p!* septy!-10, 1 63 ad-incomplete perio). The elements of this series a nt this series consists of Ac, gradual filling of 64 orb Complete and va written as follows. Here [Xe}se Complete configuration (sit shetis) A configuration Valence-she 4, 6d-series (4th series: 71h pet resent in Tth period which is an incomplete pestod. AL ps Kajag, Hajgs and Unk, v elements). These elements involve ‘Scanned with CamScannerProgressive fill i iJ hence donot tals are Lw filling of 5f orbitals and hen / FaHals te vacan (57° cong ital se compete sled, Conese a eye 3f nhigg (three elements), Sf orbitals oy Mle in the remaining clemems viz, Kuo, Hajos and Falence-shell configurations of we cue COMPlEtely-filled (5f" configuration). Complete and Rags = 2, 8.18, 32, 18g Gir ‘hells of Geh-serics elements can be written as follows. Here Complete configuration [Rog 5" gg! 7,2 2. 8 18, 32, Sept!" os'p'd!—*, 722 (7 shells) Valence-shell configuration = 5/818. gg ie nnd ne ee |__ Physico-chemical Properties | The transition elements show several propenies. Some of these properties and ther trends of Variation are discussed below: 1. Atomic radii ‘The atomic radii of the atoms of d-block elements are given in Table 6.2. The following ends may be observed (1) Variation of atomic radii in a given series (period). Te swine radii of tre elements uf a paniculer series decrease eradually upto the midway element and then these values remain almost constant upto the element of group 1B (Cu, Ag and Au). The last element of each series (Zn, Cd and Hg) shows an increase in its atomic radius. For example, for the elements of Ist transition series the atomic radii decrease gradually from Sc to Mn but from Fe to Cu these values remain practically constant. The atomic radius of Zn is higher than that of Cu. Similar behaviour has been observed for the elements of 2nd and 3rd transition series. Age ech Table 6.2 Atomic radié (pm) of d block elements oa vnee! i _ neon mB VB OYB VB VIB <——vin—> BB 4 ) 9 6 OM © 9 ay a) «ay Sen T Vo Cr Mn Fe Co Ni Cu Zn 162 W701 127 212612524128 TB. And series -Yyp ee a fh i ae) ng ery 18) WoO 146139136 134134137144 AS Bid series Lay Why Tr Wo Re Os tr PAu Hew 187 | 165 156 | 158 146 139137135 136138 445 14 lanthanides ‘evcase Explanation, For the elements from Sc to Mn the atomic radii decrease. This decrease Godis because of the gradual increase in nuclear charge with the increase inatorme numbey, The increased nuclear charge makes the atom to shrink in size and hence tié sizeof the atom decreases. However, since the elecuons added to 3d orbitals screen the ds electrons), the attraction between the mucieus and the 4s electron(s) decreases, ie., due to the screening effect caused by 3d electrons she magnitude of nuclear charge decreases and consequently the atomic tadii for the elements ‘tom Fe to Cu remain almost uncharged. Towards ihe end of each series, there is an increase in electon-electron repulsion between the electrons being added to 3d orbitals. | This increase in repulsion becomes greater than that of the attraction betwees ive nucleus peel 9 Imev iat tm welaar chen 5 Shoot Jn sr 4 jae =) Held on YS cbeerrtates ~ ae te Segeeminy ee Rae ‘Scanned with CamScannernese | wese | we > Less 66=t+ |sorerr | soe : iN pt seit | vozze | z= = one ee ny a a es=cr |sseer | 69= = gol=z+ | O6= cr | ree = cor =t+ | 6zi= i+ | coors te | sos = . p> ay Pa we 2 ow | souas pug | as = 9 = - ay : sree ogee £9 = t+ 9 e boa te | KK aes sere | tents | cence | ocr ve - eae | oinece ovuz "9 IN °9 au uw 2 ‘ log wD (on 6) 2) (73) wo | wm ~ aq al ma a | ‘Scanned with CamScannerTike ave charge _ can ensity donate, & fa . all these elements are metals. " siti : 2 as electrons can easily be lost ae Clements have low values for their ionisation energies, show metallic ¢ YY them to form M* or M™ cations and thus these elements ctr. AS usual, the meta basic character of the Pentoxides 9 erases a5 V0, NO. Of the elements of group VB (V;0s. Nby0s and Ta,0,) 2 S , 20s. Thus V0; is amphor basic than acidic z 05 is amphoteric (but more basic than acidic) 20; and Ta,O. are mote basic than acidic. vy The menallic charact 7 waracter of the trai vi wing properties sc cloner nsition elements is evident from the following properti while (i) Electrical and thermal conductivity. These clements are good conductors of electricity and heat because of the cxistance of metallic bonding (ice.. presence of free mobile electrons) among the atoms of these elements. Cu, Ag and Au show exceptionally high thermal and electrical conductivity Cu Agand Aus < (ii) Hardness. These elements are hard (ie., cannot be cut with a knife) and brite. Their bardness is due to the presence of strong metallic bonding among the atoms of these elements. The metallic bonding arises due to the overlap benveen the singly-filled eebitals of different +> atoms of the clements. Greater is of unpsired electrons, grea: & the number of ameltallic bonds and, therefore, greater is the strength of these bonds or hardness of the clement _Mo and W have maximum nuinber of unpaired electrons, these are very herd metals, and Hg contain no unpaired electrons, and hence are not very hard. As a maiter of fact [-SHg is a liquid and is soft like alkali metals (iii) Crystal structure. These elements have simple hexagonal close-packed (hep), cubic close-packed (ccp) or body-centred cubic (cc) lattices which are characteristic of metals. mgr ke Wreol. 