ee ‘Objective quetions - Fill in the 4 1 —~— 3 = 1% Marks — % Marks 2% 123 Marks CU uick Review ) the last shell con ; at shell contains one or two + Numbe J clements in the periodic table is 40. aes orbit (ns) but the last electron enters in + Group a rey tad Act and group 12-clements ees Boe clement SUP shell (0-1) are aso tnd Uub| are non typical transition elements eines ter] Remaining, 32 are transition clement + The dhl ck elements are also known as transition Bo naar ganar gories- Sey, t0 “Zp cond transition series/4d series~ 49 0 CAyg rd transition seres/sdseries- Las, Ho 10 Hyp + Fourth transition series/6d series-Acgy, RFjo, 0 Uub, 2 Tl ts Zn. Cd, Hg and Uub have : Hess Ci a an fl lod ois, + Hletrston elements oecupy positon in between sandp ion series WB we VB By iis B HB. Clas? tet 4 5 6 | 7] 8 | 9 | wo Joo 2 3d | Sea } Tin | Ves} Cray | Mm | Fes | Cox | Nie | Cio | Zmo 4d | Yo | Ztm | Nbw | Mon | Tes | Rum | Rhys ] Pde | Age | Cd sd | tay | Hts | Tas | Wor | Rem | Osu | tn | Phe | Aww | He 6d | Ace | Réior | Dbies | Sei | Bho | Hive | Ml } Dsno | Reni | Uubuz Electronic configuration of transition elements 3 + The general electronic configuration of transition clements is (n-1) d!-! ns! 2 Seren Second Transition Series Third Transition Series cain [aunts | #0 | cmguratn | tment | gntguraton tAriadlast [39 Y | ikriad'sse [57 Ta [el Sa! 6s? 22 Ti [Ar] 3d? 49? 40, ie [Ke] 4? 5s n Ht __ |e] at** 54°63" 23 Vv | tadaeae [at Nb | ikelaatse [73 Ta |[Xe] at 5a°6s* 24 cr | andadas! | 42 Mo | iKyad'ss' | 74 W_|ixel ai sa°6s" 25 Ma | tadadae | 43 Te__| tknadse [75 Re |[xe} at sees 26 Te Tansee [4 Ru | ikelad' ss! [76 Os [fixe] at sa’os* 27 Co Ar] 34” 4s 45 Rh [Ks] 4a 5st 7 ir (Xe) At" Sd” 6s? 28 wi | tariadtast | 46 pa_| tkriad?ss” [78 PL_| [Xe] at 5a°6st 29 Gu | pAradieas! | a7 ‘Ag_| (kriddss' | 79 ‘Au__[[Xe] 4t'*5d!%6s! 30 Ta | tanisdeas [48 co _| tkriadse [#0 Hig_ [1c] af sao" Exceptions have high densities. : SCN TAT] 348 4s! + Cu fl’ Hogs! + Thess lements have high meting points, boiling points “hal 1s Guanlitliflogs) and higher heats of vaporization a | Wilke af4sgS Gs? + Atigy [Xe] 4f145d16s! Gory form coloured ions [due to the presence of unpaired {Chromium (Cr) has six unpaired electrons. «Seed tendency to form complexes ‘They form interstitial compounds with N, C, H & B has four unpaired electron: elements, Cd and Hig, transition el ments are hard and _ a av oe @ scanned with OKEN Scanneriod rom Se to Cu, The density ‘configuration because the metalic Density inoreases ina pe Znin ess because of d bonds are weaker + They show variable oxidation states, ‘Atomie and ionie Radit . + In first transition element, the size decreases from Se to Mn, Than MaFeCoNi, size remains same and after that ost the same as that of 4d seriey tion, ca (4 ize of Tel: (4d) cof Ru(dd) + Size of Rh(4d) » Size of Ir (Sd) Size of Pd(4d) = Size of Pt (Sd) Tonic radii of transtion elements are less than their Tonic size of ions with same oxidation number deo ong size increases. 5 case cr cI cs + Inagroup, we know that size increases. But the size of Sd- with increase in atomic number in the period, 4 ‘Table : Lonic size Ton me Lv | ce | Mn? [re co [nite [cut | znt Tonic adit oo [as [a [a0 [76 am | 2 o | 7 + Transition elements are less electropositive than s-block clements and more electropositve than p-block elements [duc to high ionisation enthalpy of d-block elements than s-block elemetnts and but less man p-block. ‘Oxidation states + They have a special feature to show many oxidation states [The energies of 3d and 4s orbitals are almost the same, therefore electrons present in them may take part in by formation + Except few elements [Zn Cd and Hg] all show difeay oxidation states, + The first oxidation state of an element is equal tothe munky of s-clectrons. + Unpaired electrons of (n-1) d-orbitals take part in bondig one by on Ma [Fe | Co | Ni | Gu | ae | a | ae | ate | aye apefapata ion states Sez) 3 Tip #24344 +] Vo 4243, 44 45 Crag 121341546 Mnas 42,4344. 45, 46,47 Fe; 42,4344, 46 Cozy 42,4344, +5 cd ize F434 Cury #142 Znx #2 *+ Oxides of transition elements in lower oxidation states like +1. #2 and +3 are basic in nature. Thus CrO, MnO, TiO, Cu,0, CuO and ZnO are basic oxides. Oxides of elements in intermediate oxidation states i.e. 3 and 4 show amphoteric behaviour Thus Cr.03, Mn 0; & MnO, are amphoteric oxides. Oxides of elements in higher oxidation states ie. +6 and +7 are acidic in nature. CrO3. MnO MnO, are acidic oxides. The capacity of F~ ion to stabilise a metal ion with higher oxidation state is due to its small size and higher lattice energy. For ex. CoF3 VF, CrF are stable. All halides of Cu?* ion are known except the iodides.In case of iodide, Cu?* ion oxidises the I” into Ip, : 2Cu?