| Position in the period the periodic table. Therefore transition clement non — metallic. table : Transition clemen Electronic Configuration Anta? (n~ 1) d and ns orbitals have very slight differen orbitals are most stable. 3d series Se— Zn 27 30) Table of outer electronic configurations of the transition elements (ground Stee) 4d ser ies Y>Cd 39 49 Carrer 9 jon elements are those elements which have partially filled d — orbital, ‘Transition Elements Sd series 6d series La-Hf— Hg Ac-RE— Uub $7 72 80 89 104 112 occupy position between s and p Mock tn jow change of properties from ayotullle (© in onergies, Further halt and filly ttled 8 ‘ nae ORRRES SS Ist S : sc Ti Vv cr Mn Fe Co Ni Cu ay 21 2 2300 24 25 26. 2 28 29 30 2 2 2 U 2 2 2 2 1 2 L 3S 5 6 1 8 10 7 2" Series ae Y Zr Nb Mo Te Ru Rh Pd Ag cd 39 400 41 42. 4B 44045 46 a7 a8 2 2 1 1 1.1 1 0 1 2 12 4 5 Ga 8 10 yoo | 3" Series a Ta Ar Ta W Re Os Ir re Au ie 57) 22 73 74 75 76 1 B 19 80 2 2 2 2 2 2 2 1 1 2 1 2 3 4 5 6 7 9 10 oO 4" Series Ac RF Db Sg Bh Hs Mt Uon Unu Uub $9104 105106 107 108 109. 0 ut 2Vdd 9 SOLA eee’; chee ah om Pax campieretas fd of orsitont yd") = Hoo can U Aoly aa T. Camert 2 @ econ bk Aad pst as 3d? uber da incomp: —fluud ow rent be cause 211, € ante vd, He, re 10 have fully filled outer (1) sition elem is" electro PROPERTIES OF Physical Properties configuration. [RANSITION ELEMENTS + Transition elements are hard (except Hg), malleable, ductile, good ind have high tensile strengt'» 1. Metallic charaet conductor of heat and electricity a Reason XN @_— Covalent bondi orbital) (ii) Metallic bondi ing due to d-d orbital overlap presence of partially filled Jectron sea. due to embedding of kernel in el £1 metals. due to absence rees of attraction. ZN, Cd, He are so fully filled d-orbital. ‘These result in stronger fo of strong covalent bonding due to QzHigh enthalpy of atomization: Transition elements have very high enthalpy of — mercury] CA pvegqacomization esoohi zine, caanTa M i Nera taiien Mme Reason: (i) Covalent bondi ue to paialy filed onitals. which undergo ovr ) Metallic bonding increase in number till the middle of the series duc to i jon, i.¢., Enthalpy of atomization increase’ iting in strong inter atomic forces of attract of unpaired yalance electrons resul stronger covalent bonding. Transition elements have high melting cof both (rl) d snd us.clectror sim till the middle of series, © to poor packing pattern hen it decreases regularly because ‘each seties tnelting point rises to max win, Te, Re have abnormally low melting point due stability of half filled and fully filled orbitals and 1 electrons are paired. Reasons Increase in number of unpaired electron ti the middle of series hence strong ded overlap and then due to pairing sr Giestor i dorbital and of stronger forces of attraction. Atomic no, ——————> of hear “Requimt 0 net hem,> ’ , case in, atomic > 4 / \Atomie raat size of transition elements decreases with increave JP ( umber till middle of series, Lo = : us 10 d-orbital , With increas in one mune, an ext lero fs beng ade 10 oi) > 4 ease in effective nuclear eharge which pulls outer elestron more 8 » ‘Size décrenses, (After the idl oF series sine fs almost sume, i. fn el? Varltton:y ) CSS . ion counter 1. -PeoReasons: Due to pairing of electron in d-orbital, electron-electron repulsion ) balances increase in effective nuclear cha ' "Last element of each series hns slightly bigger siz” igh fe sighs : Reasons: Duc to fully filed drbta, the electron - electron repulsion overvel ffective nuclear charge resulting in increase , 1 Meng the group, the atomic size increases from 3e/ series to Ad series, ) * Reasons: Due to addition of new shell, size-increas Size of Sd series elements is almost same as 4d clements. » Reasons: Lanthanide contraction, i.e. due 40. poor shielding effect-by intervening 4f picettons and increased effective nuclear charge, outer electrons are held more tightly hence, size decreases, 5. Density : Transition elements have high density and density inereases along the series. Reasons : Decrease in metaitic radius (atomic-volume)-along with increase in atomic ‘Mass results in increase indensity, 6. Ionization enthalpy : The ionization enthalpy-of d-block-clement etween sand p blosk elements, hence d-block elements are less ¢lectro-positive.