d & f-Block Elements d-Block elements The elemnts in which the last electron (or differentiating electron) enters (n - 1) d-subshell are known as d- Block elements. Their outer two shell are incompletely filled with electrons. Their general outer electronic configuration is (n - 1) d'-!"ns'. Inthe long form of periodic table, d-Block elements are placed between s-and p-Block elements in the middle of the periodic table. Technically, transition elements may be defined “as elements which have incompletely filled d-orbitals in atomic form or in some of their common oxidation states, «Some ofthe typical properties of transition elements like paramagnetic or ferromagnetic behaviour, formation of coloured salts, high melting and boiling points (due to strong metallic bonds) are due to incompletely filled orbitals There are four series of transition elements in the periodic table : () First transition series or 3d-series : , Se. Zn (ii) Second transition series : or 4d-series : ,,Y.. (ii). Third transition series : or Sd-series : ,,La, HE. wot (iv) Fourth transition series : (Incomplete filled series) or 6d-series : Ac, Zz Group 12 elements Zinc (Z=30), Cadmium (Z=48) and Mercury (Z=80) are not regarded as transition elements because their (n — 1) d sub-shell are fully filled with electrons, ie., they have (n— 1) 4” configuration in elemental as well asin ionic forms. Their d-electrons do not take part in bond formation, Hence, many of the properties of transition elements are not shown by these elements, Even then they are included in the series of transition elements because their last electron enters the (n— 1) d-sub-shell, © Copper (3d 4s!), Silver (4a'” 5s") and Gold (Sd 6s!) are transition elements although their (1-1) d-sub- shell are completely filled with electrons. It is due to the fact that their (n— 1) d-electrons participate in bond formation Cu’ (<), Ag” (d?) and Au (<), They show all the characteristics of transition elements. «Group 3 elements (Se, ¥ and La) form only tripositive ions with noble gas configuration. Their properties are quite different than that of other transition elements, e.g., their compounds are colourless and diamagnetic. These do not show variable oxidation states. But these elements have incompletely filled d-subshell in their elemental form, these are considered as transition elements. © Group3 (Sc, Y and La) and group 12 (Zn, Cd and Hg) are sometimes referred to as ‘non-typical’ transition elements. + Alltransition elements are d-block elements but all d-block elements are not transition elements neral aracteristics . Transiton elements resemble in their physical and chemical properties as they have similar ns* configuration in their outermost energy shell. They are hard metals, have high tensile strength, ductility, malleability and are good conductors of heat and electricity. They have high M.P. and B.P. and form alloys with other metals, Theit reactivity decreases with the increase in their atomic number, ¢ Metallic character : All the transition elements are metals - They exhibit all the three types of structure hep, bee and cep. @ Metallic bonding is due to ns‘orns? and unpaired electrons of (n-1)¢* oO¢ Cr, Mo and W have max. number of unpaired (n-1)d electrons and they are hard where as Zn, Cd and Hg. are soft as they do not have any unpaired electrons. ¢ Atomic radii - Smaller than s-block and larger than p-block elements of corresponding period. The atomic radii of the elemenets of a given series are decrease with increase in atomic no, but this decrease becomes smaller after mid way. This is due to screening effect and muclear charge effect which oppose eachother. ‘The value of atomic radii at the end of each series ae bit higher. This is due to electron-electron repulsions among (n-I)d electrons. These repulsions become predominant at the end of each series and thus size increases. Inthe vertical column atomic radii increase down the group from Ist transition series to the second transition series but the similarity in the atomic radii ofthe elements of 2nd and 3rd transiton series is due to lanthanoid contraction. Se, t vo Mn Fe Co Ni Cu Zag, 144A 132, 1201187116 IS LI7 1.25 Yu zr Pb Mo Te Ru Rh Pa Ag Cay 162A 145 13413000 1251.25 1281.34 1.48 La Hn Ta W Re Os Ir Pt Au Hg 1.68A 144 134 1300-128 1.26 1.26 129134 149 Jonic Radi: Ionic radii follow the same trend as the atomic radii, In the same oxidation state the ionic radii generally