The d-and f-Block Elements THE TRANSITION ELEMENTS (d-BLOCK) A typical transition element shall have an incompletely filled d-sublevel either chemically significant O.S. Electronic Configurations/(n-1) dns", 1. Cr= 4s! 34° 2, s! 3d" 3. Pd = Ss°4d"° Transition Seri 1* | 3dseries ts elemental form or in any of its Exceptions: ‘omic number —> Fig Tends in meling points of transition elements 2 | 4d series 3" | Sd series e ries | 9+1=10 GENERAL PROPERTIES OF TRANSITION ELEMENTS + The transition elements exhibit typical characteristic properties due to their small atomic sizes, large nuclear charges and the presence of unpaired d - electrons. Enthalpy of atomization: V > Ti > Ni> Co> Fe>Cr> Cu> Se >Mn > Zn (1) Trends in M.P of Transition Elements ‘In any row the melting points of these metals rise to a maximum at d* except for anomalous values of Mn and Te and fall regularly as the atomic number increases. They have high enthalpies of atomization, The maxima at about the middle of each series indicate that one unpaired electron per d orbital is particularly favorable for strong, interatomic interaction, = 9+1=10 ‘Number of valence electrons increase 4 strong bonding higher enthalpy of atomisation | higher boiling point | | higher standard electronic potential | ) More noble character (After chromium, the number of unpaired electrons ) goes on decreasing. Accordingly, the melting points | | decrease after middle (Cr) because of increasing | pairing of electrons. (2) Size of Atoms and lons “The covalent radii of the elements decreases from left to right across a row in the transition series, until near the ‘end when the size increases slightly. 4 Metallic radii: Se>Ti>Mn=Zn> V>Cr>Cu>Co=Ni (3) lonization Energies of 3d Series ‘© [Pvalues generally increase from left to right in any series but the increase is less than that of s block elements because the increase in nuclear charge is opposed by screening effect. 4 Ionization Enthalpy: Zn > Fe > Co > Cu> Ni >Mn> Ti> Cr> V>Se (4) Oxidation States ‘Transition elements exhibit variable oxidation states due to small energy difference of ns and (n — 1)d electrons. So(+3) and Zn(+2) exhibit only one oxidation state 4 Common oxidation state is +2 3d series highest oxidation state is +7 (Mn) e t oxidation state is +8 (Os, Ru) ( ® In carbonyl compound oxidation state of metals is) zero due to synergic effects. | | The common examples are [Ni(CO),), [Fe(CO),] in | Which nickel and iron are in zero oxidation state.Their higher oxidation states are more stable in fluoride and oxides 4 Higher oxidation states in oxides are normally more stable than fluorides due to capability of oxygen to form multiple bonds. 4 In the +6 O.S, the most important species formed by chromium are chromate CrO,* and dichromate Cr.02 ion 7 ‘Some more stable oxidation states of d-block elements ~ Mn+2 Sc+3 Pi+4 Aut3 ‘Common oxidation states VCS) Cr(43,+6) Co2, 43) NiG2) Agtt Ni+2 TH 4) Fe(+2, +3) Mn (#2, +4, 47) PH(+2, +4) & In p-block lower oxidation states of heavier elements are more stable while in d-block heavier element, higher oxidation states are more stable, (5) Electrode Potentials and Chemical Reactivity ‘Trends in the M*/M standard electrode potentials 4 S.RP of M?/M values increases from left to right as IP values increases. (except Zn) Cu cannot displace H, from acids because it has hi est S.RP value which is +0.34 V. % Mn, Ni and Zn have more negative S.R.P values than expected because Reason: Mn & Zn have d° & d® stable electronic configuration and Ni has highest hydration energy. (AH,,, Ni? =-2121 ki/mole) Trends in the M*/M* standard electrode potentials & B® saqgo im the 3d series observed for some metals are w/a CoCo? > Mn"/Mn"> Fe"'/Fe> Ti/Ti> Sey) Sc>V/V"2 (6) Magnetic Properties of Transition Metals Paramagnetic substances contain unpaired electron spins or unpaired electrons, Ex : K[Fe(CN),}, Se, Cr” ete Diamagnetic substances contain electron pairs with opposite spins. Ex. Ti, V % Diamagnetic substances e etic field Sc, Zn, Hg, Cd ete xxhibit decrease in weight in the presence of magi % Ferromagnetic substances are considered as a special case of paramagnetic substances. Paramagnetism of substances (molecules, atoms oF ions) is due to the spins of the unpaired electrons and also due to angular orbital momentum. In terms of number of unpaired electrons (n), the magnetic moment is given by the formula. in(n+2) BM (7) Colours of Transition Metal lons Colour in transition metal ions is associated with d-d transition of unpaired electron from t,, to e, set of energies My (8) Formation of Complexes ‘The great tendency of transition metal ions to form complexes is due to : small size of the atoms and ions, high nuclear charge and availability of vacant d-orbitals of suitable energy to accept lone pairs of electrons donated by ligands. (9) Catalytic Properties of Transition Metals Good catalysts due to the presence of free valencies and also variable oxidation states. (10) Formation of Interstitial Compounds ¢ Form interstitial compounds: As they are able to entrap atoms of elements having small atomic size like H. C, N. Bete. ‘ The general