-Thé ionization enthalpy of transition elements is furly high aiid i increases along the series’ but not regularly. Reason : Small size of transition elements and high effective nuclear charge, i.c., electrons aré ghtly held with nucleus tence, difficult to remove.The ionization enthilpy of Chromium and Copper are exceptionally high due to extra stability of half and fully filled orbitals. The third ionization enthalpy is very high for copper, nickel, and zine hence, it is difficult to obtain oxidation state Greater than two for these elements. Significance of Ionization enthalpies ower the sum of ion izatin:: (It predicts the relative stability of oxidation states enthalpies, greater the stability of oxidation stat ii) It predicts the existence of compounds, e.g. Ke (Pt Cle exists but Ky [NiCI6] does not exist. In Ke [Pt Cle] Pe (IV) sum of 4 ionization enthalpies is 9.36 » 10? kJ/mol. In Ke [NiCle] Ni (IV) sum of 4 ionization enthalpies is 11.29 x 10° ki/mol. Sum of 1Ey + TE + IE3 + IE is less of Pt (IV) in Ke {PL Cle] as compared t : (IV) in Kz [NiCle}. Therefore, K, [Pt Clg exists. (9? How fol You accoune tor He’ itreaLa, Vatiaton of LE (Lai (is oe far Oates of inne Paras ¢ 4m) Chie many Ray fae x fy, conf he . . : - ae Ct Hl totes Plate. So Rowany. £ 4a Actorparle TE, > Le, Lee rrer ttt.+ DS ee ne ® Pat, of FPS yin ts fA cr comps. Changed Fmoze, SPER cho oh g oxidation stat 2 Oxigation state + “Transition elements show variable osilatlon =H Cu* ete Jpation of eleetvons. scboth (usLiLand.ns in howd formation. Both nisperviss> 3a! 4s*-(42) is? (42) 4344 Vv 23 SASF 4DHI4 ATO Crd Ba Ast (LF DHI HAVES) AG Min] 25 3 4s? 2(43) HA +S (HO) AT Q:3 NCERT. ; 26 3a 452 +243 (+ 4) 45) (+ 6) Mn 4n 3d Aeties ALow You: Co... 27 Bd" 4s?+ 2.43 (+ 4) 5) Nef. OS Fd ys Ni 28 3a" 4574243) (4 4) Yan PD Cu 29 3s! ast e142 Zn 30 3d! 4s? 42 © [Rugiestoxidation statgis due to.sum of loss of clectrons of both (n-1)d and ns orbital. < to par «Nature of highest oxidation increases tll the middle of the series and then decreases. Reesons: @. Due to increase in number of unpaired slectrons in C8" (a) Bromuhy oft Mute —3- eye An eoluuins ) &)-yrom Fez ee rnpows < seer Sey , a3, ~ hy ste unit comb ese Ry 3 ne Se nS oe e a at Moe QT hy ty et values “for tw | mt pagialy. fed. d-obital anc Vea Alen aan-vansiion element vars by 2 unl — ympounds_of transition .clementSin lower oxidation states.are. 1Onle igher oxidation state. , © Highest oxidation state 3dseries = Mn +7 Adseries Ru +8 — Sdseries Os 48 Gites STABILITY OF THE OXIDATION STATE IN SOLUTION g Aurlimation ionitad (ion potential liyoro" = Healer @ explained on the basis of electrod My flr fer the reduction potential, greate ty of the oxidation state. a ee Nek a ar 3 E* (np cul oy ve, “My > Mn “ea ene" Gy weERT BS (r4"/r) ire pecs 7" 4-26" > CA ag. = +e° Cu Cu +20" > Cu e Ee isee = 40.50V o a” BS pe ycy = 403 4V. VE e vi i Therefore, Cu is more stable than Cut, -7 (Comp, a Porta @ als ult, Aga Ye (ii) Born — haber’s ele : Lower the sum of enthalpies, greater the sMBNGOE oxadaion —) state. CY Mu >My 4H, =+ve ; My >M'e +e" AH, =4ve Mz+aq— My, +e~ AH ave. 4 AH gg = OHye, $LE+ AB yn ‘ Smaller the size, higher the hydration