* +41” > Cugl(s) +12 + Many Cut salts are unstable is aqueous solution. They undergo disproportionation to form Cu2* 2Cut + Cu +cu ‘Thus Cuféy) is more stable than Cufegy + Many transition elements are electro Positive and soluble in mineral acids, But some of the metals like Pt Pd and AU are not affected by simple acid Magnetic Properties *+ Magnetic properties of transition ‘magnetic moment of an electron H=n(¥2) Here nis the number. ‘of unpaired electrons. + When a substance repels the lines of force of the magetit field o reduces the strength ofthe magnetie fel, itis call a dismagnctic substance and the phenomenon ig known iamagnetism. elements depend upeo @ scanned with OKEN Scanneronan tem er # Cemex (87)___——_—# KOS: Dinmagnetie effect —~ indiamagnetic substances, the atoms or ‘ithe electrons in the paired form, When a substance pliced in magnet inagnetic lines of force and thus inerease the intensity of ihe magnetic field is known as paramagnetic sub tithe phenomenon is known as paramagetisn 1 =@"|s Paramagnetic effect ubstances which are highly paramagnetic \ttracted strongly towards the pee field They mnetic properties even after the removal of the magnetic field. That is why, they become permanent magnets. The substances of this type arc called as ferromagnetic substances and the phenonenon is known as ferrogamgnetism, Example Fe.Co, Ni, FeO, and alloys of Mn. 1 Fons present have field attracts the Stew Outer] Number] Magnet Ne Configuration | of | moment unpaired | (BAL) clectrons_| ealeuaied T i ° 0 2 3 1 173 3 3 2 283 4 3a 3 387 5 3 5 502 ‘ 3a 4 499 1 30 3 337 & 3d 2 28 9. a 1 13 0 a” o 0.00 * The ions contaning all paired electrons {d°d!9s°] are generally colourless. + Theions containing even one unpaired clectron are coloured. * Ifa body absorbs all the colours of ‘visible region. Then it ‘appears black. * Ifa body does not absorbs any radiation, ic. all radiation are re-emitted then it appears white or colourless. * Ifa body absorbs radiations of particular colour or wave length then the complimentary colour of that radition is remitted, Wavelength [Absorbed | Emit colour / ‘colour complimentary colour 400047 Violet ‘Greenish yellow 4500 A" ‘Yellow BOAT Ted ST00A eae S800 Dark hve SOOT Blue SODA" Red Blush green * Wave Tength and colours of some radiations and th complimentary colours are given in following table. Interstitial compounds + In transition metal ‘erystals, there are some voids in the at lattice known as interstices. Smaller atoms ike N.C. may be trapped in these voids and tho compounds so formed are called interstitial compounds. These compounds are very hard, malleability and: ductility are less, than that of the metal. Formation of Alloys * Transition metals have propel metals, 5 * Alloys are of high melting point and high tensile strength. + Thy are resistant to corrosion. + Some examples of alloys are ~ (1) Brass (Cu + Zn) (2) Stainless steel (Fe + Cr + Ni) (3) Chrome steel (Fe + Cr) (4) Tungston steel (Fe + W) (5) Bronze (Cu + Sn) Formation of complex compounds «Transition metals have the property to form complex ions and complex compounds, Following are the reasons for their formation. 1. onic radii of transition metals are small. Thus they have high positive charge density. 2. The ions have vacant (n-1)d, ns and np orbitals of approximately same energy and they undergo hybridisation. Catalytic properties * + Transition metals and their compounds show catalytic properties. + Due to this they can form intermediate compounds with the reactants. The intermediate compounds are unstable, they easily undergo decomposition into the desired products and the catalyst is regenerated. During this process the physical state of the catalyst may change. Non- Stoichiometric compounds + Some transition metals form compounds with 16 group elements [0.S.Se.Te] with uncertain composition or non stoichiometric composition. For example In FeO the ratio of Fe and O atoms is 1:1 but its formula varies in between Fey o40 and Fegg,0 Inner transition Elements— + The elements is which electfon enters (n-2) f orbitals are called f-block elements and are placed in the bottom of the periodic table. + Total number of these elements is 28 + These elements may also be called as inner transition elements, + The general electronic configuration of these elements is (n-2) f1"4 (1) d°! ns? + These elements consist of two series (a) Lanthanides (b) Actinides Lanthanide Series + Having fourteen elements Cesg to Lup, with electronic configuration’ [Xe] 4f9-14 50“! 65? sty to form alloys with other @ scanned with OKEN Scannerre represented by Ln Electronic configuration ta ! sche, catenin 1a rites Ree ss eee tet ee soi hae we ; S| Rye a ara ao Relates ett Rat are] 3 | Nelathset| a to seat rat | ay te] area] 's° 2s", 2pS, 35° 3p" 3d! ds? dp? ddl? S52 Sp* Note-In gadolinium Gd, and Lavetim Lu, the last electron is added to Sd and not to 4f. * The following elements Ce, Gd and Lu are having one , In +2 oxidation state [9s d- orbitals are partly filed therefore Agi a transition element, Q.7. (a) What are interstitial compounds, give an example. (b) Calculate the spin only, magnetic moment of M2* (aa) ion (e= 29 "aj Board 2015, 2023) Ans. (a) The smaller atoms like H. B. Nand C ete are ‘rapped in the interstices (voids) of the crystal lattice of transition metals. Such compounds are known as interstitial compounds, Ex~ TiC. MngN and FesH. (0) Z=29, atomic number of Cu, The electronic configuration of Cu?