/_4EE MASTERS CRASH COURSE rh Pn se 2A YE Ne One Shot D & F Block eSae Topicy to be covered oy Coe sae "){_ D-block } (,) ¢ Number of groups 10 © They one often called ‘transition elements’ because their position in the periodic Pel een eee ele eee ee eee Tne CM Aye OMe COMES (nM Lome Teeny) chm (re me (A Le eee eR ew me aaa Noe ao lontae ¢ Since Zn group has d!° configuration in their ground state as well as in stable oT eE TM CMU AR LAK OM CM SRC COTM LCE SOLS A TKR 1) Fete eo (erica ese e2/£lectronic configuration : (n - 1) d!-!ns!-? CRU le eae UNE UL elDa em Celele Reena Coomera (cleo (6 t dak eres > maximum van Fy ct Ma eee eS ca} due a ae os = . : # fs A, are involved in metallic bonding ie Gamelan Pu Ss ela OksWace hg ) Noa tl iyo Co att [Oty Zn ed eters PE Ey Pte crercy Fey acm ea eile: org co Pon PA Gir hi eam aS A a rN aN A a a rN a A y | Zr Nb Mo Te Ru Rh Pd Ag Cd—> IDWS A rN AS nN AS aN AS aN rN aS La/ Hf Ta W Re Os Ir Pt Au Hg—»ZredlTS he ee Abo 2 earn Pee ELC OCCA SE Re DCm cme losin oa In 3d series highest density - Cu , lowest density - Sc Enthalpy of atomization, D,H-/kJ mol Maximum : V (515) Minimum : Zn (126) Less eo aS Oxidation states of the I* transition series ee ; ea Chev ic oe Zn A eee haccacal Lo eae RS 3s RES ES Bs ee eee eee ee most common ones are in bold typ GE Eo} eH Bee ew es tees) rer ee P46 1467 +7 Cy eae pa¥ | | Q (OC eCk eae. ON Sol. AgO supposed to be paramagnetic due to d? configuration. But actually eR M ne ete WS Ce ey. PY O| te eae ine oe aol 7D ae Catalytic properties : ) @ (eed LUI TiCl, ——> Used as the Ziegler - Natta catalyst in the production of polythene. V,0, —— > Convert SO, to SO, in the contact process for making H,SO, MnO, —~> Used as a catalyst to decompose KCIO, to give 0, Fe | —+» Promoted iron is used in the Haber-Bosch process from making NH3 PdCl, —> Wacker process for converting C,H, + H,0 + PdCl, to CH;CHO + 2HCI + Pd. Pd —+» Used for hydrogenation (e.g. phenol to cyclohexanone). Pt/PtO —> Adams catalyst, used for reductions. a da — Formerly used for S0, —~> SO; in the contact process for making H,SO,Pt/Rh —> Formerly used in the Ostwald process for making HNO; to oxidize @ NH; to NO =< - lorry — Isused in the direct process for manufacture of (CH3)2SiCl, used to make silicones. Cu/V —~ Oxidation of cyclohexanol/cyclohexanone mixture to adipic acid which is used to make nylone-66 (0 Pe mee ceo Bee Cea Own e SOF Nt — Raney nickel, numerous reduction processes FeSO,+H,0,—> Used as Fenton's reagent for oxidizing alcohols to aldehydes. paca eeMorcaans DeLay eRe} Dissolve in water Se bi Le eNO LO lero CoS eat Ca a ES tome ree nt Q.S.P Lime (CaO) added with Na,CO; which keeps the mass porous so that air has Enc eOr Bee CR KAO eT En a | Step (ii) 2Na,CrO, + H,SO, —> Na,SO, +.Na,Cr,0, + HO ors p07 aU ita } Hence, suitable temp. is to be upto 32°C increases Crore ose n eats eran teed Na,SO, first. Yc) C110 ere aed Col Meee CeO See ed Presta NaCl crystallises out first and filtered off, Then K,Cr,O, crystallised out on cooling2 | Q _ Inlaboratory K,Cr,0, is used mainly not Na,Cr,0,. Why? | Sol: Na,Cr,0, is deliquescent enough and changes its concentration and can cher) ela e ree erin ae ue cere Wii Win el OO COR ORAL of crystallization and not deliquescent.Effect of Ph : The chromates and dichromats are interconvertible in aqueous solution depending a7 Te emo meee MMM ele eIcRe meena eect Clemo ea et cers AO aer: Rae Or ae PLO) Cr,03- + 20H~ > 