energy. Larger the salvation energy, greater is the Therefore, salvation/hydration energy is important, Soo Ti VY Cro Mn Fe Co Ni Gyan Eley 210 1.60 1.18 -0.71 -1.18 -044 -028 924 4934 —0.76v thee is irregularity in the trend of reduction potential in the elements of 3d series. due to the imegular vari tion in (IE; + IE2) sublimaticn energy, hydration cnergy. The E values i : heer ate HC ed Re for the ‘s ‘/Mn** couple is much more positive than that for Cr*/C* and Fe’? / Fe", Given Boge = FLT ia.) , sa G4 7 why OF Rect. ae Hinton 20 Me 4 au Banos | -OAIV nse both Rar allt configures °, : Bees +077V EMeke of Cte oy oe ty a ye more Srtyalliion Gy Hudration. en nay sa for + Joo TE. — Mme~ @ € S © » Mn?" @> = Mn? e \ ad a - = ea . . = Bue to high reduction potenti! sian, more stable \ uk pad 1 (ad) and also led fontzal y of half filed : orbitals. aoe As ol + 2 ie 8 Coloured ions: Transition elements are coloured and they form coloured ions. @ “ Reason (iy’ Presence of unpaired electrons. _ p e ude) Gity ded transition. . | = € field splitting theory. € « It is explained on the basis of Cryst coe Gay \\ Busy ta oft gir ate da) ap dese nstable B. Colour-is complementary 10 the absorbed light. ZC] Hg are colourlesshecaiss the i onbitals-are fully filled and there i Fe ons. KMNOs is purple it be. ¢ @ ap Solour. The oxidation state 0 ‘Min in. KMNOs.is-* — ( 4 A tty cf As? qa hve Mn™* =3d°4s° Y 1 electtn Aa and the colour is due to chasse transfer from (I, I) eh wrsal In #7 oxidation state, all elect cwesal Oxygen to the vacan bital of Mi GuSOz is white whereas CuSOr + 2H,0 is blue due to Presence of unpaired election in 23a? 450.(iif d-d tran tion ‘sn approach of Ha0 Tigand ant splitting of d-orbital Ti oitTéss and Ti’” 15 co} joured. Tad 4s TP 3a! 4s® presence of a Tit 3d? 43° presence of un alts _appears.purple- jn-+3-state because they emit r n state of Cr = *6 cro"3d°4s° As it is attacl eit onyees, Te charge is transferped. 9. Alloy formation: Alloy is an homogenous mixture of 2 or more elements. E.g. Brass 's an alloy of Copper and Zine. Stainless steel is an.alloy.of iron, chromium. and Wickel. ‘Transition elements Form Targe number ofalloys. transition elements therefore, Ae Reason: Almost iimilar sizes of t can fit better into the crystal lattice of the other. packing spatter 10, Interstitial compounds: Tt ransition_elements show different types of cop, bee, hep, fecte. the packing pattem ¢ antains voids or interstiual SP al Spaces. These ar Tamir and are neither tonic nor covalent ° * nonstoich .n unpaired electron paired electron w, KyCr207 is orange. ed and_yellos 1 hed to highly electro — negative atoms of one elementCNN, Sm pounds wre due (o the tapping, of small non-metal Tks CaF Na e.g. borides behave like diamonds in _Giy” thas high melting point whieh is higher than the pure element. Gif They retain metallic conductivity. ‘avy The compounds are chemically inert. 2Na + Hz + 2NaH (interstitial hydride) Gili) Availability of vacant d-orbitals dere to which the central metal atom can form ©o- ordinate bond with ligand (electron right species). w , 11) Complex formation: Transition elements form complexes like Ka (Fe (CN)sl snd , [Cu(NH)4]?* etc. _— ¥ Reasor v AJ. Small size. * a ii) High nuclear charge.