* ion is [Cu*] 1522s?2p93e23p63q9490 ° ee va) Cu? jon contains one unpaired electron therefore the ‘magnetic moment b= ying +2) fid+2) = V3 =1.73 BM Q8. Why Zn is not a transition element Ans. In Zn, Full filled d-orbitals ae} ‘are = therefore Zn is not a transition element, Explain by giving reasons. (a) The atomic radii of second transition series (4a) elements and third transition series (Sd) elements are virtually same. 3 (b) The ionisation enthalpies ofthe early actinoids are lower than for early lanthanoids, (Ra Boned 016 Ans. (a) 4d and 5d orbitals have 4f; in between and the electrons in 4f orbitals are filled after Lanthanum. ‘The atomic size decreases in the lanthanide series due to the shielding effect of 4f electrons and is known as lanthani Contraction. The decrease in almost equal to the increase size when we go from fifth period to sixth period and these two effects balance each other. Itis due to this thatthe atomic sizes ofthe third transition series (Sd) and second transition series (4d) are almost equal. (b) The size of early actinoides is larger than the size of carly lanthanoide. Therefore the ionisation enthalpies of carly actinoids are lower than early lanthanides. . Q.10. (a) Write the name of two metals used in maxi- mum composition in mish metal. (b) Calculate the value of magnetic moment of V+ ion, Ans (a) Lanthanide + Iron (b) V__ [Ar] a's? Its magnetic moment x= Jain?) = ¥3G+2) = V5 =3.87 BM. QuI1. Write electronic configuration of ‘Chromium, =m). (Raj. Board ang Ans. Cr= 24 1s? 2s? 2p* 3s*3p* 3d* 4s! Q.12, Write name and symbol of one transurenie ment aj Board ‘Ans. Neptunium (Np) a Q.13. Write general oxidation state of Lanthanide, Ans. The oxidation state of Lanthanide is +3 Q.14. Write spin only formula for calcul; ‘magnetic moment of transition element. ‘Ans, Magnetic momentum (11) = /n(n+2) Where n= number of unpaired e- Q.15. Write electronic configuration of Actinium @=89) Rs Ans. «AC=[Rn]5?,6d'7s? Q.16. Write names of the elements, which shows +1 oxidation states in first transition series. Ans. Both Cr and Cu show +1 oxidatic te. Elements of Is transition series (Except Cu and Cr) do not show +1 oxidation state 0.17. Read the given paragraph and give answers of the following questions. aj. ‘The rare earth elements of the modern periodic are known as lanthanoids, They have separate block in lating As we move from let there is regular decrease in : is knownn as lanthan sontraction. There are many industrial application as formation of mischmetal, prod ris of Seton hi luction of parts of Jet. engine. (A) The basic nature of hydroxides of lanthanoid the n any one lanthanoid element 1g +4 oxidation state, Ans.(A) As we move from left to ri ize of Lanthanoids decreases due to the Lanthanowd centucren 0 it is more difficult to break Ln-OH bond. Here more bigger lanthanoid easily form OH" ion so it is more basic but smaller Lanthanoids hhave more attraction on electrones soit doesnt give electrons to form OH: ion so it is less basic, ing OH- ion. sive electrons 10 @ scanned with OKEN ScannerLado on asi Nature of Lanthanoid Hydroxide (nycerimn (Co), Neodymium (Na) (erornumn (Co) Q.18, Explain with reason. {a) The solution of transition metal compo iy coloured. misition metal exhilats more t o (a) In transition mo d it lex) and ey (dx?,y?, de!) group. Energy og 18 very less 80 if unpaited electrone absorbs enemy from environmental i goes to higher eg orbitals, When it jumps a "RY is released which ts responsible fav the colour oF fransition metal compounds, SB (dxyde) C1 dogenorate (0-1) orbitals yet) (b) For variable oxidation metal, va- cent (o- Id orbitals and less energy gap between ns and (n- iM orbitals are responsible, Q.19, (a) Why transition elements form interstitial compounds? (b) The atomic radii of lanth comoving from left to right, Ans, (a) Inter particle sp ements in which small particl form interstitial compounds, (b) Ducto lanthanide contraction, the atomic radii of| lahanides decrease on moving left to right in lanthanid or 4F sens {mn Ianthanide, New € comes in 4f orbitals which are ence shell so shielding effect increases very n (Z) inereases fastly as compared ‘avelding constant (a), Hence effective nuclear charge (Zt) {= Z-a). It tends to decreases the atomic ide clements decreases in, foun of HCN move casily to 9.20, The metal showing maximum number of ‘nidation states is— (wy (b) Min (Fe (d) Ni Ans (b) Mn 21, Write the names of metals elements present in po eNO) om [Kaj, Board 2022, 2023) (Cu) and Zine Zn) ficulate the spin only magnetic moment for tag (© 25), Ris. M"(Z. © 25) Shows 493d configuration and possessor 5, unpaired electrons (n). pe (atart we ED we fi .23, What the highest oxidation by V, Cr and Ma, ‘Ans, ‘The highest oxidation states are as follows GV. 3d'4s?) = Maximum = +5 (it) Cr3d"4s!) = Maximum = + 6 Git) MnQd"4s?) © Maximum = +7 Q. 24. Calculate the spin only magnetic moment of Muy) ion (Z.