Ayan Sir (VMC The d & f-Block Elements Electronic Configurations/(n—1) a1? ns, higher boiling point Exceptions: 1. Cr= 4s! 3° 1 2. Cu=ds'3¢” higher standard electronic potential 3, Pd= 55°40) 1 Traut Sets a 7 [aie [55,7 Bt [ad series | Yop ~ Coy 3" |Sdseries |La,,, HE,,- Hay, 4% [Gdseries [Acyy, Ung,.,- Uub,,, General Properties of Transition Element > 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>Ma> Zn (2) Trends in M-P of transition elements(TE) > In any row the melting points of these metals rise to a maximum at a° except for anomalous values of Ma 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. ‘Number of valence electrons increase L strong bonding 4 higher enthalpy of atomisation 4 ‘Trent ineingpoinsof Tension cena ‘After chromium, the umber of unpaired electron goes on decreasing. Accordingly, the melting points’ decrease after middle (Cr) because of increasing pairing of electrons. Q) Size of atoms and ions. > The covalent radii of the elements decreases from. left fo vight across a row in the transition series, until near the end when the size increases slightly. > Metallic radii: Se > Ti> Mn ~Zn > V>Cr>Cu> Co=Ni @) Ionization Energies of 3d Series > IP values generally inerease from lef to right in any series but the imerease is less than that of s block elements due to increase in nuclear charge is ‘opposed by screening effect. > Ionization Enthalpy: Zn >Fe> Co > Cu> Ni> Mn> Ti>Cr>V>Se(4) Oxidation State Transition elements exhibit variable oxidation st ate due to small energy difference of ns and (n ~ 1)d electrons. > Sc(+3) and Zn(+2) exhibit only one oxidation state > Common oxidation state is +2 > 3d series highest oxidation state is +7 (Mn) > Ind-block series highest 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. > Higher oxidation states in oxides are normally more stable than fluorides due to capability of oxygen to form multiple bonds. (6 Magnetic Property of Transition Metals > Paramagnetic substances contain unpaired electron spins or unpaired electrons, > Ex: K[Fe(CN)g} Sc, Cr ete > Diamagnetic substances exhibit decrease in weight in the presence of magnetic field > Ex:TV4.V%, Sc, Zu, He, Cd ete > Diamagnetic substances contain electron pairs with opposite spins. > Ferromagnetic substances are considered as special case of paramagnetic substances. > Paramagnetism of substances (molecules, atoms or ions)is due to the spins of the unpaired electrons and also due to angular orbital momentum. Roane In terms of number of unpaired electrons (n), the ! jmetedemonentis sirenbythefomcia. | ‘Some moze stable oxidation states of d-block elements Git? Mn+2 Pid Ag cus3 Se+3_ Aut3——_Ni+2 ‘Common oxidation states Tea) VG) C335) Maca, 7) ESSE SoS) NR In p-block lower oxidation states of heavier elements are more stable while in d-block heavier element, higher oxidation state are more stable. (5) Electrode potentials and chemical reactivity ‘Trends in the MM Standard electro potential > S.RP of M/M values increases from left to right as IP values increases. (except Zn) a cannot displace H from acids because it haa highest SRP value which is +0.34 V. > Mn, Ni and Zn have more negative SRP values than expected because, » Reason: Mn & Zn have d° & d'® stable electronic configuration Ni has highest hydration energy. (AH yy, Ni? =—2121 Kole) ‘Trends in the M*"/MP" Standard electro potential > E* pogo? iin the 3d series are observed for some metals are CoCo? > MaiMa®> FeOFe? > TT? Se7/Se>V3V2 u, =fo(n+2) BM Sa ‘Q. The magnetic moment of Ni ion (atomic number of Ni= 28) in BM unit i: aL b. 481 «. 