“ t € 12, Actas catalyst: Transi n elements act as catalyst, €.g. V20s, Pt, Pd etc. Reason: (i) _ large surface area. fii)... variable oxidation state va 7 _Gii) lower the energy of activation due to the formation of intermediate compound, SO, 4 to, 42550, SO; +V,C, —>SO, +V,0, +5 +4 V,0, #40, —V,0, Ferric ion catalyses the oxidation of iodide to iodine by persulphate ion S20; ion. 21" +807" 1, +2807" (high E,) 21° +8,07 41, +2807 (low Ex) 21° +2Fe* 2" 41, +2Fe* 2Fe™ +$,0}° > 2Fe™ +280a @ 5 Magnetic Properties :[in the presence of external magnetic Felt substance can behave 23 erties :[in the presence of external magnetic cca ee Paramagnetic or diamagneti spelled by. the ppl paramagnetic substances a S ‘re very strongly attracted and can behave as magnate even in absence of magnet agnetic. Transition elements unpaired electron, The magnetic ransition elements are paramagnetic due to the presence @r-uake electron. The magnet moment of unpaired electron is associated with its orbital angular ak etal ‘iv angular moment WW) eee red e*, higher the paramagnetism. me : M= Ya(+2)| (spin only formulae) tectron. in B.M. Bohr magneton A single electron \ (magnetic moment) _ = no. of unpai has a magnetic moment of |.73 BM. Which Cr, Ce*, Cu**, Fe" is more paramagnetic and why? More number of united £165 a greater the magnetic moment higher the. paramagnetism Cr 24 3d°4s' Gunpaired e” = (a6 = V8 O Cr* 21 3@°4s° 3unpaired e = 3040 =VI5 J Cet 27 34s Lunpairede” = bOD=3 Fe* 23 30° 4s° Sunpairede” = [54D = V35 Cusce* < Fe" t Some of the transition metals are sufficiently electropositive which dissolve in rmineral = ye eids, While few are noble hence unaffected by simple acids. ¢ -anium, vanadium are passive to dilute non ~ oxidizing acies at room temperature. + The metals of the first series with the exception of copper are relatively more reactive and are oxidized by | MH" slowly. ¢ Higher the reduction potential, stronger the oxidizing agent. E° values for the redox couple M?*/M*" shows that Mn’", Co* ions are strongest oxidizing agents in aqueous solutions. The ions Ti2*, V2" and Cr** are strong reducing agents and will liberate hydrogen from dilate acids, Due to lower reduction potential 6.8: EX iny —1185 — Egpq~!-60V Cr* 3d'4g9 (smaller size, higher hydration energy hence greater stability. of Cr).@ 2Crz 42H 9201) + Hae, xy to form divalent M™" + ‘There is a decreasing tendenc; Gf, dueto increase in reduction potential. ; 7 i sum of Gi Along the series, there is a decrease in atomic size hence increase in ionization enthalpies (I and Il). 4 g Reduction potential for Mn, Ni, Zn are more negative. Explain. D7 Mn 25 aha Mn?" 3d Zn 30 ad 4s? 5 Zn?" 3d'° ed and fully filled Li r reduction pot oe orbitals. ickel, due ‘sinall size, hij ONE" ion. ~ Comparison of 1" Row Transition Elements d-olectron configurati eee Sc 21 3d! 4s?-+ Sc Mn 3d° 4s? + Mn’* e.g. Sc™, Ti, V™, Cr’, Mn? d' except vanadium (IV) (V“) all transition disproportionation reaction, —i.e., reduction. 3MnO} +4H* — 2MnO; + MnO, +2H,0 e?, eg, Ti is strongly reducing while Fe’* is strongly oxidizing Ti 2230 4% Ti 3d Ti Te TP em Reducing agent Fe 26 3d° 4s* 3d Fe 3d Fe™+ 30" Fe* V (ll) reducing V23 3d 4s* 3d Voile Reducing agent @' + eg. Cr* stable and used in complex formation is ility_ of half-filled ils for there is due tea sali Chale Sle an stability, elements show d' undergo the same element undergo oxidation- as well as _— - ag @ on et Ft.© . 5. d‘ —.no stable species ‘ eis strongly reducing and Mn’ disproportionate : Cr 24 3d as! crt 3d . crt Ce +e (RA) : Mn — disproportionate ‘ ¢ Mn?* — Mn?* + Mn* & > Fe", Mn Fe? +e” = Fe d& — eg, Fe™,co* Fe?* — mild reducing age agent. 7 * d’ — eg. CO™ stable in aqueo! presence of strong ligands. 