= 26). ‘Ans. Atomic number 26 is Fe whose outer electronic configuration is 3d/4s? So Fe!? = 3d64s0 ‘The no. of unpaired electrons n= 4 in it Magnetic moment we fn(n+ 2) = GD = fq =4.9BM Q.25. The oxidation number of Fe in [Fe(CO)s] is— mM [Raj. Board 2024) (a0 (b) 42 (43 (a) +4 Ans. (a) 0 Q.26, The chemical formula of chromite ore is ~ [Raj. Board 2024) (a) MnO, (b) NayCrO, (e) FeCrs0, () NayCrO, Ans. (c) FeCr,0, Q.27.. ‘and actinides are called inner transition elements, [Raj, Board 20724] ‘Ans, Lanthanides Q.28, Write any three physical properties of interstitial compoun Ans. (i) Their melting points are higher than pure metals. ii) They are very hard. (ii) ‘Their metalic conductivity remains sate. (iv) These are chemically inert (¥) These compounds are non-stoichiometric, (vi) These are not ionic and not covalent __ (vii) These compound did not show any common oxidation state of metals 7 bjective Qu he highest oxidation state 1s represented by Co (0) Cr (©) Mn 2, The number of unpaired ¢- in (a3 (b) 5 @ scanned with OKEN Scanner(oa (6 ; 3. From the following in which compound the oxidation state of Fe is zero. (a) FeSO, (c) KylFetCN) 1 4. From the following which have maximum magnetic moment ve (yer (Fe (d) Co $. ‘The common ovidation state in lanthanide series is~ war 4 (92 (3 6. Lanthanide contraction occurs duc to the increase in— (a) Effective Nuclear charge(b) Atomic number (6) Size of 4f orbital (a) None of these 7. Which member of lanthanide series show +4 oxidation state (a) Ce (b) Lu (©) Eu (a) Pm 8. Which of the following is diamagnetic— (a) Cu? (b) Zn?" «cr (@ Tr 8. Which of the following have maximum Ist ionisation Potential~ (a) Ti () Mn (©) Fe Ni 10. Which ion have all es- paired (a) Cr? (b) Cu’? (©) Cu! (@) Ni‘? 11. The following property is generally not found in d-block elements (a) Alloy formation (b) Coloured compounds formation (©) Interstitial compounds formation (@) displacement of H, from dilute acids, 12. The electronic configuration of Pd is (a) 5s24a? (b) Ss'40? (c) 5s?4a"® (@) 5st4a” 13, Radioactive lanthanide is~ (a) Pm (b) Np (©) Eu @ 14, Transurenic elements have the atomic number— (a)Z>90 (b)Z> 2 ()Z>93— I) Z>91 15. ‘The atomic radius of Zirconium (Zr) and Haffnium (Hf) is about same due to~ (a) Actinide contraction (b) placed in same group (©) Lanthanide contraction (d) Placed in same block 16. Dilute and less basic KMnO, solution is called~ (a) Nessler reagent (b) Bayer reagent 17, 20. a 22. 23, 24, 25, (c) Frankland reagent (d) Tollen's reagent From the following which is an amphoteric oxi. (a) ALO, (b) Zn0 (©) Cr.0, (a) All of these ‘The configuration of a transition clement in +3 g 3d! then the atomic number of clement will be (a) 24 (b) 25 (c) 26 (d) 27 From the following which is a d-block clement. (a) Gd (b) Ce () Cs (d) Pt Which group is known as ‘Coin metal group" (a) Fe, Co, Ni (b) Cu, Ag, Au (c) Se, Ti, V (d) None of these Which group of clement are called transition elem, (a) p-block (b) d-block (0) s-block (a) block An essential consitituent of Amalgum is~ (a) Fe (b) Po (© Hg (d) Ti By which substance acidic KMnO, react and beste: colourless~ (@) Bleaching powder (b) Mohr’s salt (c) Tollen's reagent (d) None of these Transition element and their mostly compounds are (@) Diamagnetic (b) Ferromegnetic (©) Peramagnetic (d) Anti ferromagnetic ‘The total no. of elements in 1* transition series is- (a) 12 (b) 10 © (d) None of these ae 1© 2@ 3. (b) 40) 5.@ 6a) 7.(a) 8.(b) 9.0) 10.) 1d) 12. 13.) 14.) 15.(¢) 16. (0) as @ us ) 19. @) 20.(0) 2 2. ao © 23.(b) 24.0) Theclements of group 3to 12 in periodic table areca! ‘The clements whose atoms or ions h Hee! have incomy orbitals are called... “ ‘The general electronic configuration of d-plock elam™® is ‘Thereare ~~ Sets oF d-block elements in pois @ scanned with OKEN Scannerrho elements of lanthanide series hg ve general oxidation stale “ ‘The atomic size of third tran ion series, similar to the elements of second tr sition series d the Variable oxidation state is a major property of, elements block elem ls and .. does not show le oxidation ’ ane fectrons. jo. Cerium is an clement of lanthanide series which show oxidation state 1 There are series of inner transition elements n periodic table. 12, The electronic configuration of copper is . round state and general oxidation state the d-orbitals of Zn, Cd, He ol are . The atomic radius of elements of Hh! tra (ad) and 11 tra jon series ion series (Sd) is about equal due to 18, The value of atomi is generally. 16 does not show variable oxidation state although it is a transition elements. 17. The higher oxidation state of transition elements seen in jon enthalpy of transition elements fluorides and a 18, In transition clements formation of coloured ions is due to 19. Small sized atom transition clements to form. 20. Interstitial compounds are chemically. are trapped in crystal lattice of Answers |, deblock elements 2. Transition elements 3.