5.96 a. 2.84 Ans. (4) Nig~ [Ar] 3¢° 45° Nie= [Ar] 34° EEE enn? w= yn(a+ 2) = J22+2) = (2(4) = V8 = 2.84BM] Q. The correct order of magnetic moments (spin only values in B.M.) among is a. (Fe(CN),I* > [MnCl }*> [CoC] b. [MnCl }-> [Fe(CN),}*> [CoC ¢. [MnCl }-> [CoCI, > > [Fe(CN)] 4, [Fe(CN) J+ > [CoC > [Moc } Ans. (©, au wor [1 [1 [1] 1 TE) Namber of unpaired etn =F rooeu[y [0] 1] 1/1 umber of unpaired elon ro A Naber of oped esto(7) Colours of Transition Metal Tons Colour in transition metal ions is associated with d-d transition of unpaired electron from t,, to e, set of energies (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 meclear charge and availability of vacant orbitals of suitable energy to accept lone pairs of electrons donated by ligands, (©) Catalytic properties of transition metals Good catalysts due to the presence of free val and also variable oxidation states (10) Formation of Interstitial Compounds > From 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 : © High melting poluts which are higher than those of pure metals. © Retain metallic conductivity ie. of pure metals, © Very hard and some borides have hardness as that of diamond. © Chemically inert. (11) Alloy Formation Solid mixture of metals in a definate ratio (15% difference in metallic radius) ‘They are hard and having high melting point. eg, Brass (Cu+Zn) Bronze (Cu + Sa) et. Hg when mix with other metals form semisolid amalgam except Fe, Co, Ni, Li Potassium Dichromate (K,Cr,0,) Properties (@) Physical: ‘wo tetrahedra unit Fig.: Dichromate ton orange, red colour K,C1,0, is preferred over NajCr,0, as a primary standard in volumetric estimation because ‘Na,Cr,0, is hygroscopic in nature but K,Cr,0, is ot. () Chemical: fe 2K,C,0, 2 52K,C10, +C4,0, +30, K,Cr,0, + 2KOH > 2K,C10, +H,0 C1,02+ 2087 > 2Cr0? + H,0 Orange Yellow— (color change in basic medium) 2010} + 2H" —> C1,02-+H,0 Yellow Orange — (color change in acidie medium) CcO} and Cr,0} exist in equilibrium and ar interconvertable by altering the pH of solution. 2CrO} + 2H* = 2HCr0; = Cr,0-+H,0 Tracts as a powerful oxidising agent in acidic ‘medium (dilute H,S0,) E02 + 4B + Ge" — 208° + THO. (B= 133) CSO) Reaction of Acidified potassium dichromate | | K,Cr,0, + 3Na,S0, + 4HL,S0, —+ Cr, ($0,), +3Na,S0, +K,S0, I ,c1,0, +350, + 1,50, | LP O80), +K,504 (Q. Theseaction ofacidified potassium dichromate swith Na,SO, produces a compound that show green colour. Identify the compound. a, Cr, (SO,)s b. KO, c. Cr,0,2- d. Mn0,, “Ans. (a) K,Cr,0, + 3Na,SO, + 4H,SO, —> Cr, (S0,), +3Na,S0,+K,S0, green colour Potassium Permanganate (KMnO) Preparation > Commercially it is prepared by fusion of MnO, with KOH followed by electrolytic oxidation of manganate (green) —> MnO,- (purple) + e~> Inthe lab 2Mn2* + $8,0}-+ 8H,O —> 2Mn0; + 1080; +16 Properties (a) Physical: @ __..xbond | dori? 7 IO) Port ° ‘Tetrahedral manganate | Terahedral permanganate (green) ion (purple) ion (Paramagnetic) (Diamagnetic) een) & MnO, contains one and zero! ‘unpaired electron respectively J Q. Predict the magnetic nature of manganate and permanganate ion a. Paramagneti, diamagnetic ». Diamagnetic, Paramagnetic «, Paramagnetic, Paramagnetic 4. Diamagnetic, Diamagnetic ‘Ams. (@) Manganate (20) The green manganat is paramagnetic with cncunpaired electron but the permanganate is diamagnetic, (Mn0,2) Paramanganate () Chemical: @ Eqlect of heating 2kMn0, 25 K,Ma0, + MnO, +0, In alkaline & neutral medi 2KMa0, + 2KOH —> 2K, MnO, + H,O + [0] (cone) manganate Ifsotution is dilute 2K,Mn0, + 2H,0—+ 2MnO, + 4KOH ~ 2[0] Brown pp) 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; + Se +8" > ske!*+Mn2* +410 Green yellow. oxidised — 2Mn0; + $80, +2H,0—+ 580}-+ 2Mn™* + 4° ——_—__—__. ‘The Inner Transition f-Block Elements =, Lanthanides Actinides Lanthanides Electronic configuration -4f! Sd" 6s La to Lu 6) aD 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 d-electron by another with the increase in nuclear charge along the series. RON nea) The net result ofthe lanthanoid contraction is that [he socond andthe tid d seis exhibit similar radii (¢, Zr 160 pm, HF 159 pm) and have very | Silar physical and chemical properies much ‘more than that expected on the basis of ustal fanily relationship. 4 (Q. The par thats refered as “chemical twins is: a Ac,Cf b.HfTa c.Te,Re dla,Ac Ans. () Te & Re belongs o same group. The atomic radius of elements of second transition series is similar to that of third transition elements, due 10 poor shielding of forbitals.