9. d+ eg. Ni* 10. d+ eg. Cu 1. di@ eg. Zn, Cut Cut is easily oxidized to cut wnt, CO2 — stable in the presence of strong complexing us solutions but gets oxidized to CO” in complexes in jum; common oxidat Group 4: Titanium, Zire mn Zigeonium and Hafnium exist ogether dueta idation state = +5, Group 5: Vonadium, Niobium, Tantalum, Foner oxi rium as a catalyst my fased 1 increase the strength of steel an the sire steel bium in Jet. engines... in making analytical weights, Molybdinum, Tungsten; oxidation state = +6 + 6 is exhibited in Crin aq. solution. while Cr** is strongly reducing. ating, Molybdinum in X-ray tubes, Molytodinum ion. Group 6: Chromium, oxoanions. +3 is stable for Use: Chromium in alloys, chromop 4 Tungsten in catalyst. Group 7: Manganese, Technitium, Rhenium ‘oxidation state + 2 t0+ 7 Radioactive Manganese in steel, Rhenium in electronic filaments, high thermoce :. bulbs Group 8: Iron, Ruthinium, Osmium \ t Fe'Sdoes (highest oxidation state + 8) wn but others do not. tin Ru and Os = +3, #2 dom not exist iron —+ undergoes corrosior Fe?! and Fe** are known but Group 9: Cobalt, dium, Iridium: ot exist. P88} III)e > > > ’ > > b \ Group 12:Zine, Cadmium, Mercury Disproportionate reacti in aqueous medium, ©. 3MAO(" + 4H1* —>2Mn0; + MnO, +2H,0 Chemical Properties L Group 10:Nickel, Palladium, Platinum +2 and +4 are Group 11:Copper, Silver, Gold (coinage metals) 5 aft ye \ re ‘ re even oxidizes Common oxidation state of cobalt +3, +2 + * is strong oxidizing agent, even 0: H20 to Oz Rhodium and Iridium — +3 is important. CO* — forms complexes with ligands hay N donar atom Uses of cobalt compous aint industs ramics, cataly . fare important. Alloys of Nickel — Nichrome Zn + 40% Ag) Palladium (60% Nickel + 40% Cr) German silver (30% Cu + 30% and Platinum — catalysts L J 4 +2 +1 B (Configuration 3d'° 4s?) Hg exists as Hg" + ic. Hg* (unstable) 7 ‘When the same element can undergo oxitlation as well as reduction Oxides Qxides of Transition Metals in Different Oxidation State Mo MO} M,03 M30, M05 M07 (M = Metal) | M = Mn Oxides in lower oxidation state +2, +3 are basic in nature. Neer {— -Oxides in higher oxidation state + 6, +7 are acidic in nature. Oxides of intermediate oxidation-state.are-amphoteric. eg. MnO MnO, Mno, 2 “ “1 fe Sonate wee Se and amphoteric oxides dissolve in water and form hexaaqua ions. (M (H20)6]* ion Oxometallic Salts 7 oxidation state of chromium = +6 hak Quy I. Potassium dichromate KC: Preparation of KzCr07 From chromite or FeO.Cr303 From vomit or 80,C104) FeCrO. (green) Preparation (a) Alkali fusion of chromite oreith H,SO« to oranee (b) Acidification solution of sodi jichromate- Firing C104 1,501 fractional orystaltization; .) and NaxSOu being less so jive shining orange separates oul ion “of NaxCn07 (©) Saturation of-orange seystlline solid of KxCr20r a. 200 ‘oe with KCI t 8 Properties of KzCrz07 Orange crystalline solid. It is soluble in hot water. KqCr07 has a high melting point Effect of heat on K2Cr207 8 52K ,CrO, +C10 #02 /BK:Cr01 Seer Sines a N, +4H,0 iene Effect of pit on gets converted to yellow chromate ion. In alkali ph, K2Cra! In acidic pH, it gets donverted to dichromate ion. Both forms are interconvertible by change ‘of pl! and can exist in equilibrium. crore He 9 HCHO; _siisie_, C077 +H,0 ells rite Or 2010 +2H* —20n07 +H,0 +20H" —>2Cr07" +H,0 i 1s used for cleaning of glass apparatus. 1,0; @ H2CrO, chiomic aci nopneeerVee i 21° —41, +2e7]x3 I acts as oxidizing agent in acidic medium, Cr,0F-4 62 14H" > 2C¢""+ 71,0 ‘The equivalent weight of chromium in Cr,0}-in acidic medium Mol. wt valent we. = Equival No. of electrons lost or gained Moi Wt Ba, wt Eth of molecular weight of K:Cri0> (@ K2Cr20; oxidises Fe to Fe™* Cr, OF + 6e" + 14H* —42Cr* +7H,0 — eae Fe —5Fe* 4076 eee ares nae! C UN EER Cr,O} +6Fe* +14H* —+2Cr* +6 Fe* +7H,0 (b) K2C120; oxidises F to ly 4 Ch OF + 6c" +14H* —42Cr* +7H,0 Cr,05" + 61” +14H* —+2Cr** +31, +7H,0 (c) K2Cr20 oxidises H2S to S Cr,0} +60" +14H* —52Cr* +7H,0 Y H,S—S+2e" +2H"}x3 Cr,0;” +3H,S +8H* —+2Cr** +38+7H,O @) K2Cr20; oxidises Sn”* to Sn** Cr? + 6c" +14H* —92Cr* 4. 