(0-1) dite ns? 4, four $43 6, Lanthanide contraction 8. Transition 8. Scandium (Sc), Zine (Zn) 9. unpaired 10. +4 HL. Two 12, 3d'ds! 14, Lanthanide contraction Cee ‘completely fled d-orbitals (4d) QuL. Silver 0 is a transition in its ground state. How ean you say th clemen ‘Ans. Silver exhibits +2 oxidation state in AgF and AgO. In this state its electronic configuration is [Kr}4d?, 5s. Due to partly filled d-orbitals it is transition element. : Q.2. Which of the 3d series transition element exhibits the largest number of oxidation states and why? Ans. Mn (Z = 25) exhibits the largest number of oxidation states (+2, +3, +4, +5, +6, +7) because it has the largest number of unpaired electrons in 3d orbitals. Q.3. For the first row of transition metals the E? values are Te [eo [mi [er] Emr tar pose | was toe} Explain the irregularity in the above values. Ans. The irregularity in E° values is duc to irregular variation of ionisation due to irregular variation of ionisation ‘enthalpies (AH, + AsH,) and sublimation enthalpies which are relatively much less in case of Mn and V. Q.4. Why is the highest oxidation state of a metal exhibited in its oxides and fluoride only. ‘Ans, Because oxygen and fluorine have small size, greater clectronegativity. Therefore they casily oxidise metals to highest oxidation state. Higher value of lattice energy of F~ and 0? further stable the componds formed. Q.5. Which is stronger reducing agent Cr2+ or Fe2* and why? Ans. Cr? is a stronger reducing agent than Fe?*. The reason for this is that the configuration of Cr?" changes from d* to di, The d° configuration is stable due to half filled to, oribitals, Q.6. What is meant by disproportionation of an ation state, Give example. ‘Ans, When a particular oxidation state of an element is less stable in comparison to the other oxidation states, one lower and one higher, then that oxidation state changes in to cone lower and one higher oxi said to undergo disproportionation, For example 07 2Cu" > Cu" + Cu oO ad © MnO} +4H* -> 2MnO, +MnO; +2H,0 wv) (vy) (vu) Q.7. Explain why Cut is not stable in aqueous solution? ‘Ans. Cu*gq) is not stable because of its less negative enthalpy of hydration than Cu? ion. Thus Cu‘ undergoes Cu ag) + CU Q.8. Name the member of Lanthanide series which is well known to exibit +4 oxidation state? Ans. Cerium (Ce atomic no, 58) @ scanned with OKEN Scannerii) Mn" ans. s|Arp 3d? ii) Pm; [Xe] 4/* (iit) Cu, [Ar] 3d! et Ie] (9)Co® , [Ar] 3d es [Xe} 404, Sd (vil) Mies {Arp 3d (vit) THY [Ro Q.10. Explain briefly how #2 state becomes more and more stable in the first half of first row transition, clesments with increasing atomic number, ‘Ans. In going from left to right in the series the sum of first (JE,) and second (IE,) ionisation enthalpy increases, Thus the reduction potential becomes less and less negative, AS a result +2 state becomes more and more stable in first half of, the series Q.1L. Name the oxometal anions of the first series of transition metals in which the metal exhibits the oxidation ‘Ans. MnO}, oxidation state of Mn = +7 (group no. 7) Cr} oF Cr,03 oxidation state = + 6 (Group no. = 6) Q.12. Explain giving reasons. (a) Transition metals and many of their compounds show paramagnetic character, (b) The enthalpies of atomisation of the transition metals are high. (©) The transition metals generally form coloured compounds. Ans. (a) The presence of unpaired electrons in transition ‘metals and their compounds make them paramagnetic. Their ‘magnetic moment (1) is given by 4. = Yn +2) BM. n= no. of unpaired electrons. (b) Due to the presence of unpaired electrons the atoms of transition metals have strong interatomic interactions, This results in strong metallic bond among the atoms. Thus the enthalpies of atomisation become high (c) The transition metal ions have unpaired electrons. ‘When light radiations fall on them, the unpaired clectrons are promoted to the higher energy level within the d ~ subshell (ty, > 6 0F 6, -> ty). This is called d-< transition, ‘The complimentary colour of the wavelength absorbed is emitted and the respective colour is given by the metal ion or its compound, Q.13. Describe the preparation of potassium jromate from Iron Chromite ore. What is the effect of ion of potassium dichromate, dic increasing pH on a sol ‘Ans, (i) Conv te ore in to so chromate ~ Chromite ore (FeCr,0,) is heated with seq carbonate in the presence oO, sodium chromates APcCr0, + 8Na,CO, +70, > 8Na,C10, +2Fe,0, + 4¢q (ii) Conversion of sodium chromate in to Sodiy, dichromate Yellow solution of sodium chromate is tea with H,SO, to form orange coloured sodium dichromate 2Na,C104 141180, NaC +10 +Na,so, (ii) To the solution of sodium dichromate potas, chloride is added, less soluble potassium dichromate ery are formed. Na,Cr,0, + 2KCI > 2NaCl+K,Cr,0, pot. dichromate By change in pH of the solution, chromate and dichromzs ions may be interconverted. 