(MinO-) ‘The green manganate is paramagnetic with one unpaired electron but the permanganate is diamagnetic. Physical Properties Density: Increases with increase in atomic number. Electropositive Character: Highly clectropositive due to their low Tonisation energy. Tonisation Energy: Low ionisation energies, IE, 8:1, are equal to calcium ionisation enthalpyianagaotic Colour > The colour is due to Ef transitions since they have arly filled f-orbitals. Radioactivity > All Lanthanides except promethitim and samarium are non-radioactive Oxidation States, > Common oxidation state +3. > + oxidations state stable in La, Gd and Lu. > +3 oxidation state in Lanthanum, Gadolinium and Latetium are especially stable because +3 ions of these elements have an empty (f°), a halffilled [f] and completely filled (#4) configurations. > Al though the formation of Eu?* is favoured by the extra stability of its configurations, but Eu"™ is a strong reducing agent and changes to Eu’ inits reactions. Samarium (Sm) also shows +2 and +3 oxidation states. The E° Value for Ce*/Ce™ is +1.74 V whieh suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is @ good analytical reagent, The formation of Ce" is favoured by its noble! eesconfizuation _ 4 Q Although +3 is the characteristic oxidation’ state for lanthanoids but cerium also shows ~4 oxidation state because: a. Tthas variable ionisation enthalpy b It has a tendency to attain noble gas configuration . Ithas a tendency to attain f°configuration 4. Thresembles Pb Ans. (be) Electronic configuration —_of | Ce =54[Xe]4f?5d° 6s". Thus, it has a tendency to attain noble gas configuration and attain f° 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 4 gradually from La(OH), t0 LwOH), due to Lanthanide contraction Fig: Chemical reactions of the lanthanotd's Actinoids — > General electronic configuration + Sf46d° 75? D Aegy toLawags Properties Atomic Size Decrease in size of Macross series due to actinoid contraction (poor shielding by Sf electron) Oxidation States, Large number of OS due to comparable energy ol Sf, 6d and 7s energy level. > Common +308 > Also exhibit +4, +5,+6, +7 0.8 > After uranium — elements knows as transuranic elementSt GEE ED . The st 1, Which of the following pair will have effective ‘magnetic moment equal? a. Cr? and Mn b. Cr? and Fe? ©. Vand Se? 4. Ti? and V" ‘The mamber of d-electrons in Fe* (at no, of Fe = 2r) is not equal to that of the a. p—electrons in Ne (at. no. ~ 10) », electrons in Mg (at. no. = 12) ©. d—electrons in Fe 4. p—electrons in CI (at. no. of C1= 17) ty of a particular oxidation state of a ‘metal in aqueous solutions is determined by: 1. Enthalpy of sublimation ». Ionisation enthalpy ¢. Enthalpy of hydration 4. All ofthese |. Which oxide of Mn is acidic in nature? a. MnO ©. MnO, Which of the following element exhibits ‘maximum oxidation state? a. Ma b. Co ©. Fe Zn ‘Which one of the following transition metals ions is colourless in aqueous solution? a. Tit be ©. Mn Fe . Which of the following has maximum unpaired d-clectrons? a. Zn b. Fee ©. Nt aor . The spin only magnetic moment of Fe ion (in BM) is approximately a4 b7 eS 46 . Transition metal show paramagnetic behaviour. ‘This is because of their: a, High lattice energy ’, Variable oxidation state . Characteristic configuration d. Unpaired electrons 10, The magnetic moment ofa divalent ion in aqueous solution with atomic mumber 25 is: a. S9BM b. 29BM ©. 69 BM 4. 9.9BM, 11, The comrect order of mumber of unpaired electron is a, Cu > NE*> Cr > Fe b. NEY > cue > Fe > cre ¢, Fe*> Cr+ > NE Cu 4. Cr > Fe" > NE“> Cu 12, Which of the following pairs magnetic moment is, a MnCl,,CusO, ——_b, CuCl, , TIC, ¢. TiO, .Cuso, 4. TiCl, . Nicl, 13, Electronic configuration of a transition clement X in +3 oxidation state is [Ar] 34°. What is its atomic number? a. 25 b.26 «27 dm 14, The correct order of decreasing second ionization enthalpy of Ti (22), V(23), Cr(24), and Ma (25) is: aTi>V>Cr>Mn —b, Cr>Mn>V>Ti ce. V>Ma>Cr>Ti d. Ma>Cr>Ti>V 18, When calomel reacts with NH, OH, we get a. HgNH,Cl b. NH, -Hg-Hg-Cl ©. HO 4. Hgo 16, Which one of the following oxides is ionic? a. MnO ©. Ma, ©. C10, 4. Mao 17. KMnO, in basic medium is reduced to a. K.Ma0, 4. Mano, ©. Ma(O¥), @ Mat 18, Which of the following statement is not true? a. Colourless compounds of transition elements are paramagnetic. . Coloured compounds of transition clements are paramagnetic. © Colourless compounds of transition elements are diamagnetic. Transition clements form the compounds. complex19, 20. 