7H,0 Sn* —sSn* +2e7]x3 eee el ace Cr,OF" +3Sn™ +14H* —>2Cr* 438n** +7H,0 It is a test used for confismation of chloride ion during qualitative Chromylchloride tes analysis,Ce Ulead 2KC}—4K,Cr0, #H,S0, —210,Ch, +2K,80, + CGO); +20 cbs CL Lyd bb x C10, Cl, ++ 2NaOH —+ Na,Cr0, + NaCl+H,0 CrOFKCH,COO), Pb #4 PLCrO, +2CH,COOH wat alone ‘Na cle ©} KxCrs0) is eotoured, duc to tage tanser by xpzen nthe vacant in oF hearin 8 Structure of Cro Hybridisation of Cr} is sp”. 9, Structure of Cr,0}" hybridization of Cr,0}" is sp*. 2 ° ° one 0 of WN ‘0 Uses ‘ 1, K;Cr207 is used for chromyl chloride tes. ‘ 2) tis used in titration as an oxidizing agent jgment, chrome yellow. ! 2° tis used for making coloured pig 4. Itis used in tanning of leather. Potassium permanganate KMnOx Onidation state of Manganese is +7 Preparation of KMnOx From Pyrol MnOz Pyros Oe ak brown) (a) Alkali fusion of pyrolusite ore —45K,Mn0, +H; 0 y) ~ Arln0, + 2KOH +20 0 Cn a 2? Foxmion mange ee") ‘ctrlytie oxidation of aqueous solution of Potassium manganate - K»MnO, —2K+ +Mn07 H,0 —> H*+ 0H" Atanode, CU" > Mundy t 2eul ) 2k Min0u Ue hi ak t Dy 2 oxidahun @ iaahon voit) 4(ve —> MnO} > MnOz +e At cathode, L (ve > Ht +e SH In solution, K" + OH” ~ KOH K*+MnO; > KMn0, On cooling shining violet crystals of KMnOs separate out. or ; By disproportionation of manganate ion in acidic solution to @.4 3MnO}" +4H* — 2MnO; +MnO;+2H,O NRT Properties of KMnO, In Kew 1, Itis presents shiny violet crystal. 2. _ Itis soluble in hot water. 3. KMnOs has high melting point. @ Effect of heat 2KMnO, —*> K2Mni 5. KMnO, acts as an ox: () In acidic medium, MnO; +5e~ +8H* —>Mn™ +4H,O Equivalent weight = 3» Mol. (a) It oxidizes Fe** to Fe** MnO; +5Se” +8H* —>Mn** +4H,0 _Fe* —>Fe** +e7]x5 Mn; +5Fe"* 48H" —>Mn” +5Fe”* +4H,0 oO (b) KMn0O, oxidises I” to I, \2Min0; +1017 +16H* —>2Mn®* +51, +8H,0 a (c) KMn0, oxidises Sn** to Sn** MnO; +5e~ +8H* —+Mn™ +4H,0]x2 Sn” —4Sn** +2¢7]x5 7 2Mn0; + 58n2* +16H* —2Mn** + 58a +8H,0 (¢) KMnO, oxidises oxalate ion to CO, @ give permanganate/ fo 4 8H! ——> Mn?" + 4H, 0] x2 > 2CO, + 2e7)x5 coo~ PF MnO, +16 H => 10CO2 + 2Mn* + 8 FO “ SC; (c) KMn0, oxidises nitrite to nitrate 2MnO; +5NO} +6H* —>2Mn™ +5NO; +3H,0 QQ» o~X, —™s ™-. Se dizes sulphite to a sulphate ~s }SS0)" + 2MnO, 46H" —-=-> 2Mn** + 3H,0 + SSO¢ “ So (a) Oxidises sulphide to sulphur. ~S ) \S?+2MnO4' + 16H? —> 2Mn?*+8H20 + 5S “ i) In basic medium, (dilute) MnO; +3e” +2H,O—>MnO, +40H7 +7 +4 Equivalent weight = 1/3" (jodate) * Mol. wt. (a) It oxidizes F to 105 MnO; +3e" +2H,0—>Mn0, + 40H" }x2 . I 60H” —710; +6e" +3H,0 ) o\n0; +1" +H,0—>2Mn0, +10; + 20H" G \t oxidizes thiosulphate to sulphate MnO,’ +3 $2037 + H:0 -—> skn0y" +6500" +2007 se “so “So So o 9 > ? » (6), It oxidizes manganous salt to MnO2 | [NPMnOs + 3Mn®* +2H;0 —-—-> SMnOz + 4H"* Structure of KMnO; or MnO; Hybridisation of MnO, is sp*= m1. Uses AA,.KMn0j is used as an oxidizing agent in volumetric analysis. SE-KMaOe used in qualitative analysis, Itisused.as a disinfectant in-water. Halides : Transition elements form halides in different oxidation states. Halides like chlorides, bromides and iodides are covalent in nature whereas, fluorides are ionic in nature. TiCl, +2H,0—> Tio, +4HCI Chloride of copper is covalent in nature and is a polymeric 3-dimensional network structure, Halides on hydrolysis form oxides, Sulphides Sulphides of transition ‘elements are coloured in nature. CuS - black CaS - yellow 2nS — dirty white MnS — buff NiS— black CoS — black FeS — black INNER TRANSITION ELEMENTS wa L 6. Flock elements (1-2) (n — 1) d "ns I — Lanthanoids Actinoids. (After Lanthanum) (After Actinium) Cerium to Lutetium, Thorium to Lawrencium Of 5d" 66? sf" 6a” 7g Rare earth elements, Synthetic elements man-made. After U-92, all elements are man-made and called transuranic. Non ~ radioactive except Promethium (Pm). Allate radioactive Common oxidation states are +2, +3, +4, * Common oxidation states are 42,43, +4, 45, +6, Distribution of oxi dation states in actinides is uneven. +3, +4 ions tend to hydrolyse, Do not form oxocations. Form oxo-cations UO’, PuO* . TF: FPRERRITLRRRA3 Qohar are oS Tribe by Nera mm Lu Lutetium af! Sd! 6s? Oxidation state Common oxidation state of lanthanoid is{E3] Others are #2"and +4. Lantlianoids can act as oxidizing as well as reducing agent. 