2Cr0} +2H* > Cr,0} +H,0 yellow orange Cr,0} +20H” > 2CrO} +H,0 orange yellow Chromate and dichromate are in equilibrium at pH =4, On increasing pH orange colour of dichromate changes in to yellow colour of chromate ion. Cr,07+H,O +, 2¢102- 42H" (orange) (yellow) Q.14. Describe the preparation of KMnO4. How does the acidified KMnO, solution reacts with, @ (ii) Fe2* solution ‘Ans. (i) ion 2KMn0, +10K1+8HS0, > 2MnSO, +6K 20, +51; +8H;0 Fe2* solution 2KMnO, + 10FeSO, +18H1,80, > KSO, +2MnSO, +5Fe,(SO4)3 +4H;0 Gi) Has eae 2KMnO, +8HS0, +5H,S K2S0, +2MnSO, +58 +8H;0 . ind suggest 1 for the following features ofthe transition metal chemistry | (a) The lowest oxide of a transition metal is basi¢ Whereas the highest is amphoterie/acidie (b) The highest oxida F Q.15. Give example ai @ scanned with OKEN Scannerpo = a Baaimination/Iden tay ei chemtstey Att @ (68) Monnions of w metal “Aus. (a) l0 Lower ONidation state the oxide ion given by the ets as a base. 08 +H, 52011 As the oxidation state increases the oxide become more gat more covafent, Is tenleney {0 give O> decreases and ornation of OH become difficult, basie character decreases patouwle Become more and more acide, (b) Ducto high electronegativity of oxygen and its greater cxwlising power, Metals form OXoanions in their higher te the oxides are ionic in gare. THe +m forms hydroxide ion with eran owwdation states, For example Cr,OF (0x. no, of Cr = +6) MnO, (0.110, of Mn = +7), Q.16, The chemistry of the actinide elements is not so sooth as that of the lanthanides, Justify this statement tysiving some examples fromy the oxidation states of these ats s. Lanthanides show very few oxidation states ie. +2, 43,4 (13 oxidation state is the main), Itis because of large enorgy gap between Sd and 4f subshell Actinides also show +3 as the main oxidation state tut show other oxidation states also. For example Np.(94) shows oxidation states +3, +4, +5, +6 and +7. Similarly uranium (Z = 92) exibits oxidation states of +3, +4, +5 and 46 This is because of small difference in the energy of Sfand 44 subshell Q.17, Name the members of the lanthanide series which exhibit +4 oxidation states and those which ext +2oxidation states, Try to correlate this type of behaviour withthe electronic configurations of these elements. ‘Ans, +4 oxidation state is exhibited by : Ce (58), Pr (59), Nd (60), Tb (65) and Dy (66) This oxidation state is exhibited by elements which acquire configuration close to 4P° (e.g., 4 4P, or 4%) and 4f" (eg, 48 or 40), +2 oxidation state is exhibited by Na (60), Sm (62), Eu (63), Tm(69) and Yb(70) Eu and Yoexhibit +2 oxidation state to acquire half filled (4%) and filled (4P) configurations. Others Nd** (51), Sm?" * (4) are also observed though less stable than de Q.18, Write down the number of 3d electrons in each tthe following fons "Tis, Vis, CP", Mn, Fed, Co™, NB* 441 Cu, Indicate how would you expect the five 3d ‘wbitals to be occupied for these hydrated ions (octahedral), Ans. Since water forms octahedral hydrated ions, score the crystal field produce by water molecule will split Se doxbitals ito ty (lower energy) and, (higher enerey) bias, Water forms high spin complexes. Therefore nner ‘sbitals remains undisturbed. @ 3a? 414 be “e Gi) VO: 3d? or Oy 444 Gi) Cres 3a 414h4 (iv), Mn" 414 (v) Fe" 44 (vi) Co V4 (vit) Ni?* 4h (iti) Cut Hl 4 14 Q.19.(a) Explain the following terms with suitable examples Ferromagnetism and Ferrimagnetism, (b) Give reasons— (i There is a gradual decrease in the size of atoms with increasing atomic number inthe series of Lanthanides. ii) Sc (z= 21) is a transition clement but Ca (z= 20) is not. (iii) The Fe2* ion is much more easily oxidised to Fe* ion than Mn2* ion to Mn>* ion. Ans.(a)Ferromagnetism-These are those substances which are strongly attracted by external magnetic field. They have maximum number of unpaired electrons, e.g. Iron, cobalt and nickel ete Ferrimagnetism-When magnetic moments in a substance allign in parallel and anti parallel directions in unequal numbers so that there is net magentic moment, the substances are ferrimagnetic eg. Fey, MgFex04. (b) (i) Asthe atomic number increases, each succeeding clement contains one more electron in 4f orbital and one extra proton in the nucleus. The 4f electrons are rather ineffective in screening the @ scanned with OKEN ScannerI ‘As a result, there is a gradual a attractions forthe outer electron, Asa result ofthis the atomic gradually decreases. : os eye (z= 21) isa transition clement but Ca (z= 20) is not because in Se dfd!} orbitals are partially filled while in e of Ca atom d orbitals are empty. . (iii) Electronic configuration of Mn?" is 345 which is half filled and hence more stable therefore 3rd ionisation ‘enthalpy is very high tc. 3rd clectroon can not be lost easily ‘of Mn ion, Therefore Mn?* is not casily oxidised to in case of Mi Mn ion In case of Fe?" ion, the electronic configuration is 346, Thus it can lose one electron easily to give the stable configuration 345. Thus Fe2* ion is easily oxidised to Fe?! 20.