4. AMomic volumes and densities peried > arc cewes The atornic volurnes (in ml) and density (in g/cm’) of transition elements are given below llic character of these elements increases on descending the group, eg. <«/e™ 2 6.4. The values given against m/ are atomic volumes while those given against g/cm” in Table 6.4. The values given ag jomie vol given against g/cm ot ve represent densities, Table 6.4. Atomic volumes (mii and densities (z'cm") of d-block elemenis mB WB VB VIB VNB «— Vi =_— 1B ns Tix | CMa Fe Ni 2nyg 10.60 739 7.10 6.00 920 431 TR 186 ) as Zty = Nb Mo Bi az Cdy It 1S “94 89 SBT gem 447 689 84901021 1200 1081863 La, Hy Re p ml 2050 13.60 10.91 S85 9.10 gem 6173.10 16.60 21.00 2.40 1360 ‘Atomic volumes of d-block elements are much lower than those of the elements of s- and ~p-blocks. We know that density and atomic volume ate inversely proportional to cach other, All the > sition Is have low values for their atomic volumes and hence their densities are high. THE atomic volumes are low because the electrons are added 16 (n - 1) d orbitals and wOT-fo rng orbital, The increased nuclear charge is partly screened by (n ~ 1) d electrons and ns electrons ‘Scanned with CamScannerai 29 VD 2 F-76- paewsitlo are strongly attracted by the ™ high Yariation of atoraic_yolum =) volumes of the elements first de valve for the elements of gr0UP clements of group IB and IB. Variation of densities in a coqi” = increases on ‘moving from left to right It then stants decreasing as we move is dve 10 the sal racus Variation of densities i sub-group increases on moving down series are only slightly higher than while these values for the transition ele series) are almost double these values for of 2nd transition series) a9 (= 447). ‘The variation of densities of transition series el for Note that the density of Lasy ( = and close jocreas Vill given above, can be explained as follows: 4 {a) The atomic weights of the elements Zomic weights of the comesponding elements of of the elements of 31d transition series almost double 2nd transition series. {b) Because of lanthanide contraction occur “ements of 316 transition series coming after Lun, (i.e. € very small. Consequently the packing of the atoms in cleus. Consequently 0 es in a given series. fe on proce’ ‘They then st series. Ina given and attain further to the eleme! packed structure of the ao na given sub-group. Densities of the sub-group. The those of the correspondin ments from In from left to i vat increasing as We proce: a maximum value for nts of groups 1B ns of these elements. longing to the same 1s of 2nd transition Hf, 10 the elements from Zi20 6.17) is not of 3rd transition f 2nd transition series. This makes those of the corresponding elements of Ye gensiee ~ f elements bel jemen l Ist transition s= ‘ments of 3rd transition respectively (elements le that of the value densities of the ek 2 elements of Viggo (ele to Cas double ue cl ight and at 2 given transition series, the at ain 2 maxinne _ 16 further t0 the she density of the elements Jements of group VIL and IL B. This variation es Jements in a given sub-group, a5 discused series are almost double the mdch compact that their densities become very high. Thus the den Jd transition series become almost double the densities of the corresponding ‘nd transition series. ‘Melting and boiling points The melting and boiling points of transition that these are very high values. The high values are Inve strong metallic bonding belween their atoms. the densities ing in lanthanides. the atomic sizes of the Jements from Hfy) 10 Hggo) become heir metallic crystals become so sities of the elements of lements of metals are given in Table 6.5. These values due to the fact that wansition metals, \ * LN room aN eleme: values 6) eleme althor or sie charg force elect Table 6.5. Melting and boiling points (°C) of d-block elements [eo Ad-series : 2na fons: «Ses Ge Mn Fe Co Ni Cu Zn (su Pec) 1539 «1668 «1900 187512451536 4951453 10834195 BP (rec) 2730 3260 345026652150 3000 290027302595 906.00 Sr 4d-seris (ee elements: Y L Nb Mo fe Ru Rh Pd Ag Ca ere) 15091852 IS 2610-2500 1966-1552 940.8 3209 BP rc) 2927-1500 3300 S569 | — 4900 4500 39802210765 = } in Sd-series { 5 j ae fonenw ta SE Ta Wf Re Ose A prc) 920-222-2996 410 | 180-2700, (1769— 1063-384 Bpec) 3470 540054255930 | sou 500 530045302920 357 = 5 shi > [As we proceed along a particular series, the melting points increase from Sc 10 Cr in Ist | gre! series (V and Cr have almost equal melting points), from Y to Mo in 2nd series and from La tk See) 3rd series, and then GSAS, This variation ean be explained a fllows yiel qu ‘Scanned with CamScanner