1. AtNo. Element Electronic configuration « 37 La Lanthanum 4p sd' 63? s 58 Ce Cerium ap sd 65? a ee 4 © 59 Pr —-Prascodymium = 4°sd’ 6s? Og. ee e 630 «Ew beep e sd 63? ‘Se ome ie 64 Gd Gadolinium af sd! 63? 4D Oh ¢ 70 Yb Ytterbium afsd 62 Kesun 0:8 ¢ ce ¢ ‘ ‘ Stable oxidation state = +3. Lanthanoids at as reducing agent in +2 oxidation state while in +4 state act as oxidizing agent _ ; = HD ete pte 43 { Elements loose or gain electron to revert back to stable + 3 oxidations state. 1g or reducing agent and why? ) Among ce", Yb", Eu” which is oxi ‘They loose or gain electron to revert back to Stable oxidation state of lanthanoids is + stable +3 oxidation state. ‘| Reducing agent ‘Atomic size : Size of Sd elements are smaller, due to » Janthanaid contraction. .e in atomic size due to poor shielding by. intervening _y Lanthanoid Contraction: sinks gfelectrons, and increasing effective nuclear charge. : Consequences 1. Elements of 4d and Sd co-exist. 1 Eg. Zirconium and Hafnium (2r, 9}; ‘Molybdenum and Tungsten (Mo, W) exist together. Reason: They co-exist because of their similar sizes. Atomic size of Zr = 160 pm (picometre) Atomic size of Hf= 159 pm Atomic size of Mo = 146 pm Atomic Size of W = 139 pm2 Sq ition of lanthanoides is difficult, Due to similar_sizes and ionizal chemical methods cannot.be-used. Tanthanoids are separated by ion - exchange method. 3. Basic strength of hydroxides of Lanthanoid decreases, La (OH); —+ Lu (OH); : size decreases, Bond dissociation energy increases; basic strength decreases, therefore release of OH" is difficult. : ann ‘5 ike 4. lanthanoids are very reactive, behave like calcium and at times, also behave more Ii luminium. Calcium CaCy LnCz (general formula) Lanthanoids form carbides Aluminium AlOs Ln:03 Lu0; Al(OH) Ln(OH); Lu (OH); ro. NX te Ca x, inc, H0 | * Lach +H, A 1a LOH)+H,+ Lax, Uses |. Lanthanoids are used in alloys king pipes and plates as in steel: Misch metal (95%) lanthanioids +5% Iron + Traces of S, C, Ca, Al when mixed with Mg, is used for making bullets, shells, and the fin in lighte 4-2 Mixed oxides of lanthanoids are used in pertroleum i ~3. Some lanthanoids are used as phosphours in Television screens, ~4s Actnoids are silvery in appearance. - 5. They are highly reactive in finely divided state, Actinoids — sf!" 6d! 752 istry for cracking. AUNo, Element Electronic configuration 89 AC Actinium Sf 6d! 73% 90 Th Thorium Sf 6d 18 a Qn TTT ELERATARAAA ty SAN, FA| ve wevrewrwwwrrvreerrr wee wewe GB = Pcknae contr Ghemerr tem banthansd Conitrachon: * satis PHP as compared to 4f electrons. Hence, 95 Am Americium sf od 18° 96 Cm Curium sf" 6d! 1 102 No —_Nobelium sft 6d 15? 103 Lr Lawrencium sf! 6d! 19° Oxidation state : Number of oxidation states in actionoids are greater than fanthanoids dueto the comparable energies of Sf 6d and 7s levels ; : ‘13 is the most common oxidation state. The elements of the fist half series shew higher oxidation state e.g. (U), #7 (Nb) but, then decreases. in the size of M™* atoms. contraction. vation energy-of Lagshanoids. ielding effect from thenuclear charge loosely held (Pa), Tonic size: There is gradual decreas as Lanthan ids ae lower than io ing and hen: tore s ‘outer electrons are ran Lanthanotds. Magnetic propert ‘Actinoid contractions: Sam Tonization energies of A 5f electrons are less penetati jes ave due w 3) fore complex th Magnetic propert