(a) Which clement in the 34 transition series ceahibits +1 oxidation state most frequently and why. (b) Which of the following cations are coloured in aqueous solutions and wh Sc, V3, TH} Mn2* [At nos Se= 21; V = 23; Ti=22 and Mn =25] (©)_ How would you account for the following () Transition metals exhibit variable oxi states. ) Zr (z= 40) and Hf (z = 72) have almost identical radii, (d) Complete the following chemical equation () Cr2072- + 6Fe* + 14H — Gi) 2CrO2- + 2H" — (ii) 2MnO ye + $C,0,2- + 16H* — Ans (a)Cu isthe only metal in the first series which shows +1 oxidation state because Cu has 3d!0 4s! configuration and after losing one s electron it acquires a stable 3d!0 configuration. (b) The colour of cations is dependent on the number of unpaired electrons present in d-orbitals (i) Sc [z= 21] 3d 4s? In Sc3* ion 3d° 450 Here d-orbital is empty so itis colourless (ii) V [z= 23] 343 4s2, In V3* ion 3a2 450 d-orbitals are having two unpaired electrons, it undergoes d-d electronic transition and shows green colour. (iii) Ts [2 = 22) 342452. In Ti4* ion 340 450 Here d-orbital is empty, itis colourless. (iv) Mn [z = 25] 3454s? In Mn?* ion 345450 d-orbitals are having five unpaired electrons, It undergoes d-d electronic transition and shows pink colour. (©) (i) The variable oxidation states of transition clements Lower oxidation state is exhibited when ns clectrons take part in bonding (i) Itis because the atomic radii of 4d and 54 trans elements are nearly the same. This similarty in size ie consequence of lanthanide contraction. Because of thig i of HF becomes nearly equal to that of Zr. thy (0) (0 6Fe2* 4 CROP HME -» 20° HOF 47H 5 (ii) 20107" + 2H* + Cr,0F +H,0 (ii) 2Mn03 +5C,07° + 16H" — 2Mn?* +10€0, +4149 Q.21.(a) How do you prepare~ (i) K2MnOy from MnOz (ii) NagCr207 from NazCrOy (b) Account for the following- (i The enthalpy of atomisatio series of the transition elements. (i) Actinide elements show wide range of oxidation states. ‘Ans.(a) (i) KzMnO4 can be prepared from pyroluste [MnO3]. The ore is fused with KOH in the presence of either atmospheric 02 or an oxidising agent such as KNO3 or KCIO, to give KyMnOq lowest for Zn ing 2MnO2 +4KOH +0,» 2K MnO, +2H0 gen (ii) NayCr207 can be prepared from Na2CrOj in th: following way, For the preparation of sodium dichromate the yellow solution of sodium chromate is acidified with sulphric acidto give a solution from which orange sodium dichromate NayCr207. 2H20 can be crystallised 2Na,C1O, +2H* -» NayChO, +2Na* +H,0 yellow (b) (i) The extent of metallic bonding in an element decides the enthalpy of atomisation, In case of Zn [34° 4s2] due to absence of unpaired lectrons, the interatomic electromic bonding is the weakest, Asa result it has the least enthalpy of atomisation, (ii) Actinides exhibit larger oxidation states because of veosmal energy difference between Sf, 6d and 7s sub energy level Since all orbitals can is Jarger oxidation numbers, Q.22.(i) Name the etem that shows maximum number this happen? (ii) Which transition metal of i aE De paldesuaen fal of 3d series has +ve E’ Gi) Out of Cr3* and Mn3+ ing agent and why? involve in bonding, this results in lent of 3rd transition series, of oxidation states. Why does ‘heh is a stronger @ scanned with OKEN Scannerknown to exhibit +2 oxidation state, (y) MnO" +8H* + 5e-— Ans.(i) In 3d'series of transition metals manganese has anatomicmumber of 25 that wives the electronic configuration sind 30 48° vel 3d5 ooo oF Wesco that the maximum number of unpaired electrons se found in manganese atom and therefore it can show a savmum number of oxidation states, (i) Coppers the transition metal of 3d series that exhibits yg E(M? IM) the value of E M2*/M for Cu is +0.34. This tnppes because the E°[M2*/M] value of a metal depends spanthe energy changes involved in the following, (a) Sublimation energy— Mi) -> Mig) ASH (sublimation energy) (b) Ionisation energy— 4s May > Mi > Ai (lonisation energy) (c) Hydration energy- Mj, > My > Anya (Hydration energy) Since Cu has a high energy of atomisation and low ‘ndration energy.the E® [M2*/M] value for Cu is +ve. (ii) Out of Cr3* and Mn3*, Mn3* is a stronger oxidising, ‘gent because it has 4 electrons in its valence shell. When it ‘ins one clectron to form Mn2* it results in the half filled (&) configuration that has extra -stabi (iv) Europium (Eu) is well known to exhibit +2 xidation state due to its half filled f (£7) orbital in +2 oxidation sat, (v) MnOj +8H* +5e~ > Mn?* +4H,0 Q.23. (a) Account for the following— Transition metals form complex compounds. (b)Complete the following equations CO} +8H* +3NO7 > Ans.