2Cr03- + H20 leat last leo a foro Pert)NON re Sas Ve Preparation of Manganate (Mn0O,”-) : - Mno, —K°#____ ino? (2MnO, + 4KOH + 0, —> 2K,MnO, + 2H,0] aot ee melt MnO, + 2KOH + KNO, —» K,MnO, + KNO, +H,0 3MnO, + 6KOH + KCIO, —» 3K,MnO, + KCl + 3H,0 Structure es @ Die aoe T KNO,—> KN0,+ © ore Pe ae TO a ea Penrenics Peannhenn ei isn ea mene moyen ae aan aa aye aes) oO)—— va ca oc) Te @ bia e att a. aH naar A rw0z Cae &= aaa zerh bs a 2- R) UVC yA eee AO Ue acest inden =) eA) i Saad a) Bren cer eat 2 SY id u 3K MnO, + 2H,S0, — 2KMnO, + MnO, J +2 K,S0, + 2H20Tesla Oxidising Prop. of KMnO, : (in acidic medium) () MnO; + Fe*? + H* > Fet? + Mn*? + HO (ii) Mn03 + I7 + H* — Mn*? +1, + H20 (iii) MnO; + H202 + H+ — Mn*? + 0, + H20 (COR Un Oren erd Les Mn*? + H,SO4 (v) Mn0z + NOz +H*+ — Mn*? + NOz + HO (vi) Mn0z + H2C,0, + Ht — Mn*? + CO, +H20 (CHR Ores nee wt ane en Pe) (CTE Ora ee VU Ca RE OY aOxidising Prop. of KMnO, in neutral or faintly alkaline solution. @ 2Mn0; + 20H~ — 2Mn03- + H,0 +0 (Craters aaa KI — 2Mn0, + 2KOH + KIO, (ii) 2KMnO, + 3H,0, — 2KOH + 2MnO, + 2H,0 + 30, Heating Effect : 2KMnO, 2 K:Mn0, + MnO, +0, Pc ESS 2K,Mn0, —,-> 2K,MnO, +0,Aner erte cc) a) 4 BR a Sa tte es N Black [4Ag + 2HyS +0,—2Ag,$ + 2H0] H,SO, by eee 0 Panne. nea OE SLA) NWOT TN Le nier Ag + 2HNO;—>AgNO;#NO, + H,0 Pernt ae Eolas el 4 ")a ® It is called as philosopher's wool due to its wooly flock type appearance Preparation: [1] 2Zn + 0, —> 2ZnO [2] Calcination of ZnCO, or Zn(NO,), or Zn(OH), PurestZnO: 4ZnSO,+4Na,CO, + 3H,0—> ZnC0;. 3Zn(OH), + 4Na,SO, + 3CO, Sze a white basic zinc Ti nN 4ZnO + 31,0 T + CO, T caBCs (RTE Ta (el ZnO + 2HCI — ZnCl, + H,0 ZnO + H2S04 — ZnSO, + H,0 BSTC Re cS ZnO + 2NaOH — Na2Zn02 + H20 eto mye by Sa ZnO + HJ —— Zn + H,0 PCs C Rte eelasleil Zn0 +C — Zn+COPANE: (oe Aone} Zn + Cl, > ZnCl, Zn + 2HCI (dry) — ZnCl, + H2 Zn + HgCl, — ZnCl, + Hg Properties: (i) It is deliquescent VTC cee Com (when anhydrous) (ii) ZnCl, + Hy S > ZnS Cod Em C+ NaOH — Zn(OH)2——>Nap[Zn(OH),] eG fea POLO ey ATOLL ad Uses: Used for impregnating timber to prevent destruction by insects 2] As dehydrating agent when anhydrous ‘AS, 3] Zn0 - ZnCl, used in dental filling ")\ con Daas er-te- tHe ed Zn + dil H,SO, ——> ZnSO, + H, Zn0 + dil H,S0, ——> ZnSO, + H,0 ae ie crewed >70°C OTT al >s00°c 4 CS eS Le ee ae Lo SRST (ce leon) 2. Lithophone (ZnS + BaSO,) is used as white pigmentrf a {cuo_) Dae sjerveta (ied oO (i) CuCO3 - Cu(OH)2 By 2Cu0 + H,0 + CO,( Commercial process) MalachiteGreen) Deaecyerve-ta (ies (i) CuO is insoluble in water (TOPS melee) yom Rel I CeCe CuO + H,S0, > CuSO, + H,0 CuO + HCI — CuCl, oe ae (iii)It decomposes when, heated above 1100°C Proton ee ao (iv) CuO is reduced to Cu by H, or C under hot condition oO ee ee AOE Cee a nee a hn ")con SE eres See aa eee Te Sea Kem ec en Dayo rlele (OED) Itis crystallised as CuSO, isd a tone @ — cuso,5H,o ===* cyso, 34,0 == SMES sd re feroyg Ae) aS) take places Pale blue SINT SINC Prt e lb SS i ---O aS CuSO,(anh.) a Sine ea ae yon Cyseen (,) retry From Kipp's waste FeS + H2SO,( dil ) — FeSO, + H2 ST ead baer oat co —— (0) Tata Coeoloee ue eae E OOM ia tien mem Oiled wa CIOs 1 Oe Or ieee a By 4 ee, PR 9) alk on om aT ye anh. white (iii) Itis a reducing agent o il 4 4 ‘4 (a) Fe*+ + MnOj + H* — Fe3* + Mn?* +H,0 () Fe2* + Cr03- + Ht — Fe** + Cr+ + 1,0 rd aly (c) Au3* + Fe?