rhly same as Janthanoids. electrons, and is rougl Oxides + Hydroxides alHo autacked ess by HNO, <———— Actions + anche imore by Hel atmoderate,|.Nonemetals tempt like, N: Oxides, Nites et. tective covering of rnetallic ogent oxidizes the metal r0 form pro . . x aiken 2 22a fem Gem enr to HINO; being un oxtdizi oxide. \ sus a pete ose Ani fo an acineias stan YP 2 tm amtarcis anna nae ee ener rare >>3d ott sof saan i et Wesallé to Me 1 of the transition metal: i oiling points and melting pointsis.0-2 St So Neston sen eee. Sn seni SO > © coloured compounds. goss wnQOed a" oe > ind their many compounds act as good catalyst. (ramen thn 599” C8 Transition eloments form interaiial compounds. oe ’ fansition elements form complexes. (y spell «i wth wale ba Ce asniety h (8) Transition etements form alloys. Gwudied dh@ende Od ‘eh de okt “EXER, zit ate 1 #3. 2n, Cd and Hig are not considered as transition elements, Lomgicisry Gee d° 3% Compieeh f Q. Transition elements are paramagnetic in nature. (remseee sh wingasied @~ '“TTT” Copper is regarded asa transitional metal though it has completely filled d orbitals. because TOT, STO # 12. lonisationenergies of 5 d elements are greater than 34 elements. a2 08 oe ea . Melting and boiling points of Zn, Cd and Hg are low 24(aal } 4, Mat" compounds are more stable than Fe” towards oxidation to their 43 satenat(gas) FE"GAY et 5 Fo is more stable than Fe, . qatar. BPy nD G- Chemistry of all lanthanoids is identical. fa Ss Dovahonadd Su aportard (2° 17, Aghits a completely filed d orbital in ground Sate but itis stil a engifon Metals ea yy 0S EENISO Ww 18. Why is europium (II) more stable than cerium (I)?- ce 9 44% sa).6s™ HnetrnglD Ci, Pad lr seiined 9. Cris more stable in aq. Solutions Ex~ GFT sd%is™ is colourless while Cu® is coloured. Or Cu" is diamagnetic whereas Cu™ is paramagnetic. Sc is regnrded as a transition clement but not zine. 22. Co (I!) is stable in ag. solution but in presence of strong ligands and air it is oxidized into CoC). Ce (Il) is easily oxidized to Ce(IV) of the: species Cea) : strongly reducing while Mn({II1I) is strongly oxidizing. dudn patrol , In series Sc to Zn, enthalpy of atomisation of Zn is the lowest. : yg don Bay Cd ‘The E? M'"/M value for copper is positive, 's-0 = x we OS = tnt Roa Oxidising power increases fom VO;' BMnOs + + > 2G MnOg +1-+ H-> ‘ LATE Mn0y+ Fe® + > si Mn0,: + C,0f"+ Ht ->. 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Dr 4) West in mole” & e : : » Caen a Shetty 8 Ligne finns o 3 4 5 Q.29 (NrERT 1) 2 1823 The chemiy of the sctindid ements le not v0 smooths that of Ge anthansll +4 +2 FOG, \S stent yng sme comp rom he aon st of he seen | cos Lanthanoids show limited number of oxidation stale, viz, + 2, + 3 and + 4 (out of whist = 2 i) ae ‘common. This is because of large exergy gap between 4nd 5 d subsbells. The haswhrcctvm macel , ther ox CRE, ISR ‘state of actnoid is also + 3 but they show a number of other oxidaifon states also, and plutonium (2 =94), show + 3, +4, + 5 and + 6, neptunium (Z = 94) shows + 3, ‘This is due to small energy difference between 5 f, 6d and 7 s subshells of the actin Uker Armor + Mn, + Ihre 9-22, simitay, Cr (V) undergoes disproportionation in acidic medium a follows “tl Gop + 8nt —> 2:0} + C+ 44,0, 4 (0.823. Which metal in the frst transition series exhibits + 1 oxidation sate most fequentiy: ‘Ans, Cu bas the electronic configuration 3d'®4s!. It can easily lose 4s" electron to give the tion. Hence, it shows +1 oxidation state. We write it as Cu (1). configuration. Q. 8.24. Calculate the number of unpaired electrons inthe follawing gaseous ions: Mn®, Cr, V2" and TF. eeed unpaired electron, CP = 343= 3 unpaired = 1 unpaired electron. Cr*is most stable out ofthese in aqueous solution