21. 24. Which of the following bas character? a. INICL?- b. [Cor c. [Fe(HO)/* é NONE In the dichromate dianion: a. 4.Cr-O bonds are equivalent b. 6 Cr-O bonds are equivalent ¢. All Cr-O bonds are equivalent 4. All Cr-O bonds are Nom-equivaleat ‘When KMnO, reacts with acidified FeSO, a. Only FeSO, is oxidised »b. Only KMnO, is oxidised ¢. FeSO, is oxidized and KMnO, is reduced 4d. KMn0, and FeSO, oxidised diamagnetic . Acidified K,Cr,0, solution tums green when 1Na,SO, is added to it. This is due to the formation b. Cr, (80), 4. Cx{S0,), Identify the correct structure of dichromate ion: oO I ] * Cr, Cr, No 810718 oO ° °o sto Ker 071 S07 10 oO ~f 2% Cr, LS o | oe af oy oo ‘The electronic configuration of cerium is: a. [Xe}4 f5d'6s! b. [Xe}4 Fsd'6s? c. [Ke] F5d°6s! 4. Both (b) and (c) ‘Which of the following is not the configuration of lanthanoid? a. [Red F263 c. [Ke]4 5463! Cr. | “o °o ° b. [Xe}4 Psd 65? o. [Xe] FSa6s? 26, 27, 28, 29, 30, 31 32, Zc and HE have almost equal atomic and ionic radii because of ‘a, Diagonal relationship b. Lanthanoid Contraction ©. Actinoid contraction 4. Belong to the same group Gd (64) gives an oxidation state of only +3 because: a. It contains 3 unpaired electrons >. In+3 oxidation state ithas unstable configuration ¢. In4+3 oxidation state it has stable configuration 4. There are 3 electrons present in 4f in +3 oxidation state ‘Across the lanthanide series, the basicity of the Janthanoide hydroxides: a, Increases b. Decreases o, First increases and then decreases 4, First decreases and then increases 4K,C,0, 4K, C10, +30, +X. In the above reaction X is a. C10, b. cr, «. Cr,0, 4. Cro, Arrange Ce", La”, Pur” and Yb" in increasing order oftheir ionic radi a. Yo3 < Pmt < Ce has no unpaired electron. It is diamagnetic. 20. (b) Resonance Resonance 21.0 22. (b) K,Cr,0, + 3NaSO, + 411,80, —. 3Na, SO, + K,S0, + 44,0 + Cr{S0,),i ror] 23. (a) a oe \ AK “Io [e719 S071 So 8 O° 6 24.0) 25. (0) 26. (b) The atomic and ionic radii of Zr and Hf are equal in size due to lanthanoid contraction. 27. (0) In + 3 oxidation state its configuration is 4f", Sd, 63, which i stable as per the rule of extra stability 28. (b) Across lanthanoide series, due to lanthanoid contraction, size of cation decreases, increase covalent character and decrease ionic character. So; basicity of hydroxides decreases. 29. (0) Potassium dichromate, on heating gives oxygen and chromic oxide (Cr,0,). 30. (a) Due to Lanthanoid contraction order will be Yb" Mn" + 4H,0] x2 Oxidation half C0 2€0, + 2] 2 Overall equation 2Mn0;+ 16H" + 5C, 3H, End point of this reaction Colourless to light pink + 2Mn"* +1000, + 32. (a) Gadolinium belongs to 4f series and has atomic number 64. The correct electronic configuration of gadolinium is Gd = ,Xe]sPSd'65* It has extra stability due to halffiled f ‘subshell. 33. (@) When small atoms are trapped inside the crystal lattice of metals interstitial compounds are formed, Some of their important characteristics are as follows (i) They are very hard and rigid. (ii) They have high melting point which are hhigher than those of the pure metals. (iii) They show conductivity like that of the pure metal (iy) They acquire chemical inertness. 34, (a) Copper does not liberate H, tromacidsas Copper lies below hydrogen in the electrochemical series. Therefore, option (a) is not correct. Other three options (b,c, d) are conect 3. (€) Due to lanthanoide contraction, Zr and Hf possess nearly same atomic and ionic radii ie, Z:= 160 pm and Hf = 159 pm, Zr* = 79 pm and Hf" = 78 pm, Therefore, these two elements show similar properties (physical and chemical properties). 36. (b,c) In d-block elements, for heavier elements. the higher oxidation states are more stable, Hence, ‘Mo(V1) and W(VD) are more stable than Cr (VD, ‘That why, Cr (VD) in the form of dichromate isa stronger oxidising agent in acidic medium ‘whereas MoO, and WO, are not. 37. (ab) General electronic configuration of actinoids is (n—1) *¥ (n—1)d ns? . U and Np each have one electron in 6¢ orbital