* — Au + Fe3*+ (C\ ream eet LO Pa mre ooo Seeeta Pee Nee e eure outeCeere eM mc eee men Ore ee oe heated iron fillings. The vapors are condensed in a bottle attached to the outlet of the Poy Tne ae Daee) lane ; cS TN, Tei e om OO ey: Come ae(iv) baste eater ace eRe eel Anetta @ (b) © (Cy) 109) Teese Cele ieee an oe eR ORT LUL een Cone Cele Pea ew 0 SO It oxidizes SO. to H2SO4 2FeCl, + S02 + 2H,0 — 2FeCl, + HyS0, + 2HCI It oxidizes Hz S to S 2FeCl, + H2S > 2FeCl, + 2HCI +S Tate leering ee PA rad e130 Nascent hydrogen reduces FeCl, into FeCl, eee ee ce ean [el PTO PEED Az (ON) PRESS) PB CC Peau ny ")[Feblock } The Aree in which the additional electron enters in (n - 2)f orbitals are Pe R Homers uth a lea une Number of Series Lanthanide series (Z=58-71) (Ce - Lu) 7 Pashtu (Z=90 - 103) (Gi esky ote LANTHANIDES (RARE EARTHS OR LANTHANONES) A CMC e meen itatrecleer mem Eileen eee lg fi © Cesg Prsg, Ndgo, Pmgy, SMe, Eulg3, Gd 4, Thgs, Digg, HOg7, Egg, TM¢g, Yb7o, Lu, ¢ Pmis the only synthetic radioactive lanthanide se Lice A eeElectronic Configuration : (@ The general configuration of lanthanides may be given as 4f-!5s?Sp*Sd16s? ‘Atomic Element Symbor CGN ed na a 58 Corn roy Pre Td 59 eecomtt iy ig cr Oi Co Neco y ST cre ny Gl omen) cy koa) oy 62 SSC my cos) co CH arn rn cre my 64 Gadolinium: Ga Pree Td cS Tron 1 Ta ae CS Dynes) yy cr rn 67 Ont ry cr ng Cy ony Er cre en Co Bun nvy orn cats rT 70 any at Clear cl 71 Pere tk io Cred a adCee ee BRUCE Caen Tet PRUE e eee ROC TRIER a MOELLER Lcere MULL SEN tt aden and Terbium exhibit higher oxidation state (+4). Eu and Yb exhibit +2 oxidation state 4 (TOM PRC Beer Uc) hutlec Baronet Yn PoC RCRA eno ili eee han) a Eu2+ is a strong reducing agent changing to the common +3 state. Sa Cam eC rc eter nee hiaMagnetic properties : @ @) In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to Gadolinium (0 to 7) and then continuously (Tere oe non cele Aon) (ii) lanthanum and lutecium ions are diamagnetic, while all other tripositive lanthanide ions are paramagnetic. (Exception - Neodymium is the most paramagnetic lanthanide). (iii) | Ce+4 and Yb+2 are also diamagnetic ions.Color : @ ) Gi) The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible region of light and undergo f — f transition and hence exhibit eo a — The color exhibited depends on the number of unpaired electrons in the 4f ites The ions often with 4f" configuration have similar color to those ions having Cy meetsOther Properties : + All the lanthanoids are silvery white soft metals and tarnish rapidly in air. @ re) MUIR e ee R Te eee COREL eT TELM LTR Can ec Lae * They have typical metallic structure and are good conductors of heat and electricity. * Highly dense metals with high m.pts. do not show any regular trend. Ionization Energies : Lanthanides have fairly low ionization energies comparable to Elen ere-laenm i (oie om * Electro positive character : High due to low LP. Bees eed etna mine tered de ere density because of their large size. Lu*# is smallest in size can only form complex. aOhio aco @ * Reducing Agent : They readily lose electrons so are good reducing agent. se itt Sauna Ly soy PURO METEOR Mee em Vitro mnt ec] IVnT Moet eee) i) lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. = aa coats Nature : La(OH), is most basic in nature while Lu(OH), least basic. * Carbide : Lanthanides form MC, type carbide with carbon, which on hydrolysis gives ono ieee elements Eu and Yb dissolve directly in very high concentration in liquid anaes EePe uiebe estroge Ti aN) ron ere) ea okey KelApplication of lanthanides : @ eT ERO a RSM RLS tC Ne (Sce © Ceramic application - CeO,, La,03, Nd,0, and Pr,0, are used as decolourizing ETO es Oma Eom © CeS (m.p. - 2000°C) is used in the manufacture of a special type of crucibles and refractories. CPPCC CRMO LOC CceeSu OMY Ne CMe eI IMU Tce Cor eReT) Poesy e Intextile and leather industries (Ce salts). e Mish metal is pyrophoric and is used in cigarette & gas lighter.ACTINIDES (5f - BLOCK ELEMENTS) @ CRP RO Nes HR oO eS ue Ree) cee ele mea sees CIE ETeoe on OE le Cec CMM W EER avon SUR ee ed placed beyond uranium in the periodic table and are © Collectively called trans-uranium elements. CONC RON eta c eet COE CRC Rae L © Electronic configuration : 5f'-!* 6d°-1,7s*, apCa @ SUC OL EAT uu cok TCC st PU EM Moe UEC OBE eins eee R CeCe MRE UL eee cancer. CERO ECR een Ce ec wim oR Oe ec REECE ena cele imparting green color). textile industry and also in medicines. aOR eg CRS eB met marae ERC CREO Rel — =Electronic Configuration : The general configuration of actinides may be given as 5f!-!46d°-!, 7s? oe RCs Pm ‘Symbol__| Electronic Configuration 90 ire in st Or Ponty ay Buca 2 Cet tw Se ox OULD Ny Sn 4 Conny ra Sia oo rere zn Scr 77 orn cory Se 7 Berkellium ig Scr Oy Oona a Sian 99 Finstenium is Clare ti) Pec) iy BT ae oT Nims roaniny We Stier 102 Sey i San rs) ey a SeYN CeCe eee @ @ PHBE Meese UCR Ae meme ceOmt Reema eie em lee kegels Routes cou (ii) This oxidation state becomes increasingly more stable as the atomic number Tate UUme b Cena eae CUO ciao Cer lene commence Cantilo (o eee LN eet aa eye a unstable. al Highest stable oxidation state Ona allen4 ris Properties: ia re) Sas yc eee tC eR UC ie Oe ome Ro) exposed to the attack of alkalies. a Siew Rene Catia e(oe eo MUO CTC Oe LUMI ACT iRe oun te (oom Color : Actinide ions are generally colored. The colour of actinide ions depends upon the number of 5 f-electrons. The ions containing no unpaired 5 f-electrons (exactly full filled subshell) are colorless, as expected. Ionization energies : Ionization energies values of actinides are low. Electropositive character: All the known actinide metals are highly electropositive. WV meu CREME Crone Reiss ce Melting Boiling properties : They have high melting and boiling points. They do not bo) aE me eC eRe miley comes Oem ee eke Rome Comme Leoiy Se CTs a ae sas oem Wie eee Rone ee cic le eee Ronee oa ekel es Tee Tince Ro rennet : Peon PET ee RUE ot ne Orem ecCelle (ae eRe = Actinide contraction : The size of atom/cation decrease regularly along the actinides ou MMR Meee ROC M VIB aeRO Cena (eel to as actinide contraction. This is due to poor shielding of 5 -electrons.Noreen er Cem) Points of Resemblance : Tg PITRE CSE Heese Oe ROEM Cee Le @) (ii) Both are electropositive and act as strong reducing agents. Va COMUNE ern an Ran nearer atts (iv) Most of the cations of lanthanides and actinides are colored. (COMME Meme ea RCC hme (acc mT eit oom lel eli emer Roe (oom MULTI eCLalertcnelle Como am CLL neeLun Ce CR ae Lee las COO CDH Eas balls CORSON CAS LIL foelalex-(es(e) 0ioe oted eC T Nee weet nts xp Terns ered 1. Besides the most common oxidation state of +3 1. Besides the most common oxidation state of +3, lanthanides show +2 and +4 oxidation states in actinides show +4, +5 and +6 oxidation states ee Rec ke anoe ites oom or ee aC ay ean ae eS Se en eh 3. Except promethium, they are nonradioactive, 3. Alltheactinidesare radioactive. POT ee oto ets PRO nce nites less basic. easy" &