decreases as the atomic number increases in a particular series. Jon STR VC Mn Fe Co** NI Cu Tonic radii 095 0.90 088 084 0.80 0.76 0.74 0.72 0.69 ‘¢ Tonic radii decreases with increase in charge on the ion, "Re <'Fe®,'Ni* <'Ni®, ‘Mn <'Mn®* Density : Except last two elements density increases from left to right in the series due to increases in atomic ‘mass and decrease in atomie radii © 6, =2261gr/ee and p,, =22.57¢t/ except Se, Ti and Y all transiton elements have densities greater than Sgm/c.. MP. and B.P. - have high M.P. and B.P, due to strong metallic bonding In cach series, the melting point and B.P. of these metals rise to a maximum value and then decrease with increase in atomic number. Ps is lowest (3.1 gm/ce) an transition elements. Mn and Te have abnormally low melting points. ‘Tungesten (W) has the highest M.P. amongst transition elements. Zn, Cd and Hg have low MP. as they do not contain unpaired electrons, Tonisation enthalpies - Lie in between s and p-block elements ‘Transiton elements do not form ionic compounds so readily as s and p-block elements do, Generally in oxidation state, compounds are ionic whereas in higher oxidation state compounds are covalent, Tonisation potential values inercase in a period from left to right the increase however is not regular. LE, For Cu and Cr are sufficiently higher than those of neighbouring elements. This is due to completely filled and half filled configuration of 34-subsehll ‘¢ In vertical columns ie, In groups, Ionisation potential decreases from first member to 2nd member in most of the ‘eases as expected however, the third member has the higher value than 2nd member. This is duc to lanthanoid contraction.Variable oxidation states The characteristic property of transitional elements is to show several oxidation states. This is because both (n—1) dand ns electrons can take part in bond formation due to small energy difference between them, ‘The maximum variation in oxidation state is observed when the electronic configuration is (n-1) d°ns*. The highest oxidation states are found in the compounds with fluorine and oxygen since they are highly electronegative elements. The highest oxidation state shown by the transition metals eight, c.g., Os, The relative stabilty of diferent oxidation states w.rt. oxidation can be determined with the help of standard electrode potential data, For example, E? values for couples Cr°/Cr? =—0.41 V and Mn"'/Mn"?=* 1.51 V. These values suggest that Cr’? get easily oxidised to Cr’’ while Mn gets easily reduced to more stable ‘Mn’? in aqueous solutions. Similarly, Fe" is unstable in aerated water and gets oxidised to Fe". The common oxidation state of elements of 3d-series is +2 (Scandium is an exception) but Cr (Chromous ion) is unstable in water with respect to oxidation. In the +2 and +3 oxidation states, bonds formed are el trovalent. As the oxidation state of the transitional element increases, the covalent nature of the bond also increases. For example, in MnOj ion, all the Mn— O bonds are covalent. Within a group, the maximum oxidation state increases with atomic numbers. For example, iron shows the ‘common oxidation state of +2 and +3 in its compounds but ruthenium and osmium in the same group give compounds in +4, +6 and +8 oxidation states. Transitional metals also form compounds in low oxidation states like zero and +1. For example, in metal carbonyls M(CO),, the metal M is in zero oxidation state, e.g, Ni(CO),, Fe(CO), ete Oxidation states Colour Most of the compounds of transition metals are coloured in solid state or in solution states. This is due to the presence of incompletely filled d-orbitals. Colour is due to d- d transiton. Se, Tit”, V* are colourless as they have 34° configuration, Cu, Ag’, Au’, Zn”, Ca", Hg” are colourless because they have completely filled d-orbitals. Colours of Cr,0}, CrO}, MnO;,MnO}- are duc to charge transfer Compounds of s and p-block elements are generally colourless as high energy is requried for promotion of elecetrons which is not available in visible region. The required energy is available in u-v region. Magnetic properties Majority of substances show paramagnetic nature. Transition Metal compounds are paramagnetic due to presence of unpaired electron in (n-1) d subshell, Transition metal compounds are diamagnetic due to absence of unpaired electron in (n-1) d-subshell Magnetic Moment : (1) is given as anos) BM. 1BM= 7 Complex formation :~ Transition metals form a large no. of complexes due to (a) small size (b) high charge and (c) presence of vacant d-orbitals in their outermost cells. Alloy formation :- transiton metals form large number of alloys since they are similar insize. Alloys containing Hg are led amalgams. Elements of (VIII) group do not form amalgam. Catalytic property :~ d-block elements and their compounds act as catalyst in various reaction due to utilisation of (t-1) orbtials or formation of interstitial compound.Inner-transiton elements ‘¢ Element having Z = 58 to Z=71 are lanthanides or Lonthanoes or lanthanoids i.e. Lanthanides are Ceg, to L @ Thy, to Lwio, are Actinides or actinones or actinoids. ‘© Lanthanides mostly form ionic compounds in +3 oxidation state, Atomic and Ionic size The ionic radii of lanthanoids show a progressive decrease with increasing atomic number. The decrease in size of Ln™ is known as Lantanoid contraction. ‘¢ Duc to Lanthaide contraction, the elements of 4d and Sd transtion series resemble cach other much more closely than do the elements of 3d and 4d series, ‘¢ Oxidation states - The common oxidation states of al the lanthanides is +3. Other oxidation states are +2 and +4 in particular. La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu BBB 2 2 8B OF 8 Bo 8 42 8 448 BOHM BOB 4 8 “4 “4 ¢ Colours of ions - Ions of lanthanides are coloured in the solid state as well as in aqueous solution (except ~ La®, Ce, Gd", Yb" and Lu") Colour of these ions are due to f-Ftransition, ‘© Magnetic properties - Ions having 4f° (L other configuration are paramagnetic. + Cel) and 4p (Yb™* and Lu**) are diamagnetic and having Chemical reactivity = tae LaQ(Ce0) » no, ©,2500°C HO. Ln(OH),+H¢ tn bon, ON H w sja ; Lol, Lol, Ln’ H, Ins, ACTIONOIDS ‘¢ have three shell (1-2), (n-1) and n shell incompletely filled and differentiating electron enters into Sf-orbital © GEC. [Rast 6d"! 757 The variation in the electronic configuration of the actionoids like those of lanthanoids is due to extra stabilities of £8," and f* electronic configuration ofthe Sf orbitals ‘@ All actionoids are radioactive and are o ~ray emitters, ‘Atomic and Ionic Size :- The ionic radii for the M’* and M"" ions contract slightly with inereasing atomic number, The decrase in size of An” is known as actinoide contraction. ‘* Oxidation states :- The actinide in gencral show +3 oxidation stole. There is also a greater range of oxidation states due to comparable energies of Sf, 6d and 75. ‘« The actinoids resemble the lanthanoids in having more compounds in +3 state than in +4 state but they tend ot hydrolyse.U™ in aqueous solution evolves H, on standing. Aq. solution of Np** and Pu*” are stbale but are easily oxidised to Np** and Pu** ‘¢ U" and Np" are stable to water but are slowly oxidised by air to UO?" and NpO? ‘© Pu* disproportionates to Pu’* and Pu?* when solutin is strongly acidic, ‘© Li} disproportionates to Li** and Li0? ‘¢ Ionisation energy of the early actinoids are smaller than those of early lanthanoids. IMPORTANT COMPOUNDS 1. Copper sulphate (Blue vitriol), CuSO,.5H,O - (i) Preparation - By dissolving CuO or CuCO, or malachite in dil, H,SO, and evaporating the solution to cxystalization point CuO +H)S0,—> CuSO, +H,0 CuCO3 +H2S03 —+CuS04 +H20+CO. (ii) Properties - (a) Blue crystalline solid, soluble in water. (b) Action of heat : CusO,.5H,0 2 Cuso,.H,O SO, + CuO <25— cuso, white (annydrous sat) Gi) Uses - (a). Used in copper r (b) Also used in the preparation of Bordeaux mixture (a mixture of CuSO, solution + lime), used as @ fungicide for fruit trees, grapes, and vine plants (a) Action of NH,OH : With ammonia solution; it forms the soluble blue complex. First it forms a precipitate of Cu(OH), which dissolves in excess of ammonia solution. ing, electroplating, dying, calico printing and Fehling’s solution, CuSO, + 2NH4OH—> Cu(OH), ppt + +(NH4), SO4 Cu(OH), +2NH,OH +(NH,), SO, —>[Cu(NH3),]SO4+4H,0 Ia a 4). $04, 13 )4]SO4+ 4Hy! Tetrammine cuprie sulphate [Cu(NH,),] SO, isknownas Schwizer’s reagent (b) Action of alkalies : ‘Alkalies forma pale blue precipitate of copper hydroxide. CuSO, +2NaOH—>Cu(OH), + +Na2S0,4 (©) Action of potassium iodide@ (e) ® (h) wa a 2._Mercurous Chloride (Hg,Cl First ofall cupric iodide is formed which decomposes to give white cuprous iodide and iodine. [CuSOq +2KI—> Cul, +K,$0,]x2 2Culy —>Cugly + 1p 2CuSO4 + 4KI—> Cul + 2K S04 +1) Action of potassium cyanide First ofall