characteristic physical and chemical properties of these compounds are: (i) High melting points which are higher than those of pure metals. (ii) Retain metallic conductivity i.e., of pure metals. (iii) Very hard and some borides have hardness as that of diamond. (iv) Chemically inert. (11) Alloy Formation 4 Solid mixture of metals in a definite ratio (15% difference in metallic radius) 4 They are hard and have high melting point. eg., Brass (Cu+ Zn) Bronze (Cu + Sn) ete. 4 Hg when mixed with other metals form semisolid amalgam except Fe, Co, Ni, Li. ES Peels litel Wal eet ae} Properties (a) Physical two tetrahedra unit Fig.: Dichromate ion orange, red colour aeK,Cr,0, is preferred over Na,Cr,O, as a primary standard in volumetric estimation because Na,Cr,O, ic in nature but K_Cr,O, is not (b) Chemical / 3 1» 242K ,CrO, +Cr,0, +50, ,0, + 2KOH —> 2K,Cr0, + H,0 Cr,0}+ 20H” —> 2Cr0> + 1,0 : Orange Yellow — (color change in basic medium) 2CrO} + 2H" —> Cr,0? + H,0 Yellow Orange —+ (color change in acidic medium) DN a ( * CrO} and Cr,0? exist in equilibrium and are interconvertable by altering the pH of solution. 2CrO} + 2H’ = 2HCrO, = Cr,02 + H,0 % It acts as a powerful oxidising agent in acidic medium (dilute H,SO,) Gr, OF + 14H + 6 —> 2Cr* + THO. (E°= 1.33 V) Reaction of acidified potassium dichromate K,Cr,0, + 3Na,SO, + 4H,SO, —> Cr, (SO,), + 3Na,SO, + K,SO, K,Cr,0, + 380,(g) + H,SO, —> Cr, (SO,), + K,SO, POTASSIUM PERMANGANATE (KMn0O,) Preparation ‘ Commercially it is prepared by fusion of MnO, with KOH followed by electrolytic oxidation of manganate. MnO,> (green) —> MnO,; (purple) + e~ Inthe lab 2Mn** + 58,02 + 81,0 —> 2MnO, + 1080? +16H* Properties (a) Physical d orbital p orbital bond a, Tetrahedral permanga- nate (purple) ion (Diamagnetic) Tetrahedral manganate (green) ion (Paramagnetic) MnO,> & MnO, contain one and zero unpaired electron respectively (b) Chemical {i Effect of heating 2KMno, —2!%> K,MnO, + MnO, + O, In alkaline & neutral medium < +2K 2K, MnO, + H,0 + [0 2KMnO, + 2KOH —> 2K, MnO, + H,0 + [0] conc.) __manganate If solution is dilute 2K MnO, + 2H,O —> 2MnO, + 4KOH + 2[0] ; (Brown ppt) This type of behaviour is shown by KMnO, itself in neutral medium 3e- + 2H,O + MnO, —> Mno, + 40H In alkaline or neutral medium KMnO, shows oxidising properties. In acidic medium (in presence of dilute H,SO,) oxidised MnO, + SFe®* + 8H*—> 5Fe + Mn** + 4H,O. * "Green yellow oxidised 2MnO, + 5SO, +2H,O—> SSO} + 2Mn** + 4H" THE INNER TRANSITION ELEMENTS (f-BLOCK) aD EaaERTaS Lanthanoids Electronic configuration - 4f-'* 5d™! 6s? La to Lu 7) ay Actinides Properties Atomic sizes ‘There is decrease in atomic and ionic radii from lanthanum to lutetium due to lanthanoid contraction. However, the shielding of one 4f electron by another is less than a electron by another with the increase in nuclear charge along the series. The net result of the lanthanoid contraction is that the second . and the third d series exhibit similar radii (c.g., Zr 160 pm, Hf 159 pm) and have very similar Physical and chemical properties much more than that expected on the basis of usual family relationship. Physical Properties Density: Increases with increase in atomic number. Electropositive Character: Highly electropositive due to their low ionisation energy, Jonisation Energy: Low ionisation enei energy? ies, IE, & IE, are equal to calcium ionisation enthalpy ne© (P)La i ("Ga ed)Lu e Magnetic Behaviour é M?* ions are aramagnetic $ 3° Laces Yee e Gs —.— Diamagnetic Colour % The colour is due to £-f transitions since they have partly filled f-orbitals. Radioactivity * All Lanthanides except promethium and samarium are non-radioactive Oxidation States Common oxidation state is + 3. oe +3 oxidation state stable in La, Gd and Lu. +3 oxidation state in Lanthanum, Gadolinium and Lutetium are especially stable because +3 ions of these elements have an empty (f°), a half filled [£7] and completely filled (f") configurations. Although the formation of Eu’ is favoured by the extra stability of its {” configurations, but Eu” is a strong reducing agent and changes to Eu® in its reactions. Samarium (Sm) also shows +2 and +3 oxidation states. + The formation of Ce'Y is favoured by its noble gas configuration. Chemical Reactivity of Lanthanides + Earlier members of the series are quite reactive similar to calcium but, with increasing atomic number, they behave more like Al % Size of M” ion | the covalent character in M-OH bond and their basic strength in their hydroxides | gradually from La(OH), to Lu(OH), due to Lanthanide contraction Lac, Ln(OH), + H, Fig.: Chemical reactions of the lanthanoids ACTINOIDS * General electronic configuration — Sf“ 6d! 7s? + Acyy f, Lrg) Properties Atomic Size % Decrease in size of M’* across series due to actinoid contraction (poor shielding by 5f electrons) Oxidation States Large number of O.S due to comparable energy 0 Sf, 6d and 7s energy level, The E® Value for Ce*/Ce** is +1.74 V which suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent. % Common oxidation state is +3 > Also exhibit +4, +5, +6, +7 oxidation states > After uranium — elements are known as transuranic elements.