(a) Following are the reasons for the complex maton Ionic radii of transition elements is very small and are “ing high positive change density. ions having vacant (n-1) d, ns and np-orbitals of “oximately same enrgy undergo hybridisation. () ci,03- +3NO; +8H* > 3NO5 +2CP* +4H20 7 io What are typical and non-typical transition im The clements of groups 3 and 12 are non-typical te “Wsiion elements and the remaining group 4 to 1 members — are typical transition element ‘Q.25. What is the general configuration of d-block elements. ‘Ans. General configuration of transition elements is - (n=1)d"™" ns? Q.26. Why Cr(24) and Cu(29) have anomalous electronic configuration. ‘Ans, Since half filled (d®) and completely filled (d!0) d- orbitals have greater stability. Thus, electronic configuration of Cray is [Ar]3d°, 4s! rather than [Ar]3d*, 4s? and the lectronic configuration of Cuzy is 344s! rather than 34432. Q.27. What are rare earth elements, why they are called inner transition elements? ‘Ans. Lanthanides arc called rare earth elements. They are called inner transition elements because the electrons are added in to (n-2)f orbitals which areinner to the (n-1)d orbitals ‘which are filled in transition elements. Q.28, What are f-block elements write down their electronic configuration in general. Ans. The elements in which last e~ enters in (n— 2) orbitals are called f-block elements. (i) Lanthanide in which last electron is added in 4f orbitals. (ii) Actinides in which last electron is added in Sf orbitals. Their general electronic configuration is (n=2)f°"* (n= 1)d°" ,ns* Q.29. Which is the general oxidation state of Lanthanides. ‘Ans, The general oxidation state of Lanthanides is +3 Q.30. Cerium (Ce) shows +4 oxidation state why? Expl ‘Ans. Because Ce" has 4f° configuration which is more stable. Q31. Write down the electron configuration of the elements whose atomic numbers are given below. (j) 58 (ii) 64 (iii) 71 (iv) 63 (v) 70 Ans. Co(58) [Xe] 4A, Sd!, 6s? Gd(64) [Xe] 4f7, 5d, 652 Lu(71) [Xe] 4f"4, Sd!, 6s? Eu(63) [Xe] 4f7, 5d, 6s? Yb(70) [Xe] 414, 5d, 632 Q.32. Explain Why (a) +4 oxidation state is more stable for Pt than Ni where +2 state is more stable for Ni than Pt ‘Ans. The sum of the first four ionisation enthalpies is less for Pt than Ni whereas sum of first two ionsiation enthalpies is less for Ni than Pt. Hence Pt(iv) is more stable than Ni (+4) whereas Ni (+2) is more stable than Pt (+2) Q.33. Which of the following oxides as acidic, basic & amphoteric @ scanned with OKEN Scanneree and pipes. It consists of 95% Lanthanides and 5% iro = ‘Ans. Acidic oxides : MnO> [due to highest OS. i.e. +7] Basic oxides : MnO: MnO; [0.S. is +2, + 3] Amphoteric oxide : MnO, [0.S. is +4] Q.34. Which of the following pair is of tran metals Cu, Zn; Ag,Cd; Mn, Zn; Se.Hg; Se, Mn; Ans, Sc, Mn; Q.35. (i) How ferromagnetic property is different then antiferromagnetic property. i) CrO} is ferromagnetic at 298 K but at 395 K it is paramagnetic. Ans. In ferromagnetic substances the atoms have ‘unpaired electrons and the group of atoms form “domain” which orient themselves in the direction of magnetic fied. ‘Thus produce strong magnetic field and are permanent magnet. Inantiferromagnetic substances clectrons remain unapired but the domain formed are oriented in opposite direction to cancle the magnetic moment of each other. As a result the magnetic ‘moment is neutralised and the magnetic effect is lost. (ii) At298 K the domains are in the direction of magnetic field, thus CrO, shows ferromagnetic character. On increasing ‘temperature to 395 K the orientation of domains is disturbed and CrO, shows paramagnetic character. Q36. Transition metals have characteristic property of forming complex compounds. What is the reason? Ans. Due to the following reasons the transition elements have characteristic property of forming complex ‘compounds : (i) Smaller size of cations. (i) Greater charge on ions, ie. greater charge density to attract ligands. (iii) They have vacant 34, 4s, 4p orbitals of approximately same energy so that they are capable of forming hybrid orbitals (iv) The metals have more than one oxidation states Q37. What are mish-metals with reference to Lanthanides. Ans. Mishmetals are the alloys of Lanthanides with other metals. A well known alloy is steel which is used for plates traces of S, C, Ca, Al ete, Addition of 3% mi magnesium parts ! ish metal t jereases its strength and is used for jet engin Q38. What are Transuranic elements Ans: These are prepared by man. The clements fron Atomic number 93 to 112 are transuranic elements, Q39. Arrange the following oxides in decreasing or der of their acidic nature MnO, Mn,0, MnO, ‘Ans: MnO, > Mn0, > MnO Q40. All compounds of Se are colourless explain ? Ans: Scandium shows +3 oxidation state. Oxidation stat of Sc, does not have any unpaired electron. Therefore all com pounds of Se are colourless. Q41. Number of unpaired electrons (Gdq.) are. Ans: Gd (64) [Xe] 4f” Sd'6s? in gadolinium element ha 8 unpaired electrons. Q.42. Write the electronic configuration of Cu** & als calculate the magnetic moment? ‘Ans. Cu [Cu=29] Is? 2s? 2p°3s"3p°3d° 4s” Its # = Ja@+2) = Vide -B = 1.73 Q.43. Au (79, Ag(47) having same ionisation poten tial Ans. The size of Ag & Au is equal due to Lanthanid contraction therefore the IP of these two element is same 44. Calculate the magnetic moment (11) of Mn KMnO,, ‘Ans: In KMnO, the Oxidation number of Mn is +7 The electronic configuration of Mn” is (Ar)d°s? ‘The magnetic moment is zero, @ scanned with OKEN Scanner