cupric cyanide is formed which decomposes to give cuprous cyanide and cyanogen gas. Cuprous cyanide dissolves in excess of potassium cyanide to forma complex, potassium cupro cyanide K,[Cu(CN),] 2CuS04 +10KCN —>2K3[Cu(C! Action of potassium ferrocyanide : Reddish brown precipitate of cupric ferrocyanide is formed. (test of Cu” ion) :)4]+2K3804 +(CN), 2CuSO4 + K4[Fe(CN)g] —+ Cug[Fe(CN)g]+2K S04 Addition of electropositive metals CuSOq(aq) + Fe —> Cu + FeSO, CuSOq(aq) + Zn —+Cu+ZnSOg Action of H,S When HS is passed into copper sulphate solution, a black precipitate of copper sulphide is formed. CuSO4 +H)S—> CuS + H,S0, The black precipitate dissolves in cone. HNO, 3CuS + 8HNO; —>3Cu(NO3), +2NO +38 +4H,0 Action of potassium sulphocyanide : Cupric sulphocyanide is formed. 2CuSO4 + 2KCNS +809 +2H{O0—> Cup (CNS), +Ky8O4 +2HySO04 Double sulphates : Copper sulphate forms double salts with alkali sulphate K,SO,. CuSO, 6H,0 and with ammonium sulphate as (NH,),SO,CuSO, 6H,0. Action of sodium thiosulphate : Sodium thiosulphate reacts with copper sulphate to form cupric thiosulphate which is reduced by sodium thiosulphate. The cuprous compound thus formed dissolves in excess of sodium thiosulphate to form a sodium cuprothiosulphate CuSO4 + NagS:0; —>CuS203 + NazSO4 2CuSyO3 + NayS30; —+CuyS03 +Nay$4Oe 3Cu8,03 +2Naz$0; —> Naq[Cug (S205), |} Sodiuns euprothiosulphate Calomel) Methods of preparation : (i) Hg,Cl, (calomel) is formed as white precipitate when soluble chloride (say ‘NaCl is added to soluble mercurous salt (say Hg, (NO,),Hg(NO3), +2NaCI—+Hg2Cl; 4 +2NaNO3 (i) HgpCly is also formed when aq HgCl, and ag. SnCl, are mixed in 1 : 1 molar ratio or HgCl, is reduced by Hg, 2 HgCly + SnCl) —> HgyCly +SnCly Excess of SnCl, would reduce Hg,Cl, to Hg HgjCly +SnCl] —>2Hg +SnCly ny HgCh +Hg —4> He,Ch, inion tank Properties of Hg,Cl, : It is an amosphous, tasteless, odourless, non-poisonous, white power which is sparingly soluble in water. HgCl, HgCl+ Hg Nl He(NO), NOH SnCl,+Hg HgNHC1+ Hg « Mercurous ion is diamagnetic; this indi Hg’ but Hg es that there is no unpaired electron, hence mercurous ion is not 3. Mereuric Chloride (HgCl, - Corrosive Sublimate) Preparation (@ _Itisprepared by heating a mixture of mercuric sulphate with common salt, in presence of little manganese dioxide (was o prevent the formation of any mercurous chloride), Mercurie chloride sublimes offand condenses on the cooler parts of the vessel. HgSOq +2NaCl—> HgCly + NaySOq (i) Byheating the Hg in a current of chlorine. Hg +Cl) —>HgCly ii) It canbe prepared by dissolving mercuric oxide in hydrochloric acid. HgO + 2HC1—+ HgCl, + H,0 (i) It can also be prepared by dissolving Hg or Hg, Cl, in aqua-regia. 3HC1+ HNO; —> NOCI+2H30+2C1 Hg +2ClI—> HCl HgyCly +2CL—> 2HgClyProperties : @ _ Itisawhite crystalline compound having highly poisonous nature, Its less soluble in cold water but more soluble in hot water. It behaves like a covalent compound as itis soluble in organic solvents and very slightly ionised in water, i) Itisreduced by stamous chloride first into mercurous chloride (w! (¢) and then into mercury (black) 2HgCly +SnCl; —> Hg,Cl; +SnCly White 2HgClz +SnCl —> 2Hg + SnCl, Black (ii) Potassium iodide forms scarlet precipitate of mercuric iodide when added to HgC, solution. HgCl) +2NaQH—> Hg0 + 2NaCl+H,0. HgCly +2KI—>2KCl+Hgly Hgl) +2KI—> KpHgly The precipitate of mercuric iodide dissolves in excess of potassium iodide forming a complex, K lel, The alkaline solution of K,Hgl, is known as Nessler’s reagent. This reagent is used for testing ‘ammonia, (iv) When aqueous ammonia is added to the solution of mercuric chloride, a white precipitate of mercuric amino chloride is formed, NH, HgCly +2NH4OH —> He + NH,C1+2H,0 Cl (8) Mercurie chloride absorbs gaseous ammonia and forms.an addition compound HgCl) +2NH; —>HgCl;.2NH3 (vl) When H,S is passed into its solution, it forms black precipitate of mercuric sulphide. HgCly +H)S—> Hg 4 42H black (vil) When heated with sodium carbonate or sodium hydroxide in solution, a yellow precipitate of mercuric oxide is formed HgCly + NayCO; —>Hg0 + 2NaCl+ CO} 4. Potassium dichromate ‘A. Preparation. It is obtained fom chromite (FeO.Cr,O.) by the following steps :- (@) Fusion of ore with caustic soda - 4(FeOCr,0,) + 16NaOH + 70, —> 8Na,CrO, + 2Fe,0, + 8H,O (b) Acidification of extract 2Na,CrO, + H,SO, —> Na,Cr,0, + Na,SO, + H,O (©) Conversion into Pot. dichromate - Na,Cr,0, + 2KCI —> K,Cr,0, + 2 NaCl